Damping hybrid catalyst

Abstract

A method of making a decaying light-off hybrid catalyst comprising: a catalyst having a faster light-off rate; and an effective amount of a catalyst having a 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 hybrid catalyst exhibiting an attenuated light-off kinetic profile (compared to the profile of the faster light-off catalyst), wherein the faster light-off catalyst is selected from the group consisting of a hydroxyl group, ... k (X) x (I) A method and related methods, compositions, and uses, wherein the hybrid catalyst (i.e., the unactivated "coordination entity" or "ligand-metal complex") of (I) is prepared by activating the hybrid catalyst.

Description

[Technical Field]

[0001] Olefin polymerization catalyst, method, and polyolefin produced thereby.

[0002] Introduction Published patent applications and patents in this field include European Patent No. 0188914(A2), European Patent No. 0748823(A1), European Patent No. 1778738(A1), European Patent No. 2121776(A1), European Patent No. 2609123(A1), U.S. Patent No. 5,624,878, U.S. Patent No. 5,965,677, U.S. Patent No. 6,083,339(B2), U.S. Patent No. 6,967,184(B2), U.S. Patent No. 7,705,157(B2), U.S. Patent No. 8,455,601(B2), U.S. Patent No. 8,609,794(B2), U.S. Patent No. 8,835,577(B2), U.S. Patent No. 9,000,108(B2), and U.S. Patent No. Patent No. 9,029,487(B2), U.S. Patent No. 9,234,060(B2), U.S. Patent No. 9,718,900(B2), U.S. Patent Publication No. 2009 / 0306323(A1), U.S. Patent Publication No. 2017 / 0081444(A1), U.S. Patent Publication No. 2017 / 0101494(A1), U.S. Patent Publication No. 2017 / 0137550(A1), U.S. Patent Publication No. 2018 / 000246 4(A1), U.S. Patent Application Publication No. 2018 / 0282452(A1), U.S. Patent Application Publication No. 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 / 087520(A1), International Publication No. 2012 / 027 Examples include publications 448, International Publication No. 2013 / 070601(A2), International Publication No. 2014 / 105411(A1), International Publication No. 2016 / 172097(A1), International Publication No. 2017 / 058858, International Publication No. 2017 / 058981(A1), International Publication No. 2018 / 022975(A1), International Publication No. 2020 / 055893(A1), and International Publication No. 2018 / 183026(A1).

[0003] In particular, U.S. Patent Nos. 8,609,794(B2), 9,000,108(B2), 9,029,487(B2), U.S. Patent Publication No. 2017 / 0081444(A1), U.S. Patent Publication No. 2017 / 0101494(A1), U.S. Patent Publication No. 2017 / 0137550(A1), U.S. Patent Publication No. 2018 / 0002464(A1), U.S. Patent Publication No. 2018 / 0282452(A1), International Publication No. 2017 / 058858, and International Publication No. 2018 / 022975(A1) are from Dow Global Technologies, a subsidiary of The Dow Chemical Company. This document, transferred to LLC, describes biphenylphenoxy (BPP) type pre-catalysts and catalysts, their synthesis, and their use in olefin polymerization reactions.

[0004] U.S. Patent No. 6,967,184(B2) was issued to Timothy T. Wenzel ("Wenzel") and U.S. Patent No. 9,718,900(B2) was issued to Garth R. Giesbrecht ("Giesbrecht"), both of which have been transferred to Univation Technologies, LLC, a wholly owned subsidiary of 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) was issued to Richard A. Hall et al. ("Hall") and is described as having been assigned to BP Corporation North America Inc. Hall refers to the problems that arise when metallocene catalysts are supplied to polymerization reactors in olefin monomer streams. "Metallocene catalysts are difficult to use directly in conventional polymerization processes, particularly in gas-phase processes where the catalyst system is dispersed in hydrocarbons or monomers and metered into the reactor through a feedline. Supported metallocene catalysts are optimally active when pre-activated, i.e., combined with co-catalyst components before being introduced into the reactor. Dispersing such catalysts in an olefin monomer stream and directly supplying them to the reactor system results in polymer formation and causes severe clogging of the feedline. Furthermore, polymerization proceeds before the catalyst system is sufficiently and uniformly dispersed through the polymer bed in the reactor, resulting in highly active hot spots that promote clump formation and plating out. The reactor is rapidly fouled, catalyst yield is reduced, and frequent shutdowns are necessary for cleaning." (Column 2, lines 50-65, emphasis added.)

[0006] Hall details solutions previously attempted by others: "Temporarily reducing the activity of metallocene catalysts has been described in the art. For example, adding 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, such treatment only partially delays the catalyst activity. Catalysts directly treated with dialkyborane or dialkylaluminum retain sufficient activity to initiate polymerization when dispersed in the monomer feed stream. Furthermore, the recovery period is very short, too short, to allow sufficient dispersion of the catalyst system in the stirred reactor gas-phase reactor bed before the catalyst recovers and polymerization proceeds." (Column 3, lines 14-26, emphasis added.)

[0007] Hall sought a method to temporarily and reversibly passivate a metallocene catalyst so that its catalytic activity would be reduced to a level that would allow the catalyst to be supplied to a reactor in contact with olefin monomers and sufficiently dispersed in the reactor polymer bed before reactivation (column 3, lines 49-55). In other words, Hall sought a method to supply a temporarily substantially inactivated metallocene catalyst to a polymerization reactor in a stream of olefin monomers.

[0008] Hall's solution relates to a metallocene catalyst that can be transiently and reversibly passivated by contact with an effective amount of an unsaturated hydrocarbon passivation compound (abbreviation). Hall's solution also relates to a method for transiently and reversibly passivating a metallocene catalyst that can be transiently and reversibly passivated by contact with an effective amount of a passivation compound (column 3, rows 58-62). The transiently and reversibly passivated metallocene catalyst is further characterized as a potential olefin polymerization catalyst, having substantially reduced activity for olefin polymerization (column 3, rows 63-66).

[0009] Therefore, Hall sought to transiently substantially inactivate (suppress the activity of) the metallocene catalyst so that the resulting transiently substantially inactivated metallocene catalyst could be fed into the reactor in the olefin monomer stream without polymerizing the olefin monomers in the feed stream or clogging the feed line. This gave Hall time to disperse the transiently substantially inactivated metallocene catalyst into the polymer bed in the reactor, where it would be reversibly reactivated. Thus, Hall's metallocene catalyst is either fully active or substantially inactivated, and the substantially inactivated metallocene catalyst is fed into the reactor in the presence of olefin monomers in the olefin monomer feed stream. [Overview of the project]

[0010] We have identified problems when a hybrid catalyst (i.e., a catalyst having only one cyclopentadienyl-containing ligand) is supplied separately (i.e., away from monomer particles and polyolefin polymer particles) to a gas-phase olefin polymerization reactor. Olefin polymerization is an exothermic reaction that can be carried out in solution, slurry, or gas phases. The nature of gas-phase polymerization is such that the mass available to absorb the heat of reaction is minimized. We have found that even when an active hybrid catalyst is supplied separately from the olefin monomer feed (and even separately from the active polyolefin polymer particles) to a gas-phase polymerization reactor containing moving beds of olefin monomers and polyolefin polymers, for example, when the active hybrid catalyst is supplied to the reactor as a solution or slurry in an inert hydrocarbon solvent (e.g., alkane or xylene), the active hybrid catalyst can rapidly light off in the gas-phase polymerization reactor when it experiences polymerization conditions (e.g., high temperature and high pressure) in the reactor. In other words, when a hybrid catalyst is supplied (e.g., injected), the catalyst begins to form polymer particles within the reactor near the catalyst injection site before the "faster light-off" catalyst can be fully dispersed in the moving resin bed. This generates heat locally faster than the heat can be absorbed, causing the polymer particles to fuse together and form aggregates. These aggregates contaminate the reactor components and / or impair the properties of the polyolefin product.

[0011] Furthermore, hybrid catalysts that light off faster, when paired with metallocene catalysts that light off slower, can create a multi-modal (e.g., bimodal or trimodal) catalyst system in the reactor that is mismatched in reactivity. This results in the production of polyolefin polymer particles whose flow index and / or density fluctuate undesirably depending on particle size.

[0012] These problems did not surface with metallocene catalysts, which contain two cyclopentadienyl groups (independently unsubstituted or substituted). In the above circumstances, metallocene catalysts exhibit relatively slow light-off.

[0013] Our technical solution to the problems arising from "faster burn-off" hybrid catalysts is that the resulting structurally modified hybrid catalysts have a new molecular structure and remain active, but when separately supplied from an olefin monomer feed to a gas-phase polymerization reactor, an effective amount of a kinetic modifier compound is used to modify the molecular structure of the hybrid catalyst so that it exhibits a characteristic decay burn-off kinetic profile ("decay burn-off hybrid catalyst" or more simply "decay hybrid catalyst"). For example, the decay kinetic profile may include that the length of time to the peak reaction temperature (temperature peak ) of the decay hybrid catalyst is longer, and / or the value of the temperature peak is lower compared to that of the faster burn-off catalyst from which it was made. The length of the delay is long enough to reduce or prevent the formation of aggregates, and as a result, delay or prevent fouling of the reactor components and / or minimize impairing the properties of the polyolefin product produced thereby. Despite the delayed start, all other things being equal, many embodiments of the decay hybrid catalyst exhibit a catalyst activity / polymerization productivity expressed as the number of grams of dry polyolefin product produced per gram of catalyst added to the reactor per hour (g of PE / g of catalyst-hour), which is not significantly lower than that of the faster burn-off non-metallocene catalyst and may be higher in some embodiments. This result is unpredictable in the art.

[0014] A method of making a decay burn-off hybrid catalyst ("decay hybrid catalyst"), comprising a faster burn-off catalyst and an effective amount of a compound of formula (A 1 ), (B 1 ), or (C 1 ): R 5 -C≡C-R 6 (A 1 ), (R 5 )2C=C=C(R 6 )2 (B 1 ), or (R 5 )(R 7 )C=C(R 6 )(R7 ) (C 1 The process involves combining a kinetic modifier compound with a kinetic modifier compound under effective reaction conditions to obtain a decayed hybrid catalyst that exhibits a decayed light-off kinetic profile (compared to the profile of a catalyst that lights off faster), wherein the catalyst that lights off faster is defined herein by structural formula (I):(Cp)(L) k (X) x A method prepared by activating the hybrid precatalyst of (I) (i.e., an inactive "coordination entity" or "ligand-metal complex").

[0015] A damped hybrid catalyst produced by the manufacturing method.

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

[0017] A multimodal (e.g., bimodal or trimodal) catalyst system comprising a damped hybrid catalyst and one or more different olefin polymerization catalysts.

[0018] A method for supplying a multi-modulus (e.g., bimodal or trimodal) catalyst system to a gas-phase polymerization reactor containing a moving bed of olefin monomer and polyolefin polymer, comprising: preparing a decayed hybrid catalyst according to the above method; contacting a solution of the decayed hybrid catalyst and an activated metallocene catalyst in an inert hydrocarbon solvent with a support material (e.g., fumed silica) to prepare a slurry of a multi-modulus (e.g., bimodal or trimodal) catalyst system essentially consisting of the decayed hybrid 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 a multi-modulus catalyst system in neat (dry powder) form; and supplying the slurry of the multi-modulus catalyst system or the neat form of the multi-modulus catalyst system to the gas-phase polymerization reactor through a supply line that does not contain olefin monomers.

[0019] A method for producing a polyolefin polymer, comprising contacting at least one 1-alkene monomer with a decayed hybrid catalyst or a multi-modal (e.g., bimodal or trimodal) catalyst system under gas-phase polymerization conditions in a gas-phase polymerization reactor containing a moving bed of polyolefin resin, thereby producing a polyolefin polymer.

[0020] Polyolefin polymer produced using the same manufacturing method.

[0021] A manufactured product made from polyolefin polymer. [Modes for carrying out the invention]

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

[0023] Embodiment 1. A method for producing a decaying hybrid catalyst ("decaying light-off hybrid catalyst"), comprising a catalyst that lights up faster, and an effective amount 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 The present invention relates to obtaining a decaying light-off hybrid catalyst that exhibits a decaying light-off kinetic profile (compared to the profile of a catalyst that lights up faster), by combining a kinetic modifier compound ("KMC") of ) under effective reaction conditions, wherein the catalyst that lights up faster has the structural formula (I): (Cp)(L) k (X) x (I) is produced by activating the hybrid precatalyst, in formula (A1), (B1), or (C1), R 5 and R 6 Each of these is independently H or R 7 And each R 7 (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 However, together they form a (C3-C6) alkylene, but each R 7 It lacks a carbon-carbon double bond, and each (C1-C 20 Hydrocarbyl is independently unsubstituted or has 1 to 4 substituents R S It is substituted with each substituent R SThese are independently halogens (e.g., F), unsubstituted (C1-C5)alkyls (e.g., CH3), -C≡CH, -OH, (C1-C5)alkoxys, -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(= The group is selected from O)2-N(H)(unsubstituted (C1-C5)alkyl), -S(=O)2-N(unsubstituted (C1-C5)alkyl)2, -C(=)S-(unsubstituted (C1-C5)alkyl), and -COO(unsubstituted (C1-C5)alkyl), where in formula (I), metal M is Ti, Hf, or Zr, subscript k is 0 or 1, subscript x is 1, 2, or 3, Cp group is unsubstituted cyclopentadienyl group, hydrocarbyl-substituted cyclopentadienyl group, or organohetylene-substituted cyclopentadienyl group, group L is monodentate organoheteryl group, and each X is a halogen atom, ((C1-C 20 )alkyl) 3-g -(phenyl) g Si-(wherein the formula, the subscript g is 0, 1, 2, or 3), CH3, (C2-C 20 )Alkyl-CH2, (C6-C 12 )aryl-((C0-C 10 )Alkylene)-CH2(for example, (C6-C 12 )aryl is phenyl, (C0-C 10 )If the alkylene is a (C0) alkylene, then benzyl, (C1-C6) alkyl substitution (C6-C 12 ) Aryl, (C1-C6)alkoxy substitution (C6-C 12 )A monodentate group independently selected from aryl, (C1-C6)alkoxy-substituted benzyl, and (C1-C6)alkyl-substituted benzyl, or one X is 4-(C1-C 20A method in which an alkyl-substituted 1,3-butadiene molecule is formed, and each of the remaining X groups, if present, is independently a monodentate group X. Each monodentate group X may provide M with 1 coordination site κ, at least one group X acts as a leaving group during the activation step, and optionally at least one group X acts as a leaving group during the mixing step. In some embodiments, at least one X does not leave and remains coordinated to M. X is 4-(C1-C 20 ) an alkyl-substituted 1,3-butadiene molecule, with M having 2 or 4 haptic numbers η (eta 2 ("η 2 ) or Eta 4 ("η 4 It can provide '')) and each of the remaining X, if present, is independently a monodentate group X. The Cp group can be an unsubstituted cyclopentadienyl group, with M having a hapto number η (eta) of 5. 5 ("η 5 The Cp group may provide a coordination number κ of 0, or it may be a hydrocarbyl-substituted cyclopentadienyl group consisting of carbon and hydrogen atoms, with M having a hapto number η (eta 5 ("η 5 The Cp group may provide a coordination number κ of 0, or it may be an organoheterylene-substituted cyclopentadienyl group, with M having a hapto number η (eta 5 ("η 5 The group L is a monodentate organohetyl group and can provide M with a coordination number of 1 κ. In some embodiments, each R 7 (C1-C 20 ) is a hydrocarbyl, which can independently be unsubstituted or substituted with 1 to 3 substituents selected from halogens (e.g., F) and alkyls (e.g., CH3), provided that each R 7 It lacks a carbon-carbon double bond. To eliminate all doubt, monodentate group X does not contain a carbon-carbon double bond or a carbon-carbon triple bond; that is, monodentate group X is not an alkenyl group or an alkynyl group.

[0024] Embodiment 2. A catalyst that turns off the lights faster, using formula (II): (Cp)(L) k(X) x-1 A - (II), wherein the subscript k and x, metal M, and ligand L, and the leaving group X are as defined for formula (I), and the attenuated hybrid catalyst is of formula (III): (Cp)(L) k (X) x-2 (R)A - (III), wherein the subscript k and x, metal M, and ligand L are as defined for formula (I), each X is a monodentate group as defined for formula (I), A - is an anion (used to formally balance the positive charge of metal M), and R is of formula (A), (B), or (C): respectively, -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) ligand, wherein R 5 ~R 7 are each as previously defined for formula (A 1 ), (B 1 ), or (C 1 ), the method according to embodiment 1. To remove all ambiguities, the ligand R of formula (A), (B), or (C) is each obtained from or derived from a kinetic modifier compound of formula (A 1 ), (B 1 ), or (C 1 ). To remove all ambiguities, each ligand R of formula (A) and (B) contains a carbon-carbon double bond (i.e., an alkenyl group). To remove all ambiguities, the ligand R does not have the same structure as the leaving group X, i.e., the definition of the ligand R does not overlap with the definition of the leaving group X.

