Weakened postmetallocene catalysts

Abstract

A method for making a weakened light-off post-metallocene catalyst ("weakened post-metallocene catalyst" or "weakened PM catalyst"), comprising: adding a fast light-off catalyst to a catalyst having an effective amount of a compound represented by formula (A1), (B 1 ), or (C 1 ):R 5 -C≡CR 6 (A 1 ), (R 5 )2C=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 obtain a weakened post-metallocene catalyst exhibiting an attenuated light-off kinetic profile (compared to that of the fast light-off catalyst), wherein the fast light-off catalyst is represented by structural formula (I): (D): d M(T) t (Q) q (X) x (I) a postmetallocene pre-catalyst (i.e., an unactivated "coordination entity" or "ligand-metal complex") prepared by activating the postmetallocene pre-catalyst, and related methods, compositions, and uses.

Description

[Technical Field]

[0001] Olefin polymerization catalysts, methods, and polyolefins made thereby.

[0002] Introduction Publications and patents in the field include European Patent Application Publication Nos. 0188914(A2), 0748823(A1), 1778738(A1), 2121776(A1), 2609123(A1), U.S. Patent Nos. 5,624,878, 5,965,677, 6,083,339(B2), 6,967,184(B2), and 7,705,157(B2). No. 8,455,601 (B2), No. 8,609,794 (B2), No. 8,835,577 (B2), No. 9,000,108 (B2), No. 9,029,487 (B2), No. 9,234,060(B2), 9,718,900(B2), U.S. Patent Application Publication No. 2009 / 0306323(A1), 2017 / 0081444(A1), 2017 / 0101 494(A1), 2017 / 0137550(A1), 2018 / 0002464(A1), 2018 / 0282452(A1), 2018 / 0298128(A1), International Publication No. 2006 / 066126(A2), International Publication No. 2009 / 064404(A2), International Publication No. 2009 / 064452(A2), International Publication No. 2009 / 064482(A1), International Publication No. 2011 / 0875 20(A1), 2012 / 027448, 2013 / 070601(A2), 2014 / 105411(A1), 2016 / 172097(A1), 2017 / 058858, 2017 / 058981(A1), 2018 / 022975(A1), 2020 / 055893(A1), and 2018 / 183026(A1).

[0003] Among others, U.S. Patent Nos. 8,609,794 B2, 9,000,108 B2, and 9,029,487 B2, U.S. Patent Application Publication Nos. 2017 / 0081444 A1, 2017 / 0101494 A1, 2017 / 0137550 A1, 2018 / 0002464 A1, 2018 / 0282452 A1, and WO 2017 / 058858 and WO 2018 / 022975 A1, assigned to Dow Global Technologies LLC, a subsidiary of The Dow Chemical Company, describe biphenylphenoxy-type (BPP-type) precatalysts and catalysts, their synthesis, and their use in olefin polymerization reactions.

[0004] U.S. Patent No. 6,967,184 (B2) issued to Timothy T. Wenzel ("Wenzel") and U.S. Patent No. 9,718,900 (B2) issued to Garth R. Giesbrecht ("Giesbrecht"), both assigned to Univation Technologies, LLC, a wholly owned subsidiary of The Dow Chemical Company (Midland, Michigan, USA). Wenzel and Giesbrecht describe HN5-type precatalysts and catalysts, their synthesis, and their use in gas-phase olefin polymerization reactions.

[0005] U.S. Patent No. 6,803,339 (B2) issued to Richard A. Hall et al. ("Hall") and is listed as being assigned to BP Corporation North America Inc. Hall addresses problems that metallocene catalysts have when they are fed to a polymerization reactor with the olefin monomer stream. "Metallocene catalysts are difficult to use directly in conventional polymerization processes, especially in gas-phase processes where the catalyst system is dispersed in a hydrocarbon or in monomer and metered to the reactor via a feed line. Supported metallocene catalysts are optimally active when preactivated, i.e., combined with a cocatalyst component before being introduced into the reactor. Dispersing such catalysts in an olefin monomer stream for direct feed to the reactor system results in polymer formation and causes severe plugging of the feed lines. Furthermore, polymerization proceeds before the catalyst system is sufficiently and uniformly dispersed throughout the polymer bed in the reactor, resulting in hot spots of high activity that promote agglomeration and plate-out. The reactor quickly becomes fouled, resulting in reduced catalyst yields and the need for frequent shutdowns to clean the reactor." (Column 2, lines 50-65, emphasis added)

[0006] Hall goes on to elaborate on solutions previously tried by others: "Temporarily reducing the activity of metallocene catalysts has been described in the art. For example, adding a dialkyborane or dialkylaluminum to the reactor during polymerization to temporarily delay the activity of the metallocene catalyst has been disclosed as a method for process control. However, catalyst activity is only partially delayed by such treatment. Catalysts directly treated with a dialkyborane or dialkylaluminum retain sufficient activity to initiate polymerization once dispersed in the monomer feed stream. Furthermore, this recovery period is too short to allow the catalyst to recover and for the catalyst system to become adequately dispersed within the gas-phase reactor bed of a stirred reactor before polymerization can proceed." (Column 3, lines 14-26, emphasis added).

[0007] Hall sought a method for temporarily and reversibly passivating a metallocene catalyst so that the catalyst would be in a reduced catalytic activity state to a level that would allow it to be fed to a reactor in contact with an olefin monomer and properly dispersed in the reactor polymer bed before reactivation (column 3, lines 49-55). That is, Hall sought a method that would allow a polymerization reactor to be fed with a temporarily substantially deactivated metallocene catalyst in an olefin monomer stream.

[0008] Hall's solution relates to metallocene catalysts that can be temporarily and reversibly passivated by contact with an effective amount of an unsaturated hydrocarbon passivating compound (Abstract section). Hall's solution also relates to a method for temporarily and reversibly passivating metallocene catalysts, in which a fully active metallocene catalyst can be temporarily and reversibly passivated by contact with an effective amount of a passivating compound (Column 3, lines 58-62). The temporarily and reversibly passivated metallocene catalyst is further characterized as a latent olefin polymerization catalyst and has substantially reduced activity for the polymerization of olefins (Column 3, lines 63-66).

[0009] Thus, Hall attempted to temporarily substantially deactivate (poison) the metallocene catalyst so that the resulting temporarily substantially deactivated metallocene catalyst could be fed to a reactor with an olefin monomer stream without the temporarily substantially deactivated metallocene catalyst polymerizing the olefin monomer in the feed stream or clogging the feed lines. This gave Hall time to distribute the temporarily substantially deactivated metallocene catalyst through a polymer bed in the reactor, where it could be reversibly reactivated. Thus, Hall's metallocene catalyst is either fully active or substantially deactivated, and the substantially deactivated metallocene catalyst is fed to a reactor in the presence of olefin monomer in the olefin monomer feed stream. Summary of the Invention

[0010] The present inventors have discovered a problem with feeding a post-metallocene catalyst (i.e., a catalyst without a cyclopentadienyl-containing ligand) separately (i.e., apart from the monomer and polyolefin polymer particles) to a gas-phase olefin polymerization reactor. Olefin polymerization is an exothermic reaction that can be carried out in liquid phase, slurry phase, or gas phase. The nature of a gas-phase polymerization reaction is such that it has the least mass to absorb the heat of reaction exotherm. The present inventors have discovered that even when an active post-metallocene catalyst is fed separately from the olefin monomer feed (and, for that matter, separate from the active polyolefin polymer particles) to a gas-phase polymerization reactor containing an olefin monomer and a moving bed of polyolefin polymer, such as when the active post-metallocene catalyst is fed into the reactor as a solution or slurry in an inert hydrocarbon solvent (e.g., alkane or xylene), the active post-metallocene catalyst may light off too quickly in the gas-phase polymerization reactor once it is in the reactor and experiences polymerization conditions (e.g., high temperature and pressure). That is, upon delivery (e.g., injection) of the post-metallocene catalyst, and before the "fast light-off" catalyst can be adequately dispersed within the moving resin bed, the catalyst begins to create polymer particles within the reactor near the catalyst injection site. This causes heat to be generated locally faster than it can be absorbed, causing the polymer particles to fuse and form agglomerates. These agglomerates foul reactor components and / or impair the properties of the polyolefin product.

[0011] Also, fast light-off post-metallocene catalysts, when paired with slow light-off metallocene catalysts, can create a reactivity-mismatched multimodal (e.g., bimodal or trimodal) catalyst system in the reactor, which produces polyolefin polymer particles with undesirable variations in flow index and / or density with particle size.

[0012] These problems do not arise with metallocene catalysts, which are catalysts containing two cyclopentadienyl groups (independently unsubstituted or substituted), which tend to light off relatively slowly under these conditions.

[0013] Our technical solution to the problems arising from "fast light-off" post-metallocene catalysts is to use an effective amount of a kinetic modifier compound that alters the molecular structure of the post-metallocene catalyst such that the resulting structurally modified post-metallocene catalyst, when fed into a gas-phase polymerization reactor separately from the olefin monomer feed, has a new molecular structure and remains active, but exhibits a characteristic weakened light-off kinetic profile ("weakened light-off post-metallocene catalyst," or more simply, "weakened post-metallocene catalyst"). For example, the weakened kinetic profile may be characterized by a longer peak reaction temperature (Temperature) of the weakened post-metallocene catalyst compared to that of the fast light-off catalyst used to make the weakened post-metallocene catalyst. peak ) and / or lower Temp peak The length of the delay is long enough to reduce or prevent agglomerate formation, which in turn delays or prevents fouling of reactor components and / or minimizes the disruption of the properties of the polyolefin product produced thereby. Despite the delayed initiation, all other things being equal, many embodiments of the weakened postmetallocene catalyst exhibit catalyst activity / polymerization productivity, expressed as grams of dry polyolefin product produced per gram of catalyst added to the reactor per hour (gPE / gcat-hr), that is not significantly lower, and in some embodiments may be higher, than fast light-off nonmetallocene catalysts. This result is unpredictable in the art.

[0014] A method for making a weakened light-off post-metallocene catalyst ("weakened post-metallocene catalyst" or "weakened PM catalyst"), comprising: adding a fast light-off catalyst to an effective amount of a compound of formula (A 1 ), (B 1), or (C 1 ):R 5 -C≡CR 6 (A 1 ), (R 5 )2C=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 obtain a weakened post-metallocene catalyst exhibiting an attenuated light-off kinetic profile (compared to that of the fast light-off catalyst), wherein the fast light-off catalyst is represented by structural formula (I): (D): d M(T) t (Q) q (X) x (I) by activating a postmetallocene pre-catalyst (i.e., an unactivated "coordination entity" or "ligand-metal complex").

[0015] A weakened post-metallocene catalyst prepared by the above preparation method.

[0016] A method for feeding a post-metallocene catalyst to a gas-phase polymerization reactor containing an olefin monomer and a moving bed of a polyolefin polymer, the method comprising: preparing a weakened post-metallocene catalyst according to the method described above; and feeding the weakened post-metallocene catalyst in neat form (e.g., a dry powder) or as a solution or slurry thereof in an inert hydrocarbon liquid into the gas-phase polymerization reactor through a feed line that does not contain the olefin monomer.

[0017] A multimodal (eg, bimodal or trimodal) catalyst system comprising an attenuated post-metallocene catalyst and one or more different olefin polymerization catalysts.

[0018] 1. A method for feeding a multimodal (e.g., bimodal or trimodal) catalyst system into a gas-phase polymerization reactor containing an olefin monomer and a moving bed of a polyolefin polymer, the method comprising: preparing an attenuated post-metallocene catalyst according to the method described above; contacting a solution of the attenuated post-metallocene catalyst and the activated metallocene catalyst in an inert hydrocarbon solvent with a support material (e.g., fumed silica) to prepare a slurry of the multimodal (e.g., bimodal or trimodal) catalyst system consisting essentially of the attenuated post-metallocene catalyst and the activated metallocene catalyst co-supported on the same support material and suspended in an inert hydrocarbon solvent; optionally removing the inert hydrocarbon solvent from the slurry to prepare the multimodal catalyst system in neat (dry powder) form; and feeding the multimodal catalyst system slurry or the multimodal catalyst system in neat form into the gas-phase polymerization reactor via a feed line that does not contain olefin monomer.

[0019] A method for making a polyolefin polymer, comprising contacting at least one 1-alkene monomer with an attenuated post-metallocene catalyst or a multimodal (e.g., bimodal or trimodal) catalyst system under gas phase polymerization conditions in a gas phase polymerization reactor containing a moving bed of a polyolefin resin, thereby making a polyolefin polymer.

[0020] Polyolefin polymers made using the same manufacturing method.

[0021] An article of manufacture made from a polyolefin polymer. DETAILED DESCRIPTION OF THE INVENTION

[0022] The entire contents of the Summary of the Invention are incorporated herein by reference. Additional embodiments follow below, some of which are numbered for ease of reference.

[0023] Embodiment 1. A method of making an attenuated post-metallocene catalyst ("attenuated light-off post-metallocene catalyst"), comprising: adding a fast light-off catalyst to an effective amount of a catalyst of formula (A 1 ), (B 1), or (C 1 ):R 5 -C≡CR 6 (A 1 ), (R 5 )2C=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 obtain an attenuated light-off post-metallocene catalyst exhibiting an attenuated light-off kinetic profile (compared to that of the fast light-off catalyst), wherein the fast light-off catalyst is represented by structural formula (I): (D) d M(T) t (Q) q (X) x (I) is prepared by activating a post-metallocene pre-catalyst of formula (A 1 ), (B 1 ), or (C 1 ), R 5 and R 6 each independently represents H or R 7 and each R 7 are independent, (C1~C 20 ) hydrocarbyl, —C(═O)—O—(unsubstituted C1-C 20 ) hydrocarbyl), (C1-C 19 ) heterohydrocarbyl, or tri((C1-C 20 )hydrocarbyl)silyl, or two R 7 together form a (C3-C6) alkylene, provided that each R 7 lacks a carbon-carbon double bond, and each (C1 to C 20 ) Hydrocarbyl is independently unsubstituted or has 1 to 4 substituents R S and each substituent R Sare independently halogen (e.g., F), unsubstituted (C1-C5) alkyl (e.g., CH3), -C≡CH, -OH, (C1-C5) alkoxy, -C(=O)-(unsubstituted (C1-C5) alkyl), -NH2, -N(H)(unsubstituted (C1-C5) alkyl), -N(unsubstituted (C1-C5) alkyl)2, -COOH, -C(=O)-NH2, -C(=O)-N(H)(unsubstituted (C1-C5) alkyl), -C(=O)-N(unsubstituted (C1-C5) alkyl)2, -S-(unsubstituted (C1-C5) alkyl), -S(=O)2-(unsubstituted (C1-C5) alkyl), -S(=O)2-NH2, -S(=O)2-N(H)(unsubstituted (C and -COO(unsubstituted (C1-C5) alkyl), -S(=O)2-N(unsubstituted (C1-C5) alkyl), -C(=)S-(unsubstituted (C1-C5) alkyl), and -COO(unsubstituted (C1-C5) alkyl), wherein in formula (I), the metal M is Ti, Hf, or Zr; the subscript d is 0, 1, or 2; the subscript t is 0 or 1; the subscript q is 0 or 1; the subscript x is 1, 2, or 3; each ligand D is independently a bidentate organoheteryl or bidentate organoheterylene; the ligand T is a tridentate organoheterylene; the ligand Q is a tetradentate organoheterylene; and each X is a halogen atom, ((C1-C 20 )Alkyl) 3-g -(phenyl) g Si- (wherein the subscript g is 0, 1, 2, or 3), CH3, (C2-C 20 ) Alkyl-CH2, (C6-C 12 )Aryl-((C0-C 10 ) alkylene)-CH2 (e.g., (C6-C 12 ) aryl is phenyl, and (C0-C 10 ) alkylene is (C0) alkylene, benzyl), (C1-C6) alkyl-substituted (C6-C 12 )aryl, (C1-C6)alkoxy-substituted (C6-C 12 )aryl, (C1-C6)alkoxy-substituted benzyl, and (C1-C6)alkyl-substituted benzyl, or one X is a monodentate group independently selected from 4-(C1-C 20) alkyl-substituted 1,3-butadiene molecules, and each of the remaining X, if any, is independently a monodentate group X. Each monodentate group X can provide a dentate number κ of 1 to M, with at least one group X functioning as a leaving group during the activation step, and optionally at least one group X functioning as a leaving group during the combining step. In some embodiments, at least one X does not leave but remains coordinated to M. X can also provide a haptic number η (eta) of 2 or 4. 2 ("η 2 ") or eta 4 ("η 4 4-(C1 to C) that can provide M with 20 ) alkyl-substituted 1,3-butadiene molecule, and each remaining X, if any, is independently a monodentate group X. The subscripts d, t, q, and x indicate the total dentate number κ of ligands D, T, Q, and monodentate groups X, which is 5 or 6. tot ("κ tot 5 " or "κ tot 6 ") to M, so that M has a total coordination number n tot In some embodiments, each R7 is independently selected to have the formula: 20 ) hydrocarbyl, which may be independently unsubstituted or substituted with 1 to 3 substituents selected from halogen (e.g., F) and alkyl (e.g., CH), provided that each R 7 For the removal of all doubt, the monodentate group X does not contain a carbon-carbon double bond or a carbon-carbon triple bond, i.e., the monodentate group X is not an alkenyl or alkynyl group.

[0024] Aspect 2. The fast light-off catalyst is represented by Formula (II): (D) d [M + ](T) t (Q) q (X) x-1 A - (II) wherein the subscripts d, t, q, and x, the metal M, and the ligands D, T, Q, and X are as defined for formula (I), and the weakened post-metallocene catalyst is of formula (III): (D)d [M + ](T) t (Q) q (X) x-2 (R)A - (III) wherein the subscripts d, t, q, and x, the metal M, and the ligands D, T, and Q are as defined for formula (I), and each X is a monodentate group as defined for formula (I), and wherein A - is an anion (used to formally balance the positive charge of the metal M), where R is a group 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), wherein R 5 ~R 7 are the formulas (A 1 ), (B 1 ), or (C 1 For the removal of all doubt, the ligand R of formula (A), (B), or (C) is as previously defined for (A), (B), or (C), respectively. 1 ), (B 1 ), or (C 1 ) is obtained from or derived from a kinetic modifier compound of formula (A). For the removal of all doubt, each ligand R of formula (A) and (B) contains a carbon-carbon double bond (i.e., an alkenyl group). For the removal of all doubt, ligand R is not the same structure as its leaving group X, i.e., the definition of ligand R does not overlap with the definition of leaving group X.

[0025] Aspect 3. The post-metallocene pre-catalyst has Formula (Ia): (D) d M(X) xThe method of any one of the preceding aspects, wherein the metal M is Ti, Hf, or Zr, the subscript d is 1 or 2, the subscript x is 2 or 3, each ligand D is independently a bidentate organoheteryl or bidentate organoheterylene, and each X is as defined for formula (I). The subscripts d and x are determined by the total dentate number κ of the ligands D and the monodentate group X being 5 or 6. tot ("κ tot 5 " or "κ tot 6 ") to M, so that M has a total coordination number n tot Without being bound by theory, the structure of the fast light-off catalyst made from the postmetallocene pre-catalyst of formula (Ia) is selected to have the formula (IIa): (D) d [M + ](X) x-1 A - (IIa), and the weakened postmetallocene catalyst has the structure of formula (IIIa): (D) d [M + ](X) x-2 (R) (IIIa) is a weakened postmetallocene catalyst of formula (IIIa), wherein the subscripts d and x, the metal M, and the ligand D are as defined for formula (Ia), and X is as defined for formula (I), and wherein A - is as defined for formula (II), where R is as defined for formula (III).

