Attenuated post-metallocene catalyst

Abstract

A method for preparing a post-metallocene catalyst with reduced ignition, the method comprising combining a catalyst with a faster ignition with an effective amount of a kinetic modifier compound of formula (A 1 ), (B 1 ), or (C 1 ) as defined herein: 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 )(R 7 )(C 1 ) under effective reaction conditions to obtain a post-metallocene catalyst with reduced ignition, the post-metallocene catalyst with reduced ignition exhibiting a monomer absorption curve with reduced ignition (relative to the monomer absorption curve of the catalyst with a faster ignition); wherein the catalyst with a faster ignition has been prepared by activating a post-metallocene precatalyst of structural formula (I) as defined herein; and related methods, compositions, and uses.

Description

[0001] Olefin polymerization catalysts, processes, and polyolefins made therefrom. Background Art

[0002] US 6,803,339 B2 was granted to Richard A. Hall et al. (“Hall”) and is assigned to BP Corporation North America Inc. Hall noted problems with metallocene catalysts when feeding them into a polymerization reactor in an olefin monomer stream. “Metallocene catalysts are difficult to use directly in conventional polymerization processes, and especially in gas phase processes where the catalyst system is to be dispersed in a hydrocarbon or monomer and metered into the reactor through a feed line. Supported metallocene catalysts have optimal activity when pre-activated, i.e., when combined with a cocatalyst component prior to introduction into the reactor. Dispensing such catalysts in an olefin monomer stream for direct feed into a reactor system results in polymer formation and severe plugging of the feed line. In addition, polymerization occurs before the catalyst system is fully and evenly dispersed through the polymer bed in the reactor, resulting in highly active hot spots that promote the formation of lumps and plating. The reactor fouls rapidly, reducing catalyst productivity and requiring frequent shutdowns to clean the reactor.” (Column 2, lines 50 to 65; emphasis added.)

[0003] Hall elaborated on solutions previously attempted by others. “Temporarily reducing the activity of metallocene catalysts has been described in the art. For example, adding a dialkylborane or dialkylaluminum to the reactor during polymerization to temporarily retard the activity of the metallocene catalyst has been disclosed as a method for process control. However, only partial retardation of catalyst activity is achieved by such treatment. When dispersed in the monomer feed stream, catalysts treated directly with a dialkylborane or dialkylaluminum retain sufficient activity to initiate polymerization. In addition, the recovery period is very short, too short to allow the catalyst system to be fully dispersed in the stirred reactor gas phase reactor bed before catalyst recovery and polymerization proceed.” (Column 3, lines 14 to 26; emphasis added.)

[0004] Hall sought a method for temporarily and reversibly passivating a metallocene catalyst, whereby the catalyst activity is reduced to a level that will allow feeding the catalyst into a reactor in contact with an olefin monomer and fully dispersing the catalyst in the reactor polymer bed before reactivation (Column 3, lines 49 to 55). That is, Hall sought a method that would allow feeding a temporarily substantially deactivated metallocene catalyst in an olefin monomer stream into a polymerization reactor.

[0005] Hall's solution relates to metallocene catalysts that can be temporarily and reversibly passivated by contact with an effective amount of an unsaturated hydrocarbon passivating compound (abstract). Hall's solution also relates to a method for temporarily and reversibly passivating a metallocene catalyst, wherein a fully activated metallocene catalyst can be temporarily and reversibly passivated by contact with an effective amount of a passivating compound (column 3, lines 58 to 62). The temporarily and reversibly passivated metallocene catalyst is further characterized as a potential olefin polymerization catalyst and will have a substantially reduced activity for polymerizing olefins (column 3, lines 63 to 66).

[0006] Accordingly, Hall sought to temporarily substantially inactivate (poison) the metallocene catalyst such that in an olefin monomer stream, the resulting temporarily substantially inactivated metallocene catalyst could be fed into a reactor and the temporarily substantially inactivated metallocene catalyst would not polymerize the olefin monomers in the feed stream or plug the feed line. This would give Hall time to disperse the temporarily substantially inactivated metallocene catalyst in the polymer bed in the reactor, and wherein the temporarily substantially inactivated metallocene catalyst would be reversibly reactivated. Thus, Hall's metallocene catalyst is either fully activated or substantially inactivated, and in the presence of olefin monomers in an olefin monomer feed stream, the substantially inactivated metallocene catalyst is fed into the reactor. SUMMARY OF THE INVENTION