[0025] Embodiment 3. The hybrid precatalyst is of formula (Ia): CpM(X) xIt is of (Ia), wherein the metal M is Ti, Hf, or Zr, the subscript x is 1, 2, or 3, Cp is an organoheterylene-substituted cyclopentadienyl group, and each X is as defined for formula (I), the method according to embodiment 1 or 2. Without being bound by theory, the structure of the faster light-off catalyst made from the hybrid pre-catalyst of formula (Ia) is formula (IIa): CpM(X) x-1 A - It is of (IIa), and the attenuated hybrid catalyst is of formula (IIIa): CpM(X) x-2 (R) (IIIa), wherein the subscript x, the metal M, and the ligand Cp are as defined for formula (Ia), X is as defined for formula (I), A - is as defined for formula (II), and R is as defined for formula (III).

[0026] Embodiment 4. The hybrid pre-catalyst of formula (I) is of formula (Ia)-1:

Chemical formula

Chemical formula

[0027] Appearance 5. In the hybrid precatalyst of formula (Ia)-1, group R a1 However, it is 1,1-dimethylethyl, and the group R a2 and R a3 Each of them is methyl, M is Ti, the subscript x is 1, and X is molecular 1,3-pentadiene, and the hybrid precatalyst of formula (Ia)-1 is precatalyst (1) [ka] The method according to Embodiment 4, wherein the pre-catalyst (1) is ("pre-catalyst 1"). A synthetic pre-catalyst (1) according to the general procedure of U.S. Patent No. 5,624,878 (e.g., Example 17). Another embodiment of the present invention is the pre-catalyst (1) itself.

[0028] Apparatus 6. The hybrid precatalyst of formula (I) is of formula (Ib): (Cp)(L)(X) xThe method according to embodiment 1 or 2, wherein the formula is (Ib), where M, L, X, and the subscript x are as defined for formula (I), and Cp is an unsubstituted cyclopentadienyl group or a hydrocarbyl-substituted cyclopentadienyl group. In some embodiments, the hybrid precatalyst is of formula (Ib)-1: [ka] In the formula, each base R b1 (C1-C 20 ) alkyl (e.g., (C2-C5) alkyl, e.g., 1,1-dimethylethyl), and each group R b2 Independently, H or (C1-C 20 )alkyl (e.g., (C1-C4)alkyl, e.g., each being 1,1-dimethylethyl), where each subscript 1-5 is independently 0, 1, 2, 3, 4, or 5, and M and X are as defined for formula (I). Although not bound by theory, the structure of a faster light-off catalyst fabricated from the hybrid pre-catalyst of formula (Ib)-1 is given by formula (IIb)-1: [ka] The damped hybrid catalyst is given by equation (IIIb)-1: [ka] It is thought to be the case that, in the formula, each subscript 1 to 5 and base R b1 ~R b2 is as defined for equation (Ib)-1, M and X are as defined for equation (I), and A - R is as defined for formula (II), and R is as defined for formula (III). The hybrid precatalysts of formula (Ib)-1 may be any one of those described in U.S. Patent No. 5,965,677.

[0029] Appearance 7. In the hybrid precatalyst of formula (Ib)-1, M is Ti, each X is methyl, and the hybrid precatalyst of formula (Ib)-1 is precatalyst (2): [ka] The method according to Embodiment 6, wherein the pre-catalyst (2) is a pre-catalyst (2) in the formula, where Me is methyl. A synthetic pre-catalyst (2) according to the procedure of U.S. Patent No. 5,965,677 (e.g., Example 8). Another embodiment of the present invention is the pre-catalyst (2) itself.

[0030] Appearance 8. The dynamic modifier compound is limited to (i)~(vi): formula (A 1 ) or (B 1 ) of (i), equation (A 1 ) or (C 1 ) of (ii), equation (B 1 ) or (C 1 ) of (iii), equation (A 1 ) of (iv), equation (B 1 ) of (v), or formula (C 1 A method according to any one of aspects 1 to 7, which is represented by any one of (vi) of ). Although not bound by theory, formula (A 1 ) and (B 1 The dynamic modifier compounds of ) yield R ligands (A) and (B), respectively, and each of (A) and (B) is considered to have a carbon-carbon double bond as a common structural feature between them. In some embodiments, the dynamic modifier compound consists of carbon and hydrogen atoms. In other embodiments, the dynamic modifier compound consists of carbon atoms, hydrogen atoms, and at least one atom selected from halogen atoms, O, N, and Si, or the dynamic modifier compound consists of carbon atoms, hydrogen atoms, and at least one halogen atom, or the dynamic modifier compound consists of carbon atoms, hydrogen atoms, and at least one atom selected from O, N, and Si, or O and N, or O and Si, or N and Si, or O, or N, or Si.

[0031] Appearance 9. A dynamic modifier compound is of formula (A1 ):R 5 -C≡CR 6 (A 1 ) are phenylacetylene, (substituted phenyl)acetylene, diphenylacetylene, substituted diphenylacetylene, cycloalkylacetylene, formula HC≡CSi(phenyl) h ((C1-C 20 )alkyl) 3-h Acetylene (where the subscript h is an integer between 0 and 3) is given by the formula HC≡C-(CH2). m The method according to any one of embodiments 1 to 8, selected from acetylene in CH3 (wherein the formula, the subscript m is an integer from 1 to 15, or from 1 to 10, or from 2 to 15). In formula (III) of embodiment 2, each ligand R is -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 (In the formula, the subscript h is as defined above), -C(H)=C(X)-(CH2) m CH3 (wherein the formula, the subscript m is as defined above), or -CH2-C(X)=C(alkyl)2 can be selected. The subscript m can be an integer between 8 and 15, or between 1 and 7, or between 2 and 6, or between 2 and 4, or between 1 and 3.

[0032] Embodiment 10. A dynamic modifier compound is of formula (A 1 ):R 5 -C≡CR 6 (A 1 The method according to any one of embodiments 1 to 9, wherein (substituted phenyl)acetylene may be (fluorosubstituted phenyl)acetylene or (methylsubstituted phenyl)acetylene, or 3,4-difluorophenylacetylene, 3,5-difluorophenylacetylene, 3-fluorophenylacetylene, 4-fluorophenylacetylene, or 2,4,5-trimethylphenylacetylene.

[0033] Appearance 11. A kinetic regulator compound of formula (A 1 ):R 5 -C≡CR 6 (A 1 ) is of the form (A 1 The dynamic modifier compounds are KMC1~KMC14: Dynamic modifier compound (1) ("KMC1"): Phenylacetylene (i.e., (C6H5)C≡CH), Dynamic modifier compound (2) ("KMC2"): 4-Methylphenyl-acetylene (i.e., (4-CH3-C6H4)C≡CH), Dynamic modifier compound (3) ("KMC3"): 2,4,5-Trimethylphenyl-acetylene (i.e., (2,4,5-(CH3)3-C6H2)C≡CH), Dynamic modifier compound (4) ("KMC4"): 1,3,5-Triethinylbenzene (i.e., 1,3,5-tri(HC≡C)3(C6H3), Dynamic modifier compound (5) ("KMC5"): Diphenylacetylene (i.e., (C6H5)C≡C(C6H5)), Dynamic modifier compound (6) ("KMC6"): 3-fluorophenyl-acetylene (i.e., (3-F-C6H4)C≡CH), Dynamic modifier compound (7) ("KMC7"): 4-fluorophenyl-acetylene (i.e., (4-F-C6H4)C≡CH), Dynamic modifier compound (8) ("KMC8"): 3,4-difluorophenyl-acetylene (i.e., (3,4-F2-C6H3)C≡CH), Dynamic modifier compound (9) ("KMC9"): 3,5-difluorophenyl-acetylene (i.e., (3,5-F2-C6H3)C≡CH), Dynamic modifier compound (10) ("KMC10"): cyclohexylacetylene (i.e., C6H 11The method according to any one of embodiments 1 to 10, selected from the group consisting of any one of the following: C≡CH), kinetic modifier compound (11) ("KMC11"): phenyldimethylsilylacetylene (i.e., (C6H5)(CH3)2SiC≡CH), kinetic modifier compound (12) ("KMC12"): 1-pentine (i.e., CH3(CH2)2C≡CH), kinetic modifier compound (13) ("KMC13"): 1-octin (i.e., CH3(CH2)5C≡CH), and kinetic modifier compound (14) ("KMC14"): 1,7-octadiyne (i.e., HC≡C(CH2)4C≡CH).

[0034] Embodiment 12. The dynamics regulator compound is of formula (B 1 ):(R 5 )2C=C=C(R 6 )2(B 1 The method according to any one of embodiments 1 to 8, wherein the material is selected from cycloalkylalene, alkylalene, dialkylalene, trialkylalene, trialkylsilylalene, vinylidenecycloalkane, and alkyl esters of allene carboxylic acids. The cycloalkylalene may be ((C3-C8)cycloalkyl)alene or cyclohexylalene. The alkylalene may be methylalene, ethylalene, propylalene, or (1,1-dimethylethyl)alene. The dialkylalene may be 1,1-dialkylalene, 1,3-dialkylalene, or 1,1-dimethylalene. The trialkylalene may be 1,1,3-trimethylalene. The trialkylsilylalene may be trimethylsilylalene, triethylsilylalene, or dimethyl, (1,1-dimethylethyl)silylalene (i.e., tert-butyl-dimethyl-silylalene). The vinylidenecycloalkane is of the formula [ka] It may be vinylidenecyclohexane.

[0035] Appearance 13. A kinetic regulator compound of formula (B 1 ):(R5 )2C=C=C(R 6 )2(B 1 ) is of the formula (B 1 The dynamic modifier compounds of ) are KMC15~KMC17: Dynamic modifier compounds (15) ("KMC15"): Cyclohexylarene (i.e., (C6H 11 The method according to any one of embodiments 1 to 8 and 12, selected from the group consisting of any one of the following: (C(H)=C=CH2), dynamic modifier compound (16) ("KMC16"): ethyl 2,3-butadienone (i.e., H2C=C=CH-C(=O)-O-CH2CH3), and dynamic modifier compound (17) ("KMC17"): 1,1-dimethylalene (i.e., (CH3)2C=C=CH2).

[0036] Appearance 14. The dynamics regulator compound is of formula (C 1 ):(R 5 )(R 7 )C=C(R 6 )(R 7 ) (C 1 ) is of the formula (C 1 The method according to any one of embodiments 1 to 8, wherein the kinetic modifier compound is an internal alkene. Therefore, 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 to 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 the formula (III) of embodiment 2, each ligand R that can be derived therefrom may be of the formula -C(H)(CH3)-C(X)CH3, -C(H)(CH3)-C(X)CH2CH3, or -C(H)(phenyl)-C(X)phenyl, respectively.

[0037] Embodiment 15. The method according to any one of Embodiments 1 to 14, further comprising the step of producing a catalyst that lights up faster by activating a pre-catalyst of formula (I) with an activator under effective activation conditions before the mixing step, thereby producing a catalyst that lights up faster. In some embodiments, the activator is an alkylaluminoxane, an organoborane compound, or an organoborate.

[0038] Embodiment 16. The method according to any one of Embodiments 1 to 15, further comprising: preparing a mixture of a decayed hybrid catalyst, a support material, and an inert hydrocarbon solvent; and removing the inert hydrocarbon solvent from the mixture to obtain a decayed hybrid catalyst placed on the support material. The mixture may further contain an excess of activator, as the activator is typically used in excess to activate the hybrid pre-catalyst. The removal step may be achieved by conventional evaporation (i.e., conventional concentration method) from the mixture of inert hydrocarbon solvent, which results in an evaporated / supported decayed hybrid catalyst. Alternatively, the removal step may be achieved by spray drying the mixture. The spray drying embodiment gives a spray-dried / supported decayed hybrid catalyst which may have improved performance compared to an evaporated / supported decayed hybrid catalyst. Examples of support materials are alumina and hydrophobized fumed silica, or hydrophobized fumed silica. Hydrophobized fumed silica may be prepared by surface-treating untreated anhydrous fumed silica with an effective amount of hydrophobic agent. The hydrophobic agent may be dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane, or dimethyldichlorosilane. Hydrophobic fumed silica prepared by surface-treating untreated anhydrous fumed silica with dimethyldichlorosilane may be CABOSIL TS-610.

[0039] Embodiment 17. A decayed hybrid catalyst prepared by the method described in any one of Embodiments 1 to 16. The decayed hybrid catalyst may be of formula (III) described above, or may be based thereon. In some embodiments, the decayed hybrid catalyst is prepared from a hybrid pre-catalyst of formula (Ia)-1, (Ia)-1a, or (Ib)-1, or from formula (Ia)-1, or from formula (Ia)-1a, or from formula (Ib)-1.

[0040] Embodiment 18. A method for supplying a hybrid catalyst to a slurry phase or gas-phase polymerization reactor containing a moving bed of an olefin monomer and a polyolefin polymer, comprising: preparing a decayed hybrid catalyst outside the reactor according to the method of any one of Embodiments 1 to 16; and supplying the decayed hybrid catalyst in neat form (e.g., dry powder) or as a solution or slurry of the decayed hybrid catalyst in an inert hydrocarbon liquid through a supply line that does not contain an olefin monomer to the slurry phase or gas-phase polymerization reactor. In embodiments, the method further comprises transferring the decayed hybrid catalyst, or a fully active hybrid catalyst prepared in situ from there in the reactor, to a (second) gas-phase polymerization reactor, where it catalytically affects a second olefin polymerization reaction.

[0041] Embodiment 19. A multimodal (e.g., bimodal or trimodal) catalyst system comprising the decayed hybrid catalyst described in Embodiment 17 and at least one second catalyst selected from the group consisting of non-decayed hybrid catalysts, different decayed hybrid catalysts, post-metallocene catalysts, and metallocene catalysts described herein. In some embodiments, the multimodal catalyst system comprises the decayed post-metallocene catalyst of Embodiment 17 and just one second catalyst, or just two different second catalysts. The multimodal catalyst system may further include a support material, and the decayed hybrid catalyst and metallocene catalyst may be placed on the support material (e.g., spray-dried). The decayed hybrid catalyst and metallocene catalyst of the multimodal catalyst system may have a light-off profile measured by the light-off vial test method (described below), with the respective peak polymerization temperatures being... peakThe time between them is within 60 minutes, 45 minutes, or 30 minutes. When the second catalyst is a metallocene catalyst, the light-off performance of the multimodal catalyst system can be usefully adapted so that polymerization using a multimodal catalyst system to produce multimodal (e.g., bimodal or trimodal) polyolefin polymers containing high molecular weight (HMW) and low molecular weight (LMW) components made from a decayed hybrid catalyst does not produce an overproduction of HMW components relative to LMW components, thus resulting in little or no production of substandard multimodal polyolefin polymers.

[0042] Embodiment 20. A method for supplying a multi-modulus (e.g., bimodal or trimodal) catalyst system to a slurry phase or gas-phase polymerization reactor containing a moving bed of an olefin monomer and a polyolefin polymer, comprising: preparing a decayed hybrid catalyst outside the reactor according to the method of any one of Embodiments 1 to 16; contacting a solution of the decayed hybrid catalyst and the activated metallocene catalyst in an inert hydrocarbon solvent with a support material (e.g., fumed silica) outside the reactor to prepare a slurry of a multi-modulus (e.g., bimodal or trimodal) catalyst system essentially consisting of the decayed hybrid 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 multi-modulus catalyst system in neat (dry powder) form; and supplying the slurry of the multi-modulus catalyst system or the neat form of the multi-modulus catalyst system to the slurry layer or gas-phase polymerization reactor through a supply line that does not contain an olefin monomer.