[0026] Aspect 4. The postmetallocene pre-catalyst of formula (I) is represented by formula (Ia)-1

[0027] [ka] (Ia)-1 is a post-metallocene pre-catalyst of the formula (Ia)-1, wherein each Ar 1 and Ar 2are independently unsubstituted or substituted aromatic groups selected from phenyl, substituted phenyl, biphenyl, substituted biphenyl, anthracene, substituted anthracene, carbazolyl, and substituted carbazolyl, each substituent of the substituted aromatic group is independently alkyl, and each group R a1 and R a2 are independently H or (C1 to C 20 ) alkyl (e.g., (C1-C4) alkyl, e.g., each is 1,1-dimethylethyl), each subscript 0-3 is independently 0, 1, 2, or 3, and M and X are as defined for formula (I). In some embodiments, the post-metallocene pre-catalyst has formula (Ia)-1a:

[0028] [ka] (Ia)-Ia is a postmetallocene precatalyst of formula (Ia), wherein each group R a1 and R a2 are independent, (C1~C 20 ) alkyl, and M, X, Ar 1 and Ar 2 is as defined above. In some embodiments, M is Zr or Hf. Without being bound by theory, the structure of the fast light-off catalyst made from the post-metallocene pre-catalyst of formula (Ia)-1 is represented by formula (IIa)-1:

[0029] [ka] A - (IIa)-1, and the weakened post-metallocene catalyst has the structure of formula (IIIa)-1:

[0030] [ka] A - (IIIa)-1 is a weakened postmetallocene catalyst of the formula (IIIa)-1, wherein the metal M and each of the subscripts 0-3 and the group R a1 ~R b2 , Ar 1 , and Ar2 is as defined for formula (Ia)-1 or (Ia)-1a, X is as defined for formula (I), - is as defined for formula (II), where R is as defined for formula (III). The post-metallocene pre-catalyst of formula (Ia)-1 can be any one of the post-metallocene pre-catalysts described in U.S. Pat. No. 7,705,157 B2.

[0031] Aspect 5. In the postmetallocene pre-catalyst of formula (Ia)-1, the group R a1 and R a2 each of which is 1,1-dimethylethyl, and each Ar 2 is 4-fluorophenyl, M is Zr, and each X is benzyl, and the postmetallocene pre-catalyst of formula (Ia)-1 is

[0032] [ka] (1) (“Precatalyst 1”), wherein each Ar 1 The method of embodiment 4, wherein is 2,6-dichlorobenzyl. Pre-catalyst (1) is synthesized according to the general procedure of U.S. Pat. No. 7,705,157 B2 (WO 2006 / 066126 A2). Another embodiment of the present invention is pre-catalyst (1) itself.

[0033] Aspect 6. The postmetallocene pre-catalyst of formula (I) is represented by formula (Ia)-2

[0034] [ka] (Ia)-2 post-metallocene pre-catalyst, wherein M and X are as defined for formula (I), each subscript 1-5 is independently 1, 2, 3, 4, or 5, and R a3 and R a7 Each of the following is independently 20 ) alkyl (e.g., (C1-C8) alkyl) or (C6-C12 ) aryl, and R a4 ~R a6 Each of (C1 to C 20 ) alkyl, or R a4 ~R a6 The method of aspect 3, wherein:

[0035] [ka] (Ia)-2a postmetallocene precatalyst, wherein M, X, and R a3 ~R a7 is as defined above. Without being bound by theory, the structure of the fast light-off catalyst made from the postmetallocene pre-catalyst of formula (Ia)-2 is represented by formula (IIa)-2:

[0036] [ka] A - (IIa)-2, and the weakened post-metallocene catalyst has the structure of formula (IIIa)-2:

[0037] [ka] A - (IIIa)-2 is an attenuated postmetallocene catalyst of formula (IIIa)-2, wherein each of the subscripts 1-5 and the group R a3 ~R b7 is as defined for formula (Ia)-2 or (Ia)-2a, M and X are as defined for formula (I), - is as defined for formula (II), where R is as defined for formula (III).

[0038] Aspect 7. In the post-metallocene pre-catalyst of formula (Ia)-2, M is Hf and each X is methyl, and the post-metallocene pre-catalyst of formula (Ia)-2 is pre-catalyst (2) or (3):

[0039] [ka] (2) ("Pre-catalyst 2") or

[0040] [ka] The method of embodiment 6, wherein n-Oct is normal octyl, iPr is isopropyl (1-methylethyl), and nBu is normal butyl. Precatalyst (2) is synthesized according to the procedure of Kuhlman, et al., Macromolecules 2010, vol. 43, page 7903. Precatalyst (3) is synthesized according to the general procedure of Kuhlman, et al., Macromolecules 2010, vol. 43, page 7903 and in Example A of the present invention, which follows. Another embodiment of the present invention is precatalyst (3) itself.

[0041] Aspect 8. The method of Aspect 1 or 2, wherein the postmetallocene pre-catalyst of Formula (I) is a postmetallocene pre-catalyst of Formula (Ib): MT(X)2(Ib), where the metal M is Ti, Hf, or Zr, the ligand T is a tridentate organoheterylene, and each X is as defined for Formula (I). The ligand T and the monodentate group X are combined to form a total coordination number n such that M is 5. tot The total number of loci is κ, which is 5. tot ("κ tot 5 ") may be provided to M.

[0042] Aspect 9. The postmetallocene pre-catalyst of formula (I) is represented by the formula (Ib)-1

[0043] [ka] (Ib)-1 is a postmetallocene precatalyst of formula (Ib)-1, wherein M is Hf or Zr, and each subscript 0-3 is independently 0, 1, 2, or 3; and the group R b1 ~R b6 is independently H or a (C1-C0) alkyl (e.g., a (C1-C4) alkyl), and X is as defined for formula (I). In some embodiments, the post-metallocene pre-catalyst has formula (Ib)-1a:

[0044] [ka] (Ib)-Ia post-metallocene pre-catalyst, wherein each of R b1 and R b3 ~R b5 are independent, (C1~C 20 ) alkyl, and M and X are as defined above. Without being bound by theory, the structure of the fast light-off catalyst made from the postmetallocene pre-catalyst of formula (Ib)-1 is represented by formula (IIb)-1:

[0045] [ka] A - (IIb)-1, and the weakened post-metallocene catalyst has the structure of formula (IIIb)-1:

[0046] [ka] A - (IIIb)-1 is a weakened postmetallocene catalyst of the formula (IIIb)-1, wherein each of the subscripts 0-3 and the group R b1 ~R b7 is as defined for formula (Ib)-1, M and X are as defined for formula (I), wherein A - is as defined for formula (II), where R is as defined for formula (III).

[0047] Aspect 10. In the postmetallocene pre-catalyst of formula (Ib)-1, R b1 is ethyl and R b2 , R b3 , R b4 , and R b5 is methyl and R b6 and R b7 is 1-methylethyl (i.e., isopropyl), M is Hf, and each X is methyl, such that the post-metallocene pre-catalyst of formula (Ib)-1 is pre-catalyst (4):

[0048] [ka] The method of aspect 9, wherein Me is methyl. Precatalyst (4) is synthesized according to the procedure of Example B of the present invention, described below. Another embodiment of the present invention is precatalyst (4) itself.

[0049] Aspect 11. The postmetallocene pre-catalyst of formula (I) is represented by formula (Ib)-2

[0050] [ka] (Ib)-2 post-metallocene pre-catalyst, wherein M is Zr or Hf, and R 1 ~R 4 each is independently H or CH; and each R H are independent, (C1~C 20 ) alkyl (e.g., (C1-C4) alkyl, e.g., CH3), and X is as defined for formula (I), provided that at least one X is (C7-C 20 ) aralkyl (e.g., benzyl). In some embodiments, M is Zr; alternatively, M is Hf. Without being bound by theory, the structure of the fast light-off catalyst made from the postmetallocene pre-catalyst of formula (Ib)-2 is represented by formula (IIb)-2:

[0051] [ka] A - (IIb)-2, and the weakened post-metallocene catalyst has the structure of formula (IIIb)-2:

[0052] [ka] A - (IIIb)-2 is a weakened postmetallocene catalyst of formula (IIIb)-2, wherein the metal M and the group R 1 ~R 4 and X are as defined for formula (Ib)-2, wherein A - is as defined for formula (II), where R is as defined for formula (III). The post-metallocene pre-catalyst of formula (Ib)-2 can be any one of the post-metallocene pre-catalysts described in U.S. Pat. No. 6,967,184 B2.

[0053] Aspect 12. In the postmetallocene pre-catalyst of formula (Ib)-2, each of R1-R4 is H and each X is benzyl, and the postmetallocene pre-catalyst of formula (Ib)-2 is pre-catalyst (5):

[0054] [ka] (5) ("Pre-catalyst 5"), wherein M is Hf or Zr. Pre-catalyst (5) is synthesized by reproducing Procedure 2 of U.S. Pat. No. 6,967,184 (B2), column 33, line 53 to column 34, line 9.

[0055] Aspect 13. The method of aspect 1 or 2, wherein the postmetallocene pre-catalyst of Formula (I) is a postmetallocene pre-catalyst of Formula (Ic): MQ(X)2(Ic), where the metal M is Ti, Hf, or Zr, the ligand Q is a tetradentate organoheterylene, and each X is as defined for Formula (I). The ligand Q and the monodentate group X are combined to form a total coordination number n such that M is 6. tot The total number of loci is κ, so that tot ("κtot 6 ") may be provided to M.

[0056] Aspect 14. The postmetallocene pre-catalyst of formula (Ic) is a compound of formula (1c)-1

[0057] [ka] (Ic)-1 is a post-metallocene pre-catalyst, wherein L is CH2CH2, CH2CH2CH2, CH2CH2CH2CH2, CH2C(R L )2CH2, CH2CH(R L )CH(R L )CH2, CH2Ge(R L )2CH2, or CH2Si(R L )2CH2, where each R L are independently unsubstituted (C1 to C 20 ) alkyl, M is Zr or Hf, and R 1a and R 1b Each of the is independently F, (C1 to C 20 ) alkyl, or Si(CH3)2(CH2) q CH3, wherein the subscript q is an integer from 0 to 20, and each subscript r is independently an integer from 0 to 3; 2a and R 2b is independently H, F, Cl, or CH; each subscript s is independently an integer from 0 to 3; 3a and R 3b each independently is unsubstituted (C1 to C 20 ) alkyl or (C1-C 20 ) alkoxy, and each Ar 1a and Ar 1b is independently an unsubstituted or substituted aromatic group selected from phenyl, substituted phenyl, biphenyl, substituted biphenyl, anthracene, substituted anthracene, carbazolyl, and substituted carbazolyl, each substituent of the substituted aromatic group is independently alkyl, and each X is independently as defined for formula (I). In some embodiments, at least one X is selected from the group consisting of (C6-C 12)Aryl-((C0-C 10 )alkylene)-CH2 (e.g., benzyl). In some embodiments, each X is independently (C6-C 12 )Aryl-((C0-C 10 ) alkylene)-CH2, or one X is (C6-C 12 )Aryl-((C0-C 10 ) alkylene)-CH2 (e.g., benzyl), and the other X is F, Cl, or methyl, or each X is benzyl. Without being bound by theory, the structure of the fast light-off catalyst made from the postmetallocene pre-catalyst of formula (Ic)-1 is represented by formula (IIc)-1:

[0058] [ka] A - (IIc)-1, and the weakened post-metallocene catalyst has the structure of formula (IIIc)-1:

[0059] [ka] A - (IIIc)-1 is a weakened postmetallocene catalyst of formula (IIIc)-1, wherein L, the subscripts r and s, and the group R 1a ~R 3b is as defined for formula (Ic)-1, the metal M and the group X are as defined for formula (I), wherein A - is as defined for Formula (II), where R is as defined for Formula (III). The post-metallocene pre-catalyst of Formula (Ic)-1 can be any one of the post-metallocene pre-catalysts described in WO 2012 / 027448 (A1), WO 2014 / 105411 (A1), WO 2017 / 058981 (A1), WO 2018 / 022975 (A1), or WO 2018 / 183026 (A1).

[0060] Aspect 15. The post-metallocene pre-catalyst of Formula (Ic)-1 is represented by Formula (Ic)-1a:

[0061] [ka] (Ic)-1a: A postmetallocene precatalyst of the formula (Ic)-1a, wherein L is CH2CH2, CH2CH2CH2, CH2CH2CH2CH2, CH2C(R L )2CH2, CH2CH(R L )CH(R L )CH2, or CH2Si(R L )2CH2, where each R L are independently unsubstituted (C1 to C 20 ) alkyl, M is Zr or Hf, and R 1a and R 1b Each of the is independently F, (C1 to C 20 ) alkyl, or Si(CH3)2(CH2) q CH3, where the subscript q is an integer from 0 to 9, and R 2a and R 2b is independently H or CH3, and R 3a and R 3b is independently unsubstituted 1,1-dimethyl-(C-C) alkyl; 4a , R 4b , R 5a , R 5b is independently H or unsubstituted 1,1-dimethyl-(C2-C4)alkyl, and each X is independently as defined for formula (I).

[0062] The postmetallocene precatalyst of embodiment 16 (Ic)-1a is selected from the group consisting of postmetallocene precatalysts (6) to (10):

[0063] [ka] (6) ( "Pre-catalyst 6"),

[0064] [ka] (7) ("Pre-catalyst 7"),

[0065] [ka] (8) ("Precatalyst 8"),

[0066] [ka] (9) ("Precatalyst 9"), and

[0067] [ka] The method of embodiment 15, wherein the precatalyst (6) is any one of (10) ("precatalyst 10"). Precatalyst (6) is synthesized according to the procedure of WO 2014105411 A1. Precatalyst (7) is synthesized according to the procedure of WO 2017058981 A1. Precatalyst (8) is synthesized according to the procedure of WO 2012027448 A1. Precatalyst (9) is synthesized according to the procedure of WO 2018 / 022975 A1 (e.g., Example E-19). Precatalyst (10) is synthesized according to the procedure of WO 2018 / 183026 A1 (e.g., Example 26).

[0068] Aspect 17. The kinetics modifier compound is a compound represented by the formula (A) of Restrictions (i) to (vi): 1 ) or (B 1 ) (i), formula (A 1 ) or (C 1 ) (ii), formula (B 1 ) or (C 1 ) (iii) of formula (A 1 ) (iv), formula (B 1 ) (v) of the formula (C 1 The method of any one of embodiments 1 to 16, as described by any one of (vi) of formula (A). 1 ) and (B 1The kinetic modifier compounds of formula (I) are believed to result in R ligands (A) and (B), respectively, each of which has a carbon-carbon double bond as a common structural feature between them. In some embodiments, the kinetic modifier compounds consist of carbon and hydrogen atoms. In other embodiments, the kinetic modifier compounds consist of carbon, hydrogen, and at least one atom selected from halogen atoms, O, N, and Si; alternatively, the kinetic modifier compounds consist of carbon, hydrogen, and at least one halogen atom; alternatively, the kinetic modifier compounds consist of carbon, hydrogen, and at least one atom selected from O, N, and Si; alternatively, O and N; alternatively, O and Si; alternatively, N and Si; alternatively, O; alternatively, N; alternatively, Si.

[0069] Aspect 18. The kinetics modifier compound is represented by the formula (A 1 ):R 5 -C≡CR 6 (A 1 ) kinetic modifier compounds of the formula HC≡CSi(phenyl) including phenylacetylene, (substituted-phenyl)acetylene, diphenylacetylene, substituted diphenylacetylene, cycloalkylacetylene, h ((C1~C 20 )Alkyl) 3-h (wherein the subscript h is an integer from 0 to 3), and acetylenes of the formula HC≡C—(CH m The method of any one of aspects 1-17, wherein the kinetic modifier compound is selected from acetylenes of CH3, where subscript m is an integer from 1 to 15, alternatively 1 to 10, alternatively 2 to 15. In formula (III) of aspect 2, each ligand R is selected from the group consisting of -C(H)=C(X)-phenyl, -C(H)=C(X)-(substituted-phenyl), -CH2-C(X)=C(H)-cycloalkyl, -CH2-C(X)=C(H)-Si(phenyl). h ((C1~C 20 )Alkyl) 3-h where the subscript h is as defined above, -C(H)=C(X)-(CH2) mCH3, where the subscript m is as defined above, or -CH2-C(X)=C(alkyl)2. The subscript m can be an integer from 8 to 15, alternatively from 1 to 7, alternatively from 2 to 6, alternatively from 2 to 4, alternatively from 1 to 3.

[0070] Aspect 19. The kinetics modifier compound is represented by the formula (A 1 ):R 5 -C≡CR 6 (A 1 18. The method of any one of aspects 1 to 17, wherein the kinetics modifier compound is of the formula: (substituted-phenyl)acetylene. The (substituted-phenyl)acetylene can be (fluoro-substituted-phenyl)acetylene or (methyl-substituted-phenyl)acetylene, or 3,4-difluorophenylacetylene, 3,5-difluorophenylacetylene, 3-fluorophenylacetylene, 4-fluorophenylacetylene, or 2,4,5-trimethylphenylacetylene.

[0071] Aspect 20. The kinetics modifier compound is a compound of the formula (A 1 ):R 5 -C≡CR 6 (A 1 ) a kinetic modifier compound of formula (A 1The kinetic modifier compounds of KMC1 to KMC14 are: kinetic modifier compound (1) ("KMC1"): phenylacetylene (i.e., (CH)C≡CH), kinetic modifier compound (2) ("KMC2"): 4-methylphenylacetylene (i.e., (4-CH-CH)C≡CH), kinetic modifier compound (3) ("KMC3"): 2,4,5-trimethylphenylacetylene (i.e., (2,4,5-(CH)-CH)C≡CH), kinetic modifier compound (4) ("KMC4"): 1,3,5-triethynylbenzene (i.e., 1,3,5-tri(HC≡C)(CH), kinetic modifier compound (5) ("KMC5"): diphenylacetylene (i.e., ( Kinetic modifier compound (6) (“KMC6”): 3-fluorophenyl-acetylene (i.e., (3-F-C6H4)C≡CH), Kinetic modifier compound (7) (“KMC7”): 4-fluorophenyl-acetylene (i.e., (4-F-C6H4)C≡CH), Kinetic modifier compound (8) (“KMC8”): 3,4-difluorophenyl-acetylene (i.e., (3,4-F2-C6H3)C≡CH), Kinetic modifier compound (9) (“KMC9”): 3,5-difluorophenyl-acetylene (i.e., (3,5-F2-C6H3)C≡CH), Kinetic modifier compound (10) (“KMC10”): cyclohexylacetylene (i.e., C6H 11 kinetic modifier compound (11) ("KMC11"): phenyldimethylsilylacetylene (i.e., (CH)(CH)SiC≡CH), kinetic modifier compound (12) ("KMC12"): 1-pentyne (i.e., CH(CH)C≡CH), kinetic modifier compound (13) ("KMC13"): 1-octyne (i.e., CH(CH)C≡CH), and kinetic modifier compound (14) ("KMC14"): 1,7-octadiyne (i.e., HC≡C(CH)C≡CH).

[0072] Aspect 21. The kinetics modifier compound is represented by the formula (B 1 ):(R 5 )2C=C=C(R6 )2(B 1 18. The method of any one of aspects 1-17, wherein the kinetics modifier compound is selected from cycloalkylarenes, alkylarenes, dialkylarenes, trialkylarenes, trialkylsilylarenes, vinylidenecycloalkanes, and alkyl esters of arenecarboxylic acids. The cycloalkylarenes can be ((C3-C8)cycloalkyl)arenes or cyclohexylarenes. The alkylarenes can be methylarenes, ethylarenes, propylarenes, or (1,1-dimethylethyl)arenes. The dialkylarenes can be 1,1-dialkylarenes or 1,3-dialkylarenes or 1,1-dimethylarenes. The trialkylarenes can be 1,1,3-trimethylarenes. The trialkylsilylarenes can be trimethylsilylarenes, triethylsilylarenes, or dimethyl,(1,1-dimethylethyl)silylarenes (i.e., tert-butyl-dimethyl-silylarenes). Vinylidenecycloalkanes have the formula

[0073] [ka] vinylidenecyclohexane.

[0074] Aspect 22. The kinetics modifier compound is a compound represented by the formula (B 1 ):(R 5 )2C=C=C(R 6 )2(B 1 ) a kinetic modifier compound of formula (B 1 ) kinetic modifier compounds are KMC15-KMC17: kinetic modifier compound (15) (“KMC15”): cyclohexylarene (i.e., (CH 11 )C(H)=C=CH), kinetic modifier compound (16) (“KMC16”): ethyl 2,3-butadienoate (i.e., HC=C=CH—C(=O)—O—CHCH), and kinetic modifier compound (17) (“KMC17”): 1,1-dimethylallene (i.e., (CH)C=C=CH).

[0075] Aspect 23. The kinetics modifier compound is a compound represented by the formula (C 1 ):(R 5 )(R 7 )C=C(R 6 )(R 7 )(C 1 ) a kinetic modifier compound of formula (C 1 The method of any one of aspects 1-17, wherein the kinetic modifier compound of formula (III) is an internal alkene. Thus, the internal alkene does not have a terminal carbon-carbon double bond or a terminal carbon-carbon triple bond. The internal alkene can be selected from KMC18-KMC20: kinetic modifier compound (18) (“KMC18”): 2-butene, kinetic modifier compound (19) (“KMC19”): 2-pentene, and kinetic modifier compound (20) (“KMC20”): 1,2-diphenylethene. In formula (III) of aspect 2, each ligand R can be derived therefrom and can be a ligand of formula —C(H)(CH)—C(X)CH, —C(H)(CH)—C(X)CHCH, or —C(H)(phenyl)-C(X)phenyl, respectively.