[0007] We have found problems with feeding a post-metallocene catalyst (i.e., a catalyst without a cyclopentadienyl ligand) separately (i.e., separate from the monomer and polyolefin polymer particles) into a gas-phase olefin polymerization reactor. Olefin polymerization is an exothermic reaction that can be carried out in the solution phase, slurry phase, or gas phase. The nature of the gas-phase polymerization reaction is such that it has a minimum mass for absorbing the heat of the reaction exotherm. We have found that even when the active post-metallocene catalyst is fed separately from the olefin monomer feed (and thus, separate from the active polyolefin polymer particles) into a gas-phase polymerization reactor containing an olefin monomer and a moving bed of polyolefin polymer, such as when the active post-metallocene catalyst is fed into the reactor as a solution or slurry in an inert hydrocarbon solvent (e.g., an alkane or xylene), once the active post-metallocene catalyst is inside the reactor and subjected to polymerization conditions (e.g., high temperature and high pressure), the active post-metallocene catalyst may ignite too quickly in the gas-phase polymerization reactor. That is, upon feeding (e.g., injecting) the post-metallocene catalyst, and before the "quickly igniting" catalyst can be fully dispersed into the moving resin bed, the catalyst begins to form polymer particles in the reactor near the catalyst injection site. This generates heat locally faster than it can be absorbed, causing the polymer particles to fuse together, thereby forming aggregates. These aggregates foul the reactor components and / or degrade the properties of the polyolefin product.

[0008] In addition, when a post-metallocene catalyst with a faster light-off is paired with a metallocene catalyst with a slower light-off, a multimodal (e.g., bimodal or trimodal) catalyst system with mismatched reactivity may be produced in the reactor. This causes the flow index and / or density of the polyolefin polymer particles to vary undesirably with particle size.

[0009] These problems do not occur with metallocene catalysts, which are catalysts containing two cyclopentadienyl groups (independently unsubstituted or substituted). In the above cases, the light-off of the metallocene catalyst is relatively slow.

[0010] Our technical solution to the problem of "faster light-off" post-metallocene catalysts is as follows: an effective amount of a kinetic modifier compound is used to change the molecular structure of the post-metallocene catalyst so that the resulting structurally modified post-metallocene catalyst has a new molecular structure and remains active, but exhibits a characteristic monomer absorption curve with reduced light-off when fed separately from the olefin monomer feed to a gas phase polymerization reactor ("post-metallocene catalyst with reduced light-off", or more simply "reduced post-metallocene catalyst"). For example, the reduced monomer absorption curve may include a peak reaction temperature (Temperature) of the reduced post-metallocene catalyst relative to the faster light-off catalyst from which it is prepared. peak ) for a longer period of time and / or Temp peak The value of is low. The length of delay is long enough to reduce or prevent aggregate formation, which in turn delays or prevents fouling of reactor components, and / or minimizes the damage to the characteristics of the polyolefin product thus prepared. Although the start is delayed, under all other conditions being equal, many embodiments of the weakened post-metallocene catalyst show that the catalytic activity / polymerization productivity (expressed as the grams of the prepared dry polyolefin product / grams of the catalyst added to the reactor per hour (gPE / gcat-hr)) is not significantly less than the catalytic activity / polymerization productivity of the non-metallocene catalyst that ignites faster, and in some embodiments may be greater than the catalytic activity / polymerization productivity of the non-metallocene catalyst that ignites faster. This result is unpredictable. DETAILED DESCRIPTION

[0011] The entire content of the Summary section is incorporated herein by reference.Additional embodiments follow; some embodiments are numbered for ease of reference.