[0043] Embodiment 21. A method for producing a polyolefin polymer, comprising contacting at least one 1-alkene monomer with a decayed hybrid catalyst prepared by the method of any one of Embodiments 1 to 16, or the multi-modulus catalyst system described in Embodiment 19, in a slurry phase containing a moving bed of polyolefin resin or in a gas-phase polymerization reactor, under slurry phase or gas-phase polymerization conditions, thereby producing a polyolefin polymer. The method may include a step prior to the contact step, in which a decayed hybrid catalyst prepared by the method of any one of Embodiments 1 to 16, or the multi-modulus catalyst system of Embodiment 18, is supplied to a slurry phase containing a moving bed of polyolefin resin and at least one 1-alkene monomer, or to a gas-phase polymerization reactor, under slurry phase or gas-phase polymerization conditions, thereby enabling decay light-off of the decayed hybrid catalyst and subsequent polymerization of at least one 1-alkene monomer, thereby producing a polyolefin polymer. The moving bed may be a stirred bed or a fluidized bed. At least one 1-alkene monomer may 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 may be a slurry-phase polymerization reactor and the polymerization conditions may be slurry-phase polymerization conditions. In some such embodiments, the method may further include transferring active polymer granules, which in either case contain an active hybrid catalyst (in the granules), prepared in a first gas-phase polymerization reactor under first gas-phase polymerization conditions or in a slurry-phase polymerization reactor under slurry-phase polymerization conditions, to a second gas-phase polymerization reactor under second gas-phase polymerization conditions, wherein the second gas-phase polymerization conditions differ 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, and may, in some cases, thereby, multimodal (e.g., bimodal or trimodal) polyolefin polymers (i.e., multimodal (e.g., bimodal or trimodal) molecular weight distribution M w / M n A polyolefin polymer having ) can be prepared in a (second) gas-phase polymerization reactor.

[0044] Aspect 22. Polyolefin polymer prepared by the preparation method described in Aspect 21. The polyolefin polymer obtained in virgin form from a slurry-phase polymerization reactor or a gas-phase polymerization reactor may be in the form of granules having fewer aggregates (fused granules) than comparative polyolefin polymers obtained in virgin form from a slurry-phase polymerization reactor or a gas-phase polymerization reactor, respectively, under the same polymerization conditions, except that the decaying hybrid catalyst is replaced with a catalyst that lights off more quickly.

[0045] Embodiment 23. A manufactured article (e.g., an inflated or cast film) made from the polyolefin polymer described in Embodiment 22. The manufactured article may have a lower gel count than a comparative manufactured article made from a comparative polyolefin polymer.

[0046] Embodiment 24. An embodiment of the present invention according to any one of Embodiments 1 to 23, wherein the damped hybrid catalyst does not contain a support material. For example, it does not contain fumed silica or alumina.

[0047] Embodiment 25. A hybrid precatalyst selected from the group consisting of the aforementioned hybrid precatalysts of formulas (1) to (2).

[0048] Embodiment 26. A hybrid catalyst prepared by contacting the hybrid pre-catalyst of Embodiment 25 with an activator.

[0049] In some embodiments, metal M is Zr or Hf, or M is Zr or Ti, or M is Ti or Hf, or M is Zr, or M is Hf, or M is Ti.

[0050] Unsubstituted cyclopentadienyl group. Formula [C5H5] - The carbanion.

[0051] A hydrocarbyl-substituted cyclopentadienyl group. A carbanion formally derived by substituting one or more hydrogen atoms of an unsubstituted cyclopentadienyl group with one or more hydrocarbyl groups, and / or substituting two hydrogen atoms on adjacent ring carbon atoms with one or two hydrocarbylene groups. An example of such a hydrocarbyl group is (C1-C 10 Alkyl compounds, such as methyl, ethyl, 1-methylethyl, propyl, and butyl. Examples of such hydrocarbylene groups include -C(H)=C(H)-C(H)=C(H)- (for example, an indenyl group, or a fluorenyl group if two such groups are used), -C(CH3)=C(H)-C(H)=C(H)-, -C(H)=C(CH3)-C(H)=C(H)-, -C(H)=C(H)-C(CH3)=C(H)-, -C(H)=C(H)-C(H)=C(CH3)-, and -C(H)=C(CH3)-C(H)=C(CH3)- (for example, a 1,5-dimethylindenyl group (where one methyl group is on a five-membered ring and one methyl group is on a six-membered ring) and a 4,6-dimethylindenyl group (where both methyl groups are on six-membered rings)).

[0052] Organohetterylene-substituted cyclopentadienyl group. A cyclopentadienyl group that is substituted with an organohetterylene group as defined later, and is a divalent heteroatom-containing organo group having a radical on a carbon atom and a radical (e.g., N) on a heteroatom. For example, (when used in formula (Ia)-1) formula-(R a1 )N(R a2 )2Si-organoheterylene group, for example, tert-(C4-C8)alkylamino-dimethylsilyl group.

[0053] A method for fabricating a damping hybrid catalyst. This method involves a catalyst that turns off the lights faster and formula (A 1 ), (B 1 ), or (C 1The process involves combining an effective amount of a kinetic modifier compound with a decaying hybrid catalyst under effective reaction conditions. The catalyst that lights up faster may be of formula (II), and the decaying hybrid catalyst may be of formula (III). The mixing step can be carried out in the absence of the pre-catalyst of formula (I). The mixing step can be carried out in the presence of unreacted activator if the activator is used in excess in the activation step. The catalyst that lights up faster contains a leaving group X bonded to a metal atom M. In the mixing step, the leaving group X is replaced from the catalyst that lights up faster by reacting the kinetic modifier compound with the catalyst in this manner, and is replaced by a ligand R derived from the kinetic modifier compound. The ligand is bonded to the metal atom M in the resulting decaying hybrid catalyst. In some embodiments, the decaying hybrid catalyst is of formula (III), the catalyst that lights off faster is of formula (II), and the pre-catalyst is of formula (I), where in all formulas M is Ti, each X is either methyl or one X is 1,3-pentadiene.

[0054] The embodiment of the manufacturing method may include any one of synthesis schemes 1 to 11.

[0055] Synthesis Scheme 1: Step (a) Hybrid pre-catalyst + excess activator → Intermediate mixture of activated hybrid catalyst + residual activator. Step (b) Intermediate mixture + effective amount of kinetic modifier compound → Damped hybrid catalyst.

[0056] Synthesis Scheme 2: Step (a) Hybrid pre-catalyst + effective amount of kinetic modifier compound → intermediate hybrid pre-catalyst (unreacted mixture or reaction product of hybrid pre-catalyst + kinetic modifier compound). Step (b) Intermediate hybrid pre-catalyst + activator (e.g., alkylaluminoxane such as methylaluminoxane ("MAO")) → decayed hybrid catalyst.

[0057] Synthesis Scheme 3: Step (a) Hybrid pre-catalyst + activator (e.g., alkylaluminoxane such as methylaluminoxane ("MAO")) → activated hybrid catalyst (a catalyst that lights up faster). Step (b) Activated hybrid catalyst + effective amount of kinetic modifier compound → decayed hybrid catalyst.

[0058] 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 + hybrid pre-catalyst → decayed light-off hybrid catalyst.

[0059] Synthesis scheme 5: Step (a) Activator → Hybrid pre-catalyst ← Effective amount of kinetic modifier compound (simultaneous but separate addition of activator and kinetic modifier to the hybrid pre-catalyst) → Damped hybrid catalyst. Step (b): None.

[0060] Synthesis scheme 6: Step (a) Hybrid pre-catalyst + support material → Supported hybrid pre-catalyst. (b) Supported hybrid pre-catalyst + amount of activator → Intermediate mixture of activated hybrid catalyst + residual activator placed on (or in equilibrium with) the support material. Step (c) Intermediate mixture + effective amount of kinetic modifier compound → Damped hybrid catalyst placed on (or in equilibrium with) the support material. In some embodiments, step (a) further comprises an inert hydrocarbon solvent, and deposition on the support material is carried out by evaporation of the solvent or by spray drying. The amount of activator may be stoichiometric relative to the metal M of the hybrid catalyst (e.g., a molar ratio of 1.0 to 1.0), or less than stoichiometric relative to it (e.g., a molar ratio of 0.1 to 0.94), or in excess (e.g., a molar ratio of 1.1 to 10,000).

[0061] Synthesis scheme 7: Step (a) Hybrid pre-catalyst + effective amount of kinetic modifier compound + support material → intermediate mixture of hybrid pre-catalyst and kinetic modifier compound placed on (or in equilibrium with) the support material. Step (b) Intermediate mixture + activator (e.g., alkylaluminoxane such as methylaluminoxane ("MAO")) → decayed hybrid catalyst placed on (or in equilibrium with) the support material. In some embodiments, step (a) further comprises an inert hydrocarbon solvent, and deposition on the support material is carried out by evaporation of the solvent or by spray drying.

[0062] Synthesis scheme 8: Step (a) Hybrid pre-catalyst + support material + activator (e.g., alkylaluminoxane such as methylaluminoxane ("MAO")) → activated hybrid catalyst (a catalyst that lights off faster) placed on (or in equilibrium with) the support material. Step (b) Supported activated hybrid catalyst + effective amount of kinetic modifier compound → decayed hybrid catalyst placed on (or in equilibrium with) the support material. In some embodiments, step (a) further comprises an inert hydrocarbon solvent, and deposition on the support material is carried out by evaporation of the solvent or by spray drying.

[0063] Synthesis scheme 9: Step (a) Activator (e.g., alkylaluminoxane such as methylaluminoxane ("MAO")) + effective amount of kinetic modifier compound → intermediate solution. Step (b) Intermediate solution + hybrid pre-catalyst + support material → decayed light-off hybrid catalyst placed on (or in equilibrium with) the support material. In some embodiments, step (b) further comprises an inert hydrocarbon solvent, and deposition on the support material is carried out by evaporation of the solvent or by spray drying.

[0064] Synthesis scheme 10: Step (a) Activator → Hybrid pre-catalyst + support material ← Effective amount of kinetic modifier compound (simultaneous but separate addition of the activator and kinetic modifier compound to the hybrid pre-catalyst + support material mixture) → Damped hybrid catalyst placed on (or in equilibrium with) the support material. Step (b): None. In some embodiments, step (a) further comprises an inert hydrocarbon solvent, and deposition on the support material is carried out by evaporation of the solvent or by spray drying.

[0065] Scheme 11: Step (a): Activator (e.g., alkylaluminoxane such as methylaluminoxane ("MAO")) + support material (e.g., hydrophobic fumed silica) + inert hydrocarbon solvent → slurry of supported activator placed on (or in equilibrium with) the support material. Step (b): Spray-dried slurry of Step (a) → spray-dried supported activator (e.g., spray-dried MAO ("SDMAO" or "sdMAO") on hydrophobic fumed silica as a dry powder) placed on the support material in the form of a dry powder. Step (c): Mixing of hybrid pre-catalyst + spray-dried supported activator of Step (b) + inert hydrocarbon solvent → suspension of supported, faster-light-off hybrid catalyst placed on (or in equilibrium with) the support material. Step (d): Mixing of the suspension from Step (c) with an effective amount of kinetic modifier compound → suspension of supported, attenuated hybrid catalyst placed on (or in equilibrium with) the support material in the inert hydrocarbon solvent. Optional step (e): Remove the inert hydrocarbon solvent from the suspension of the supported decayed hybrid catalyst → the supported decayed hybrid catalyst is placed on a support material in the form of a dry powder. Step (e) may 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).

[0066] The multimodal catalyst system can be supplied to the gas-phase polymerization reactor. If necessary, additional amounts of decayed post-metallocene catalyst or additional amounts of a second catalyst (e.g., metallocene catalyst) can be supplied separately to the reactor as a solution thereof in an inert hydrocarbon solvent and brought into contact with the multimodal catalyst system. Such separate catalyst solutions may be referred to as trim catalysts. Alternatively, the multimodal catalyst system may come into contact with a trim catalyst supply in the supply line leading into the reactor. In other embodiments, the multimodal catalyst system can be constructed in situ within the gas-phase polymerization reactor by adding the decayed post-metallocene catalyst and at least one second catalyst separately to the reactor and bringing them into contact with each other to construct the multimodal catalyst system in situ within the reactor.

[0067] Any one of the above embodiments of the method may further include the step of transferring polymer granules, which are prepared in a gas-phase or slurry-phase polymerization reactor and contain a fully active hybrid catalyst in the granules, to a (second) gas-phase polymerization reactor.

[0068] Dynamic modifier compound ("KMC"). Formula (A 1 The dynamic modifier compound of ) is R 5 -C≡CR 6 (A 1 ) is the equation (B 1 The dynamic modifier compound of ) is (R 5 )2C=C=C(R 6 )2(B 1 ) is the equation (C 1 The dynamic modifier compound of ) is (R 5 )(R 7 )C=C(R 6 )(R 7 ) (C 1 ) is the equation (A 1 ), (B 1 ), or (C 1 The kinetic modifier compound of formula (A) is beneficial in that it does not act as an activity inhibitor for hybrid catalysts, or at best, acts in such a mild manner. 1 The compound of formula (B) is an alkyne, and formula (B 1 The compound of the formula (C) is allene, and the formula is (C 1The compound is an internal alkene. The kinetic modifier compound does not contain a vinyl functional group (i.e., it lacks the group of formula -C(H)=CH2).

[0069] In some embodiments, the dynamics modifier compound is as defined in any one of the numbered embodiments described above.

[0070] Formula (A 1 ), (B 1 ), or (C 1 In some embodiments of the kinetic modifier compounds, (C1-C 20 The hydrocarbyl is (C2-C6)alkyl, (C3-C8)cycloalkyl, or phenyl. In some embodiments, -C(=O)-O-(unsubstituted C1-C 20 Hydrocarbyl is either -C(=O)-O-(unsubstituted C1-C5)alkyl) or -C(=O)-O-ethyl.

[0071] In some embodiments, at least one X is ((C1-C 20 )alkyl) 3-g -(phenyl) g Si-, where the subscript g is 0, 1, 2, or 3, or the subscript g is 0 or 1, or 0 or 1. In some embodiments, at least one X is (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(C1-C6)-CH2 (e.g., benzyl), and the other X is F, Cl, or methyl, or each X is benzyl. In some embodiments, 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 (C1-C6)alkoxy-substituted (C6-C 12 ) are aryl or (C1-C6)alkoxy-substituted benzyl. Although not bound by theory, the structure of the decaying hybrid catalyst is considered to be similar to that of the faster light-off catalyst, except that one of the leaving groups X of the faster light-off catalyst is replaced by a decaying leaving group R in the decaying hybrid catalyst, where R is later defined and derived from a kinetic modifier compound. The decaying leaving group R of the decaying hybrid catalyst is structurally different from the leaving group X of the faster light-off catalyst, resulting in slower elimination.

[0072] Ligand R derived from kinetic modifier compounds. The ligand in a decaying hybrid catalyst derived from a kinetic modifier compound may be the group R ("ligand R"). Although not theoretically bound, ligand R is thought to primarily contribute to the improved kinetic profile of decaying hybrid catalysts (e.g., formula (III)) compared to those of faster light-off catalysts (e.g., formula (II)) in which it was fabricated. Ligand R is derived from formulas (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) may be, where X and R 5 ~R 7Each of these is as described above. In some embodiments, R is a ligand of formula (A) or (B), or R is a ligand of formula (A) or (C), or R is a ligand of formula (B) or (C), or R is a ligand of formula (A), or R is a ligand of formula (B), or R is a ligand of formula (C). Both ligands of formula (A) and (B) contain a carbon-carbon double bond, which is thought to polymerize extremely slowly under gas-phase polymerization conditions.

[0073] While we do not wish to be bound by theory, the reaction between alkene monomers (e.g., ethylene, propylene, 1-butene, 1-hexene, 1-octene, etc.) and decaying light-off catalysts is thought to involve the insertion of the alkene monomer into the bond between the M metal center and the decaying leaving group R. This insertion may be much slower than the corresponding insertion reaction of the alkene monomer into the bond between the M metal center and the leaving group X of a faster light-off catalyst. The slower reaction of the present invention can delay the initiation of polymerization. After the initial one (or several) insertion reactions of the alkene monomer, the decaying leaving group R is no longer bonded to the metal center, and as a result, all subsequent insertions occur at a rate similar to that of a faster light-off catalyst. Since only the first one (or some) of the thousands to millions of insertion reactions performed by the catalyst are slower, the overall productivity of the catalyst may not be significantly reduced. In fact, decaying light-off catalysts may have increased productivity because their exothermic reaction is reduced compared to that of faster light-off catalysts. This is because exothermic reactions that increase the temperature the catalyst experiences can lead to faster deactivation of the catalyst, and this deactivation can reduce the productivity of some catalysts, such as some hybrid catalysts.

[0074] In the ligand R of formula (A), (B), or (C), 5 and R 6 Each of these is independently H or R 7 And each R 7 (C1-C 20 ) Hydrocarbyl or (C1-C 17) Although heterohydrocarbyl, each R 7 It lacks a carbon-carbon double bond. (C1-C 20 Hydrocarbyl can be unsubstituted and may consist of carbon and hydrogen atoms, or (C1-C 20 Hydrocarbyls may be substituted and consist of carbon, hydrogen, and one or more halogen atoms. Each halogen atom can be independently selected from F, Cl, Br, and I, or F, Cl, and Br, or F and Cl, or F, or 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 ) May be aryl-(C1-C6)alkyl. Substitution (C1-C 20 ) Hydrocarbyl is the aforementioned unsubstituted (C1-C 20 ) may be a monofluoro or difluoro derivative of hydrocarbyl, for example, 2-(3,4-difluorophenyl)-ethen-1-yl (of formula (A)).