[0076] Aspect 24. The method of any one of aspects 1-23, further comprising, prior to the combining step, forming the fast light-off catalyst by activating the pre-catalyst of Formula (I) with an activator under effective activating conditions, thereby forming the fast light-off catalyst. In some embodiments, the activator is an alkylaluminoxane, an organoborane compound, or an organoborate.

[0077] Aspect 25. The method of any one of Aspects 1 to 24, further comprising: forming a mixture of the weakened post-metallocene catalyst, the support material, and the inert hydrocarbon solvent; and removing the inert hydrocarbon solvent from the mixture to obtain the weakened post-metallocene catalyst disposed on the support material. Because an excess of activator is typically used to activate the post-metallocene pre-catalyst, the mixture may further comprise an excess of activator. The removing step may be accomplished by conventional evaporation of the inert hydrocarbon solvent from the mixture (i.e., conventional concentration methods), resulting in an evaporated / supported, weakened post-metallocene catalyst. Alternatively, the removing step may be accomplished by spray-drying the mixture. Spray-drying embodiments provide a spray-dried / supported, weakened post-metallocene catalyst, which may have improved performance compared to the evaporated / supported, weakened post-metallocene catalyst. Examples of support materials are alumina and hydrophobized fumed silica, or alternatively, hydrophobized fumed silica. Hydrophobized fumed silica can be prepared by surface treating untreated anhydrous fumed silica with an effective amount of a hydrophobizing agent. The hydrophobizing agent can be dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane, or dimethyldichlorosilane. The hydrophobized fumed silica prepared by surface treating untreated anhydrous fumed silica with dimethyldichlorosilane can be CABOSIL TS-610.

[0078] Embodiment 26. A weakened post-metallocene catalyst made by the method of any one of embodiments 1 through 25. The weakened post-metallocene catalyst can be of or based on the aforementioned formula (III). In some embodiments, the weakened post-metallocene catalyst is made from a post-metallocene pre-catalyst of formula (Ia)-1, (Ia)-2, (Ib)-1, (Ib)-2, or (Ic)-1; alternatively, the weakened post-metallocene catalyst is made from a post-metallocene pre-catalyst selected from the group consisting of any four of the post-metallocene pre-catalysts of formula (Ia)-1, (Ia)-2, (Ib)-1, (Ib)-2, and (Ic)-1 (i.e., the group in which any one of formulas (Ia)-1, (Ia)-2, (Ib)-1, (Ib)-2, and (Ic)-1 is omitted); alternatively, the weakened post-metallocene catalyst is made from a post-metallocene pre-catalyst of formula (Ia)-1 or (Ia)-2. Alternatively, the weakened post-metallocene catalyst may be made from a post-metallocene pre-catalyst of formula (Ib)-1 or (Ib)-2; alternatively, the weakened post-metallocene catalyst may be made from a post-metallocene pre-catalyst of formula (Ia)-1; alternatively, the weakened post-metallocene catalyst may be made from a post-metallocene pre-catalyst of formula (Ia)-2; alternatively, the weakened post-metallocene catalyst may be made from a post-metallocene pre-catalyst of formula (Ib)-1; alternatively, the weakened post-metallocene catalyst may be made from a post-metallocene pre-catalyst of formula (Ib)-2; alternatively, the weakened post-metallocene catalyst may be made from a post-metallocene pre-catalyst of formula (Ic)-1.

[0079] Aspect 27. 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 a polyolefin polymer, the method comprising: preparing an attenuated post-metallocene catalyst outside the reactor according to the method of any one of Aspects 1-25; and feeding the attenuated post-metallocene catalyst in neat form (e.g., a dry powder) or as a solution or slurry thereof in an inert hydrocarbon liquid into the slurry-phase or gas-phase polymerization reactor through a feed line that does not contain the olefin monomer. In an embodiment, the method further comprises transferring the attenuated post-metallocene catalyst, or a fully active post-metallocene catalyst prepared in situ therefrom within the reactor, to a (second) gas-phase polymerization reactor, where the transferred catalyst catalyzes a second olefin polymerization reaction.

[0080] Aspect 28. A multimodal (e.g., bimodal or trimodal) catalyst system comprising the attenuated post-metallocene catalyst of aspect 26 and at least one second catalyst selected from the group consisting of a non-attenuated post-metallocene catalyst, a different attenuated post-metallocene catalyst, and a metallocene catalyst described herein. In some embodiments, the multimodal catalyst system comprises the attenuated post-metallocene catalyst of aspect 26 and only one second catalyst, or only two different second catalysts. The multimodal catalyst system can further comprise a support material, and the attenuated post-metallocene catalyst and the metallocene catalyst can be disposed (e.g., spray dried) on the support material. The attenuated post-metallocene catalyst and the metallocene catalyst of the multimodal catalyst system can have a light-off profile as measured by the Light-Off Vial Test Method (described below), where the time to the respective peak polymerization temperature Temp peakare within 60 minutes, alternatively within 45 minutes, alternatively within 30 minutes, of each other. When the second catalyst is a metallocene catalyst, the catalyst light-off performance of the multimodal catalyst system can be beneficially compatible such that polymerizations using the multimodal catalyst system to produce multimodal (e.g., bimodal or trimodal) polyolefin polymers comprising a high molecular weight (HMW) component and a low molecular weight (LMW) component made from an attenuated post-metallocene catalyst do not produce an excess of the HMW component relative to the LMW component, and therefore produce little or no off-specification multimodal polyolefin polymer.

[0081] Embodiment 29. A method of feeding a multimodal (e.g., bimodal or trimodal) catalyst system to a slurry-phase or gas-phase polymerization reactor containing an olefin monomer and a moving bed of a polyolefin polymer, the method comprising: preparing an attenuated post-metallocene catalyst outside the reactor according to the method of any one of embodiments 1 to 25; contacting a solution of the attenuated post-metallocene catalyst and the activated metallocene catalyst in an inert hydrocarbon solvent with a support material (e.g., fumed silica) outside the reactor to form a slurry of the multimodal (e.g., bimodal or trimodal) catalyst system consisting essentially of the attenuated post-metallocene catalyst and the activated metallocene catalyst co-supported on the same support material and suspended in an inert hydrocarbon solvent; optionally removing the inert hydrocarbon solvent from the slurry to form the multimodal catalyst system in neat (dry powder) form; and feeding the multimodal catalyst system slurry or the multimodal catalyst system in neat form into the slurry-phase or gas-phase polymerization reactor via a feed line that does not contain the olefin monomer.

[0082] Embodiment 30. A method of making a polyolefin polymer, comprising contacting at least one 1-alkene monomer with an attenuated postmetallocene catalyst made by the method of any one of embodiments 1 to 25, or with a multimodal catalyst system according to embodiment 29, under slurry-phase or gas-phase polymerization conditions in a slurry-phase or gas-phase polymerization reactor comprising, respectively, a moving bed of polyolefin resin, thereby making the polyolefin polymer. The method can include a step comprising, prior to the contacting step, providing the attenuated postmetallocene catalyst made by the method of any one of embodiments 1 to 25, or the multimodal catalyst system according to embodiment 29, under slurry-phase or gas-phase polymerization conditions, respectively, into a slurry-phase or gas-phase polymerization reactor comprising a moving bed of polyolefin resin and the at least one 1-alkene monomer to allow attenuated light-off of the attenuated postmetallocene catalyst and subsequent polymerization of the at least one 1-alkene monomer, thereby making the polyolefin polymer. The moving bed can be a stirred bed or a fluidized bed. The at least one 1-alkene monomer can be ethylene or a combination of ethylene and a comonomer selected from propylene, 1-butene, 1-hexene, and 1-octene. In embodiments, the reactor is a first gas phase polymerization reactor and is under first gas phase polymerization conditions. Alternatively, the reactor can be a slurry phase polymerization reactor and the polymerization conditions can be slurry phase polymerization conditions. In some such embodiments, the method comprises transferring activated polymer granules produced in a first gas phase polymerization reactor under first gas phase polymerization conditions or produced in a slurry phase polymerization reactor under slurry phase polymerization conditions, in either case comprising (within the granules) an active post-metallocene catalyst, into a (second) gas phase polymerization reactor, optionally under (second) gas phase polymerization conditions different from the first gas phase polymerization conditions used in the first gas phase polymerization reactor or the slurry phase polymerization conditions used in the slurry phase polymerization reactor, thereby producing a multimodal (e.g., bimodal or trimodal) polyolefin polymer (i.e., a multimodal (e.g., bimodal or trimodal) molecular weight distribution M w / M n The method may further comprise producing a polyolefin polymer having the formula (II) in a (second) gas phase polymerization reactor.

[0083] Aspect 31. A polyolefin polymer made by the process of aspect 30. The polyolefin polymer obtained in virgin form from a slurry phase or gas phase polymerization reactor can be in the form of granules having a lower amount of agglomerates (fused granules) than a comparable polyolefin polymer obtained in virgin form from a slurry phase or gas phase polymerization reactor, respectively, run under identical polymerization conditions except that the weakened postmetallocene catalyst is replaced with a fast light-off catalyst.

[0084] Embodiment 32. An article of manufacture (e.g., a blown film or a cast film) made from the polyolefin polymer of embodiment 31. The article of manufacture can have a lower gel count than a comparative article of manufacture made from a comparative polyolefin polymer.

[0085] Aspect 33 The embodiment of the invention according to any one of aspects 1 to 24, wherein the weakened post-metallocene catalyst does not comprise a support material, for example, does not comprise fumed silica or alumina.

[0086] Aspect 34. A post-metallocene pre-catalyst selected from the group consisting of the aforementioned post-metallocene pre-catalysts of formulas (1)-(10). In some embodiments, the post-metallocene pre-catalyst is selected from the group consisting of post-metallocene pre-catalysts of formulas (1), (3), and (4). In some embodiments, the post-metallocene pre-catalyst is a post-metallocene pre-catalyst of formula (10).

[0087] Embodiment 35. A postmetallocene catalyst made by contacting the postmetallocene precatalyst of embodiment 34 with an activator.

[0088] Aspect 36. A method of making a postmetallocene pre-catalyst, comprising reacting a compound of formula (I)(D) in an aprotic solvent under effective reaction conditions d M(T) t (Q) q (X) x The post-metallocene pre-catalyst of (I) is reacted with a compound of formula X 1 MgR or M1 R n Or, for example, by contacting LiCuR2 with x molar equivalents of an organometallic compound, thereby forming a compound of formula (IV): (D) d M(T) t (Q) q (R) x (IV) a post-metallocene pre-catalyst of formula X 1 is Cl, Br, or I, and M 1 is selected from Li, Na, K, Zn, Sn, Tl, Hg, and Cu, the subscript n is an integer from 1 to 4, and M 1 and R is a compound 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) is a ligand of R 5 and R 6 each independently represents H or R 7 and each R 7 are independent, (C1~C 20 ) hydrocarbyl, —C(═O)—O—(unsubstituted C1-C 20 ) hydrocarbyl), (C1-C 17 ) heterohydrocarbyl, or tri((C1-C 20 )hydrocarbyl)silyl, or two R 7 together form a (C3-C6) alkylene, and each (C1-C 20 ) Hydrocarbyl is independently unsubstituted or has 1 to 4 substituents R S where each R 7 is devoid of a carbon-carbon double bond, and each substituent R Sare 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); the metal M is Ti, Hf, or Zr; the subscript d is 0, 1, or 2; the subscript t is 0 or 1; the subscript q is 0 or 1; the subscript x is 1, 2, or 3; each ligand D is independently a bidentate organoheteryl or bidentate organoheterylene; the ligand T is a tridentate organoheterylene; the ligand Q is a tetradentate organoheterylene; and X is a monodentate group X as defined in formula (I). The subscripts d, t, q, and x represent the total dentate number κ of the ligands D, T, Q, and R, which are 5 or 6. tot ("κ tot 5 " or "κ tot 6 ") to M, so that M has a total coordination number n tot In some embodiments, each R 7 are independent, (C1~C 20 ) hydrocarbyl, which can be independently unsubstituted or substituted with 1 to 3 substituents selected from halogen (e.g., F) and alkyl (e.g., CH). In some embodiments, subscript x is 1 or 2, alternatively 1 or 3, alternatively 2 or 3, alternatively 1, alternatively 2, or alternatively 3. In some embodiments, the postmetallocene pre-catalyst of Formula (I) used in the process is any one of Formulas (Ia)-1, (Ia)-2, (Ib)-1, (Ib)-2, and (Ic)-1, or any one of Formulas (Ia)-1, (Ia)-2, (Ib)-1, and (Ic)-1, or any one of Precatalyst 1 through Precatalyst 4 and Precatalyst 6 through Precatalyst 10.

[0089] Embodiment 37. A method of making a weakened postmetallocene catalyst, comprising contacting a postmetallocene precatalyst of Formula (IV) according to embodiment 36 with an activator under effective activating conditions, thereby forming a weakened postmetallocene precatalyst of Formula (V)(D): d [M + ](T)t (Q) q (R) x-1 A - (V) wherein the subscripts d, t, q, and x, the metal M, and the ligands D, T, Q, and R are as defined for formula (IV), and wherein A - is an anion (used to formally balance the positive charge of the metal M). In some embodiments, the subscript x is 1 or 2, alternatively 1 or 3, alternatively 2 or 3, alternatively 1, alternatively 2, or alternatively 3. The weakened postmetallocene catalyst of Formula (V) may differ in at least one characteristic from the weakened postmetallocene catalyst of Formula (III). For example, the time or temperature used to prepare the weakened postmetallocene catalyst of Formula (III) from the fast light-off postmetallocene catalyst of Formula (II) may be shorter or lower, respectively, than the time or temperature used to prepare the weakened postmetallocene catalyst of Formula (V) from the postmetallocene pre-catalyst of Formula (IV). Another difference between the weakened postmetallocene catalysts of Formulas (III) and (V) is the different kinetic profiles (e.g., the time zero (Time0) to peak temperature (Temp), both measured by the light-off vial test method described below). peak ), the length of time to and / or the peak temperature reached, different catalyst activities, different polymer productivity, bed temperature in gas phase polymerization, ethylene partial pressure, molar ratio of molecular hydrogen to ethylene (H2 / C2), and / or comonomer to ethylene (C x / C2) and / or different properties of the polyolefin polymer product under the same gas-phase polymerization conditions. Other differences between the weakened postmetallocene catalysts of formula (III) and (V) may include the greater solubility of the weakened postmetallocene catalyst of formula (V) in an inert hydrocarbon compound (e.g., n-hexane) than the solubility of the weakened postmetallocene catalyst of formula (III) in that inert hydrocarbon compound, particularly when at least one X is present and is a halide in formula (III). Thus, the weakened postmetallocene catalyst of formula (V) may be better suited than formula (III) for feeding to a polymerization reactor as its solution in an inert hydrocarbon solvent.

[0090] A method for preparing a weakened post-metallocene catalyst. The method comprises reacting a fast light-off catalyst under effective reaction conditions with an effective amount of a compound of formula (A 1 ), (B 1 ), or (C 1 The fast light-off catalyst may be a fast light-off catalyst of Formula (II), and the weakened post-metallocene catalyst may be a weakened post-metallocene catalyst of Formula (III). The combining step may be carried out in the absence of the pre-catalyst of Formula (I). If an excess of activator is used in the activation step, the combining step may be carried out in the presence of unreacted activator. The fast light-off catalyst contains a leaving group X bonded to a metal atom M. In the combining step, the kinetic modifier compound reacts with the fast light-off catalyst to displace the leaving group X from the fast light-off catalyst and replace it with a ligand R derived from the kinetic modifier compound. The ligand is bonded to the metal atom M in the resulting weakened post-metallocene catalyst. In some embodiments, the weakened post-metallocene catalyst is a weakened post-metallocene catalyst of Formula (III), the fast light-off catalyst is a fast light-off catalyst of Formula (II), and the pre-catalyst is a pre-catalyst of Formula (I), all in which M is Zr and each X is benzyl.

[0091] In some embodiments, the metal M is Zr or Hf, alternatively M is Zr or Ti, alternatively M is Ti or Hf, alternatively M is Zr, alternatively M is Hf, alternatively M is Ti.

[0092] Embodiments of the method of preparation may include any one of synthetic schemes 1-11.

[0093] Synthesis Scheme 1: Step (a) Postmetallocene pre-catalyst + excess activator → activated postmetallocene catalyst + intermediate mixture of residual activator. Step (b) Intermediate mixture + effective amount of kinetic modifier compound → weakened postmetallocene catalyst.

[0094] Synthetic Scheme 2: Step (a) post-metallocene pre-catalyst + effective amount of kinetic modifier compound → intermediate post-metallocene pre-catalyst (unreacted mixture or reaction product of post-metallocene pre-catalyst + kinetic modifier compound). Step (b) intermediate post-metallocene pre-catalyst + activator (e.g., alkylaluminoxane such as methylaluminoxane (“MAO”)) → weakened post-metallocene catalyst.

[0095] Synthesis Scheme 3: Step (a) Post-metallocene pre-catalyst + activator (e.g., alkylaluminoxane such as methylaluminoxane ("MAO")) → activated post-metallocene catalyst (fast light-off catalyst). Step (b) Activated post-metallocene catalyst + effective amount of kinetic modifier compound → weakened post-metallocene catalyst.

[0096] Synthesis Scheme 4: Step (a) activator (e.g., alkylaluminoxane such as methylaluminoxane (“MAO”)) + effective amount of kinetic modifier compound → intermediate solution. Step (b) intermediate solution + post-metallocene pre-catalyst → weakened light-off post-metallocene catalyst.

[0097] Synthesis Scheme 5: Step (a) Activator → Post-metallocene pre-catalyst ← Effective amount of kinetic modifier compound (simultaneous but separate addition of activator and kinetic modifier to post-metallocene pre-catalyst) → Weakened post-metallocene catalyst. Step (b): None.

[0098] Synthetic Scheme 6: Step (a) post-metallocene pre-catalyst + support material → supported post-metallocene pre-catalyst. (b) supported post-metallocene pre-catalyst + an amount of activator → an intermediate mixture of activated post-metallocene catalyst + residual activator disposed on (or in equilibrium with) the support material. Step (c) intermediate mixture + an effective amount of kinetic modifier compound → weakened post-metallocene catalyst disposed on (or in equilibrium with) the support material. In some embodiments, step (a) further comprises an inert hydrocarbon solvent, and deposition onto the support material is carried out by evaporating the solvent or by spray drying. The amount of activator can be a stoichiometric amount relative to the metal M of the post-metallocene catalyst (e.g., a 1.0 to 1.0 molar ratio), or a substoichiometric amount relative thereto (e.g., a 0.1 to 0.94 molar ratio), or an excess amount relative thereto (e.g., a 1.1 to 10,000 molar ratio).

[0099] Synthetic Scheme 7: Step (a) post-metallocene pre-catalyst + effective amount of kinetic modifier compound + support material → intermediate mixture of post-metallocene pre-catalyst and kinetic modifier compound disposed on (or in equilibrium with) the support material. Step (b) intermediate mixture + activator (e.g., an alkylaluminoxane such as methylaluminoxane ("MAO")) → weakened post-metallocene catalyst disposed on (or in equilibrium with) the support material. In some embodiments, step (a) further comprises an inert hydrocarbon solvent, and deposition onto the support material is carried out by evaporating the solvent or by spray drying.

[0100] Synthetic Scheme 8: Step (a) post-metallocene pre-catalyst + support material + activator (e.g., an alkylaluminoxane such as methylaluminoxane ("MAO")) → activated post-metallocene catalyst (fast light-off catalyst) disposed on (or in equilibrium with) the support material. Step (b) supported activated post-metallocene catalyst + effective amount of kinetic modifier compound → weakened post-metallocene catalyst disposed on (or in equilibrium with) the support material. In some embodiments, step (a) further comprises an inert hydrocarbon solvent, and deposition onto the support material is carried out by evaporating the solvent or by spray drying.