[0075] (C1-C 19 ) R containing heterohydrocarbil 5 ~R 7 Each of the embodiments (C1-C 19 ) Heterohydrocarbyls may be unsubstituted and may consist of a carbon atom, a hydrogen atom, and at least one heteroatom selected from N and O, or (C1-C 17 A heterohydrocarbyl may be substituted and may consist of at least one heteroatom selected from carbon atoms, hydrogen atoms, N, and O, and one or more halogen atoms. Unsubstituted (C1-C 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 ) may be heteroaryl-(C1-C6)alkyl. Substituting (C1-C 17 ) Heterohydrocarbyl is the same as the unsubstituted (C1-C) mentioned above. 17 ) Monofluoro or difluoro derivatives of heterohydrocarbyl, for example, 2-(3,4-dimethoxyphenyl)-ethen-1-yl (of formula (A)).

[0076] The structure of ligand R is different from the structure of ligand X, and more specifically, anion A - Its structure is also different from that of [another entity].

[0077] Damping hybrid catalysts. Damping hybrid catalysts (e.g., of formula (III)) are prepared according to this method from catalysts that light off faster (e.g., of formula (II)). A damping hybrid catalyst is a hybrid catalyst containing a ligand (e.g., R) derived from a kinetic modifier compound bonded to its metal atom M (e.g., Ti, Zr, or Hf). Damping hybrid catalysts are novel hybrid catalysts. In some embodiments, the damping hybrid catalyst is the damping hybrid catalyst of formula (III).

[0078] All other than the above, a decaying hybrid catalyst (e.g., of formula (III)) may act without significantly reducing the overall catalytic activity compared to a faster-light-off catalyst (e.g., of formula (II)) from which it was prepared. That is, despite the delayed start, the catalytic activity / polymerization productivity, expressed as grams of dry polyolefin product prepared per gram of catalyst added to the reactor per hour (g of PE / g of catalyst-hours), may not be significantly lower than, and in some embodiments may even be higher than, that of a faster-light-off hybrid catalyst. For example, a damped hybrid catalyst may have a productivity of over 200% of a faster-light-off catalyst that it is fabricated from, or 70.0% to 180%, or 70.0% to 150.0%, or 70.0% to 120%, or 80.0% to 120%, or 90.0% to 120%, or 100.0% to 120%, or 110% to 120%, or 70.0% to 110%, or 80.0% to 110%, or 90.0% to 110%, or 100.0% to 110%, or 70.0% to 100%, or 80.0% to 100%, or 90.0% to 100%.

[0079] The decaying hybrid catalyst of formula (III) can suppress catalyst light-off, and compared to catalysts that light-off faster than those fabricated (e.g., of formula (II)), it is thought that this can beneficially improve the operability of the gas-phase reactor by reducing the rate of fouling and increasing the time between reactor shutdowns.

[0080] The decaying hybrid catalyst (e.g., formula (III)) is thought to exhibit an improved polymerization kinetic profile compared to the faster light-off catalyst profile of formula (II) from which it was fabricated. This improved polymerization kinetic profile beneficially increases the compatibility of the decaying hybrid catalyst (e.g., formula (III)) with slower light-off olefin polymerization catalysts, such as some metallocene catalysts, and improves the performance of the resulting light-off compatible multi-modal (e.g., bimodal or trimodal) catalyst system compared to that of the faster light-off catalyst (e.g., formula (II)) from which it was fabricated.

[0081] In addition, it is conceivable that a decaying hybrid catalyst (e.g., of formula (III)) can be stored and transported at ambient temperature until it can be used in a chemical process, instead of the cold storage and cold transport desired for the faster-light-off catalyst (e.g., of formula (II)) from which it was fabricated. It is conceivable that a decaying hybrid catalyst (e.g., of formula (III)) can achieve any one or combination of any two or more such benefits.

[0082] In some embodiments, the method of polymerizing a decaying hybrid catalyst (e.g., formula (III)) and an olefin monomer involves an excess amount of formula (A 1 ), (B 1 ), or (C 1 ) does not contain the kinetic modifier compound. In other embodiments, the decayed post-metallocene catalyst and method have an excess amount of the kinetic modifier compound. Such embodiments of decayed hybrid catalysts (e.g., of formula (III)) can be prepared by matching a catalyst that lights off faster (e.g., of formula (II)) in a molar ratio of moles of the kinetic modifier compound to moles of metal M of formula (II) in the range of 0 to 1.0, or 1.1 to 50, or 0.5 to 40, or 0.5 to 30, or 0.5 to 20, or 0.5 to 10, or 0.5 to 2, or 0.8 to 1.2, or 0.9 to 1.1 (e.g., 1.0). In such embodiments, the kinetic modifier compound (A 1 ), (B 1 ), or (C 1The kinetic modifier compound is used in stoichiometric amounts (a molar ratio of 1.0) or less than stoichiometric amounts (a molar ratio greater than 0 to 0.99). When the kinetic modifier compound is used in less than stoichiometric amounts, the resulting decayed hybrid catalyst (e.g., of formula (III)) has partially decayed light-off activity compared to that of the faster light-off catalyst (e.g., of formula (II)) from which it was prepared. Partially decayed light-off activity may be useful when the faster light-off catalyst (e.g., of formula (III)) exhibits only mild overactivity. In general, the higher the molar ratio of the kinetic modifier compound to the molars of metal M (e.g., of formula (II)), the greater the decay of the overactivity of the faster light-off catalyst (e.g., of formula (II)).

[0083] In some embodiments, the method of polymerizing a decaying hybrid catalyst (e.g., formula (III)) and an olefin monomer involves an excess amount of formula (A 1 ), (B 1 ), or (C 1The catalyst contains a kinetic modifier compound (KMC) of formula (III). Such embodiments of the decaying hybrid catalyst (e.g., formula (III)) can be prepared by matching a faster-light-off catalyst (e.g., formula (II)) with a molar ratio of more than 1.0 moles of the kinetic modifier compound to the moles of metal M of formula (II), for example, a KMC / M molar ratio of 1.1 to 50, or 1.1 to 40, or 1.1 to 30, or 1.1 to 20, or 1.1 to 10, or 2 to 20, or more than 20. Notably, in some embodiments, even when the kinetic modifier compound is used in excess within the aforementioned range (KMC / M molar ratio up to about 50), the catalytic activity of the decaying hybrid catalyst (e.g., formula (III)) and / or the productivity of the gas-phase polymerization reaction using it does not decrease significantly, and may even increase, compared to that of the faster-light-off catalyst (e.g., formula (II)) from which it was prepared. In other embodiments, when an excess amount of the kinetic modifier compound is used, the catalytic activity of the decaying hybrid catalyst (e.g., formula (III)) and / or the productivity of the gas-phase polymerization reaction using it may be significantly reduced compared to that of the faster-light-off catalyst (e.g., formula (II)) from which it was prepared. The reason for this reduction is not understood, but it is possible that the excess kinetic modifier compound may compete with the alkene monomer to substitute the decaying leaving group R of formula (III) in an equilibrium manner. Using an excess amount of the kinetic modifier compound may be useful when the exact molar amount of metal M in the faster-light-off catalyst (e.g., formula (II)) is not precisely known or may vary from lot to lot.

[0084] Damped right-off dynamics profile. A damped hybrid catalyst (e.g., equation (III)) exhibits a damped right-off dynamics profile. For example, the damped dynamics profile is the peak reaction temperature of the damped hybrid catalyst. peak The length of time until is longer, and / or T maxThis may include a lower value compared to that of a faster-light-off catalyst that was prepared. From the injection of the catalyst into a reactor containing olefin monomers but no catalyst (time zero (time 0)) to the time (time) required to reach the peak polymerization reaction temperature. peak The time until ) is longer, at least 0.65 minutes. peak The larger the value, the greater the delay in the catalytic light turning off.

[0085] 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.

[0086] An effective amount of kinetic modifier compound (KMC). The amount of kinetic modifier compound (KMC) sufficient to dampen the light-off of the catalyst. The effective amount of KMC can be expressed as an absolute value compared to the amount of (pre)catalyst metal M, as a relative value compared to the damping light-off performance, or as a combination thereof.

[0087] In some embodiments, the absolute value is such that the effective amount of the dynamic modifier compound is the molar ratio of the moles of the dynamic modifier compound to the moles of the metal M ("KMC"). モル / M モル It can be expressed as ) in the formula, where M is M of the hybrid precatalyst of structural formula (I), for example, M is a group 4 metal. In some embodiments, the effective amount of KMC is 0.50 / 1.0 or more, or 0.9 / 1.0 or more, or 1.0 / 1.0 or more, or 1.5 / 1.0 or more, or 1.9 / 1.0 or more, or 3 / 1.0 or more, or 5 / 1.0 or more, or 6 / 1.0 or more, or 9 / 1.0 or more, or 10.0 / 1.0 or more, or 10.0 / 1.0 or less, or 20.0 / 1.0 or less, or 30.0 / 1.0 or less, or 40.0 / 1.0 or less, or 50.0 / 1.0 or less of KMC モル / M モルIt is expressed as follows: In other words, the previous embodiment uses an effective amount of KMC in the inverse molar ratio of moles of metal M to moles of the dynamic modifier compound ("M モル / KMC モル It can be described as follows, expressing each as 1.0 / 0.5 or less, or 1.0 / 0.9 or less, or 1.0 / 1.0 or less, or 1.0 / 1.5 or less, or 1.0 / 1.9 ​​or less, or 1.0 / 3.0 or less, or 1.0 / 5.0 or less, or 1.0 / 6.0 or less, or 1.0 / 9.0 or less, or 1.0 / 10.0 or less, or 1.0 / 20.0 or less, or 1.0 / 30.0 or less, or 1.0 / 40.0 or less, or 1.0 / 50.0 or less. Generally, KMC higher than approximately 50 / 1.0 モル / M モル It is thought that this may undesirably interfere with the light-off or function of the post-metallocene catalyst containing it. However, for practical reasons (e.g., the cost of KMC, and / or the post-polymerization process operation / cost (e.g., stripping excess KMC from the polyolefin resin)), in some embodiments, KMC モル / M モル This 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.

[0088] In terms of the relative values ​​of decaying light-off performance, the effective amount of kinetic modifier compound (KMC) can be expressed by the results measured by the light-off vial test method described below. For example, when measured separately using the light-off vial test method described below with a decaying hybrid catalyst and a catalyst that lights up faster using the kinetic modifier compound, the effective amount of kinetic modifier compound (KMC) is characterized by the following features observed after catalyst injection: (i) exothermic reaction, i.e., the time delay of the start of the reaction temperature rise (i.e., from zero addition time (time 0) to the start of the exothermic reaction time (time 0) exo(ii) the longer duration of time in minutes up to (0), (ii) the slower maximum rate of increase in reaction temperature per minute (°C / min) (e.g., the lower maximum slope in a plot of reaction temperature on the y axis against time after catalyst injection on the x axis), (iii) the lower peak reaction temperature reached (°C). peak (°C), (iv) time from addition time at time 0 to peak temperature time (hour peakT For a time of at least 0.65 minutes longer than ) up to ), (v) is both (i) and (ii) and not (iii) or (iv), (vi) is both (i) and (iii) and not (ii) or (iv), (vii) is both (ii) and (iii) and not (i) or (iv), (viii) is both (i) and (iv) and not (ii) or (iii), (ix) is both (ii) and (iv) and not (i) or (iii), (x) is both (iii) and (iv) and not (i) or (ii), (xi) may have any three of (i) to (iv) and each of (xii) may have one of (i) to (iv). In some embodiments, the attenuated light-off and effective amount of KMC are characterized by at least feature (iv), or feature (iv) only. In some embodiments, the longer time of feature (iv) is at least 0.65 minutes, or at least 1.0 minute, or at least 1.5 minutes, or 1.5 to 55 minutes, or 1.6 to 100 minutes, or 1.6 to 55 minutes, or 1.6 to 10.0 minutes, or 10.1 to 20.0 minutes, or 20.1 to 30.0 minutes, or 30.1 to 40.0 minutes, or 40.1 to 50.0 minutes, or 50.1 to 55 minutes, or 2.0 to 29 minutes, or 30.1 to 50.4 minutes from the time of addition to the peak temperature (time peakTThe time is at least 0.65 minutes (39 seconds or more) until ), and all are measured according to the light-off vial test method described below. In some embodiments, the decayed light-off and the effective amount of KMC are characterized by feature (viii). In some embodiments, the decayed light-off is characterized by feature (ix). In some embodiments, the decayed light-off and the effective amount of KMC are characterized by feature (x). In some embodiments, the decayed light-off is characterized by feature (xi).

[0089] Damping hybrid catalyst at temperature max The catalyst that lights up faster in the time it takes to reach the temperature max The delay in the time to reach the destination can be between 0.70 and 500 minutes (for example, 293 minutes in this example), or between 0.70 and 120 minutes, or between 1.0 and 120 minutes, or between 5 and 90 minutes, or between 10 and 70 minutes.

[0090] In some embodiments, the dynamic profile of the decayed hybrid catalyst was prepared when performed under the same polymerization conditions according to the light-off batch reactor test method described later, with respect to the catalyst temperature at which it lights off faster. peak Peak temperature for (temperature) peak This can be characterized as a decrease in the temperature of the decaying hybrid catalyst. In the light-off batch reactor test method, the temperature of the decaying hybrid catalyst is max The catalyst that was created to light off faster is T max The temperature may be 1°C to 16°C, 2°C to 15°C, or 3°C to 14°C lower than that. In some embodiments, the hybrid catalyst that lights up faster is made from one of the aforementioned hybrid pre-catalysts (1) to (2).

[0091] In some embodiments, the dynamic profile of a decaying hybrid catalyst can be characterized as the absolute weight / weight ratio (C2(1h) / C2(0.1h)) of ethylene (C2) uptake after 1 hour (h) to C2 uptake after 0.1 hours. In some embodiments, the decaying hybrid catalyst may have a C2(1h) / C2(0.1h) ratio of 2.1–11, or 2.2–10.4, or 2.4–10.0, or 3–9.9. In some embodiments, a hybrid catalyst that lights off faster is made from any one of the hybrid pre-catalysts (1)–(2) described above.

[0092] In some embodiments, the dynamic profile of a decaying hybrid catalyst can be characterized as the relative C2(1h) / C2(0.1h) ratio of the decaying hybrid catalyst to the C2(1h) / C2(0.1h) ratio of a catalyst that lights off faster when performed under the same polymerization conditions according to the light-off batch reactor test method described later. The relative C2(1h) / C2(0.1h) ratio may be 1.05–6, or 1.1–6, or 1.2–5.4, or 1.5–5.0.

[0093] As measured by the light-off vial test method described later, an alternative or additional way to represent an effective amount of kinetic modifier compound (KMC) in terms of the relative decay light-off performance is that the decay hybrid catalyst and the faster light-off catalyst produced therefrom may have a light-off profile measured by the light-off vial test method (described later), and the respective peak polymerization temperatures are... peak The times are, for each other, at least 0.7 minutes, or more than 1.0 minute, or more than 5 minutes, or more than 10.0 minutes, or more than 20.0 minutes, or more than 30.0 minutes, or more than 40.0 minutes, or more than 50.0 minutes. The decayed hybrid catalyst and the faster light-off catalysts produced therefrom may have a light-off profile measured by the light-off vial test method (described later), with the respective peak polymerization temperatures being the temperature.peak The time intervals are, for each other, within 60 minutes, or within 45 minutes, or within 30 minutes. The temperature is the peak polymerization temperature of the decayed hybrid catalyst. peak The time it takes for the catalyst to light off faster than it was made is the temperature of the catalyst. peak The effect of the dynamic modifier compound on delaying the time may vary depending on (a) the structural class of the decaying hybrid catalyst (e.g., formula (Ia) or (Ib)), or structural subclass (e.g., formula (Ia)-1 vs (Ia)-1a, or formula (Ia)-1 vs (Ib)-1) and / or (b) the structural class of the dynamic modifier compound (e.g., acetylene, allene, or internal alkene), or structural subclass (e.g., arylacetylene vs alkylacetylene, or monoacetylene vs diacetylene or triacetylene, or acyclic allene vs cycloalkylene vs vinylidene allene, or aryl internal alkene vs alkyl internal alkene). In some embodiments, the temperature of the decaying hybrid catalyst peak And the temperature of the hybrid catalyst that is manufactured to light off faster peak One of the endpoints for the range of time differences between the two can be determined based on the data given later in the example.

[0094] In some embodiments, the dynamic profile of the damped hybrid catalyst may be characterized as any two, all but one, or a combination of each of the embodiments described above.

[0095] Comparative examples or non-inventive examples either do not contain a dynamic modifier compound or contain a dynamic modifier compound in an effective amount less than the amount present.

[0096] Catalytic activity. (For example, the catalytic activity of a decaying hybrid catalyst (of formula (III)) is the peak polymerization reaction temperature of the decaying hybrid catalyst (temperature) peak ) is the T of a catalyst that lights up faster than measured by the light-off vial test method at Celsius (°C). pIf the temperature is reached within ±5°C, ±4°C, ±3°C, ±2°C, or ±1°C, the catalytic activity is considered substantially the same as that of a catalyst that lights up faster. Alternatively, catalytic activity is determined by catalytic activity / polymerization productivity, expressed as grams of dry polyolefin product produced per gram of catalyst added to the reactor per hour (g of PE / g of catalyst-hours), and, all other equal, is not significantly lower than that of a hybrid catalyst that lights up faster, and may even be higher in some embodiments.

[0097] A catalyst that lights up faster. Embodiments of a catalyst that lights up faster (e.g., of formula (II)) may require a decay of the light-off kinetics for the slurry phase and / or gas-phase polymerization of the 1-alkene monomer for the reasons stated above. The same or other embodiments of a catalyst that lights up faster (e.g., of formula (II)) may require a ligand R for different reasons, such as to change the solubility of the catalyst in alkane solvents or to improve NMR studies of hybrid catalyst structures and catalyst structure design.

[0098] Anion A - The faster-light-off catalyst (of formula (II)) and the decaying hybrid catalyst (of formula (III)) are each derived from an activator used to produce a faster-light-off hybrid catalyst from the hybrid pre-catalyst of formula (I), or from an anion A derived from the leaving group X. - It may contain. The activator activates the hybrid pre-catalyst of formula (I) by removing the leaving group X therefrom, thereby enabling a faster light-off hybrid catalyst (e.g., of formula (II)) and anion A. - It functions to obtain the following. The resulting activated hybrid catalyst, i.e., the faster light-off catalyst of formula (II), is conventionally depicted as representing a positively charged metal atom M. This positive charge indicates a catalytic site to which the olefin monomer can be bonded during the polymerization reaction. Anion A -This formally balances the positive charge so that the faster-light-off hybrid catalyst (e.g., of formula (II)) and the decayed hybrid catalyst (e.g., of formula (III)) produced therefrom are overall neutral.

[0099] A hybrid catalyst that lights up faster than (for example, formula (II)) and anion A in a decaying hybrid catalyst (for example, formula (III)) - The properties of are not considered important. As mentioned above, it is X (that is, X - ) may be an anionic derivative of or an anionic derivative of the activator. The activator is an alkylaluminoxane, and anion A - If it is the anion derivative, then anion A - It may be an alkylaluminoxane anion, or the activator may be an organoborane compound, and anion A - If it is the anion derivative, then anion A - It may be an organoborane anion, or the activator may be an organoborate compound, and anion A - If it is the anion derivative, then anion A - This could be an organoborate anion. Anion A - Anion A in the decay hybrid catalyst (for example, of formula (III)) is formed during the activation step of embodiment 1. - However, anion A in the catalyst lights up faster. - Anion A in a hybrid catalyst that lights off faster (for example, in equation (II)) can be the same as... - It is thought to be transported through the mixing process. Nevertheless, anion A in the decayed hybrid catalyst (e.g., equation (III)) - Anion A in a hybrid catalyst that lights off faster than (for example, in equation (II)) is - It may be the same as or different from the same. For example, anion A in a hybrid catalyst that lights off faster than (for example, equation (II)). -This can be an anionic derivative of the activator, and the anion A- in the decaying hybrid catalyst (for example, formula (III)) is X - It is possible.

[0100] Catalyst structure. Although not bound by theory, the molecular structure of the faster-light-off hybrid catalyst of formula (II) and the molecular structure of the decaying hybrid 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 ligand R in formula (III) can be determined by quenching an NMR sample of the decaying post-metallocene catalyst of formula (III) with a protic solvent such as isopropanol, CH3OH, or H2O, a partially deuterated protic solvent such as isopropyl-OD, CH3OD, or HDO, a perdeuterated protic solvent such as perdeuterated isopropanol (CD3)2C(D)OD), perdeuterated methanol (CD3OD), or D2O to obtain a byproduct of formula HR or DR, and determining the structure of the byproduct by proton NMR ( 1 This can be determined by analysis using NMR (such as 1H-NMR) or gas chromatography / mass spectrometry (GC / MS).

[0101] Activation step. In some embodiments, the method for producing a decaying hybrid catalyst (e.g., of formula (III)) further includes an activation step as a pre-step, which may be completed before the start of the mixing step. The activation step involves contacting the pre-catalyst of formula (I) with an activator under effective activation conditions for producing a hybrid catalyst that lights off more quickly. The activation step may be carried out in the absence of a kinetic modifier compound.

[0102] Activators. Activators for activating the hybrid precatalyst of formula (I) may be alkylaluminoxanes, organoborane compounds, organoborate compounds, or trialkylaluminum compounds. Activators may also be any combination of two or more of these. For example, activators may include alkylaluminoxanes and organoborate compounds, such as methylaluminoxane and organoborates having amine,bis(hydrohydrate-alkyl)methyl,tetrakis(pentafluorophenyl)borate (amine,bis(hydrohydrate-alkyl)methyl,tetrakis(pentafluorophenyl)borate(1-)) as the CAS name. Activators for activating cyclopentadienyl-containing ligand-metal (Ti, Zr, or Hf) complexes to obtain metallocene catalysts may be trialkylaluminum compounds.

[0103] Alkylaluminoxane: Also called alkylaluminoxane. Partial hydrolysis product of trialkylaluminum compounds. Embodiments include (C1-C 10The alkylaluminoxane may be an alkylaluminoxane, or (C1-C6)alkylaluminoxane, or (C1-C4)alkylaluminoxane, or (C1-C3)alkylaluminoxane, or (C1-C2)alkylaluminoxane, or methylaluminoxane (MAO), or modified methylaluminoxane (MMAO). In some embodiments, the alkylaluminoxane is MAO. In some embodiments, the alkylaluminoxane is supported on untreated silica such as fumed silica. Alkylaluminoxanes can be obtained from commercial suppliers or prepared by any preferred method. Preferred methods for preparing alkylaluminoxanes are well known. Examples of such preparation methods are 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, and This is described in European Patent Nos. 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, and 5,693,838 in the European Patent Publications, as well as in European Patent Nos. 0 561 476(A), 0 279 586(B1), and 0 594-218(A) in the European Patent Gazette, and in PCT International Publication No. 94 / 10180.

[0104] The maximum amount of alkylaluminoxane can be selected to be in a 5,000-fold molar excess of the precatalyst, based on the molar ratio of Al metal atoms in the aluminoxane to the molar ratio of metal atoms M (e.g., Ti, Zr, or Hf) in the precatalyst. The minimum amount of activator to precatalyst may be a 1:1 molar ratio (Al / M). The maximum value may be an Al / M molar ratio of 150 or 124.

[0105] Organoborane compounds. Tri(fluorofunctional organo)borane compounds such as tris(pentafluorophenyl)borane ((C6F5)3B), tris[3,5-bis(trifluoromethyl)phenyl]borane ((3,5-(CF3)2-C6H3)3B), or any two or more mixtures thereof.

[0106] Organoborate 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 any two or more mixtures thereof. Organoborate compounds are methyl di((C) tetrakis(pentafluorophenyl)borate. 14 -C 18 This may be an alkyl)ammonium salt, which may be available from Boulder Scientific or prepared by the reaction of a long-chain trialkylamine (Armeen® M2HT, available from Akzo-Nobel, Inc.) with HCl and Li[B(C6F5)4]. Such preparations are disclosed in Example 2 of U.S. Patent No. 5,919,983. Organoborate compounds may be used herein without (further) purification. Also, amine, bis(hydrogenated trialkyl)methyl, tetrakis(pentafluorophenyl)borate.

[0107] Trialkylaluminum compounds can be used as activators for pre-catalysts (metallocene pre-catalysts) or as scavengers to remove residual water from polymerization reactors before their startup. Examples of suitable alkylaluminum compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.

[0108] Activators, also known as co-catalysts, can affect the molecular weight, degree of branching, comonomer content, or other properties of polyolefin polymers. These activators can enable coordination polymerization or cationic polymerization.

[0109] While not bound by theory, the choice of activator used to activate a hybrid catalyst that lights up faster is not thought to affect the structure of a decaying hybrid catalyst fabricated from a hybrid catalyst that lights up faster. That is, only the cation portion of equation (III) is considered (i.e., anion A). - Ignoring the following, it is expected that the structures of decaying hybrid catalysts prepared using different activators will be identical. The structure of unsupported decaying hybrid catalysts may be easier to determine by NMR than that of supported decaying hybrid catalysts due to the heterogeneity of the latter (typical supporting materials do not dissolve in NMR solvents).

[0110] In some embodiments, A - The selection of this may have an additional effect on the dynamic profile of the damped hybrid catalyst. - Any such effect, however, does not completely negate the beneficial effect of the dynamic modifier compound on the dynamic profile of the damped hybrid catalyst.

[0111] Effective conditions. The reactions described herein (e.g., mixing, activation, polymerization) are carried out independently under conditions that allow the intended reaction to proceed. Examples of effective conditions include reaction temperature, type of atmosphere (e.g., inert atmosphere), purity of reactants, stoichiometry of reactants, stirring / mixing of reactants, and reaction time. Effective conditions for the activation and polymerization steps may be described in the art and well known to those skilled in the art. For example, effective conditions for activation may include techniques for handling the catalyst, such as in-line mixers, catalyst preparation reactors, and polymerization reactors. The activation temperature may be 20°C to 800°C, or 300°C to 650°C. The activation time may be 10 seconds to 2 hours. Examples of gas-phase polymerization conditions are described later herein. Effective conditions for the mixing process used to produce decayed hybrid catalysts may include a reaction temperature of -50°C to 30°C, an inert atmosphere (e.g., nitrogen, helium, or argon gas free of water and O2), reactants free of water and O2 and with a purity of 90% to 100%, a quantity of reactants to minimize waste and maximize product yield, stirring or mixing of the reactants, and a reaction time of 1 minute to 24 hours.

[0112] Effective reaction conditions for preparing the hybrid precatalyst of formula (IV). Such conditions may include air-sensitive and / or water-sensitive reagents, as well as techniques for handling the reactants, such as the Schlenklein technique and an inert gas atmosphere (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 -78°C to 120°C, or -30°C to 30°C. Each reaction pressure may independently be 95 to 105 kPa, or 99 to 103 kPa. The progress of a particular reaction step may be monitored by analytical methods such as nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry to determine an effective reaction time for maximizing the yield of the desired product. Alternatively, each reaction time may independently be 30 minutes to 48 hours.

[0113] A hybrid pre-catalyst of formula (I). The pre-catalyst of formula (I) can be synthesized according to methods known in the art, including those methods referenced above. Alternatively, the hybrid pre-catalyst can be obtained from pre-catalyst suppliers such as Boulder Scientific.

[0114] Polyolefin polymers prepared by polymerization 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 the 1-alkene monomer is an ethylene-based polymer having 50 to 100 weight percent (wt%) repeating units derived from ethylene and 50 to 0 weight percent repeating units derived from a 1-alkene monomer selected from propylene, 1-butene, 1-hexene, 1-octene, and any two or more combinations thereof.

[0115] In some embodiments, the polymerization method 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 polymerization also uses a diene monomer, the polyolefin polymer is an ethylene / propylene / diene monomer (EPDM) copolymer. The EPDM copolymer may be an ethylene / propylene / 1,3-butadiene copolymer.

[0116] Multimodal (e.g., bimodal or trimodal) catalyst systems. A bimodal catalyst system comprises a decayed hybrid catalyst and at least one other olefin polymerization catalyst selected from different decayed hybrid catalysts, hybrid catalysts, and metallocene catalysts. The multimodal catalyst system produces a multimodal polyethylene composition containing HMW polyethylene components and LMW polyethylene components in a single reactor. Some of the problems relate to undesirable gelation in the melt-blended multimodal (e.g., bimodal or trimodal) polyethylene composition after the reactor. Other problems relate to the complexity of migration and the stability of the multimodal (e.g., bimodal or trimodal) catalyst system. Even in the absence of gelation, problems may exist due to variability in the sedimentation of catalyst particles of different sizes. In some embodiments, variability in the melt index (I2) can be measured as a function of particle size instead of using gelation.

[0117] Methods for producing decayed hybrid catalysts may 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 includes activating the metallocene pre-catalyst with the same or a different activator. Typically, methods for producing decayed hybrid catalysts are carried out in the absence of a metallocene (pre) catalyst.

[0118] Metallocene catalysts. Metallocene catalysts can be prepared from any one of the metallocene precatalyst components listed in U.S. Patent No. 7,873,112 (B2), column 11, line 17 to column 22, line 21. In some embodiments, metallocene precatalysts are prepared from metallocene precatalyst species named in U.S. Patent No. 7,873,112 (B2), column 18, line 51 to column 22, line 5. In some embodiments, metallocene precatalysts are bis(η 5 -Tetramethylcyclopentadienyl)zirconium dichloride, bis(η 5 -tetramethylcyclopentadienyl)zirconium dimethyl, bis(η) 5 -Pentamethylcyclopentadienyl)zirconium dichloride, bis(η 5-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 The following are selected: (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 activation reaction product of an activator and one of the aforementioned metallocene pre-catalysts.

[0119] Unsupported or supported catalysts. Hybrid pre-catalysts of formula (I), faster light-off hybrid catalysts such as the faster light-off catalyst of formula (II), decaying hybrid catalysts such as the decaying hybrid catalyst of formula (III), and multi-modal catalyst systems may be independently placed on unsupported or solid particulate support materials. In the absence of support material, hybrid pre-catalysts of formula (I), faster light-off hybrid catalysts such as the faster light-off catalyst of formula (II), decaying hybrid catalysts such as the decaying hybrid catalyst of formula (III), and / or multi-modal catalyst systems may be injected into a slurry phase or gas-phase polymerization reactor as a solution in a hydrocarbon solvent. When hybrid pre-catalysts of formula (I), faster light-off hybrid catalysts such as the faster light-off catalyst of formula (II), decay hybrid catalysts such as the decay hybrid catalyst of formula (III), and / or multi-modal catalyst systems are arranged on a support material, they can be injected into the 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).

[0120] A hybrid catalyst that lights up faster than (e.g., formula (II)) and / or a decaying hybrid catalyst (e.g., formula (III)) may be prefabricated in the absence of a support material and then placed on the support material. Alternatively, a hybrid pre-catalyst of formula (I) or a hybrid catalyst that lights up faster than (e.g., formula (II)) may be placed on a support material, and then a hybrid catalyst that lights up faster than (e.g., formula (II)) and / or a decaying hybrid catalyst (e.g., formula (III)) may be fabricated in situ on the support material.

[0121] A supported hybrid pre-catalyst of formula (I), a supported faster light-off catalyst (e.g., a supported catalyst of formula (II)), and / or a supported decaying hybrid catalyst (e.g., a supported catalyst of formula (III)) may be prepared by a concentration method, which involves evaporating the hydrocarbon solvent from a suspension or solution of the supporting material in a solution of the pre-catalyst of formula (I), the faster light-off catalyst (e.g., of formula (II)), and / or the decaying hybrid catalyst (e.g., of formula (III)). Alternatively, a supported pre-catalyst of formula (I), a supported faster light-off catalyst (e.g., a supported catalyst of formula (II)), and / or a supported decaying hybrid catalyst (e.g., a supported catalyst of formula (III)) may be prepared by a spray-drying method, which involves spray-drying the suspension or solution. In some embodiments, spray-drying is used.

[0122] Support material. The support material is a particulate solid that may be non-porous, semi-porous, or porous. The carrier material is a porous support material. Examples of support materials include talc, inorganic oxides, inorganic chlorides, zeolites, clays, resins, and mixtures of two or more of these. Examples of suitable resins are functionalized or crosslinked organic supports such as polystyrene and polystyrene-divinylbenzene polyolefins. The support material may independently be untreated silica, calcined untreated silica, silica treated with a hydrophobic agent, or calcined and hydrophobic silica. The hydrophobic agent may be dichlorodimethylsilane.