[0101] Synthetic Scheme 9: Step (a) activator (e.g., an alkylaluminoxane such as methylaluminoxane ("MAO")) + effective amount of kinetic modifier compound → intermediate solution. Step (b) intermediate solution + post-metallocene pre-catalyst + support material → weakened light-off post-metallocene catalyst disposed on (or in equilibrium with) the support material. In some embodiments, step (b) further comprises an inert hydrocarbon solvent, and deposition onto the support material is carried out by evaporating the solvent or by spray drying.

[0102] Synthetic Scheme 10: Step (a) activator → post-metallocene pre-catalyst + support material ← effective amount of kinetic modifier compound (simultaneous but separate addition of activator and kinetic modifier compound to the post-metallocene pre-catalyst + support material mixture) → weakened post-metallocene catalyst disposed on (or in equilibrium with) the support material. Step (b): None. In some embodiments, step (a) further comprises an inert hydrocarbon solvent, and deposition onto the support material is carried out by evaporating the solvent or by spray drying.

[0103] Scheme 11: Step (a): Activator (e.g., an alkylaluminoxane such as methylaluminoxane ("MAO")) + support material (e.g., hydrophobic fumed silica) + inert hydrocarbon solvent → slurry of supported activator disposed on (or in equilibrium with) the support material. Step (b): Spray drying the slurry from step (a) → spray-dried supported activator disposed on the support material in the form of a dry powder (e.g., MAO spray-dried onto hydrophobic fumed silica ("SDMAO" or "sdMAO") as a dry powder). Step (c): Mixing post-metallocene pre-catalyst + spray-dried supported activator from step (b) + inert hydrocarbon solvent → suspension of supported fast light-off post-metallocene catalyst disposed on (or in equilibrium with) the support material. Step (d): Suspension from step (c). with an effective amount of a kinetic modifier compound → a suspension of supported weakened post-metallocene catalyst disposed on (or in equilibrium with) a support material in an inert hydrocarbon solvent. Optional step (e): removing the inert hydrocarbon solvent from the suspension of supported weakened post-metallocene catalyst → a supported weakened post-metallocene catalyst disposed on a support material in the form of a dry powder. Step (e) can be carried out by conventional evaporation of the inert hydrocarbon solvent from the suspension from step (d) or by spray-drying the suspension from step (d).

[0104] The multimodal catalyst system may be fed into a gas-phase polymerization reactor. If desired, an additional amount of the attenuated post-metallocene catalyst or an additional amount of a second catalyst (e.g., a metallocene catalyst) may be separately fed into the reactor as a solution thereof in an inert hydrocarbon solvent and contacted with the multimodal catalyst system in the reactor. Such a separate catalyst solution is sometimes referred to as a trim catalyst. Alternatively, the multimodal catalyst system may be contacted with a feed of trim catalyst in a feed line leading into the reactor. In other embodiments, the multimodal catalyst system may be prepared in situ in the gas-phase polymerization reactor by separately adding the attenuated post-metallocene catalyst and at least one second catalyst into the reactor, where they contact each other, thereby preparing the multimodal catalyst system in situ in the reactor.

[0105] The method according to any one of the above aspects can further include transferring the polymer granules produced in the gas-phase or slurry-phase polymerization reactor and containing the sufficiently active post-metallocene catalyst in the granules into a (second) gas-phase polymerization reactor.

[0106] Kinetic Modifier Compound ("KMC"): 1 ) kinetic modifier compounds are R 5 -C≡CR 6 (A 1 ) is the formula (B 1 ) kinetic modifier compounds are (R 5 )2C=C=C(R 6 )2(B 1 ) is the formula (C 1 ) kinetic modifier compounds are (R 5 )(R 7 )C=C(R 6 )(R 7 )(C 1 ) is the formula (A 1 ), (B 1 ), or (C 1 ) advantageously do not function as poisons to the post-metallocene catalyst, or may function as such at most moderately. 1 ) is an alkyne, and the compound of formula (B 1 ) is an allene, and the compound of formula (C 1 ) is an internal alkene. The kinetic modifier compound does not contain a vinyl functionality (i.e., lacks a group of formula -C(H)=CH2).

[0107] In some embodiments, the kinetics modifier compound is as defined in any one of the numbered aspects above.

[0108] Formula (A 1 ), (B 1 ), or (C 1 In some embodiments of the kinetic modifier compound of (C1-C 20)hydrocarbyl is (C2-C6) alkyl, (C3-C8) cycloalkyl, or phenyl. In some embodiments, -C(=O)-O-(unsubstituted C1-C 20 )hydrocarbyl) is —C(═O)—O-(unsubstituted C1-C5)alkyl) or —C(═O)—O-ethyl.

[0109] In some embodiments, at least one X is selected from the group consisting of ((C1-C 20 )Alkyl) 3-g -(phenyl) g Si-, where subscript g is 0, 1, 2, or 3, or where subscript g is 0 or 1, or 0, or 1. In some embodiments, at least one X is selected from the group consisting of (C6-C 12 )Aryl-((C0-C 10 )alkylene)-CH2 (e.g., benzyl). In some embodiments, each X is independently (C6-C 12 )Aryl-((C0-C 10 ) alkylene)-CH2, or one X is (C6-C 12 )Aryl-((C0-C 10 )alkylene)-CH2 (e.g., benzyl) and the other X is F, Cl, or methyl, or each X is benzyl. In some aspects, each X is benzyl, or one X is benzyl and the other X is F, Cl, or methyl. In some embodiments, at least one X, or each X, is a (C1-C6)alkoxy-substituted (C6-C 12 )aryl or (C1-C6)alkoxy-substituted benzyl. Without being bound by theory, the structure of the attenuated post-metallocene catalyst is believed to be similar to that of the fast light-off catalyst, except that one of the leaving groups X of the fast light-off catalyst is replaced by an attenuated leaving group R in the attenuated post-metallocene catalyst, where R is defined below and is derived from a kinetic modifier compound. The attenuated leaving group R of the attenuated post-metallocene catalyst is structurally different from the leaving group X of the fast light-off catalyst and takes longer to leave.

[0110] Ligand R Derived from a Kinetic Modifier Compound. The ligand in the attenuated post-metallocene catalyst derived from a kinetic modifier compound can be a group R ("ligand R"). Without being bound by theory, it is believed that ligand R is primarily responsible for the improved kinetic profile of the attenuated post-metallocene catalyst (e.g., the attenuated post-metallocene catalyst of Formula (III)) compared to the kinetic profile of the fast light-off catalyst (e.g., the fast light-off catalyst of Formula (II)) used to make the attenuated post-metallocene catalyst. The ligand can be a group 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), wherein X and R 5 ~R 7 wherein each of the formulas is as described above. In some embodiments, R is a ligand of formula (A) or (B), alternatively, R is a ligand of formula (A) or (C), alternatively, R is a ligand of formula (B) or (C), alternatively, R is a ligand of formula (A), alternatively, R is a ligand of formula (B), or alternatively, R is a ligand of formula (C). Both the ligands of formula (A) and (B) contain carbon-carbon double bonds, which are believed to be very slow to polymerize under gas phase polymerization conditions.

[0111] Without wishing to be bound by theory, it is believed that the reaction of an alkene monomer (e.g., ethylene, propylene, 1-butene, 1-hexene, 1-octene, etc.) with a weakened light-off catalyst is due to the insertion of the alkene monomer into the bond between the M metal center and the weakened leaving group R. This insertion may take much longer than the corresponding insertion reaction of the alkene monomer into the bond between the M metal center and the leaving group X of the fast light-off catalyst. The slower reaction of the present invention may delay the initiation of polymerization. After the first (or several) alkene monomer insertion reaction, all subsequent insertions occur at a rate similar to that of a fast light-off catalyst, because the weakened leaving group R is no longer attached to the metal center. Because only the first (or several) of thousands or millions of insertion reactions performed by the catalyst are slowed, overall catalyst productivity may not be significantly reduced. In fact, a weakened light-off catalyst may actually increase productivity because its exotherm is reduced compared to that of a fast light-off catalyst. This is because exothermic reactions that increase the temperature experienced by the catalyst can result in faster deactivation of the catalyst, which can reduce the productivity of some catalysts, such as some post-metallocene catalysts.

[0112] In the ligand R of formula (A), (B), or (C), R 5 and R 6 each independently represents H or R 7 where each R 7 are independent, (C1~C 20 ) hydrocarbyl or (C1-C 17 ) heterohydrocarbyl, provided that each R 7 lacks a carbon-carbon double bond. (C1-C 20 ) Hydrocarbyl can be unsubstituted and consist of carbon and hydrogen atoms, or (C1-C 20 ) hydrocarbyl is substituted and may consist of carbon atoms, hydrogen atoms, and one or more halogen atoms. Each halogen atom is independently selected from F, Cl, Br, and I, or from F, Cl, and Br, or from F and Cl, or from F, or from Cl. Unsubstituted (C1-C 20) hydrocarbyl is unsubstituted (C1-C 20 ) Alkyl, unsubstituted (C3-C 20 ) Cycloalkyl, unsubstituted (C6-C 12 ) aryl, unsubstituted ((C1-C4) alkyl) 1-3 -phenyl, or unsubstituted (C6-C 12 )aryl-(C1-C6)alkyl. 20 ) hydrocarbyl is an unsubstituted (C1-C) as described above, such as 2-(3,4-difluorophenyl)-ethen-1-yl (of formula (A)). 20 ) may be monofluoro or difluoro derivatives of hydrocarbyl.

[0113] Each (C1~C 19 ) heterohydrocarbyl (R containing it 5 ~R 7 (embodiment of the invention) can be unsubstituted and consist of carbon atoms, hydrogen atoms, and at least one heteroatom selected from N and O, or (C1-C 17 ) heterohydrocarbyl may be substituted and consist of carbon atoms, hydrogen atoms, at least one heteroatom selected from N and O, and one or more halogen atoms. 17 ) Heterohydrocarbyl is (C1-C 19 ) heteroalkyl, (C3-C 19 ) heterocycloalkyl, (C6-C 12 ) heteroaryl, ((C1-C4) alkoxy) 1-3 -phenyl, or (C6-C 12 ) heteroaryl-(C1-C6) alkyl. 17 ) Heterohydrocarbyl is an unsubstituted (C1-C) heterohydrocarbyl as described above, such as 2-(3,4-dimethoxyphenyl)-ethen-1-yl (of formula (A)). 17 ) may be a monofluoro or difluoro derivative of heterohydrocarbyl.

[0114] The structure of the ligand R differs from that of the ligand X in that the anion A - It is different from the structure of

[0115] Attenuated Post-Metallocene Catalyst. Attenuated post-metallocene catalysts (e.g., those of Formula (III)) are prepared from fast light-off catalysts (e.g., those of Formula (II)) according to the present method. The attenuated post-metallocene catalyst is a post-metallocene catalyst that contains a ligand (e.g., R) derived from a kinetic modifier compound bonded to its metal atom M (e.g., Ti, Zr, or Hf). The attenuated post-metallocene catalyst is a new post-metallocene catalyst. In some embodiments, the attenuated post-metallocene catalyst is a attenuated post-metallocene catalyst of Formula (III).

[0116] It is believed that, all other things being equal, a weakened post-metallocene catalyst (e.g., one of Formula (III)) may function without a significant decrease in overall catalytic activity compared to the fast light-off catalyst (e.g., one of Formula (II)) used to make it. That is, despite the delayed initiation, the activity / polymerization productivity of the catalyst, expressed as grams of dry polyolefin product made per gram of catalyst added to the reactor per hour (gPE / gcat-hr), may not be significantly less than, and in some embodiments may be greater than, the activity / polymerization productivity of the fast light-off post-metallocene catalyst. For example, the weakened post-metallocene catalyst may have a productivity of greater than 200%, alternatively 70.0% to 180.0%, alternatively 70.0% to 150.0%, alternatively 70.0% to 120%, alternatively 80.0% to 120%, alternatively 90.0% to 120%, alternatively 100.0% to 120%, alternatively 110% to 120%, alternatively 70.0% to 110%, alternatively 80.0% to 110%, alternatively 90.0% to 110%, alternatively 100.0% to 110%, alternatively 70.0% to≦100%, alternatively 80.0% to≦100%, alternatively 90.0% to≦100% of the productivity of the fast light-off catalyst used to make it.

[0117] It is believed that the weakened post-metallocene catalyst of formula (III) may inhibit catalyst light-off and may beneficially improve the operability of gas-phase reactors by reducing fouling rates and increasing the time between reactor shutdowns compared to the fast light-off catalysts (e.g., those of formula (II)) from which it was made.

[0118] It is believed that the weakened post-metallocene catalyst (e.g., of Formula (III)) may exhibit an improved polymerization kinetic profile compared to the fast light-off catalyst of Formula (II) used to prepare it. This improved polymerization kinetic profile beneficially increases the compatibility of the weakened post-metallocene catalyst (e.g., of Formula (III)) with slower light-off olefin polymerization catalysts, such as some metallocene catalysts, and improves the performance of the resulting light-off compatible multimodal (e.g., bimodal or trimodal) catalyst system compared to that of the fast light-off catalyst (e.g., of Formula (II)) used to prepare the weakened post-metallocene catalyst.

[0119] Furthermore, it is believed that the weakened post-metallocene catalyst (e.g., that of Formula (III)) may be stored and transported at ambient temperatures until it is ready for use in a chemical process, rather than at the low temperature storage and transport desired for the fast light-off catalyst (e.g., that of Formula (II)) from which it was made. It is believed that the weakened post-metallocene catalyst (e.g., that of Formula (III)) may achieve any one or a combination of any two or more of such benefits.

[0120] In some embodiments, the attenuated post-metallocene catalyst (e.g., of formula (III)) and the method for polymerizing olefin monomers comprises using an excess amount of a olefin monomer of formula (A 1 ), (B 1 ), or (C 1) kinetic modifier compound. In other embodiments, the attenuated post-metallocene catalyst and method have an excess amount of kinetic modifier compound. Such embodiments of the attenuated post-metallocene catalyst (e.g., of Formula (III)) can be made by combining a fast light-off catalyst (e.g., of Formula (II)) with a molar ratio of moles of kinetic modifier compound to moles of metal M of Formula (II) of greater than 0 to 1.0, alternatively from 1.1 to 50, alternatively from 0.5 to 40, alternatively from 0.5 to 30, alternatively from 0.5 to 20, alternatively from 0.5 to 10, alternatively from 0.5 to 2, alternatively from 0.8 to 1.2, alternatively from 0.9 to 1.1 (e.g., 1.0). In such embodiments, the attenuated post-metallocene catalyst and method have an excess amount of kinetic modifier compound. Such embodiments of the attenuated post-metallocene catalyst (e.g., of Formula (III)) can be made by combining a fast light-off catalyst (e.g., of Formula (II)) with a molar ratio of moles of kinetic modifier compound to moles of metal M of Formula (II) of greater than 0 to 1.0, alternatively from 1.1 to 50, alternatively from 0.5 to 40, alternatively from 0.5 to 30, alternatively from 0.5 to 20, alternatively from 0.5 to 10, alternatively from 0.5 to 2, alternatively from 0.8 to 1.2, alternatively from 0.9 to 1.1 (e.g., 1.0). 1 ), (B 1 ), or (C 1 The kinetic modifier compound of Formula (III) is used in a stoichiometric amount (molar ratio of 1.0) or in a substoichiometric amount (molar ratio of greater than 0 to 0.99). When the kinetic modifier compound is used in a substoichiometric amount, the resulting weakened postmetallocene catalyst (e.g., of Formula (III)) has a partially weakened light-off activity compared to the light-off activity of the fast light-off catalyst (e.g., of Formula (II)) from which it was made. Partially weakened light-off activity can be useful when the fast light-off catalyst (e.g., of Formula (III)) is only mildly overactive. Generally, the higher the molar ratio of moles of kinetic modifier compound to moles of metal M (e.g., of Formula (II)), the greater the weakening of the overactivity of the fast light-off catalyst (e.g., of Formula (II)).

[0121] In some embodiments, the attenuated post-metallocene catalyst (e.g., of formula (III)) and the method for polymerizing olefin monomers comprises using an excess amount of a olefin monomer of formula (A 1 ), (B 1 ), or (C 1) kinetic modifier compounds. Such embodiments of the weakened post-metallocene catalyst (e.g., of Formula (III)) can be prepared by combining a fast light-off catalyst (e.g., of Formula (II)) with a KMC / M molar ratio of greater than 1.0, e.g., from 1.1 to 50, alternatively from 1.1 to 40, alternatively from 1.1 to 30, alternatively from 1.1 to 20, alternatively from 1.1 to 10, alternatively from 2 to 20, alternatively greater than 20. Notably, in some embodiments, even when the kinetic modifier compound is used in excess amounts within the aforementioned ranges (e.g., KMC / M molar ratios up to about 50), the catalytic activity of the weakened post-metallocene catalyst (e.g., of Formula (III)) and / or the productivity of gas-phase polymerization reactions employing it may not be significantly decreased, and may even be increased, compared to that of the fast light-off catalyst (e.g., of Formula (II)) used to prepare it. In other embodiments, when a kinetic modifier compound is used in excess, the catalytic activity of the weakened postmetallocene catalyst (e.g., of Formula (III)) and / or the productivity of the gas-phase polymerization reaction using it may be significantly reduced compared to that of the fast light-off catalyst (e.g., of Formula (II)) from which it was made. The reason for this reduction is not understood, but it is thought that the excess kinetic modifier compound may compete with the alkene monomer for displacing the weakened leaving group R of Formula (III) in an equilibrium manner. Using an excess amount of kinetic modifier compound may be useful when the exact molar amount of the metal M of the fast light-off catalyst (e.g., of Formula (II)) is not precisely known or may vary from lot to lot.

[0122] Attenuated Light-Off Kinetic Profile. Attenuated post-metallocene catalysts (e.g., those of Formula (III)) exhibit attenuated light-off kinetic profiles. For example, the attenuated kinetic profile may be characterized by a longer peak reaction temperature Temp. of the attenuated post-metallocene catalyst compared to that of the fast light-off catalyst used to prepare the attenuated post-metallocene catalyst. peak Length of time to and / or lower T maxThe time from the injection of catalyst into the reactor containing olefin monomer but no catalyst (Time 0) to the peak polymerization reaction temperature (Temp peak ) for at least 0.65 minutes or longer. peak The larger the value of , the greater the delay in catalyst light-off.

[0123] To compare the light-off times of different catalysts, the same olefin monomer (e.g., 1-octene) and the same reactor are used. For rapid catalyst screening, a 40 mL glass vial is used as the reactor, and the light-off vial test method described below is used as the test method.

[0124] Effective amount of kinetic modifier compound (KMC). The amount of kinetic modifier compound (KMC) sufficient to attenuate catalyst light-off. The effective amount of KMC can be expressed in absolute terms compared to the amount of (pre)catalyst metal M, or in relative terms compared to the attenuated light-off performance, or a combination thereof.

[0125] In absolute terms, in some embodiments, an effective amount of kinetic modifier compound is a molar ratio of moles of kinetic modifier compound to moles of metal M ("KMC mol / M mol "), where M is the M of the post-metallocene pre-catalyst of Structural Formula (I), e.g., M is a Group 4 metal. In some embodiments, an effective amount of KMC is a KMC of ≥ 0.50 / 1.0, alternatively ≥ 0.9 / 1.0, alternatively ≥ 1.0 / 1.0, alternatively ≥ 1.5 / 1.0, alternatively ≥ 1.9 / 1.0, alternatively ≥ 3 / 1.0, alternatively ≥ 5 / 1.0, alternatively ≥ 6 / 1.0, alternatively ≥ 9 / 1.0, alternatively ≥ 10.0 / 1.0, alternatively ≤ 10.0 / 1.0, alternatively ≤ 20.0 / 1.0, alternatively ≤ 30.0 / 1.0, alternatively ≤ 40.0 / 1.0, alternatively ≤ 50.0 / 1.0. mol / M mol In other words, the immediately preceding embodiment provides an effective amount of KMC in an inverse molar ratio of moles of metal M to moles of kinetic modifier compound ("M") as follows: mol / KMCmol "), respectively: ≦1.0 / 0.5, or ≦1.0 / 0.9, or ≦1.0 / 1.0, or ≦1.0 / 1.5, or ≦1.0 / 1.9, or ≦1.0 / 3.0, or ≦1.0 / 5.0, or ≦1.0 / 6.0, or ≦1.0 / 9.0, or ≦1.0 / 10.0, or ≦1.0 / 20.0, or ≦1.0 / 30.0, or ≦1.0 / 40.0, or ≦1.0 / 50.0. Generally, a KMC higher than about 50 / 1.0 mol / M mol However, for practical reasons (e.g., cost of KMC and / or post-polymerization processing operations / costs (e.g., stripping excess KMC from polyolefin resins)), in some embodiments, KMC may be used in combination with other catalysts to reduce the amount of KMC present in the catalyst. mol / M mol is limited to a maximum of 40 / 1, or a maximum of 30 / 1, or a maximum of 20 / 1, or a maximum of 10.0, or a maximum of 6.0, or a maximum of 5.0.