[0123] Examples of the inorganic oxide support material include metal oxides of Groups 2, 3, 4, 5, 13, or 14. Preferred supports include silica, fumed silica, alumina (see, for example, PCT International Publication No. 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. Patent No. 5,965,477), montmorillonite (European Patent No. 0 511 665), phylosilicate, zeolite, talc, clay (U.S. Patent No. 6,034,187), and the like. Combinations of these support materials, such as silica-chromium, silica-alumina, silica-titania, etc., may also be used. Additional support materials include those porous acrylic polymers described in European Patent No. 0 767 184, which is incorporated herein by reference. Other support materials include the nanocomposites disclosed in PCT International Publication No. 99 / 47598, the aerogels disclosed in PCT International Publication No. 99 / 48605, the spherulites disclosed in U.S. Patent No. 5,972,510, and the polymer beads disclosed in PCT International Publication No. 99 / 50311.

[0124] The support material can have a surface area in the range of about 10 m 2 / g to about 700 m 2 / g, a pore volume in the range of about 0.1 cm 3 / g to about 4.0 cm 3 / g, and an average particle size in the range of about 5 microns to about 500 microns. The support material can be silica (e.g., fumed silica), alumina, clay, or talc. Fumed silica can be hydrophilic (untreated) or hydrophobic (treated). In some embodiments, the support is hydrophobic fumed silica, which can be prepared by treating untreated fumed silica with a hydrophobic agent such as dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane. In some embodiments, the treating agent is dimethyldichlorosilane. In one embodiment, the support is Cabosil™ TS-610.

[0125] One or more pre-catalysts and / or one or more activators may be deposited, contacted, vaporized, bonded, or incorporated, adsorbed, or absorbed onto one or more supports or carrier materials.

[0126] The metallocene pre-catalyst may be spray dried according to the general method described in U.S. Patent No. 5,648,310. The support used with the hybrid pre-catalyst may be functionalized as generally described in European Patent No. 0 802 203 or at least one substituent or leaving group may be selected as described in U.S. Patent No. 5,688,880.

[0127] Solution phase polymerization and / or slurry phase polymerization of olefin monomers is well known. See, for example, U.S. Patent No. 8,291,115 (B2).

[0128] Inert hydrocarbon solvents. Alkanes, arenes, or alkylarenes (i.e., arylalkanes). 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, or 5 to 12 carbon atoms, or 5 to 10 carbon atoms. Each alkane can independently be acyclic or cyclic. Each acyclic alkane can independently be linear or branched. Acyclic alkanes can be pentane, 1-methylbutane (isopentane), hexane, 1-methylpentane (isohexane), heptane, 1-methylhexane (isoheptane), octane, nonane, decane, or any two or more mixtures thereof. The cyclic alkanes may be cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, methylcyclopentane, methylcyclohexane, dimethylcyclopentane, or any two or more mixtures thereof. Additional examples of preferred alkanes include Isopar-C, Isopar-E, and mineral oils such as white mineral oil. In some embodiments, the inert hydrocarbon solvent does not contain mineral oil. The inert hydrocarbon solvent may contain one or more (C5-C) 12 ) Can consist of alkanes.

[0129] Gas-phase polymerization (GPP). Polymerization is carried out using GPP reactors such as stirred-bed gas-phase polymerization reactors (SB-GPP reactors) or fluidized-bed gas-phase polymerization reactors (FB-GPP reactors). Such reactors and methods are generally well known. For example, FB-GPP reactors / methods may be as described in any one of the following: U.S. Patent 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 No. 0802202(A), and Belgian Patent No. 839,380. These SB-GPP and FB-GPP polymerization reactors and processes each employ either mechanical stirring or fluidization of the polymerization medium of gaseous monomers and diluents within the reactor by a continuous flow. Other useful reactors / processes envisioned include series or multi-stage polymerization processes as described in U.S. Patents Nos. 5,627,242, 5,665,818, and 5,677,375, and European Patents Nos. 0794 200(A), 0649 992(B1), 0802 202(A), and 634421(B).

[0130] The gas-phase polymerization operating conditions are any variables or combinations of variables that may affect the polymerization reaction in the GPP reactor, or the composition or properties of the polyolefin copolymer composition product produced thereby. Variables include reactor design and size, pre-catalyst composition and amount, reactant composition and amount, molar ratio of two different reactants, presence or absence of feed gas such as H2, feed gas to reactant molar ratio, absence or concentration of interfering substances (e.g., H2O and / or O2), presence or absence of induced condensing agent (ICA), average polymer residence time in the reactor, partial pressure of components, monomer feed rate, reactor bed temperature (e.g., fluidized bed temperature), nature or sequence of process steps, and transition periods between steps. The variables described, or those altered by this method or its use, may be kept constant.

[0131] In the GPP method, ethylene ("C2"), hydrogen ("H2"), and 1-hexene ("C6" or "C6" where x is 6) are used. x Control the individual flow rates of the following to achieve a fixed molar ratio or supply mass ratio (C) of comonomer to ethylene monomer gas equal to the stated value (e.g., 0.00560 or 0.00703). x Maintain a constant molar ratio or feed mass ratio of hydrogen to ethylene gas ("H2 / C2") equal to the stated value (e.g., 0.00229 or 0.00280), and a constant partial pressure of ethylene ("C2") equal to the stated value (e.g., 1000 kPa). Measure the gas concentration by inline gas chromatography to understand and maintain the composition of the recycled gas flow. Maintain the reaction bed of polymer particles growing in a flowing state by continuously flowing replenishment material and recycle the gas through the reaction zone. Use a surface gas velocity of 0.49–0.79 m / sec (1.6–2.6 ft / sec). Operate the FB-GPP reactor at a total pressure of approximately 2068–2758 kilopascals (kPa) (approximately 300–400 pounds / 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 rate of generation of the particulate form of the polyolefin polymer composition, the generation rate of which can be 5,000 to 150,000 kilograms / hour (kg / hour). The product polyolefin polymer composition is semi-continuously withdrawn into a fixed-volume chamber via a series of valves, and this withdrawn multi-modal (e.g., bimodal or trimodal) ethylene-co-1-hexene copolymer composition is purged to remove entrained hydrocarbons and treated with a humidified nitrogen (N2) gas stream to deactivate any trace amounts of residual catalyst.

[0132] The catalyst system can be supplied to the polymerization reactor in "dry mode" or "wet mode," or in either dry mode or wet mode. In dry mode, it is a dry powder or granules. In wet mode, it is a suspension in an inert liquid such as mineral oil.

[0133] Induced condensant (ICA). An inert liquid useful for cooling materials in GPP reactors. Its use is optional. ICA is (C3-C 20 ) Alkanes, or (C5-C 20 ) may be an alkane, for example, 2-methylbutane (i.e., isopentane). See U.S. Patents 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%, or 1 to 16 mol%, or 1 to 10 mol%.

[0134] GPP conditions may further include one or more additives, such as chain transfer agents or accelerators. Chain transfer agents are well known and may be alkyl metals such as diethylzinc. Accelerators are known, such as in U.S. Patent No. 4,988,783, and may include chloroform, CFCl3, trichloroethane, and difluorotetrachloroethane. Before starting the reactor, a scavenger may be used to react with water, and during the transition of the reactor, a scavenger may be used to react with excess activator. The scavenger may be trialkylaluminum. GPP may be operated without a scavenger (without intentional addition). The GPP reactor / method may further include one or more electrostatic control agents and / or one or more continuous additives such as aluminum stearate or polyethyleneimine (e.g., 0.5 to 200 ppm based on all feeds to the reactor). Electrostatic control agents may be added to the FB-GPP reactor to suppress the formation or accumulation of static electricity therein.

[0135] The GPP reactor may be a commercially available FB-GPP reactor, such as a UNIPOL® reactor or UNIPOL® II reactor, from Univation Technologies, LLC, a subsidiary of The Dow Chemical Company (Midland, Michigan, USA).

[0136] 1-Alkene monomer. The formula for 1-alkene monomers is H2C=C(H)(CH2). n R 8 It is a compound of the base R, where the subscript n is an integer from 0 to 19. 8 is H or CH3. An example is ethylene (where the subscript n is 0 and R 8 (is H), propylene (the subscript n is 0, R 8 (is CH3), and (C4-C 20 )Alpha-olefin (where the subscript n is an integer from 1 to 19, R 8 (wherein is H or CH3). In some embodiments, the 1-alkene monomer is ethylene, propylene, 1-butene, 1-hexene, 1-octene, or any two or more combinations 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 a combination of ethylene and 1-butene, 1-hexene, or 1-octene.

[0137] Polyolefin polymers. Products obtained by polymerizing at least one 1-alkene monomer using a decaying hybrid catalyst or a multi-modulus catalyst system. Polymers or aggregates of polymers having constituent units derived from at least one 1-alkene monomer. For example, if at least one 1-alkene monomer is ethylene, the polyolefin polymer consists of a polyethylene homopolymer. If at least one 1-alkene monomer is ethylene and propylene, the polyolefin polymer consists of an ethylene / propylene copolymer. If at least one 1-alkene monomer is 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.

[0138] Polyolefin polymers may be homopolymers or copolymers. Polyolefin polymers may have a unimodal or multimodal molecular weight distribution. Polyolefin polymers prepared from multimodal catalyst systems have a multimodal (e.g., bimodal or trimodal) molecular weight distribution and include polyolefin polymer components with higher molecular weight (HMW) and polyolefin polymer components with lower molecular weight (LMW). The HMW polyolefin polymer component may be prepared by a decaying hybrid catalyst (e.g., its formula (III)), and the LMW polyolefin polymer component may be prepared by its metallocene catalyst.

[0139] Any compound, composition, formulation, material, mixture, or reaction product described herein is a compound 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 It is not required to contain any one of the chemical elements selected from the group consisting of W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, lanthanides, and actinides, provided that chemical elements required for the compound, composition, formulation, material, mixture, or reaction product (e.g., Zr required for zirconium compounds, C and H required for polyethylene, C, H and O required for alcohols) are not counted.

[0140] 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. "Does not contain" or "lacks" 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 elements is the IUPAC version as of May 1, 2018. "May" gives an optional choice, not a requirement. "Operative" means functionally possible or effective. "Optional" means either absent (or excluded) or present (or included). Properties can be measured using standard test methods and conditions. The range includes endpoints, subranges, and the total and / or decimal values ​​contained within them, except that integer ranges do not include decimals. Room temperature: 23℃ ± 1℃.

[0141] Unless otherwise specified, the definitions of terms used herein are derived from the IUPAC Compendium of Chemical Technology ("Gold Book") version 2.3.3, dated February 24, 2014. For convenience, some definitions are given below.

[0142] Alkanes (solvents). Formula C n H 2n+2 One or more acyclic, linear, or branched compounds of formula C m H 2m One or more cyclic compounds (wherein the formula, the subscripts n and m are independently integers between 5 and 50 (e.g., 6)). These compounds do not contain carbon-carbon double bonds (C=C) or terminal carbon-carbon triple bonds (C≡C).

[0143] 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) and a terminal carbon-carbon triple bond (C≡C).

[0144] Alkyl (substituted). A monovalent group formally created by substituting at least one hydrogen atom of an unsubstituted alkyl with a substituent (e.g., R s ).

[0145] Alkaryl (unsubstituted) or alkyl-substituted aryl. A monovalent group consisting of a hydrogen atom and at least seven carbon atoms, formally created by removing a hydrogen atom from the arenyl part of an alkyl-arene. For example, 4-methylphenyl.

[0146] Alkaryl (substituted) or alkyl-substituted aryl. A monovalent group formally created by substituting at least one hydrogen atom of an unsubstituted alkaryl with a substituent (e.g., R s ).

[0147] 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 part of an arenyl-alkane. For example, benzyl. It does not contain a carbon-carbon double bond (C=C) and a terminal carbon-carbon triple bond (C≡C).

[0148] Aralkyl (substituted). A monovalent group formally created by substituting at least one hydrogen atom of an unsubstituted aralkyl with a substituent (e.g., R s ).

[0149] 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. It does not contain a carbon-carbon double bond (C=C) and a terminal carbon-carbon triple bond (C≡C).

[0150] Aryl (substituted). At least one hydrogen atom of an unsubstituted aryl is substituted (e.g., R s A monovalent group formally created by substitution with ).

[0151] 4-(C1-C 20 ) Alkyl-substituted 1,3-butadiene molecule. Formula H2C=C(H)-C(H)=C(H)-(C1-C 20 Alkyl compounds.

[0152] (C # -C # (As a modification of the functional group). # or a numerical symbol 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-C 12 ) has 6 to 12 carbon atoms, (C1-C 20 ) has 1 to 20 carbon atoms.

[0153] -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 created by removing a hydrogen atom from the carbonyl carbon atom of a formic acid ester. For example, -C(=O)-O-phenyl or -C(=O)-O-ethyl. It does not contain carbon-carbon double bonds (C=C) or terminal carbon-carbon triple bonds (C≡C).

[0154] Coordination entity. An assembly consisting of a central atom (metal atom) that is attached to (bonded to) the surrounding arrangement of other groups of atoms (ligands).

[0155] Coordination number. The amount of other atoms directly linked or bonded to a given atom (e.g., M) in a chemical species. For example, in titanium tetrachloride, the coordination number of the titanium atom is 4.

[0156] Coordination site number. In coordination entities, this is the kappa (κ) number of donor groups from the same ligand bonded to the same central atom (e.g., bonded to M).

[0157] A bidentate organohetyl is a monovalent group that functions as a ligand for a metal M and consists of a carbon atom, a hydrogen atom, and at least one heteroatom selected from N, O, S, and P, wherein the monovalent group can be selected to doubly coordinate to the metal M via a carbon atom and one such heteroatom, or via two such heteroatoms. The monovalent ligand may provide M with a coordination number of 2 κ. A bidentate organohetyl may not contain terminal carbon-carbon double bonds (>C=CH2) and terminal carbon-carbon triple bonds (-C≡CH). Alternatively, it may not contain any carbon-carbon double bonds (C=C) and any terminal carbon-carbon triple bonds (C≡C).

[0158] A bidentate organohetterylene is a divalent group that functions as a ligand to a metal atom M and consists of a carbon atom, a hydrogen atom, and at least one heteroatom selected from N, O, S, and P, wherein the divalent group can be selected to doubly coordinate to the metal M via a carbon atom and one such heteroatom, or via two such heteroatoms. The divalent group may provide M with a coordination number of 2 κ. A bidentate organohetterylene may not contain terminal carbon-carbon double bonds (>C=CH2) and terminal carbon-carbon triple bonds (-C≡CH). Alternatively, it may not contain any carbon-carbon double bonds (C=C) and any terminal carbon-carbon triple bonds (C≡C).

[0159] Dry. Generally, a moisture content of less than 0 to 5 parts per million based on total weight. The material supplied to the reactor during polymerization is dry.

[0160] Effective dose. A sufficient amount to achieve the desired result.

[0161] Halogen atoms. Atoms selected from F, Cl, Br, and I, or F, Cl, and Br, or F and Cl, or F and Br, or Cl and Br, or F, or Cl.

[0162] Haptic number. In a coordination entity, the number of consecutive or uninterrupted sets of two or more atoms from the same ligand bonded to a central atom (e.g., M), known as eta (η). For example, the cyclopentadienyl group has five consecutive or uninterrupted carbon atoms coordinated to M, and therefore has a haptic number of 5 η(eta). 5 ("η 5 It may have '')). 4-(C1-C 20 The alkyl-substituted 1,3-butadiene molecule can coordinate to M via one of its two carbon-carbon double bonds, and M has a hapto number of 2 η (eta 2 ("η 2 It may provide η (eta) through both of its carbon-carbon double bonds, or M may have a haptic number of 4. 4 ("η 4 It may provide "))".

[0163] A heterohydrocarbyl is a monovalent group consisting of a carbon atom, a hydrogen atom, and at least one heteroatom selected from N, O, S, Si, and P, and is therefore an organic group, but with a free valence on the carbon atom. A heterohydrocarbyl may not contain terminal carbon-carbon double bonds (>C=CH2) and terminal carbon-carbon triple bonds (-C≡CH), or may not contain any carbon-carbon double bonds (C=C) and any terminal carbon-carbon triple bonds (C≡C). In some embodiments, 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, the R-type group is not a heterohydrocarbyl group.

[0164] High molecular weight (HMW) components. A subgroup of polymers that exhibits a peak at high molecular weight in a GPC plot of dW / dLog(MW) on the y-axis against Log(MW) on the x-axis.

[0165] Hydrocarbyl: A monovalent group formally derived by removing a hydrogen atom from a carbon atom of a hydrocarbon compound consisting of a carbon atom and a hydrogen atom. In some embodiments, each hydrocarbyl is independently alkyl, alkaryl, aryl, or aralkyl.

[0166] Hydrocarbylene. A divalent group formally derived by removing two hydrogen atoms from different carbon atoms in a hydrocarbon compound consisting of a carbon atom and a hydrogen atom.

[0167] Inert. Generally, in the polymerization reaction of the present invention, it is either not reactive (to a detectable degree) or does not interfere with it (to a detectable degree). The term “inert” as applied to the purge gas or ethylene feedstock means a molecular oxygen (O2) content of less than 0 to 5 million parts per million based on the total weight of the purge gas or ethylene feedstock.

[0168] An inert hydrocarbon solvent. A material that is liquid at 25°C and consists of carbon atoms, hydrogen atoms, and optionally one or more halogen atoms, and does not contain carbon-carbon double bonds or carbon-carbon triple bonds.

[0169] Leaving group. A group X(MX) that coordinates to metal M in the pre-catalyst (MX). Upon contact between the pre-catalyst and the activator, one such group is removed from the pre-catalyst, and the pre-catalyst becomes the activated catalyst (M). + ) and the by-product anion X - It is converted to the above A in some embodiments, a faster light-off catalyst and a decay light-off catalyst. - X - This is possible. Each single-dentation X is a leaving group that can provide M with a coordination number of 1 κ.

[0170] Ligand. A molecule or radical derived from a group 4 metal atom (Ti, Hf, or Zr) by removing a hydrogen atom that can coordinate to a transition metal atom (M).

[0171] Ligands Cp and L differ from leaving group X in that, when ligands Cp and L are present, they remain coordinated to the metal atom M in the pre-catalyst, the faster light-off catalyst prepared from the pre-catalyst, and the decaying hybrid catalyst prepared from the faster light-off catalyst. On the other hand, at least one leaving group X present in the pre-catalyst is absent in the faster light-off catalyst, and at least one leaving group X present in the faster light-off catalyst is replaced by a decaying leaving group R in the decaying hybrid catalyst.

[0172] Low molecular weight (LMW) components. A subgroup of high molecular weight components that have a peak in the low molecular weight range on a GPC plot of dW / dLog(MW) on the y axis against Log(MW) on the x axis.

[0173] Metallocene catalyst. A homogeneous or heterogeneous material containing a ligand-metal complex having two (substituted or unsubstituted) cyclopentadienyl groups (unbridged or bridged) to improve the rate of olefin polymerization. Substantially single-site or dual-site. Each metal is a transition metal Ti, Zr, or Hf.

[0174] A minute (1). A unit of time equal to 60.0 seconds. 0.1 minutes is equal to 6.0 seconds.

[0175] An organohetyl is a monovalent group consisting of a carbon atom, a hydrogen atom, and at least one heteroatom selected from N, O, S, and P, and is therefore an organic compound, but with one of the heteroatoms having a free valence. Organohetyls cannot contain terminal carbon-carbon double bonds (>C=CH2) or terminal carbon-carbon triple bonds (-C≡CH). Alternatively, they may not contain any carbon-carbon double bonds (C=C) or terminal carbon-carbon triple bonds (C≡C).

[0176] Organoheterylenes are divalent groups consisting of a carbon atom, a hydrogen atom, and at least one heteroatom selected from N, O, S, and P, and are therefore organic, but having two free valencies on one of the heteroatoms and other free valencies on the carbon atom or a different heteroatom. Organoheterylenes may not contain terminal carbon-carbon double bonds (>C=CH2) or terminal carbon-carbon triple bonds (-C≡CH). Alternatively, they may not contain any carbon-carbon double bonds (C=C) or terminal carbon-carbon triple bonds (C≡C).

[0177] Post-metallocene catalysts. Homogeneous or heterogeneous ligand-metal complexes that are neither metallocene catalysts nor hybrid catalysts. Non-metallocene molecular catalysts. Post-metallocene catalysts lack (substituted or unsubstituted) cyclopentadienyl group-containing ligands and improve the rate of olefin polymerization reactions. Substantially single-site or dual-site catalysts. Prepared by activating a post-metallocene pre-catalyst, which also lacks (substituted or unsubstituted) cyclopentadienyl ligands. Each metal is a transition metal Ti, Zr, or Hf.

[0178] Pre-catalyst (related to hybrid pre-catalysts). An inactive coordination entity or ligand-metal complex containing only one (substituted or unsubstituted) cyclopentadienyl group-containing ligand.

[0179] R-type group. "R" or "R 上付き文字 "R" is a group in a structural formula, and the superscript is a number, a letter, or both. 上付き文字 Examples of the base are, respectively, R 1 , R a1 , R a2 , R b1 And so on.

[0180] Tori (C1-C) 20 )hydrocarbyl silyl. Three independently selected (C1-C) 20 A monovalent group consisting of a silicon atom bonded to a hydrocarbyl group, with the silicon atom having its free valence.

[0181] Unsubstituted (C1-C5) alkyl groups. Alkyl groups selected from the group consisting of methyl, ethyl, propyl, butyl, and pentyl. Propyl may be n-propyl or 1-methylethyl. Butyl may be n-butyl, 1-methylpropyl, 2-methylpropyl, or 1,1-dimethylethyl. Pentyl may be n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, or 2,3-dimethylpropyl.

[0182] Ziegler-Natta catalyst. A heterogeneous material prepared by improving the polymerization reaction rate of olefins and contacting an inorganic titanium compound, such as titanium halide supported on a magnesium halide support (e.g., a magnesium chloride support), with an activator. [Examples]

[0183] Activator 1 (also called co-catalyst 1): Amine, bis(hydroalkyl hydride), methyl tetrakis(pentafluorophenyl) borate (1-).

[0184] Mineral oil: HYDROBRITE 380 PO white mineral oil from Sonneborn.

[0185] 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) is slurryed in 16.8 kg of toluene, and then 11.6 kg of 10 wt% MAO solution in toluene is added to obtain a mixture. Using a spray dryer set to 160°C with an outlet temperature of 70°C to 80°C, the mixture is introduced into the spray device of the spray dryer to generate droplets of the mixture, which are then brought into contact with a high-temperature nitrogen gas stream to evaporate the liquid from the mixture and obtain a powder. The powder is separated from the gas mixture using a cyclone separator, and the separated powder is discharged into a container to obtain SDMAO as a fine powder.

[0186] Preparation 1B: Preparation of a slurry of the activator formulation of Preparation 1A. The SDMAO powder of Preparation 1A is slurryed in a mixture of 10% by weight n-hexane and 78% by weight mineral oil to obtain an activator formulation having 12% by weight SDMAO / treated fumed silica solid in hexane / mineral oil.

[0187] Preparation 2: Preparation of spray-dried metallocene containing an activator formulation. Preparations 1A and 1B are repeated in sufficient quantities to provide a packing of 40 micromoles of Zr per gram of solid, except that the activator formulation is prepared by slurring 1.5 kg of treated fumed silica (CABOSIL TS-610) in 16.8 kg of toluene, followed by the addition of a 10 wt% MAO solution (11.1 kg) and (MeCp)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)ZrMe2 (wherein Me is methyl, Cp is cyclopentadienyl, and MeCp is methylcyclopentadienyl) in toluene. The resulting powder is slurred to obtain a 22 wt% solid activator formulation in 10 wt% isoparaffinic fluid and 68 wt% mineral oil.

[0188] Preparation 2A: Preparation of supported catalyst for use in the light-off batch reactor test method described below. In a nitrogen-purged glove box, 2.65 g of Cabosil TS-610 fumed silica is slurryed in 62.5 g of toluene in an oven-dried glass bottle until well dispersed. Then, 22 g of a toluene solution of 10 wt percent (wt%) methylaluminoxane (MAO) is added. The mixture is stirred for 15 minutes, and then a hybrid pre-catalyst (e.g., any one of pre-catalysts 1 to 2 described above) and any one of the kinetic modifier compounds KMC1 to KMC20 described above are added. The resulting mixture is stirred for 30 to 60 minutes. Using a Buchi Mini Spray Dryer B-290, the stirred mixture is spray-dried to obtain a dried sample with the following parameters: set temperature of 185°C, outlet temperature of 100°C, aspirator of 95%, and pump speed of 150 rpm.

[0189] A hybrid catalyst with faster light-off was prepared by filling a 40 ml (mL) glass vial, capped with a rubber septum and containing a poly(tetrafluoroethylene) (PTFE) coated magnetic stirrer, with 200 mg (SDMAO, prepared according to Preparation 1A) in a glove box under an inert N2 atmosphere. Then, a slurry of 10 micromoles (μmol) of a hybrid pre-catalyst (e.g., any one of pre-catalysts 1 to 2) in 0.2 mL of mineral oil was added. The resulting mixture was stirred for 5 minutes to obtain mineral oil slurries of each faster light-off hybrid catalyst supported on treated fumed silica. This procedure was repeated to prepare multiple lots of mineral oil slurries of the faster light-off hybrid catalyst, each supported on separate treated fumed silica. The hybrid catalyst can be prepared to have an aluminum-to-metal atom molar ratio (Al / M) of 120. The procedure described above is generally used to prepare catalysts for use in the light-off vial test method described later.

[0190] Damping Hybrid Catalyst: In a separate run, a certain amount of slurry containing 10 μmol of a faster-light-off catalyst (1) or (2) supported on treated fumed silica is mixed with 0.20 mL of a toluene solution of 10 μmol of a kinetic modifier compound (8), (3), or (15). The resulting mixture is stirred for 5 minutes to obtain a mineral oil / toluene slurry of a damping hybrid catalyst supported on treated fumed silica having KMC (8), (3), or (15), respectively.

[0191] Light-Off Vial Test Method: Add a mineral oil slurry of a faster-light-off catalyst supported on treated fumed silica, or a mineral oil / toluene slurry of a decayed post-metallocene catalyst supported on treated fumed silica, to a dry 40 mL glass vial. Add 5.5 mL or 11 mL of 1-octene to the vial and seal the vial with a septum cap. Record the addition time as T0 (0.00 min). Shake the vial manually (without stirring) to prevent agglomeration. Then, place the shaken vial on a hot plate / stirrer in a different well of a foam block. Immediately, insert a thermocouple into the vial through the septum cap below the liquid level inside and record the temperature (°C) of the vial contents at 5-second intervals from T0 until 300 minutes after T0. Download the temperature and time data to a spreadsheet and plot the thermodynamic profile for analysis. The results of these runs can be plotted graphically as a plot of the reaction temperature of the batch reactor contents on the y-axis versus the time starting from time 0 on the x-axis.

[0192] Inventive Examples ("IE") and Comparative Examples ("CE") were prepared by the light-off vial test method. An inventive example of a decaying hybrid catalyst was obtained by combining an effective amount of a specific kinetic modifier compound ("KMC") with a specific hybrid catalyst that lights up faster. Comparative Examples met one of three criteria (1) to (3): (1) contained a hybrid catalyst but not a kinetic modifier compound, (2) contained a hybrid catalyst but less than an effective amount of a kinetic modifier compound (e.g., CE1a), or (3) contained a metallocene catalyst and a kinetic modifier compound. The light-off effect was tested using the polyoctene of the hybrid and inventive examples that lights up faster, according to the light-off vial test method, and their relative activities were compared. In a separate vial, (a) mineral oil without 1-octene, (b) an example of a hybrid pre-catalyst, and (c) spray-dried methyl aluminoxane (SDMAO) without a kinetic modifier compound are pre-mixed for 10 minutes to obtain a slurry of a hybrid catalyst that lights off faster and does not contain 1-octene or a kinetic modifier compound. In another vial, (a) mineral oil without 1-octene, (b) a hybrid pre-catalyst, (c) SDMAO, and (d) a kinetic modifier compound are pre-mixed for 10 minutes to obtain a slurry of a decaying hybrid catalyst that does not contain 1-octene. After 10 minutes of pre-mixing (time under all conditions except (B)*), the same amount of 1-octene is added to each vial. After the addition of 1-octene, observe the temperature of the mixture increasing by 5°C to 120°C, or by 10°C to 110°C, or by any 10°C increment (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, 110°C to 120°C) as evidence of the activation of each catalyst. One of four sets of conditions is used: Condition (A) (used in Tables 1-4): 5.5 mL of Isopar-E, 8 μmol of M, the amount of SDMAO to obtain a molar ratio Al / M = 120, 0 μmol (CE) or 2 μmol (IE) of the kinetic modifier compound, 11 mL of 1-octene.Condition (B) (used in Table 5): 5.5 mL of Isopar-E, 10 μmol of M, the amount of SDMAO to obtain a molar ratio Al / M = 120, 0 μmol (CE) or 2 μmol (IE) of the kinetic modifier compound, 5.5 mL of 1-octene, where pre-mixing is 5 minutes instead of 10 minutes*. Condition (C) (used in Table 6): 5.5 mL of Isopar-E, 20 μmol of M, the amount of SDMAO to obtain a molar ratio Al / M = 120, the amount of the kinetic modifier compound to obtain 0 μmol (CE) or the amount to obtain the indicated molar ratio M / KMC (IE), 5.5 mL of 1-octene. Condition (D) (used in Table 7): 5.5 mL of Isopar-E, 2 μmol of M, the amount of SDMAO to obtain a molar ratio Al / M = 120, the amount of kinetic modifier compound to obtain 0 μmol (CE) or the amount to obtain the indicated molar ratio M / KMC (IE), 5.5 mL of 1-octene.

[0193] Table 1: Condition (A) and formula [ka] (Prophetically) expected results of the light-off vial test method performed using the pre-catalyst (1) [Table 1]

[0194] Table 2: Condition (A) and formula [ka] (Prophetically) expected results of the light-off vial test method performed using the pre-catalyst (2) [Table 2]

[0195] Examples of the Invention (A1) to (A20) (IE(A1) to IE(A20)): Using different pre-catalysts 1 and dynamic modifier compounds (1) to (20), 20 different damped hybrid catalysts are prepared (predictively) separately according to preparation 2A.

[0196] Examples of Invention (B1) to (B20) (IE(B1) to IE(B20)): Using different pre-catalysts 2 and dynamic modifier compounds (1) to (20), 20 different damped hybrid catalysts are prepared (predictively) separately according to preparation 2A.

[0197] Light-off batch reactor testing method. Outline: The relative kinetic profiles of a faster light-off catalyst and a decaying hybrid catalyst are observed in separate polymerizations performed 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 continuously added throughout a 3-hour polymerization run to maintain their concentrations at a steady state, but no further C2 is added. The ethylene uptake versus time is measured to express the catalytic kinetic profiles relatively.

[0198] Batch reactor drying and packing. Before each run, the batch reactor is dried for 1 hour. The dried batch reactor is then packed with 200 g of NaCl. The batch reactor and its contents are further dried by heating at 100°C for 30 minutes under an N2 atmosphere. Then, 3 g of silica-supported methylaluminoxane (SMAO) is added to capture the residue, the batch reactor is sealed, and the contents are stirred. The resulting dried batch reactor is then packed with 3.04 liters (L) of H2 and 1-hexane to obtain a molar ratio of 0.004 of 1-hexane to ethylene (C6 / C2). The batch reactor is pressurized with ethylene to 1.52 megapascals (MPa). The resulting system is allowed to reach a steady state.

[0199] Next, the batch reactor is packed with a catalyst (a catalyst that lights off faster or a decaying hybrid catalyst) and polymerization is started. The time of catalyst addition is recorded as time zero (time 0). The reactor temperature is raised to 93°C and maintained at that temperature for 1 to 5 hours. The reactor is cooled, vented, and the resulting polyolefin product is washed with water and methanol and dried to obtain a dry polyolefin product.

[0200] For each batch reactor run, the catalyst activity / polymerization productivity is calculated as the number of grams of dry polyolefin product produced per gram of catalyst added to the reactor per hour (g of PE / g of catalyst-hours). A higher number of g of PE / g of catalyst-hours indicates higher catalyst activity / polymerization productivity. The amount of ethylene uptake is recorded after 0.1 hours (0.1 hours of C2 uptake) (6 minutes) and after 1.0 hour (1 hour of C2 uptake) (60 minutes), and reported as the ratio of (C2 uptake per hour) / (C2 uptake per hour). All other things being equal, a larger ratio of (C2 uptake per hour) / (C2 uptake per hour) indicates greater catalyst light-off decay.

[0201] The melting temperature of the dried polyolefin product is determined using differential scanning calorimetry (DSC) according to ASTM D3418-08, with a scanning rate of 10°C per minute for a 10 mg sample, and using a second heating cycle. Some embodiments of the polyolefin products of the present invention, prepared by decaying hybrid catalysts, may have higher melting points than comparative polyolefin products prepared by their corresponding faster-light-off catalysts.