[0126] In relative terms of weakened light-off performance, an effective amount of kinetic modifier compound (KMC) may be represented by the results measured by the Light-Off Vial Test Method described below. For example, when measured separately by the Light-Off Vial Test Method described below on a weakened post-metallocene catalyst and a fast light-off post-metallocene catalyst used in its preparation with a kinetic modifier compound, an effective amount of kinetic modifier compound (KMC) may have any one of the following characteristics (i) to (xii) observed after catalyst injection: (i) the time delay for the onset of exotherm, i.e., the reaction temperature increase (i.e., the time from addition time zero (Time 0) to the onset time of temperature exotherm (Time 1)); exo (ii) a decrease in the maximum rate of increase in reaction temperature in degrees Celsius per minute (°C / min) (e.g., a decrease in the maximum slope in a plot of reaction temperature on the y-axis against time after catalyst injection on the x-axis); (iii) a decrease in the length of time (minutes) until the peak reaction temperature (Temp peak ) (℃), (iv) the time from the addition time of Time 0 to the peak temperature (Time peakT(v) neither (iii) nor (iv) but both (i) and (ii), (vi) neither (ii) nor (iv) but both (i) and (iii), (vii) neither (i) nor (iv) but both (ii) and (iii), (viii) neither (ii) nor (iii) but both (i) and (iv), (ix) neither (i) nor (iii) but both (ii) and (iv), (x) neither (i) nor (ii) but both (iii) and (iv), (xi) any three of (i)-(iv), and (xii) each of (i)-(iv). In some embodiments, the attenuated light-off and effective amount of KMC are characterized by at least feature (iv), or by feature (iv) only. In some embodiments, the longer time of characteristic (iv) is a time to peak temperature (Time 0) of at least 0.65 minutes, alternatively at least 1.0 minute, alternatively at least 1.5 minutes, alternatively between 1.5 minutes and 55 minutes, alternatively between 1.6 and 100 minutes, alternatively between 1.6 and 55 minutes, alternatively between 1.6 and 10.0 minutes, alternatively between 10.1 and 20.0 minutes, alternatively between 20.1 and 30.0 minutes, alternatively between 30.1 and 40.0 minutes, alternatively between 40.1 and 50.0 minutes, alternatively between 50.1 and 55 minutes, alternatively between 2.0 and 29 minutes, alternatively between 30.1 and 50.4 minutes, all measured according to the Light-Off Vial Test Method described below. peakT ) for a period of at least 0.65 minutes (39 seconds or more). In some embodiments, the attenuated light-off and effective amount of KMC are characterized by feature (viii). In some embodiments, the attenuated light-off and effective amount of KMC are characterized by feature (ix). In some embodiments, the attenuated light-off and effective amount of KMC are characterized by feature (x). In some embodiments, the attenuated light-off is characterized by feature (xi).

[0127] Fast light-off catalyst for Temp max Weakening by metallocene catalyst versus time to reach Temp maxThe time delay to reach may be 0.70 minutes to 500 minutes (eg, 293 minutes in one example), alternatively 0.70 minutes to 120 minutes, alternatively 1.0 minutes to 120 minutes, alternatively 5 minutes to 90 minutes, alternatively 10 minutes to 70 minutes.

[0128] In some embodiments, the kinetic profile of the weakened post-metallocene catalyst, when run under the same polymerization conditions according to the Light-Off Batch Reactor Test Method described below, may be comparable to the Temp. of the fast light-off catalyst used to make the weakened post-metallocene catalyst. max Peak temperature (Temp peak The light-off batch reactor test method can be characterized as a decrease in Temp (°C) of the weakened post-metallocene catalyst. max is the T of the fast light-off catalyst used to prepare the weakened postmetallocene catalyst. max The temperature may be 1° C. to 16° C., alternatively 2° C. to 15° C., alternatively 3° C. to 14° C. lower than the temperature of the catalyst. In some embodiments, the fast light-off post-metallocene catalyst is made from any one of the post-metallocene pre-catalysts (1) to (10) described above.

[0129] In some embodiments, the kinetic profile of the weakened post-metallocene catalyst may be characterized as the absolute weight / weight ratio of ethylene (C2) uptake after 1 hour (h) to C2 uptake after 0.1 hours (C2(1h) / C2(0.1h)). In some embodiments, the weakened post-metallocene catalyst may have a C2(1h) / C2(0.1h) ratio of 2.1 to 11, alternatively 2.2 to 10.4, alternatively 2.4 to 10.0, alternatively 3 to 9.9. In some embodiments, the fast light-off post-metallocene catalyst is prepared from any one of the aforementioned post-metallocene pre-catalysts (1) to (10).

[0130] In some embodiments, the kinetic profile of the weakened post-metallocene catalyst can be characterized as the relative C2(1 h) / C2(0.1 h) ratio of the weakened post-metallocene catalyst to the C2(1 h) / C2(0.1 h) ratio of the fast light-off catalyst used to make the weakened post-metallocene catalyst when run under the same polymerization conditions according to the Light-Off Batch Reactor Test Method described below. The relative C2(1 h) / C2(0.1 h) ratio can be from 1.05 to 6, alternatively from 1.1 to 6, alternatively from 1.2 to 5.4, or alternatively from 1.5 to 5.0.

[0131] An alternative or additional way of expressing an effective amount of kinetic modifier compound (KMC) in relative terms of weakened light-off performance may be a sufficient amount of KMC such that the weakened post-metallocene catalyst and the fast light-off catalyst used to make it can have a light-off profile as measured by the Light-Off Vial Test Method (described below), with a respective peak polymerization temperature Temp. peak are at least 0.7 minutes, alternatively greater than 1.0 minute, alternatively greater than 5 minutes, alternatively greater than 10.0 minutes, alternatively greater than 20.0 minutes, alternatively greater than 30.0 minutes, alternatively greater than 40.0 minutes, alternatively greater than 50.0 minutes from each other. The weakened post-metallocene catalyst and the fast light-off catalyst used to make it may have a light-off profile as measured by the Light-Off Vial Test Method (described below), in which the time Temp. of each peak polymerization temperature is peak are within 60 minutes, or within 45 minutes, or within 30 minutes of each other. peak The time of the fast light-off post-metallocene catalyst used to prepare the weakened post-metallocene catalyst is peakThe effectiveness of the kinetic modifier compound in delaying the Temp of the attenuated post-metallocene catalyst may vary depending on (a) the structural class (e.g., Formula (Ia), (Ib), (Ic)) or structural subclass (e.g., Formula (Ia)-1 vs. (Ia)-2, or Formula (Ib)-1 vs. (Ib)-2, or Formula (Ic)-1) of the attenuated post-metallocene catalyst and / or (b) the structural class (e.g., acetylenes, allenes, or internal alkenes) or structural subclass (e.g., aryl acetylenes vs. alkyl acetylenes, or monoacetylenes vs. diacetylenes or triacetylenes, or acyclic arenes vs. cycloalkyl arenes vs. vinylidene arenes, or aryl-type internal alkenes vs. alkyl-type internal alkenes) of the kinetic modifier compound. In some embodiments, the Temp of the attenuated post-metallocene catalyst may vary depending on (a) the structural class (e.g., Formula (Ia), (Ib), (Ic)) or structural subclass (e.g., Formula (Ia)-1 vs. (Ia)-2, or Formula (Ib)-1 vs. (Ib)-2, or Formula (Ic)-1) of the attenuated post-metallocene catalyst and / or (b) the structural class (e.g., acetylenes, allenes, or internal alkenes) or structural subclass (e.g., aryl acetylenes vs. alkyl acetylenes, or monoacetylenes vs. diacetylenes or triacetylenes, or acyclic arenes vs. cycloalkyl arenes vs. vinylidene arenes, or aryl-type internal alkenes vs. alkyl-type internal alkenes) of the attenuated post-metallocene catalyst. peak and the Temp of Fast Light-Off Postmetallocene Catalysts Used to Prepare Weakened Postmetallocene Catalysts peak Any one of the endpoints of the range of time differences between may be based on the data provided in the Examples below.

[0132] In some embodiments, the kinetic profile of the weakened post-metallocene catalyst may be characterized as a combination of any two, or all but any one, or each of the foregoing embodiments.

[0133] Comparative or non-inventive examples do not contain any kinetic modifier compounds or contain less than an effective amount of a kinetic modifier compound.

[0134] Catalyst activity. Peak polymerization reaction temperature reached in degrees Celsius (°C) peak ) is measured by the light-off vial test method, the T of the fast light-off catalyst pThe catalytic activity of the weakened post-metallocene catalyst (e.g., of Formula (III)) is determined to be substantially the same as the catalytic activity of the fast light-off catalyst if the difference is within ±5°C, alternatively ±4°C, alternatively ±3°C, alternatively ±2°C, alternatively ±1°C of the activity / polymerization productivity of the attenuated post-metallocene catalyst. Otherwise, the catalytic activity is determined to be the activity / polymerization productivity of the catalyst, expressed as grams of dry polyolefin product per hour (gPE / gcat-hr) made per gram of catalyst added to the reactor, which, all other things being equal, may not be significantly less than, and in some embodiments may be greater than, the activity / polymerization productivity of the fast light-off post-metallocene catalyst.

[0135] Fast Light-Off Catalysts. For the reasons discussed above, embodiments of fast light-off catalysts (e.g., those of Formula (II)) may require weakening of light-off kinetics for slurry-phase and / or gas-phase polymerization of 1-alkene monomers. The same or other embodiments of fast light-off catalysts (e.g., those of Formula (II)) may require ligands R for different reasons, such as to alter the solubility of the catalyst in alkane solvents or to improve NMR studies of post-metallocene catalyst structures and catalyst structure design.

[0136] Anion A - The fast light-off post-metallocene catalyst (e.g., that of formula (II)) and the weakened post-metallocene catalyst (e.g., that of formula (III)) each contain an anion A derived from an activator or from a leaving group X used to prepare the fast light-off post-metallocene catalyst from the post-metallocene pre-catalyst of formula (I). - The activator activates the post-metallocene pre-catalyst of formula (I) by removing its leaving group X to produce a fast light-off post-metallocene catalyst (e.g., that of formula (II)) and an anion A - The resulting activated post-metallocene catalyst, i.e., the fast light-off post-metallocene catalyst of formula (II), is conventionally depicted as showing the metal atom M bearing a positive charge. This positive charge represents a catalytic site to which an olefin monomer can bind during the polymerization reaction. The anion A- formally balances the positive charge, so that the fast light-off post-metallocene catalyst (e.g., that of formula (II)) and the weakened post-metallocene catalyst (e.g., that of formula (III)) made therefrom are overall neutral.

[0137] Anion A in fast light-off post-metallocene catalysts (e.g., those of formula (II)) and weakened post-metallocene catalysts (e.g., those of formula (III)) - The nature of X is not believed to be critical. As previously mentioned, it is believed that the anionic derivative of X (i.e., X - ) or an anionic derivative of the activator. - is its anionic derivative, the anion A - can be an alkylaluminoxane anion, or the activator is an organoborane compound and the anion A - is its anionic derivative, the anion A - can be an organoborane anion, or the activator is an organoboron compound and the anion A - is its anionic derivative, the anion A - can be an organoboron anion. - is formed during the activation step described in embodiment 1. Anion A in fast light-off post-metallocene catalysts (e.g., those of formula (II)) - is the anion A in the weakened postmetallocene catalyst (e.g., of formula (III)) - is the anion A in the fast light-off catalyst - It is believed that the anion A in the weakened postmetallocene catalyst (e.g., that of formula (III)) is carried through the compounding process so that it may be the same as - is the anion A in the fast light-off post-metallocene catalyst (e.g., formula (II)) - For example, the anion A in a fast light-off post-metallocene catalyst (e.g., one of formula (II)) -may be an anionic derivative of an activator, and the anion A in the weakened postmetallocene catalyst (e.g., of formula (III)) - is X - It could be.

[0138] Catalyst Structure. Without being bound by theory, it is believed that the molecular structure of the fast light-off post-metallocene catalyst of formula (II) and the molecular structure of the weakened post-metallocene catalyst of formula (III) can be determined by conventional analytical methods such as nuclear magnetic resonance (NMR) spectroscopy or gas chromatography / mass spectrometry (GC / MS). The structure of the ligand R in formula (III) can be determined by quenching an NMR sample of the weakened post-metallocene catalyst of formula (III) with a protic solvent such as isopropanol, CH3OH, or HO, a partially deuterated protic solvent such as isopropyl-OD, CH3OD, or HDO, or a perdeuterated protic solvent such as perdeuterated isopropanol (CD3)2C(D)OD), perdeuterated methanol (CD3OD), or DO to give a by-product of formula HR or DR, which is then analyzed by proton NMR ( 1 The structure of the by-products can be determined by analyzing them by NMR, such as H-NMR, or gas chromatography / mass spectrometry (GC / MS).

[0139] Activation Step. In some embodiments, the method of making a weakened post-metallocene catalyst (e.g., of Formula (III)) further includes a preliminary activation step, which may be completed before the beginning of the combining step. The activation step includes contacting the pre-catalyst of Formula (I) with an activator under activation conditions effective to make a fast light-off post-metallocene catalyst. The activation step may be carried out in the absence of a kinetic modifier compound.

[0140] Activator. The activator for activating the postmetallocene precatalyst of Formula (I) can be an alkylaluminoxane, an organoborane compound, an organoboron compound, or a trialkylaluminum compound. The activator can also be a combination of any two or more thereof. For example, the activator can include an alkylaluminoxane and an organoboron compound, such as a methylaluminoxane and an organoborate having the CAS name amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate (amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)). The activator for activating the cyclopentadienyl-containing ligand-metal (Ti, Zr, or Hf) complex to obtain the metallocene catalyst can be a trialkylaluminum compound.

[0141] Alkylaluminoxane: Also referred to as alkylalumoxane. Partial hydrolysis product of trialkylaluminum compounds. Embodiments include (C1-C 10The alkylaluminoxane may be a (C1-C6) alkylaluminoxane, a (C1-C4) alkylaluminoxane, a (C1-C3) alkylaluminoxane, a (C1-C2) alkylaluminoxane, a methylaluminoxane (MAO), or a modified methylaluminoxane (MMAO). In some aspects, the alkylaluminoxane is MAO. In some embodiments, the alkylaluminoxane is supported on untreated silica, such as fumed silica. The alkylaluminoxane may be obtained from commercial suppliers or prepared by any suitable method. Suitable methods for preparing alkylaluminoxanes are well known. Examples of such preparation methods are described in U.S. Patent Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, Nos. 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, and 5,693,838, as well as in European Patent Application Publication Nos. 0561476(A), 0279586(B1), and 0594218(A), and in International Publication No. WO 94 / 10180.

[0142] The maximum amount of alkylalumoxane can be selected to be a 5,000-fold molar excess over the precatalyst, based on the molar ratio of moles of Al metal atoms in the aluminoxane to moles of metal atoms M (e.g., Ti, Zr, or Hf) in the precatalyst. The minimum amount of activator to precatalyst can be a 1:1 molar ratio (Al / M). The maximum can be an Al / M molar ratio of 150, or alternatively, 124.

[0143] Organoborane compounds: tri(fluorofunctional organo)borane compounds ((fluoro-organo)3B), such as tris(pentafluorophenyl)borane ((CF)3B), tris[3,5-bis(trifluoromethyl)phenyl]borane ((3,5-(CF)-CH)3B), or a mixture of any two or more thereof.

[0144] Organoboron compounds. Tetra(fluorofunctional organo)borate compounds ((fluoro-organo)4B) such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or a mixture of any two or more thereof. The organoboron compounds are methyldi((C 14 ~C 18 ) alkyl) ammonium salts, which can be obtained from Boulder Scientific or can be prepared by the reaction of a long-chain trialkylamine (Armeen™ M2HT, available from Akzo-Nobel, Inc.) with HCl and Li[B(CF)4]. Such a preparation is disclosed in Example 2 of U.S. Pat. No. 5,919,983. The organoboron compounds can be used herein without further purification. Similarly, amines, bis(hydrogenated tallow alkyl) methyl, tetrakis(pentafluorophenyl) borates can also be used.

[0145] Trialkylaluminum compounds can be utilized as activators for precatalysts (metallocene precatalysts) or as scavengers to remove residual water from a polymerization reactor prior to its start-up. Examples of suitable alkylaluminum compounds are trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.

[0146] Activators, also known as cocatalysts, can affect the molecular weight, branching, comonomer content, or other properties of the polyolefin polymer. Activators can enable coordination or cationic polymerization.

[0147] Without being bound by theory, it is believed that the selection of the activator used to activate the fast light-off post-metallocene catalyst does not affect the structure of the weakened post-metallocene catalyst made from the fast light-off post-metallocene catalyst. That is, only the cation portion of formula (III) is considered (i.e., the anion A - (ignoring the NMR spectra), the structures of weakened postmetallocene catalysts made using different activators are expected to be identical. The structure of an unsupported weakened postmetallocene catalyst can be determined by MMR more easily than that of a supported weakened postmetallocene catalyst due to the heterogeneous nature of the latter (typical support materials are not soluble in NMR solvents).

[0148] In some embodiments, A - The selection of A may have additional effects on the kinetic profile of the weakened post-metallocene catalyst. - Such effects do not completely eliminate the beneficial effects of the kinetic modifier compounds on the kinetic profile of the weakened post-metallocene catalyst.

[0149] Effective Conditions. The reactions described herein (e.g., the combining step, the activation step, and the polymerization step) are independently carried out under conditions that allow the reaction to proceed. Examples of effective conditions include reaction temperature, type of atmosphere (e.g., an inert atmosphere), purity of the reactants, stoichiometry of the reactants, stirring / mixing of the reactants, and reaction time. Effective conditions for the activation and polymerization steps are described in the art and may be well known to those skilled in the art. For example, effective activation conditions may include techniques for operating the catalyst, such as an in-line mixer, a catalyst preparation reactor, and a polymerization reactor. Activation temperatures may range from 20°C to 800°C, alternatively from 300°C to 650°C. Activation times may range from 10 seconds to 2 hours. Examples of gas-phase polymerization conditions are described later in this specification. Effective conditions for the combination step used to make the weakened post-metallocene catalyst may include a reaction temperature of -50°C to 30°C, an inert atmosphere (e.g., water- and O2-free nitrogen, helium, or argon gas), reactants that are water- and O2-free and have a purity of 90% to 100%, reactant amounts to minimize waste / maximize product yield, stirring or mixing of the reactants, and a reaction time of 1 minute to 24 hours.

[0150] Effective reaction conditions for preparing the postmetallocene precatalyst of Formula (IV) are established. Such conditions may include techniques for manipulating air- and / or moisture-sensitive reagents and reactants, such as Schlenk line techniques and inert gas atmospheres (e.g., nitrogen, helium, or argon). Effective reaction conditions may also include sufficient reaction time, sufficient reaction temperature, and sufficient reaction pressure. Each reaction temperature may independently be between -78°C and 120°C, alternatively between -30°C and 30°C. Each reaction pressure may independently be between 95 and 105 kPa, alternatively between 99 and 103 kPa. The progress of specific reaction steps may be monitored by analytical methods, such as nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry, to determine effective reaction times for maximizing the yield of the desired product. Alternatively, each reaction time may independently be between 30 minutes and 48 hours.

[0151] Postmetallocene pre-catalyst of formula (I). The pre-catalyst of formula (I) can be synthesized according to methods known in the art, including those referenced above. Alternatively, the post-metallocene pre-catalyst can be obtained from a pre-catalyst supplier, such as Boulder Scientific.

[0152] Polyolefin polymers prepared by synthetic methods. When the 1-alkene monomer is a combination of ethylene and propylene, the polyolefin polymer prepared therefrom is an ethylene / propylene copolymer. When the 1-alkene monomer is ethylene alone, the polyolefin polymer prepared therefrom is a polyethylene homopolymer. When the 1-alkene monomer is a combination of ethylene and 1-butene, 1-hexene, or 1-octene, the polyolefin polymer prepared therefrom is a poly(ethylene-co-1-butene) copolymer, a poly(ethylene-co-1-hexene) copolymer, or a poly(ethylene-co-1-octene) copolymer. In some embodiments, the polyolefin polymer prepared from 1-alkene monomers is an ethylene-based polymer having 50 to 100 weight percent (wt%) repeat units derived from ethylene and 50 to 0 wt% repeat units derived from 1-alkene monomers selected from propylene, 1-butene, 1-hexene, 1-octene, and combinations of any two or more thereof.