[0202] With light-off batch reactor runs using catalysts that light off faster, the majority of ethylene uptake can occur within the first few minutes of the start of the polymerization run (e.g., within 10 minutes from time 0). In contrast to decay hybrid catalysts, ethylene uptake is more evenly distributed throughout a longer polymerization run of 3 hours. These comparisons and the results of the invention can be shown as graphs plotting the reaction temperature of the batch reactor contents on the y-axis, or the uptake of ethylene monomer ("C2") on the y-axis, with the x-axis representing the time from the start of addition at time 0.

[0203] Comparative example using a metallocemone pre-catalyst. Table 3: Formula [ka] Comparative polymerization performance results of a light-off vial test method performed using metallocene pre-catalyst 1 ("MCN1") under condition (A) with comparative metallocene pre-catalyst 1 (wherein n-Bu is n-butyl). [Table 3]

[0204] As shown in Table 3, phenylacetylene did not have an intrinsic damping effect on the kinetics of the comparative metallocene catalyst prepared from MCN1.

[0205] Table 4: Formula [ka] Comparative polymerization results of a light-off batch reactor test method performed using metallocene pre-catalyst 1 ("MCN1") (wherein n-Bu is n-butyl) under condition (A). [Table 4]

[0206] As shown in Table 4, the kinetic modifier compounds did not inherently affect the kinetics of the comparative metallocene catalyst prepared from MCN1, causing any damping.

[0207] Table 5: Formula [ka] Comparative polymerization performance results of a light-off batch reactor test method performed using a comparative metallocene pre-catalyst 2 ("MCN2") (wherein n-Pr is n-propyl) under condition (A). [Table 5]

[0208] As shown in Table 5, the kinetic modifier compounds did not degrade polymerization productivity and did not have an inherently degrading effect on the catalytic activity of the comparative metallocene catalyst prepared from MCN2.

[0209] Table 6: Formula [ka] Comparative polymerization performance results of a light-off batch reactor test method performed using metallocene pre-catalyst 3 ("MCN3") under condition (A). [Table 6]

[0210] As shown in Table 6, the kinetic modifier compounds did not inherently affect the catalytic activity of the comparative metallocene catalyst prepared from MCN3. The present specification includes the following embodiments. Section 1: A method for producing a damped hybrid catalyst, A catalyst that turns off the lights faster, and the formula for the effective amount (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 The method involves combining a kinetic modifier compound ("KMC") with a catalyst under effective reaction conditions to obtain a damped light-off hybrid catalyst that exhibits a damped light-off kinetic profile (compared to the profile of a catalyst that light-offs faster than described above), A catalyst that turns off the lights faster than the above has the structural formula (I):(Cp)(L) k (X) x (I) was produced by activating the hybrid precatalyst. Formula (A 1 ), (B 1 ), or (C 1 ) inside, R 5 and R 6 Each of these is independently H or R 7 And, Each R 7 (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 However, together they form an (C3-C6) alkylene, but each R 7 It lacks a carbon-carbon double bond, Each (C1-C 20 Hydrocarbyl is independently unsubstituted or has 1 to 4 substituents R S It has been replaced with, Each substituent R SThese are, independently, halogen, unsubstituted (C1-C5)alkyl, -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 ( Selected from 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 (C1-C5)alkyl), -S(=O)2-N(unsubstituted (C1-C5)alkyl)2, -C(=)S-(unsubstituted (C1-C5)alkyl), and -COO(unsubstituted (C1-C5)alkyl), In formula (I), Metal M is Ti, Hf, or Zr. The subscript k is either 0 or 1. The subscript x is 1, 2, or 3. The Cp group is an unsubstituted cyclopentadienyl group, a hydrocarbyl-substituted cyclopentadienyl group, or an organoheterylene-substituted cyclopentadienyl group. Group L is a monodentate organohetyl group, Each X is a halogen atom, ((C1-C 20 )alkyl) 3-g -(phenyl) g Si-(wherein the formula, the subscript g is 0, 1, 2, or 3), CH3, (C2-C 20 )Alkyl-CH2, (C6-C 12 )aryl-((C0-C 10 )Alkylene)-CH2, (C1-C6)alkyl substitution (C6-C 12 ) Aryl, (C1-C6)alkoxy substitution (C6-C 12 )A monodentate group independently selected from aryl, (C1-C6)alkoxy-substituted benzyl, and (C1-C6)alkyl-substituted benzyl. method. Section 2: A catalyst that turns off the lights faster than the above is given by formula (II):(Cp)(L)k (X) x-1 A - (II) is, In the formula, the subscripts k and x, the metal M, the ligand L, and the leaving group X are as defined for formula (I), The aforementioned damped hybrid catalyst is given by formula (III): (Cp)(L) k (X) x-2 (R)A - (III) is In the formula, the subscripts k and x, the metal M, and the ligand L are as defined for formula (I), and each X is a monodentate base as defined for formula (I). A - is an anion (used to formally balance the positive charge of metal M), R is given by equation (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 ) is a ligand of (C), and in the formula, R 5 ~R 7 These are, respectively, equation (A 1 ), (B 1 ), or (C 1 ) is as previously defined, The method described in item 1. Section 3: The aforementioned hybrid precatalyst is given by formula (Ia):CpM(X) x (Ia) is, In the formula, the metal M is Ti, Hf, or Zr, the subscript x is 1, 2, or 3, Cp is the organoheterylene-substituted cyclopentadienyl group, and each X is as defined for formula (I). The method described in item 1 or 2. Section 4: The hybrid precatalyst of formula (I) is, formula (Ib): (Cp)(L)(X) x(Ib) is, In the formula, M, L, X, and the subscript x are as defined for formula (I), and Cp is the unsubstituted cyclopentadienyl group or the hydrocarbyl-substituted cyclopentadienyl group. The method described in item 1 or 2. Section 5: The aforementioned dynamic modifier compound is of formula (A 1 ):R 5 -C≡CR 6 (A 1 ) is, Phenylacetylene, (substituted phenyl)acetylene, diphenylacetylene, substituted diphenylacetylene, cycloalkylacetylene, formula HC≡CSi(phenyl) h ((C1-C 20 )alkyl) 3-h Acetylene (wherein the formula, the subscript h is an integer between 0 and 3), and the formula HC≡C-(CH2) m Selected from acetylene CH3 (where the subscript m is an integer between 1 and 15), The method described in any one of items 1 to 4. Item 6: The aforementioned dynamic modifier compound is of formula (B 1 ) (R 5 )2C=C=C(R 6 )2(B 1 ) is, Selected from cycloalkylalenes, alkylalenes, dialkylalenes, trialkylalenes, trialkylsilylalenes, vinylidenecycloalkanes, and alkyl esters of allene carboxylic acids, The method described in any one of items 1 to 4. Section 7: The aforementioned dynamic modifier compound is of formula (C 1 ) (R 5 )(R 7 )C=C(R 6 )(R 7 ) (C 1 ) is, Formula (C 1 The kinetic modifier compound in the above is an internal alkene. The method described in any one of items 1 to 4. Section 8: The method according to any one of claims 1 to 7, further comprising: preparing a mixture of the damped hybrid catalyst, a support material, and an inert hydrocarbon solvent; and removing the inert hydrocarbon solvent from the mixture to obtain the damped hybrid catalyst disposed on the support material. Section 9: The hybrid precatalyst of formula (I) is the one of formula (Ia)-1, [ka] During the ceremony, Each group R a1 and R a2 (C1-C 20 ) is alkyl, Each group R a3 Independently, H or (C1-C 20 ) is alkyl, Each subscript character 1-5 is independently 0, 1, 2, 3, 4, or 5. M, X, and the subscript x are defined as they are for formula (I). The method described in any one of items 1 to 3. Section 10: The aforementioned hybrid precatalyst is of formula (Ib)-1, [ka] During the ceremony, Each group R b1 (C1-C 20 ) is alkyl, Each group R b2 Independently, H or (C1-C 20 ) is alkyl, Each subscript character 1-5 is independently 0, 1, 2, 3, 4, or 5. M and X are as defined for equation (I), The method described in any one of paragraphs 1, 2, and 4. Section 11: A damped hybrid catalyst prepared by the method described in any one of items 1 to 10. Section 12: A method for supplying a hybrid catalyst to a slurry phase or gas-phase polymerization reactor containing a moving bed of olefin monomer and polyolefin polymer, The decayed hybrid catalyst is prepared outside the reactor according to the method described in any one of items 1 to 10. The decayed hybrid catalyst is supplied in neat form, or as a solution or slurry of the decayed hybrid catalyst in an inert hydrocarbon liquid, to the slurry phase or gas-phase polymerization reactor through a supply line that does not contain olefin monomers. Methods that include... Section 13: A multi-modal catalyst system comprising a decaying hybrid catalyst as described in Section 11, and at least one second catalyst selected from the group consisting of non-decaying hybrid catalysts, different decaying hybrid catalysts, post-metallocene catalysts, and metallocene catalysts as described herein. Section 14: A method for producing a polyolefin polymer, comprising contacting at least one 1-alkene monomer with a decayed hybrid catalyst prepared by any one of the methods described in items 1 to 10, or a multimodal catalyst system described in item 13, in a slurry phase or gas-phase polymerization reactor containing a moving bed of polyolefin resin, under slurry phase or gas-phase polymerization conditions, thereby producing the polyolefin polymer.

Claims

1. A method for producing a damped light-off hybrid catalyst, A catalyst with faster light-off, and an effective amount of formula (A １ ): R ５ -C≡C-R ６ , formula (B １ ): (R ５ ) ２ C=C=C(R ６ ) ２ , or formula (C １ ): (R ５ )(R ７ )C=C(R ６ )(R ７ ) of a kinetic modifier compound ("KMC") are combined under effective reaction conditions to obtain a deactivated light-off hybrid catalyst that exhibits a deactivated light-off kinetic profile (compared to the profile of the faster light-off catalyst described above). A catalyst that turns off the lights faster than the above is of formula (II): (Cp)M(L) k(X) x-1 A-, and formula (I): (Cp)M(L) ｋ (X) ｘ It was produced by activating a hybrid pre-catalyst. The aforementioned damped light-off hybrid catalyst is of formula (III): (Cp)M(L) k(X) x-2(R)A-, Formula (A １ ), (B １ ), or (C １ ) inside, R ５ and R ６ Each of these is independently H or R ７ And, Each R ７ (C １ -C ２０ ) Hydrocarbyl, -C(=O)-O-(unsubstituted C １ -C ２０ ) Hydrocarbyl), (C １ -C １９ ) Heterohydrocarbyl, or tri((C １ -C ２０ ) Hydrocarbyl silyl or two R ７ But together (C ３ -C ６ ) Forms alkylene, however each R ７ It lacks a carbon-carbon double bond, Each (C １ -C ２０ Hydrocarbyl is independently unsubstituted or has 1 to 4 substituents R Ｓ It has been replaced with, Each substituent R Ｓ These are, independently, halogen, unsubstituted (C １ -C ５ ) Alkyl, -C≡CH, -OH, (C １ -C ５ ) Alkoxy, -C(=O)-(unsubstituted (C １ -C ５ )alkyl), -NH ２ , -N(H) (unsubstituted (C １ -C ５ )alkyl), -N (unsubstituted (C １ -C ５ )alkyl) ２ , -COOH, -C(=O)-NH ２ , -C(=O)-N(H) (unsubstituted (C １ -C ５ )alkyl),-C(=O)-N(unsubstituted(C １ -C ５ )alkyl) ２ , -S- (unsubstituted (C １ -C ５ )alkyl), -S (=O) ２ -(unsubstituted (C １ -C ５ )alkyl), -S (=O) ２ -NH ２ , -S (=O) ２ -N(H) (unsubstituted (C １ -C ５ )alkyl), -S (=O) ２ -N (unsubstituted (C １ -C ５ )alkyl) ２ , -C(=)S-(unsubstituted (C １ -C ５ )alkyl), and -COO(unsubstituted (C １ -C ５ Selected from alkyl, In equations (I), (II), and (III), Metal M is Ti, Hf, or Zr. The subscript k is either 0 or 1. The subscript x is 1, 2, or 3. The Cp group is an unsubstituted cyclopentadienyl group, a hydrocarbyl-substituted cyclopentadienyl group, or an organoheterylene-substituted cyclopentadienyl group. Group L is a monodentate organohetyl group, Each X is a halogen atom, ((C １ -C ２０ )(alkyl)) ３－ｇ -(phenyl) ｇ Si - (where 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, and is a monodentate group independently selected from A- is an anion (used to formally balance the positive charge of metal M), R is a ligand in equation (A): -C(R5) = C(X)R6, equation (B): -C(R5)2 -C(X) = C(R6)2, or equation (C): -C(R5)(R7)-C(X)(R6)(R7), where R5 to R7 are as previously defined for equation (A1), equation (B1), or equation (C1), respectively, and X is as previously defined for equation (I), equation (II), and equation (III). method.

2. The aforementioned hybrid precatalyst is given by formula (Ia): CpM(X) ｘ It is, In the formula, the metal M is Ti, Hf, or Zr, the subscript x is 1, 2, or 3, Cp is the organoheterylene-substituted cyclopentadienyl group, and each X is as defined for formula (I). The method according to claim 1.

3. The aforementioned hybrid precatalyst is given by formula (Ib): (Cp)M(L)(X) ｘ It is, In the formula, M, L, X, and the subscript x are as defined for formula (I), and Cp is the unsubstituted cyclopentadienyl group or the hydrocarbyl-substituted cyclopentadienyl group. The method according to claim 1.

4. The aforementioned dynamic modifier compound is of formula (A １ ): R ５ -C≡C-R ６ It is, Phenylacetylene, (substituted phenyl)acetylene, diphenylacetylene, substituted diphenylacetylene, cycloalkylacetylene, formula HC≡CSi(phenyl) ｈ ((C １ -C ２０ )alkyl) ３－ｈ Acetylene (wherein the formula, the subscript h is an integer from 0 to 3), and formula HC≡C-(CH ２ ) ｍ CH ３ Selected from acetylene (wherein the formula, the subscript m is an integer from 1 to 15), The method according to any one of claims 1 to 3.

5. The aforementioned dynamic modifier compound is of formula (B １ ): (R ５ ) ２ C = C = C (R ６ ) ２ It is, Selected from cycloalkylalenes, alkylalenes, dialkylalenes, trialkylalenes, trialkylsilylalenes, vinylidenecycloalkanes, and alkyl esters of allene carboxylic acids, The method according to any one of claims 1 to 3.

6. The aforementioned dynamic modifier compound is of formula (C １ ): (R ５ ) (Caution ７ ) C = C(R ６ ) (Caution ７ ) Formula (C １ The kinetic modifier compound in the above is an internal alkene. The method according to any one of claims 1 to 3.

7. The method according to any one of claims 1 to 6, further comprising: preparing a mixture of the damping hybrid catalyst, a support material, and an inert hydrocarbon solvent; and removing the inert hydrocarbon solvent from the mixture to obtain the damping hybrid catalyst disposed on the support material.

8. The aforementioned hybrid precatalyst is of formula (Ia)-1, 【Chemistry 1】 During the ceremony, Each group R ａ１ and R ａ２ (C １ -C ２０ ) is alkyl, Each group R ａ３ H or (C １ -C ２０ ) is alkyl, Each subscript 1-5 is independently 0, 1, 2, 3, 4, or 5. M, X, and the subscript x are defined as they are for formula (I), The method according to claim 1 or 2.

9. The aforementioned hybrid precatalyst is of formula (Ib)-1, 【Chemistry 2】 During the ceremony, Each group R ｂ１ (C １ -C ２０ ) is alkyl, Each group R ｂ２ H or (C １ -C ２０ ) is alkyl, Each subscript 1-5 is independently 0, 1, 2, 3, 4, or 5. M and X are as defined for equation (I), The method according to any one of claims 1 to 3.

10. A method for supplying a hybrid catalyst to a slurry phase or gas-phase polymerization reactor containing a moving bed of olefin monomer and polyolefin polymer, The damped hybrid catalyst is prepared outside the reactor according to the method described in any one of claims 1 to 9. The decayed hybrid catalyst is supplied in neat form, or as a solution or slurry of the decayed hybrid catalyst in an inert hydrocarbon liquid, to the slurry phase or gas-phase polymerization reactor through a supply line that does not contain olefin monomers. Methods that include...

11. A method for producing a polyolefin polymer, comprising contacting at least one 1-alkene monomer with a decayed hybrid catalyst produced by any one of claims 1 to 9 in a slurry phase containing a moving bed of polyolefin resin or in a gas-phase polymerization reactor under slurry phase or gas-phase polymerization conditions, thereby producing the polyolefin polymer.

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