[0153] In some embodiments, the polymerization process uses a 1-alkene monomer and a comonomer that is a diene monomer (e.g., 1,3-butadiene). When the 1-alkene monomer is a combination of ethylene and propylene and the polymerization also uses a diene monomer, the polyolefin polymer is an ethylene / propylene / diene monomer (EPDM) copolymer. The EPDM copolymer can be an ethylene / propylene / 1,3-butadiene copolymer.

[0154] Multimodal (e.g., bimodal or trimodal) catalyst systems. Bimodal catalyst systems include an attenuated post-metallocene catalyst and at least one other olefin polymerization catalyst selected from a different attenuated post-metallocene catalyst, a post-metallocene catalyst, and a metallocene catalyst. The multimodal catalyst system produces a multimodal polyethylene composition containing an HMW polyethylene component and an LMW polyethylene component in a single reactor. Some of the problems are related to undesirable gels in the melt-blended multimodal (e.g., bimodal or trimodal) polyethylene composition after the reactor. Other problems are related to the complexities of transition and the stability of the multimodal (e.g., bimodal or trimodal) catalyst system. Even in the absence of gels, there can be problems due to the variability in settling of catalyst particles of different sizes. In some embodiments, instead of using gel measurements, the variability of the melt index (I2) can be measured as a function of particle size.

[0155] The method for making a weakened post-metallocene catalyst can be carried out in the presence of a metallocene catalyst or a metallocene pre-catalyst. When carried out in the presence of a metallocene pre-catalyst, the method for activating the pre-catalyst of formula (I) with an activator further comprises activating the metallocene pre-catalyst with the same or a different activator. Typically, the method for making a weakened post-metallocene catalyst is carried out in the absence of a metallocene (pre)catalyst.

[0156] Metallocene Catalysts. The metallocene catalyst may be made from any one of the metallocene pre-catalyst components set forth in U.S. Pat. No. 7,873,112 (B2), column 11, line 17 to column 22, line 21. In some embodiments, the metallocene catalyst is made from the metallocene pre-catalyst species named in U.S. Pat. No. 7,873,112 (B2), column 18, line 51 to column 22, line 5. In some embodiments, the metallocene pre-catalyst is a bis(η 5 -tetramethylcyclopentadienyl)zirconium dichloride, bis(η 5 -tetramethylcyclopentadienyl)zirconium dimethyl, bis(η 5 -pentamethylcyclopentadienyl)zirconium dichloride, bis(η5 -pentamethylcyclopentadienyl)zirconium dimethyl, (1,3-dimethyl-4,5,6,7-tetrahydroindenyl)(1-methylcyclopentadienyl)zirconium dimethyl, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride, bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl, bis(n-propylcyclopentadienyl)hafnium dichloride, bis(n-propylcyclopentadienyl)hafnium dimethyl, bis In some embodiments, the metallocene catalyst is selected from the group consisting of bis(n-butylcyclopentadienyl)zirconium dichloride, (cyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl, (methylcyclopentadienyl)(1,5-dimethylindenyl)zirconium dimethyl, (cyclopentadienyl)(1,4-dimethylindenyl)zirconium dimethyl, (methylcyclopentadienyl)(1,4-dimethylindenyl)zirconium dimethyl, and bis(n-butylcyclopentadienyl)zirconium dimethyl. In some embodiments, the metallocene catalyst is the product of an activation reaction between an activator and any one of the foregoing metallocene pre-catalysts.

[0157] Unsupported or supported catalysts. The post-metallocene pre-catalyst of Formula (I), the fast light-off post-metallocene catalyst such as the fast light-off catalyst of Formula (II), the weakened post-metallocene catalyst such as the weakened post-metallocene catalyst of Formula (III), and the multimodal catalyst system can independently be unsupported or disposed on a solid particulate support material. In the absence of a support material, the post-metallocene pre-catalyst of Formula (I), the fast light-off post-metallocene catalyst such as the fast light-off catalyst of Formula (II), the weakened post-metallocene catalyst such as the weakened post-metallocene catalyst of Formula (III), and / or the multimodal catalyst system can be injected into a slurry-phase or gas-phase polymerization reactor as a solution in a hydrocarbon solvent. When the post-metallocene pre-catalyst of Formula (I), fast light-off post-metallocene catalyst such as the fast light-off catalyst of Formula (II), weakened post-metallocene catalyst such as the weakened post-metallocene catalyst of Formula (III), and / or multimodal catalyst system are disposed on a support material, they can be injected into a slurry phase or gas phase polymerization reactor as a slurry suspended in a hydrocarbon solvent or as a dry powder (i.e., a dry particulate solid).

[0158] The fast light-off post-metallocene catalyst (e.g., of Formula (II)) and / or the weakened post-metallocene catalyst (e.g., of Formula (III)) can be pre-fabricated in the absence of a support material and later disposed on the support material. Alternatively, the post-metallocene pre-catalyst of Formula (I) or the fast light-off post-metallocene catalyst (e.g., of Formula (II)) can be disposed on a support material, and then the fast light-off post-metallocene catalyst (e.g., of Formula (II)) and / or the weakened post-metallocene catalyst (e.g., of Formula (III)) can be fabricated in situ on the support material.

[0159] The supported post-metallocene pre-catalyst of Formula (I), the supported fast light-off post-metallocene catalyst (e.g., the supported catalyst of Formula (II)), and / or the supported weakened post-metallocene catalyst (e.g., the supported catalyst of Formula (III)) can be prepared by a concentration method in which a solution of the pre-catalyst of Formula (I), the fast light-off catalyst (e.g., of Formula (II)), and / or the weakened post-metallocene catalyst (e.g., of Formula (III)) in a hydrocarbon solvent is evaporated from a suspension or solution of the support material. Alternatively, the supported pre-catalyst of Formula (I), the supported fast light-off catalyst (e.g., the supported catalyst of Formula (II)), and / or the supported weakened post-metallocene catalyst (e.g., the supported catalyst of Formula (III)) can be prepared by a spray drying method by spray drying a suspension or solution. In some embodiments, a spray drying method is used.

[0160] Support material. The support material is a particulate solid that can be non-porous, semi-porous, or porous. The carrier material is a porous support material. Examples of support materials are talc, inorganic oxides, inorganic chlorides, zeolites, clays, resins, and mixtures of any two or more thereof. Examples of suitable resins are polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinylbenzene polyolefins. The support material can independently be untreated silica, or calcined untreated silica, or silica treated with a hydrophobizing agent, or calcined silica treated with a hydrophobizing agent. The hydrophobizing agent can be dichlorodimethylsilane.

[0161] Inorganic oxide support materials include oxides of metals from Groups 2, 3, 4, 5, 13, or 14. Preferred supports include silica, fumed silica, alumina (see, e.g., WO 99 / 60033), silica-alumina, and mixtures thereof, which may or may not be dehydrated. Other useful supports include magnesia, titania, zirconia, magnesium chloride (U.S. Pat. No. 5,965,477), montmorillonite (EP 0 511 665), phyllosilicates, zeolites, talc, clays (U.S. Pat. No. 6,034,187), and the like. Combinations of these support materials, such as silica-chromium, silica-alumina, and silica-titania, may also be used. Additional support materials include those porous acrylic polymers described in EP 0 767 184, which is incorporated herein by reference. Other support materials include nanocomposites such as those disclosed in WO 99 / 47598, aerogels such as those disclosed in WO 99 / 48605, spherulites such as those disclosed in U.S. Pat. No. 5,972,510, and polymer beads such as those disclosed in WO 99 / 50311.

[0162] The supporting material is approximately 10 m 2 / g~about 700m 2 / g, with a surface area of ​​approximately 0.1 cm 3 / g ~ approx. 4.0cm 3 The support may have a pore volume in the range of 1 / g and an average particle size in the range of about 5 microns to about 500 microns. The support material may be silica (e.g., fumed silica), alumina, clay, or talc. The fumed silica may be hydrophilic (untreated) or hydrophobic (treated). In some aspects, the support is hydrophobic fumed silica, which may be prepared by treating untreated fumed silica with a hydrophobizing agent such as dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane. In some aspects, the treating agent is dimethyldichlorosilane. In one embodiment, the support is Cabosil™ TS-610.

[0163] The one or more pre-catalysts and / or one or more activators may be deposited on, contacted with, vaporized, bound to, or incorporated into, adsorbed on, or absorbed onto, one or more support or carrier materials.

[0164] The metallocene pre-catalyst may be spray dried according to the general method described in U.S. Pat. No. 5,648,310. Supports used with the post-metallocene pre-catalyst may be functionalized as generally described in EP 0 802 203, or at least one substituent or leaving group may be selected as described in U.S. Pat. No. 5,688,880.

[0165] Liquid phase and / or slurry phase polymerization of olefin monomers is well known, see for example US8291115B2.

[0166] Inert hydrocarbon solvent. Alkane, arene, or alkylarene (i.e., arylalkane). Examples of inert hydrocarbon solvents include mineral oil, alkanes such as pentane, hexane, heptane, octane, nonane, decane, undecane, and dodecane, as well as toluene and xylene. In one embodiment, the inert hydrocarbon solvent is an alkane or a mixture of alkanes, each alkane independently having 5 to 20 carbon atoms, alternatively 5 to 12 carbon atoms, alternatively 5 to 10 carbon atoms. Each alkane may independently be acyclic or cyclic. Each acyclic alkane may independently be straight-chain or branched. The acyclic alkane may be pentane, 1-methylbutane (isopentane), hexane, 1-methylpentane (isohexane), heptane, 1-methylhexane (isoheptane), octane, nonane, decane, or a mixture of any two or more thereof. The cyclic alkane can be cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, methylcyclopentane, methylcyclohexane, dimethylcyclopentane, or a mixture of any two or more thereof. Additional examples of suitable alkanes include mineral oils such as Isopar-C, Isopar-E, and white mineral oil. In some embodiments, the inert hydrocarbon solvent does not comprise mineral oil. The inert hydrocarbon solvent can be one or more (C5-C6) alkanes.12 ) alkanes.

[0167] Gas-phase polymerization (GPP). Polymerization uses a GPP reactor, such as a stirred-bed gas-phase polymerization reactor (SB-GPP reactor) or a fluidized-bed gas-phase polymerization reactor (FB-GPP reactor). Such reactors and processes are generally known. For example, the FB-GPP reactor / process may be as described in any one of U.S. Pat. Nos. 3,709,853, 4,003,712, 4,011,382, 4,302,566, 4,543,399, 4,882,400, 5,352,749, 5,541,270, U.S. Patent Application Publication No. 2018 / 0079836 (A1), European Patent Application Publication No. 0802202 (A), and Belgian Patent No. 839,380. These SB-GPP and FB-GPP polymerization reactors and processes either mechanically agitate or fluidize the polymerization medium within the reactor by continuous flow of gaseous monomer and diluent, respectively. Other useful reactors / processes contemplated include series or multi-stage polymerization processes such as those described in U.S. Pat. Nos. 5,627,242, 5,665,818, 5,677,375, EP 0 794 200 A, EP 0 649 992 B1, EP 0 802 202 A, and EP 634 421 B.

[0168] Gas-phase polymerization operating conditions are any variable or combination of variables that can affect the polymerization reaction in a GPP reactor or the composition or properties of the polyolefin copolymer composition product produced thereby. Variables can include reactor design and size, precatalyst composition and amount, reactant composition and amount, molar ratio of two different reactants, presence or absence of a feed gas such as H, molar ratio of feed gas to reactant, absence or concentration of interfering substances (e.g., H2O and / or O2), presence or absence of an induced condensing agent (ICA), mean residence time of the polymer in the reactor, component partial pressures, monomer feed rate, reactor bed temperature (e.g., fluidized bed temperature), nature or sequence of process steps, and transition periods between steps. Variables other than those listed or varied by the method or use may be held constant.

[0169] The GPP method uses ethylene ("C2"), hydrogen ("H2"), and 1-hexene ("C6" or "C" where x is 6). x ") to provide a fixed molar or feed mass ratio (C ) of comonomer to ethylene monomer gas equal to the stated value (e.g., 0.00560 or 0.00703). xA constant hydrogen-to-ethylene gas molar or feed mass ratio ("H2 / C2") equal to a stated value (e.g., 0.00229 or 0.00280), a constant hydrogen-to-ethylene gas molar or feed mass ratio ("H2 / C2") equal to a stated value (e.g., 0.00229 or 0.00280), and a constant ethylene ("C2") partial pressure equal to a stated value (e.g., 1000 kPa) are maintained. The gas concentrations are measured by an in-line gas chromatograph to understand and maintain the composition of the recycle gas stream. A continuous flow of make-up feed maintains the reaction bed of growing polymer particles in a fluidized state, recycling gas through the reaction zone. A superficial gas velocity of 0.49 to 0.79 meters per second (m / s) (1.6 to 2.6 feet per second (ft / s)) is used. The FB-GPP reactor is operated at a total pressure of about 2068 to about 2758 kilopascals (kPa) (about 300 to about 400 pounds per square inch gauge (psig)) and the stated first reactor bed temperature, RBT. The fluidized bed is maintained at a constant height by withdrawing a portion of the bed at a rate equal to the production rate of the particulate form of the polyolefin polymer composition, which can be from 5,000 to 150,000 kilograms per hour (kg / hr). The product polyolefin polymer composition is semi-continuously withdrawn through a series of valves into a fixed volume chamber, and the withdrawn multimodal (e.g., bimodal or trimodal) ethylene-co-1-hexene copolymer composition is purged to remove any hydrocarbons and treated with a stream of humidified nitrogen (N) gas to deactivate any traces of residual catalyst.

[0170] The catalyst system may be fed to the polymerization reactor in "dry mode" or "wet mode," or in dry mode, either as a dry powder or granules, or as a suspension in an inert liquid such as mineral oil.

[0171] Induced Coagulant (ICA). An inert liquid useful for cooling materials in the GPP reactor(s). Its use is optional. ICA is a type of coagulant that can be used in a wide range of applications (C3-C4). 20 ) Alkanes, or (C5-C 20The ICA may be an alkane, such as 2-methylbutane (i.e., isopentane). See U.S. Patent Nos. 4,453,399, 4,588,790, 4,994,534, 5,352,749, 5,462,999, and 6,489,408. The ICA concentration in the reactor may be 0.1 to 25 mol%, alternatively 1 to 16 mol%, alternatively 1 to 10 mol%.

[0172] GPP conditions may further include one or more additives, such as chain transfer agents or accelerators. Chain transfer agents are well known and can be alkyl metals such as diethylzinc. Accelerators are known, for example, in U.S. Pat. No. 4,988,783, and can include chloroform, CFCl3, trichloroethane, and difluorotetrachloroethane. A scavenger may be used to react with moisture prior to reactor start-up, or to react with excess activator during reactor transition. The scavenger may be a trialkylaluminum. GPP may also be operated without a scavenger (i.e., not intentionally added). The GPP reactor / process may further include a certain amount (e.g., 0.5 to 200 ppm based on the total reactor feed) of one or more static charge control agents and / or one or more continuity additives, such as aluminum stearate or polyethyleneimine. A static charge control agent may be added to the FB-GPP reactor to inhibit the formation or accumulation of static charge within the FB-GPP reactor.

[0173] The GPP reactor can be a commercial-scale FB-GPP reactor, such as a UNIPOL™ reactor or a UNIPOL™ II reactor, available from Univation Technologies, LLC, a subsidiary of The Dow Chemical Company (Midland, Michigan, USA).

[0174] 1-Alkene Monomers. 1-Alkene monomers have the formula H2C=C(H)(CH2) n R 8 wherein the subscript n is an integer from 0 to 19, and the group R 8is H or CH3. An example is ethylene (subscript n is 0, R 8 is H), propylene (subscript n is 0, R 8 is CH3), and (C4 to C 20 ) alpha-olefins (subscript n is an integer from 1 to 19, R 8 is H or CH. In some embodiments, the 1-alkene monomer is ethylene, propylene, 1-butene, 1-hexene, 1-octene, or a combination of any two or more thereof. In some embodiments, the 1-alkene monomer is a combination of ethylene and propylene. In other embodiments, the 1-alkene monomer is ethylene alone or in combination with 1-butene, 1-hexene, or 1-octene.

[0175] Polyolefin polymers are products of polymerization of at least one 1-alkene monomer with a weakened postmetallocene catalyst or a multimodal catalyst system. They are macromolecules or aggregates of macromolecules having structural units derived from at least one 1-alkene monomer. For example, when at least one 1-alkene monomer comprises ethylene, the polyolefin polymer comprises a polyethylene homopolymer. When at least one 1-alkene monomer comprises ethylene and propylene, the polyolefin polymer comprises an ethylene / propylene copolymer. When at least one 1-alkene monomer comprises ethylene and a comonomer selected from 1-butene, 1-hexene, and 1-octene, the polyolefin polymer is selected from poly(ethylene-co-1-butene) copolymer, poly(ethylene-co-1-hexene) copolymer, and poly(ethylene-co-1-octene) copolymer, respectively.

[0176] The polyolefin polymer may be a homopolymer or a copolymer. The polyolefin polymer may have a unimodal or multimodal molecular weight distribution. Polyolefin polymers made from a multimodal catalyst system have a multimodal (e.g., bimodal or trimodal) molecular weight distribution and include a high molecular weight (HMW) polyolefin polymer component and a low molecular weight (LMW) polyolefin polymer component. The HMW polyolefin polymer component may be made by the weakened postmetallocene catalyst (e.g., that of formula (III)), and the LMW polyolefin polymer component may be made by the metallocene catalyst.

[0177] Any compound, composition, formulation, material, mixture, or reaction product herein may be free of any one of the chemical elements selected from the group consisting of H, Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, lanthanides, and actinides, excluding chemical elements required for the compound, composition, formulation, material, mixture, or reaction product (e.g., Zr required for a zirconium compound, or C and H required for polyethylene, or C, H, and O required for an alcohol).

[0178] Alternatively, it precedes a different embodiment. ASTM is the standardization organization ASTM International (West Conshohocken, Pennsylvania, USA). Any comparative examples are used for illustrative purposes only and are not prior art. "Free of" or "lacking" means complete absence or undetectable. IUPAC (International Union of Pure and Applied Chemistry) is the International Union of Pure and Applied Chemistry (IUPAC Secretariat (Research Triangle Park, North Carolina, USA)). The Periodic Table of the Elements is the IUPAC version dated May 1, 2018. "May" gives permitted options, not required. "Operative" means functionally possible or effective. "Optional" means absent (or excluded) or present (or included). Properties can be measured using standard test methods and conditions. Ranges include endpoints, subranges, and whole and / or fractional values ​​contained therein, except that integer ranges do not include fractional values. Room temperature: 23°C ± 1°C.

[0179] Unless otherwise stated, definitions of terms used herein are taken from the IUPAC Compendium of Chemical Technology ("Gold Book"), 2.3.3 edition, dated February 24, 2014. For convenience, some definitions are provided below.

[0180] Alkane (solvent). Formula C n H 2n+2 and / or one or more acyclic linear or branched compounds of formula C m H 2m wherein the subscripts n and m are independently integers from 5 to 50 (e.g., 6), and do not contain carbon-carbon double bonds (C=C) and terminal carbon-carbon triple bonds (C≡C).

[0181] Alkyl (unsubstituted). A monovalent group consisting of a hydrogen atom and at least one carbon atom, formally created by removing a hydrogen atom from an alkane. It does not contain a carbon-carbon double bond (C=C) or a terminal carbon-carbon triple bond (C≡C).

[0182] Alkyl (substituted). At least one hydrogen atom of an unsubstituted alkyl is replaced by a substituent (e.g., R s ) is a monovalent radical formally created by replacing

[0183] Alkaryl (unsubstituted) or alkyl-substituted aryl. A monovalent radical consisting of a hydrogen atom and at least seven carbon atoms, formally created by removing a hydrogen atom from the arenyl portion of an alkyl-arene. For example, 4-methylphenyl.

[0184] Alkaryl (substituted) or alkyl-substituted aryl. At least one hydrogen atom of the unsubstituted alkaryl is replaced by a substituent (e.g., R s ) is a monovalent radical formally created by replacing

[0185] Aralkyl (unsubstituted). A monovalent group consisting of a hydrogen atom and at least seven carbon atoms, formally created by removing a hydrogen atom from the alkane portion of an arenyl-alkane. For example, benzyl. Contains no carbon-carbon double bonds (C=C) and no terminal carbon-carbon triple bonds (C≡C).

[0186] Aralkyl (substituted). At least one hydrogen atom of an unsubstituted aralkyl is replaced by a substituent, e.g., R s ) is a monovalent radical formally created by replacing

[0187] Aryl (unsubstituted). A monovalent group consisting of a hydrogen atom and at least six carbon atoms, formally created by removing a hydrogen atom from an arene. For example, phenyl, naphthyl. Contains no carbon-carbon double bonds (C=C) and no terminal carbon-carbon triple bonds (C≡C).

[0188] Aryl (substituted). At least one hydrogen atom of an unsubstituted aryl is replaced by a substituent (e.g., R s ) is a monovalent radical formally created by replacing

[0189] 4-(C1~C 20 ) Alkyl-substituted 1,3-butadiene molecule. Formula H2C=C(H)-C(H)=C(H)-(C1-C 20 ) alkyl compounds.

[0190] (C # ~C # ) (as modifying the functional group). The # or number sign indicates the range of carbon atoms in the unsubstituted version of the functional group. For example, (C1-C6) has 1 to 6 carbon atoms, and (C7-C 20 ) has 7 to 20 carbon atoms, (C6 to C 12 ) has 6 to 12 carbon atoms, (C1 to C 20 ) has 1 to 20 carbon atoms.

[0191] -C(=O)-O-(unsubstituted C1~C 20 ) hydrocarbyl). A monovalent group consisting of a hydrogen atom, two oxygen atoms, and 2 to 21 carbon atoms, formally prepared by removing a hydrogen atom from the carbonyl carbon atom of a formate ester. For example, -C(=O)-O-phenyl or -C(=O)-O-ethyl. Contains no carbon-carbon double bonds (C=C) and no terminal carbon-carbon triple bonds (C≡C).

[0192] Coordination entity. An assembly consisting of a central atom (metal atom) attached (bonded) to a surrounding array of other groups of atoms (ligands).

[0193] Coordination number. For a particular atom (e.g., M) in a chemical species, the amount of other atoms directly connected or bonded to that particular atom in that chemical species. For example, in TiCl4, the coordination number of the titanium atom is 4.

[0194] Dendity. In a coordination entity, the number of donor groups from the same ligand attached to the same central atom (e.g., attached to M), kappa (κ).

[0195] Bidentate organoheteryl. A monovalent group that functions as a ligand to the metal M and consists of carbon atoms, hydrogen atoms, and at least one heteroatom selected from N, O, S, and P, and can be selected so that the monovalent group is doubly coordinated to the metal M through a carbon atom and one such heteroatom or through two such heteroatoms. This monovalent ligand can provide a dentate number κ of 2 to M. The bidentate organoheteryl can be one that does not contain a terminal carbon-carbon double bond (>C=CH2) and a terminal carbon-carbon triple bond (-C≡CH), or one that does not contain any carbon-carbon double bonds (C=C) and any terminal carbon-carbon triple bonds (C≡C).

[0196] Bidentate organoheterylene. A divalent group that functions as a ligand to a metal atom M and consists of carbon, hydrogen, and at least one heteroatom selected from N, O, S, and P, and can be selected so that the divalent group is doubly coordinated to the metal M via a carbon atom and one such heteroatom or via two such heteroatoms. This divalent group can provide M with a dentate number κ of 2. The bidentate organoheterylene can be one that does not contain a terminal carbon-carbon double bond (>C=CH2) and a terminal carbon-carbon triple bond (-C≡CH), or one that does not contain any carbon-carbon double bonds (C=C) and any terminal carbon-carbon triple bonds (C≡C).

[0197] Dry. Generally, a moisture content of 0 to less than 5 parts per million, based on total weight. The materials fed to the reactor(s) during the polymerization reaction are dry.

[0198] Effective amount: An amount sufficient to achieve a result.

[0199] Halogen atoms: atoms selected from F, Cl, Br, and I, or from F, Cl, and Br, or from F and Cl, or from F and Br, or from Cl and Br, or from F, or from Cl.

[0200] Haptic number. In a coordination entity, the number of atoms in a continuous or uninterrupted series of two or more atoms from the same ligand attached to a central atom (e.g., M), eta (η). For example, a cyclopentadienyl group has five continuous or uninterrupted carbon atoms coordinated to M, and therefore has a haptic number η (η) of 5. 5 ("η 5 ")) has 4-(C1~C 20 The alkyl-substituted 1,3-butadiene molecule has a haptic number η (eta) of 2 for one of its two carbon-carbon double bonds. 2 ("η 2 ") through M) or through both of its carbon-carbon double bonds (haptic number η (eta 4 ("η 4 ") to M).

[0201] Heterohydrocarbyl. A monovalent group consisting of carbon atoms, hydrogen atoms, and at least one heteroatom selected from N, O, S, Si, and P, and thus organic, but having its free valence at a carbon atom. A heterohydrocarbyl may be one that does not contain a terminal carbon-carbon double bond (>C=CH2) and a terminal carbon-carbon triple bond (-C≡CH), or one that does not contain any carbon-carbon double bonds (C=C) and any terminal carbon-carbon triple bonds (C≡C). In some embodiments, the at least one heteroatom is selected from the group consisting of N, O, and Si, or N and O, or N and Si, or O and Si, or N, or O, or Si, or S, or P. In some embodiments, an R-type group is not a heterohydrocarbyl group.

[0202] High molecular weight (HMW) components: A subgroup of macromolecules that have a peak in a GPC plot of dW / dLog(MW) on the y-axis against Log(MW) on the x-axis, and that are of high molecular weight.

[0203] HN5. The term "HN5" does not refer to a pentazole, i.e., a heterocycle of formula HN5. As used herein, HN5 generally refers to a ligand-metal complex of formula (Ib)-1.

[0204] Hydrocarbyl: A univalent group formally derived by removing an H atom from a carbon atom of a hydrocarbon compound consisting of C atoms and H atoms. In some embodiments, each hydrocarbyl is independently alkyl, alkaryl, aryl, or aralkyl.

[0205] Hydrocarbylene. A divalent radical formally derived by removing two H atoms from different carbon atoms of a hydrocarbon compound consisting of a C atom and an H atom.

[0206] Inert. Generally, not (appreciably) reactive in or not (appreciably) interfering with the polymerization reaction of the present invention. The term "inert" as applied to the purge gas or ethylene feed means a molecular oxygen (O) content of 0 to less than 5 parts per million, based on the total weight of the purge gas or ethylene feed.

[0207] Inert hydrocarbon solvent: A liquid material at 25°C that consists of carbon and hydrogen atoms and, optionally, one or more halogen atoms, and that contains no carbon-carbon double or triple bonds.

[0208] Leaving group. A group X coordinated to a metal M in a precatalyst (MX), such that when the precatalyst is contacted with an activator, one such group is removed from the precatalyst, converting the precatalyst into an active catalyst (M + ) and by-product anion X - In some embodiments, the aforementioned A in the fast light-off catalyst and the weak light-off catalyst -is X - Each monodentate X is a leaving group capable of donating 1 dentate κ to M.

[0209] Ligand. A molecule capable of coordinating to a transition metal atom M, such as a group 4 metal atom Ti, Hf, or Zr, or a radical derived therefrom by removal of a hydrogen atom.

[0210] Ligands D, T, and Q are distinct from leaving group X in that at least one leaving group X present in the pre-catalyst is absent in the fast light-off catalyst, and at least one leaving group X present in the fast light-off catalyst is replaced by a weakened leaving group R in the weakened post-metallocene catalyst, while ligand D, ligand T, or ligand Q, as the case may be, remains coordinated to metal atom M in the pre-catalyst, in the fast light-off catalyst made from the pre-catalyst, and in the weakened post-metallocene catalyst made from the fast light-off catalyst.

[0211] Low molecular weight (LMW) constituents: A subgroup of macromolecules that has a peak in a GPC plot of dW / dLog(MW) on the y-axis against Log(MW) on the x-axis, and that is of low molecular weight.

[0212] Metallocene catalysts are homogeneous or heterogeneous materials that enhance the rate of olefin polymerization and contain a ligand-metal complex having two (substituted or unsubstituted) cyclopentadienyl groups (unbridged or bridged), either single-site or dual-site, each of which is a transition metal, such as Ti, Zr, or Hf.

[0213] Minute (1). A unit of time equal to 60.0 seconds. 0.1 minutes equals 6.0 seconds.

[0214] Organoheteryl. A monovalent group consisting of carbon atoms, hydrogen atoms, and at least one heteroatom selected from N, O, S, and P, and thus organic, but having its free valence at one of the heteroatoms. Organoheteryl can be one that does not contain a terminal carbon-carbon double bond (>C=CH2) and a terminal carbon-carbon triple bond (-C≡CH), or it can be one that does not contain any carbon-carbon double bonds (C=C) and any terminal carbon-carbon triple bonds (C≡C).

[0215] Organoheterylene. A divalent group consisting of carbon atoms, hydrogen atoms, and at least one heteroatom selected from N, O, S, and P, and therefore organic, but having one of its two free valences on one of the heteroatoms and the other free valence on a carbon atom or a different heteroatom. Organoheterylene can be one that does not contain a terminal carbon-carbon double bond (>C=CH2) and a terminal carbon-carbon triple bond (-C≡CH), or it can be one that does not contain any carbon-carbon double bonds (C=C) and any terminal carbon-carbon triple bonds (C≡C).

[0216] Postmetallocene catalysts. Homogeneous or heterogeneous ligand-metal complexes that are not metallocene catalysts. Nonmetallocene molecular catalysts. Postmetallocene catalysts lack (substituted or unsubstituted) cyclopentadienyl-containing ligands, enhancing the olefin polymerization reaction rate. Substantially single-site or dual-site catalysts. Prepared by activating a postmetallocene precatalyst, which also lacks (substituted or unsubstituted) cyclopentadienyl ligands. Each metal is a transition metal, such as Ti, Zr, or Hf.

[0217] Precatalyst (see Postmetallocene Precatalyst): An unactivated coordinating entity or ligand-metal complex lacking a (substituted or unsubstituted)-cyclopentadienyl group-containing ligand.

[0218] R-type group. "R" or "R superscript " and "superscript" is a number, a letter, or both. "R superscriptExamples of " groups are R 1 , R a1 , R b1 , R 1a , R 2 , R H And so on.

[0219] Tetradentate organoheterylene. An organoheterylene as described above that is directly bonded to a metal M through four heteroatoms or through three heteroatoms and one carbon atom. The tetradentate organoheterylene can provide M with a dentity κ of 4. In some embodiments, the organoheterylene is directly bonded to M through four heteroatoms or through three heteroatoms and one carbon atom. In some embodiments, each heteroatom directly bonded to M is independently N or O, or N or O. In some embodiments, the organoheterylene is directly bonded to M through four O atoms.

[0220] Tridentate organoheterylene. An organoheterylene as described above that is directly bonded to a metal M through three heteroatoms or two heteroatoms and one carbon atom. The tridentate organoheterylene can provide M with a dentacy number κ of 3. In some embodiments, the organoheterylene is directly bonded to M through three heteroatoms or two heteroatoms and one carbon atom. In some embodiments, each heteroatom directly bonded to M is independently N or O, or N or O. In some embodiments, the organoheterylene is directly bonded to M through three N atoms.

[0221] Tori ((C1~C 20 )hydrocarbyl)silyl. Three independently selected (C1 to C 20 ) A monovalent group consisting of a silicon atom bonded to a hydrocarbyl group and having its free valence at the silicon atom.

[0222] Unsubstituted (C1-C5) alkyl. An alkyl group selected from the group consisting of methyl, ethyl, propyl, butyl, and pentyl. Propyl can be n-propyl or 1-methylethyl. Butyl can be n-butyl, 1-methylpropyl, 2-methylpropyl, or 1,1-dimethylethyl. Pentyl can be n-pentyl, 1,-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, or 2,3-dimethylpropyl.

[0223] Ziegler-Natta catalyst: a heterogeneous material that enhances the polymerization reaction rate of olefins and is prepared by contacting an inorganic titanium compound, such as a titanium halide supported on a magnesium halide support (e.g., a magnesium chloride support), with an activator. [Example]

[0224] Activator 1 (also called cocatalyst 1): amines, bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-).

[0225] Mineral oil: HYDROBRITE 380 PO white mineral oil from Sonneborn.

[0226] Preparation 1A: Preparation of an activator formulation containing spray-dried methylaluminoxane / treated fumed silica (SDMAO) in hexane / mineral oil. 1.6 kg of treated fumed silica (CABOSIL TS-610) was slurried in 16.8 kg of toluene, followed by the addition of 11.6 kg of a 10 wt.% MAO solution in toluene. A spray dryer set at 160°C with an outlet temperature of 70-80°C was used. The mixture was introduced into the spray dryer's atomizing device to generate droplets of the mixture, which were then contacted with a hot nitrogen gas stream to evaporate the liquid from the mixture and produce a powder. The powder was separated from the gas mixture in a cyclone separator, and the separated powder was discharged into a container to obtain SDMAO as a fine powder.

[0227] Preparation 1B: Preparation of a slurry of the activator formulation of Preparation 1A. The SDMAO powder of Preparation 1A is slurried in a mixture of 10 wt% n-hexane and 78 wt% mineral oil to yield an activator formulation having 12 wt% SDMAO / treated fumed silica solids in hexane / mineral oil.

[0228] Preparation 2: Preparation of spray-dried metallocene with activator blend. Preparations 1A and 1B are repeated, except that the activator blend is prepared by slurrying 1.5 kg of treated fumed silica (CABOSIL TS-610) in 16.8 kg of toluene, followed by the addition of a 10 wt. % solution of MAO in toluene (11.1 kg) and (MeCp)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)ZrMe2 (where Me is methyl, Cp is cyclopentadienyl, and MeCp is methylcyclopentadienyl) in an amount sufficient to provide a Zr loading of 40 micromoles per gram of solids. The resulting powder is slurried to obtain an activator blend of 22 wt. % solids in 10 wt. % isoparaffinic fluid and 68 wt. % mineral oil.

[0229] Preparation 2A: Prepare a supported catalyst for use in the light-off batch reactor test method described below. In a nitrogen-purged glovebox, 2.65 g of Cabosil TS-610 fumed silica is slurried in 62.5 g of toluene in an oven-dried glass bottle until well dispersed. Then, 22 grams (g) of a 10 weight percent (wt%) solution of methylaluminoxane (MAO) in toluene is added. The mixture is stirred for 15 minutes, followed by the addition of a postmetallocene precatalyst (e.g., any one of Precatalyst 1 through Precatalyst 10 described above) and any one of kinetic modifier compounds KMC1 through KMC20 described above. The resulting mixture is stirred for 30 to 60 minutes. The stirred mixture is spray-dried to obtain a dried sample using a Buchi Mini Spray Dryer B-290 with the following parameters: set temperature 185°C, outlet temperature 100°C, aspirator 95%, and pump speed 150 revolutions per minute (rpm).

[0230] Inventive Example A: Synthesis of Precatalyst 3 of Formula (3):

[0231] [ka] (3), where iPr is isopropyl (1-methylethyl) and nBu is normal butyl. Precatalyst (3) was synthesized according to the general procedure of Kuhlman, et al., Macromolecules 2010, vol. 43, page 7903.

[0232] Inventive Example B: Synthesis of Precatalyst 4 of Formula (4):

[0233] [ka] (4). In a nitrogen-filled glovebox, a 40 mL vial was charged with N-[[4-(2-ethylbenzofuran-3-yl)-1-methylimidazol-2-yl]-(2,4,6-trimethylphenyl)methyl]-2,6-diisopropylaniline (0.4 g, 0.75 mmol) and then dissolved in 5 mL of toluene. 2.4 molar (M) butyllithium in hexane (0.33 mL) was added to the solution, and the mixture was magnetically stirred for 1 hour. Solid hafnium tetrachloride (0.24 g, 0.75 mmol) was added, the vial was fitted with a small condenser, and the solution was warmed to 100 °C. The solution was maintained at this temperature with stirring for 4 hours, then the heat was turned off and the solution was stirred overnight at room temperature. The mixture was cooled to -30 °C, and 3 M bromo(methyl)magnesium (0.8 mL) was added dropwise. After attaching a small condenser, the solution was warmed to 100°C and stirred at this temperature for 7 hours. The toluene was removed under reduced pressure to give a dark solid, which was slurried in toluene (15 mL) and stirred at room temperature for 30 minutes. The solution was filtered through a fritted funnel packed with Celite. The filter cake was extracted with additional toluene (10 mL). The toluene was removed under reduced pressure, then 2 x 5 mL portions of hexane were added and removed under reduced pressure to remove residual toluene. The solid was taken up in toluene (4 mL), then pentane was added (1 mL), and the mixture was placed in a -35°C freezer. The resulting solid was collected by filtration and dried under reduced pressure. 1H NMR(400MHz,chloroform-d)δ 8.23(t,J=3.9Hz,1H),7.40(dd,J=3.9,0.5Hz,2H),7.14(s,1H),7.13(t,J=0.7Hz,2H),6.99(dd,J=5.5,4.0Hz,1H),6.70(br s,1H),6.64(br s,1H),6.03(s,1H),3.54(p,J=6.8Hz,1H),3.14(s,4H),3.01(q,J=7.6Hz,2H),2.17(s,3H),1.86(s,3H),1.59(s,3H),1.43(t,J=7.6 Hz,3H),1.36(d,J=6.7Hz,3H),1.16(d,J=6.8Hz,3H),1.12(d,J=6.7Hz,3H),0.51(s,3H),0.26(s,3H),0.14(d,J=6.8Hz,3H).

[0234] Preparation 3: Synthesis of fast light-off post-metallocene catalysts: A 40 milliliter (mL) glass vial containing a poly(tetrafluoroethylene) (PTFE)-coated magnetic stir bar and capped with a rubber septum was prepared under an inert N2 atmosphere in a glovebox by filling it with 200 milligrams (mg) of spray-dried methylaluminoxane (SDMAO, prepared according to Preparation 1A). A slurry of 10 micromoles (µmol) of a post-metallocene pre-catalyst (e.g., any one of Precatalyst 1 to Precatalyst 10) in 0.2 mL of mineral oil was then added. The resulting mixture was stirred for 5 minutes to obtain a mineral oil slurry of the corresponding fast light-off post-metallocene catalyst supported on treated fumed silica. This procedure was repeated to produce multiple lots of mineral oil slurries of fast light-off post-metallocene catalysts, each supported on a separate treated fumed silica. A fast light-off post-metallocene catalyst can be made with an aluminum atom to metal atom (Al / M) molar ratio of 120. The procedure described above is generally used to make catalysts for use in the light-off vial test method described below.

[0235] Preparation 4: Synthesis of a weakened post-metallocene catalyst: To a volume of slurry containing 10 μmol of the fast light-off catalyst of Preparation 3 supported on treated fumed silica, add a solution of 10 μmol of a kinetic modifier compound in 0.20 mL of toluene. The resulting mixture is stirred for 5 minutes to yield a mineral oil / toluene slurry of a weakened post-metallocene catalyst supported on treated fumed silica.

[0236] Inventive Examples (A1)-(A20) (IE(A1)-IE(A20)): Twenty weakened postmetallocene catalysts are separately prepared according to Preparation 2A or Preparations 3 and 4 using precatalyst 1 and a different one of kinetic modifier compounds (1)-(20), respectively.

[0237] Inventive Examples (B1)-(B20) (IE(B1)-IE(B20)): Twenty weakened postmetallocene catalysts are separately prepared according to Preparation 2A or Preparations 3 and 4 using precatalyst 2 and a different one of kinetic modifier compounds (1)-(20), respectively.

[0238] Inventive Examples (C1)-(C20) (IE(C1)-IE(C20)): Twenty weakened postmetallocene catalysts are separately prepared according to Preparation 2A or Preparations 3 and 4 using precatalyst 3 and a different one of kinetic modifier compounds (1)-(20), respectively.

[0239] Inventive Examples (D1)-(D20) (IE(D1)-IE(D20)): Twenty weakened postmetallocene catalysts are separately prepared according to Preparation 2A or Preparations 3 and 4 using precatalyst 4 and a different one of kinetic modifier compounds (1)-(20), respectively.

[0240] Inventive Examples (E1)-(E20) (IE(E1)-IE(E20)): Twenty weakened postmetallocene catalysts are separately prepared according to Preparation 2A or Preparations 3 and 4 using precatalyst 5 and a different one of kinetic modifier compounds (1)-(20), respectively.

[0241] Inventive Examples (F1)-(F20) (IE(F1)-IE(F20)): Twenty weakened postmetallocene catalysts are separately prepared according to Preparation 2A or Preparations 3 and 4 using precatalyst 6 and a different one of kinetic modifier compounds (1)-(20), respectively.

[0242] Inventive Examples (G1)-(G20) (IE(G1)-IE(G20)): Twenty weakened postmetallocene catalysts according to Preparation 2A or Preparations 3 and 4 using precatalyst 7 and a different one of kinetic modifier compounds (1)-(20), respectively.

[0243] Inventive Examples (H1)-(H20) (IE(H1)-IE(H20)): Twenty weakened postmetallocene catalysts are separately prepared according to Preparation 2A or Preparations 3 and 4 using precatalyst 8 and a different one of kinetic modifier compounds (1)-(20), respectively.

[0244] Inventive Examples (I1)-(I20) (IE(I1)-IE(I20)): Twenty weakened postmetallocene catalysts are separately prepared according to Preparation 2A or Preparations 3 and 4 using precatalyst 9 and a different one of kinetic modifier compounds (1)-(20), respectively.

[0245] Inventive Examples (J1)-(J20) (IE(J1)-IE(J20)): Twenty weakened postmetallocene catalysts are separately prepared according to Preparation 2A or Preparations 3 and 4 using precatalyst 10 and a different one of kinetic modifier compounds (1)-(20), respectively.

[0246] Light-Off Vial Test Method: A mineral oil slurry of a fast light-off catalyst supported on treated fumed silica or a mineral oil / toluene slurry of a weakened postmetallocene catalyst supported on treated fumed silica is added to a dry 40 mL glass vial. 5.5 mL or 11 mL of 1-octene is added to the vial, and the vial is sealed with a septum cap. The addition time is recorded as TO (0.00 min). The vial is manually shaken (not stirred) to prevent clumping. The shaken vial is then placed in a different well of a foam block placed on a hot plate / stirrer. A thermocouple is immediately inserted through the septum cap into the vial below the liquid level therein, and the temperature (°C) of the vial contents is recorded at 5-second intervals from TO until 300 minutes after TO. The temperature and time data are downloaded to a spreadsheet, and a thermokinetic profile is plotted for analysis. The results of these runs can be depicted graphically as a plot of the reaction temperature of the batch reactor contents on the y-axis against time starting from the addition of Time 0 on the x-axis.

[0247] Examples of the present invention ("IE") and comparative examples ("CE") prepared by the light-off vial test method. An effective amount of a specific kinetic modifier compound ("KMC") was combined with a specific fast light-off post-metallocene catalyst to obtain examples of the present invention of weakened post-metallocene catalysts. Comparative examples meet one of three criteria (1)-(3): (1) contain a hybrid catalyst but no kinetic modifier compound; (2) contain a hybrid catalyst but less than an effective amount of a kinetic modifier compound (e.g., CE). 1)or (3) a metallocene catalyst and a kinetic modifier compound. To compare their relative activities, the light-off effects of the fast light-off post-metallocene and the polyoctene examples of the present invention were tested according to the Light-Off Vial Test Method. In separate vials, (a) mineral oil without 1-octene, (b) an example post-metallocene pre-catalyst, and (c) spray-dried methylaluminoxane (SDMAO) were premixed for 10 minutes without the kinetic modifier compound to obtain a slurry of the fast light-off post-metallocene catalyst without 1-octene and the kinetic modifier compound. In another vial, (a) mineral oil without 1-octene, (b) the post-metallocene pre-catalyst, (c) SDMAO, and (d) the kinetic modifier compound were premixed for 10 minutes to obtain a slurry of the weakened post-metallocene catalyst without 1-octene. After 10 minutes of premixing (times for all conditions except (B)), add the same amount of 1-octene to each vial. After the addition of 1-octene, observe the temperature of the mixture increase by 5°C to 120°C, or 10°C to 110°C, or any 10°C increment therebetween (e.g., 10°C to 20°C, 20°C to 30°C, 30°C to 40°C, 40°C to 50°C, 50°C to 60°C, 60°C to 70°C, 70°C to 80°C, 80°C to 90°C, 90°C to 100°C, 100°C to 110°C, or 110°C to 120°C) as evidence of activation of the respective catalyst.One of four sets of conditions was used: Condition (A) (used in Tables 1-4): 5.5 mL of Isopar-E, 8 μmol of M, an amount of SDMAO sufficient to give a molar ratio of Al / M = 120, 0 μmol (CE) or 2 μmol (IE) of kinetic modifier compound, 11 mL of 1-octene; Condition (B) (used in Table 5): 5.5 mL of Isopar-E, 10 μmol of M, an amount of SDMAO sufficient to give a molar ratio of Al / M = 120, 0 μmol (CE) or 2 μmol (IE) of kinetic modifier compound, 5.5 mL of 1-octene (premixed for 10 min but not 5 min). min*), Condition (C) (used in Table 6): 5.5 mL of Isopar-E, 20 μmol of M, an amount of SDMAO to give a molar ratio of Al / M = 120, the amount of kinetic modifier compound was 0 μmol (CE) or the amount to give the molar ratio M / KMC indicated (IE), 5.5 mL of 1-octene; Condition (D) (used in Table 7): 5.5 mL of Isopar-E, 2 μmol of M, an amount of SDMAO to give a molar ratio of Al / M = 120, the amount of kinetic modifier compound was 0 μmol (CE) or the amount to give the molar ratio M / KMC indicated (IE), 5.5 mL of 1-octene.

[0248] Table 1: Conditions (A) and formulas

[0249] [ka] The results of the light-off vial test method performed using the precatalyst (1) of the formula, 1 is 2,6-dichlorobenzyl.

[0250] [Table 1]

[0251] Table 2: Conditions (A) and formulas

[0252] [ka] Results of the light-off vial test method performed using precatalyst (2).

[0253] [Table 2]

[0254] Table 3: Conditions (A) and formulas

[0255] [ka] Results of the light-off vial test method performed using the precatalyst (3).

[0256] [Table 3]

[0257] Table 4: Conditions (A) and formulas

[0258] [ka] The results of the light-off vial test method performed using the precatalyst (4).

[0259] [Table 4]

[0260] As can be seen in Tables 1-4, depending on the postmetallocene precatalyst and kinetic modifier compound used, greater or lesser delays in activation time were achieved.

[0261] Table 5: Conditions (B) and formulas

[0262] [ka] The results of the light-off vial test method carried out using the precatalyst (5) of the formula, where M is Zr.

[0263] [Table 5]

[0264] As can be seen in Table 5, the kinetic modifier compounds modify the structure of the fast light-off catalyst to create a weaker light-off catalyst with a delayed time from onset to peak reaction temperature.

[0265] Table 6: Conditions (C) and formulas

[0266] [ka] Results of the light-off vial test method performed using the precatalyst (6).

[0267] [Table 6]

[0268] As can be seen in Table 6, depending on the postmetallocene precatalyst and kinetic modifier compound used, a greater or lesser delay in activation time was achieved and a greater or lesser reduction in peak reaction temperature was achieved.

[0269] Table 7: Conditions (D) and formulas

[0270] [ka] Results of the light-off vial test method performed using the precatalyst (7).

[0271] [Table 7]

[0272] As can be seen in Table 7, depending on the postmetallocene precatalyst and kinetic modifier compound used, a greater or lesser delay in activation time was achieved and a greater or lesser reduction in peak reaction temperature was achieved.

[0273] Light-off batch reactor test method. Overview. The relative kinetic profiles of a fast light-off catalyst and a weakened postmetallocene catalyst are observed in separate polymerization runs, each conducted in a 2-liter (L) semi-batch autoclave polymerization reactor equipped with a mechanical stirrer. In the batch reactor, ethylene and 1-hexene are copolymerized in the presence of hydrogen (H2) in the gas phase. The concentrations of ethylene ("C2"), 1-hexene ("C6"), and H2 in the gas phase are analyzed by mass spectrometry and gas chromatography. The C6 and H2 components are added continuously throughout the 3-hour polymerization run to maintain their concentrations at steady state, but no additional C2 is added. Ethylene uptake versus time is measured to obtain a relative representation of the catalyst kinetic profiles.

[0274] Drying and Loading of Batch Reactor. Before each run, the batch reactor is dried for 1 hour. 200 g of NaCl is then charged to the dried batch reactor. The batch reactor and its contents are further dried by heating it and its contents to 100°C under a N2 atmosphere for 30 minutes. 3 g of silica-supported methylaluminoxane (SMAO) is then added to remove any residue, the batch reactor is sealed, and the contents are stirred. 3.04 liters (L) of H2 and 1-hexene are then charged to the resulting dried batch reactor to obtain a 1-hexene to ethylene (C6 / C2) molar ratio of 0.004. The batch reactor is pressurized to 1.52 megapascals (MPa) with ethylene. The resulting system is allowed to reach steady state.

[0275] The catalyst (fast light-off catalyst or weakened post-metallocene catalyst) is then added to the batch reactor to initiate polymerization. The catalyst addition time is recorded as time zero (Time 0). The reactor temperature is brought to 93°C and the reactor is maintained at that temperature for 1 to 5 hours. The reactor is cooled, vented, and opened, and the resulting polyolefin product is washed with water, methanol, and dried to obtain a dry polyolefin product.

[0276] For each batch reactor run, catalyst activity / polymerization productivity is calculated as grams of dry polyolefin product produced per hour (gPE / gcat-hr) per gram of catalyst added to the reactor. The higher the gPE / gcat-hr, the higher the catalyst activity / polymerization productivity. The amount of ethylene uptake after 0.1 hours (C2 uptake 0.1 h) (6 minutes) and 1.0 hours (C2 uptake 1 h) (60 minutes) is recorded and reported as the ratio (C2 uptake 1 h) / (C2 uptake 0.1 h). All other conditions being equal, the higher the ratio (C2 uptake 1 h) / (C2 uptake 0.1 h), the more attenuated the catalyst light-off.

[0277] The melting temperature of the dried polyolefin product is determined using differential scanning calorimetry (DSC) according to ASTM D3418-08 using a scan rate of 10°C per minute on a 10 mg sample and using a second heating cycle. Some embodiments of the polyolefin product of the present invention made with a weakened post-metallocene catalyst may have a melting point higher than that of a comparative polyolefin product made with its corresponding fast light-off catalyst.

[0278] From the light-off batch reactor run using the fast light-off catalyst, the majority of the ethylene uptake can occur within the first few minutes of the start of the polymerization run (e.g., within 10 minutes of Time 0). In contrast to the weakened post-metallocene catalyst, the ethylene uptake is more evenly spread throughout the 3-hour long polymerization run. The results of these comparative runs and the inventive runs can be depicted graphically as a plot of the reaction temperature of the batch reactor contents on the y-axis, or ethylene monomer ("C2") uptake on the y-axis, against time starting from the addition of Time 0 on the x-axis.

[0279] Comparative Example Using a Metallocene Precatalyst. Table 8: Formula

[0280] [ka] Comparative polymerization results of the light-off vial test method carried out using condition (A) with comparative metallocene precatalyst 1 ("MCN1"), where n-Bu is normal butyl.

[0281] [Table 8]

[0282] As shown in Table 8, phenylacetylene had essentially no debilitating effect on the kinetics of the comparative metallocene catalyst made from MCN1.

[0283] Table 9: Formula

[0284] [ka] Comparative polymerization results of a light-off batch reactor test method carried out using condition (A) with comparative metallocene precatalyst 1 ("MCN1"), where n-Bu is normal butyl.

[0285] [Table 9]

[0286] As shown in Table 9, the kinetic modifier compounds had essentially no detrimental effect on the kinetics of the comparative metallocene catalyst made from MCN1.

[0287] Table 10: Formula

[0288] [ka] Comparative polymerization results of a light-off batch reactor test method carried out using condition (A) with comparative metallocene precatalyst 2 ("MCN2"), where n-Pr is normal-propyl.

[0289] [Table 10]

[0290] As shown in Table 10, the kinetic modifier compounds deteriorated polymerization productivity and had essentially no debilitating effect on the kinetics of the comparative metallocene catalyst made from MCN2.

[0291] Table 11: Formula

[0292] [ka] Comparative polymerization results of a light-off batch reactor test method conducted using condition (A) with metallocene precatalyst 3 ("MCN3").

[0293] [Table 11]

[0294] As shown in Table 11, the kinetic modifier compounds deteriorated polymerization productivity and had essentially no debilitating effect on the kinetics of the comparative metallocene catalyst made from MCN3.

Claims

1. 1. A method for making a weakened post-metallocene catalyst, comprising: adding a fast light-off catalyst to an effective amount of a catalyst 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 (D) with a kinetic modifier compound of the structural formula (I): (D) ｄ M (T) ｔ (Q) ｑ (X) ｘ (I) is prepared by activating a postmetallocene pre-catalyst of formula (A １ ), (B １ ), or (C １ ) Medium, R ５ and R ６ each independently represents H or R ７ and each R ７ are independently １ ~C ２０ ) hydrocarbyl, —C(═O)—O—(unsubstituted C １ ~C １２ ) hydrocarbyl), (C １ ~C １７ ) heterohydrocarbyl, or tri((C １ ~C ２０ ) hydrocarbyl) silyl, or two R ７ Together, (C ３ ~C ６ ) alkylene, provided that each R ７ is devoid of a carbon-carbon double bond, and each (C １ ~C ２０ ) Hydrocarbyl is independently unsubstituted or has 1 to 4 substituents R Ｓ and each substituent R Ｓ are independently 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 in formula (I), the metal M is Ti, Hf, or Zr; the subscript d is 0, 1, or 2; the subscript t is 0 or 1; the subscript q is 0 or 1; the subscript x is 1, 2, or 3; each ligand D is independently a bidentate organoheteryl or bidentate organoheterylene; the ligand T is a tridentate organoheterylene; the ligand Q is a tetradentate organoheterylene; and each X is selected from a halogen atom, ((C １ ~C ２０ ) alkyl) ３－ｇ -(phenyl) ｇ Si—(wherein the subscript g is 0, 1, 2, or 3), CH ３ , (C ２ ~C ２０ ) alkyl-CH ２ , (C ６ ~C １２ ) aryl-((C ０ ~C １０ ) alkylene)-CH ２ , (C １ ~C ６ ) alkyl-substituted (C ６ ~C １２ ) aryl, (C １ ~C ６ ) alkoxy-substituted (C ６ ~C １２ ) aryl, (C １ ~C ６ ) alkoxy-substituted benzyl, and (C １ ~C ６ ) alkyl-substituted benzyl, or one X is a monodentate group independently selected from 4-(C １ ~C ２０ 2.) alkyl-substituted 1,3-butadiene molecules, and each remaining X, if any, is independently a monodentate group X.

2. The fast light-off catalyst is represented by the formula (II): (D) ｄ [M ＋ ](T) ｔ (Q) ｑ (X) ｘ－１ A － (II) fast light-off catalyst, wherein the weakened post-metallocene catalyst has the formula (III): (D) ｄ [M ＋ ](T) ｔ (Q) ｑ (X) ｘ－２ (R)A － (III) wherein the subscripts d, t, q, and x, the metal M, and the ligands D, T, Q, and X are as defined for formula (I), and wherein A － is an anion, where R is a group 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), wherein R ５ ~R ７ are the formula (A １ ), (B １ ), or (C １ 2. The method of claim 1, wherein the α-amino acid is as previously defined for α-amino acid.

3. The post-metallocene pre-catalyst is represented by the formula (Ia): (D) ｄ M(X) ｘ 3. The method of claim 1, wherein the postmetallocene pre-catalyst is of the formula (Ia), wherein the metal M is Ti, Hf, or Zr, the subscript d is 1 or 2, the subscript x is 2 or 3, and each ligand D is independently a bidentate organoheteryl or bidentate organoheterylene, and each X is as defined for formula (I).

4. The post-metallocene pre-catalyst of formula (I) has the formula (Ib): MT(X) ２ 3. The method of claim 1, wherein the postmetallocene precatalyst is of formula (Ib), wherein the metal M is Ti, Hf, or Zr, the ligand T is a tridentate organoheterylene, and each X is as defined for formula (I).

5. The post-metallocene pre-catalyst of formula (I) is a compound of formula (Ic): MQ(X) ２ 3. The method of claim 1, wherein the postmetallocene precatalyst is of formula (Ic), wherein the metal M is Ti, Hf, or Zr, the ligand Q is a tetradentate organoheterylene, and each X is as defined for formula (I).

6. The kinetics modifier compound has the formula (A １ ): R ５ -C≡C-R ６ (A １ kinetic modifier compounds of the formula HC≡CSi(phenyl) ｈ ((C １ ~C ２０ ) alkyl) ３－ｈ where the subscript h is an integer from 0 to 3, and acetylenes of the formula HC≡C—(CH ２ ) ｍ CH ３ 6. The method of any one of claims 1 to 5, wherein the acetylene is selected from the group consisting of:

7. The kinetics modifier compound has the formula (B １ ) (R ５ ) ２ C=C=C(R ６ ) ２ (B １ 6. The method of any one of claims 1 to 5, wherein the kinetics modifier compound is selected from cycloalkylarenes, alkylarenes, dialkylarenes, trialkylarenes, trialkylsilylarenes, vinylidene cycloalkanes, and alkyl esters of arenecarboxylic acids.

8. The kinetics modifier compound has the formula (C １ ) (R ５ ) (R ７ ) C=C(R ６ ) (R ７ ) (C １ ) a kinetics modifier compound of formula (C １ 6. The method of any one of claims 1 to 5, wherein the kinetics modifier compound of formula (I) is an internal alkene.

9. 9. The method of any one of claims 1 to 8, further comprising forming a mixture of the weakened post-metallocene catalyst, a support material, and an inert hydrocarbon solvent, and removing the inert hydrocarbon solvent from the mixture to obtain the weakened post-metallocene catalyst disposed on the support material.

10. The post-metallocene pre-catalyst of formula (I) Formula (Ia)-1 【Chemistry 1】 (Ia)-1 postmetallocene precatalyst, wherein each Ar １ and Ar ２ are independently unsubstituted or substituted aromatic groups selected from phenyl, substituted phenyl, biphenyl, substituted biphenyl, anthracene, substituted anthracene, carbazolyl, and substituted carbazolyl, each substituent of the substituted aromatic group is independently alkyl, and each group R ａ１ and R ａ２ are independently H or (C １ ~C ２０ ) alkyl, each subscript 0-3 is independently 0, 1, 2, or 3, and M and X are as defined for formula (I), and Formula (Ia)-2: 【Chemistry 2】 (Ia)-2 post-metallocene pre-catalyst, wherein M and X are as defined for formula (I), each subscript 1-5 is independently 1, 2, 3, 4, or 5, and R ａ３ and R ａ７ Each of the groups independently represents １ ~C ２０ ) alkyl or (C ６ ~C １２ ) aryl, and R ａ４ ~R ａ６ Each of the groups independently represents １ ~C ２０ ) alkyl, or R ａ４ ~R ａ６ Together they form the formula = C(H)-CH ２ CH ２ CH ２ 10. The method of any one of claims 1 to 3 and 6 to 9, wherein the catalyst is selected from the group consisting of a post-metallocene pre-catalyst forming a trivalent group of -.

11. The post-metallocene pre-catalyst of formula (I) Formula (Ib)-1 【Transformation 3】 (Ib)-1 is a postmetallocene precatalyst of formula (Ib)-1, wherein M is Ti, Hf, or Zr, and each subscript 0-3 is independently 0, 1, 2, or 3; and the group R ｂ１ ~R ｂ６ Each of the is independently H or (C １ ~C ２０ 10. The method of any one of claims 1, 2, 4, and 6-9, wherein X is alkyl and X is as defined for formula (I).

12. 12. A method for feeding a post-metallocene catalyst to a slurry or gas phase polymerization reactor containing an olefin monomer and a moving bed of a polyolefin polymer, the method comprising: preparing the weakened post-metallocene catalyst outside of the reactor according to the method of any one of claims 1 to 11; and feeding the weakened post-metallocene catalyst in neat form or as a solution or slurry thereof in an inert hydrocarbon liquid into the slurry or gas phase polymerization reactor through a feed line that does not contain an olefin monomer.

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