[0012] Aspect 1. A method for preparing a weakened post-metallocene catalyst ("a post-metallocene catalyst with weakened light-off"), the method comprising reacting a catalyst with a faster light-off under effective reaction conditions with an effective amount of a catalyst of formula (A 1 )、(B 1 ) or (C 1 ): R 5 -C≡CR 6(A 1 )、(R 5 )2C=C=C(R 6 )2(B 1 ) or (R 5 )(R 7 )C=C(R 6 )(R 7 )(C 1 ) kinetic modifier compound (“KMC”) combinations to obtain a post-metallocene catalyst with reduced ignition, and the post-metallocene catalyst with reduced ignition exhibits a monomer absorption curve with reduced ignition (relative to the monomer absorption curve of the catalyst with faster ignition); wherein the catalyst with faster ignition has been prepared by activating a post-metallocene precatalyst of structural formula (I): wherein in formula (A 1 ), (B 1 ) or (C 1 ), each of R 5 and R 6 is independently H or R 7 , and each R 7 is independently a (C 1 -C 20 ) hydrocarbyl group, -C(=O)-O-(unsubstituted C1-C 20 ) hydrocarbyl group), (C1-C 19 ) heterohydrocarbyl group or tris((C1-C 20 ) hydrocarbyl group) silyl group, or two R 7 together form a (C3-C6) alkylene group; provided that each R 7 lacks a carbon-carbon double bond; wherein each (C1-C 20 ) hydrocarbyl group is independently unsubstituted or substituted with 1 to 4 substituent groups R S ; wherein each substituent group R SIndependently selected from halogen (e.g., F), unsubstituted (C1-C5) alkyl (e.g., CH3), -C≡CH, -OH, (C1-C5) alkoxy, -C(=O)-(unsubstituted (C1-C5) alkyl), -NH2, -N(H)(unsubstituted (C1-C5) alkyl), -N(unsubstituted (C1-C5) alkyl)2, -COOH, -C(=O)-NH2, -C(=O)-N(H)(unsubstituted (C1-C5) alkyl), -C(=O)-N(unsubstituted (C1-C5) alkyl)2, -S-(unsubstituted (C1-C5) alkyl), -S(=O)2-(unsubstituted (C1-C5) alkyl), -S(=O)2-NH2, -S(=O)2-N(H)(unsubstituted (C1-C5) alkyl), -S(=O)2-N(unsubstituted (C1-C5) alkyl)2, -C(=)S-(unsubstituted (C1-C5) alkyl) and -COO(unsubstituted (C1-C5) alkyl); and wherein M is Ti, Zr or Hf, alternatively M is Zr or Hf; R 1 to R 4 each of which is independently H or CH3; each R H is independently (C1-C 20 ) alkyl (e.g., (C1-C4) alkyl, e.g., CH3); and X is independently a monodentate group selected independently from: a halogen atom; ((C1-C 20 ) alkyl) 3-g -(phenyl) g Si-, where the subscript g is 0, 1, 2 or 3; CH3; (C2-C 20 ) alkyl-CH2; (C6-C 12 ) aryl-((C0-C 10 ) alkylene)-CH2 (e.g., when (C6-C 12 ) aryl is phenyl and (C0-C 10 ) alkylene is (C0) alkylene, benzyl); (C1-C6) alkyl-substituted (C6-C 12 ) aryl; (C1-C6) alkoxy-substituted (C6-C 12 ) aryl; (C1-C6) alkoxy-substituted benzyl; and (C1-C6) alkyl-substituted benzyl; or one X is a 4-(C1-C 20 ) alkyl-substituted 1,3-butadiene molecule, and each of the remaining Xs, if any, is independently the monodentate group X; provided that at least one X is (C7-C 20)Arylalkyl (e.g., benzyl). In some aspects, M is Zr, alternatively M is Hf. At least one group X serves as a leaving group during the activation step, and optionally, at least one group X serves as a leaving group during the combination step. In some embodiments, at least one X does not leave but remains coordinated to M. In some aspects, at least one X is (C6-C 12 )aryl-((C0-C 10 )alkylene)-CH2 (e.g., benzyl). In some aspects, each X is independently (C6-C 12 )aryl-((C0-C 10 )alkylene)-CH2; alternatively, one X is (C6-C 12 )aryl-((C0-C 10 )alkylene)-CH2 (e.g., benzyl), and the other X is F, Cl, or methyl; alternatively, each X is benzyl. To eliminate all doubts, the monodentate group X does not contain a carbon-carbon double bond or a carbon-carbon triple bond, i.e., the monodentate group X is not an alkenyl group or an alkynyl group. In some aspects, each R 7 is independently a (C1-C 20 )hydrocarbyl group, which may independently be unsubstituted or substituted with 1 to 3 substituting groups selected from halogens (e.g., F) and alkyl groups (e.g., CH3), provided that each R 7 lacks a carbon-carbon double bond. The post-metallocene pre-catalyst of formula (I) can be any of those described in US 6,967,184 B2.

[0013] Aspect 2. The method according to aspect 1, wherein the faster light-off catalyst has formula (II): And wherein the attenuated post-metallocene catalyst has formula (III): Wherein each of the groups R 1 to R 4 and R H and X are as defined in formula (I); wherein A - is an anion (for formally balancing the positive charge of the metal M); and wherein R are ligands of formula (A), (B), or (C): -C(R 5 )=C(X)R 6 (A), -C(R 5 )2-C(X)=C(R 6 )2 (B), or -C(R 5 )(R 7 )-C(X)(R 6 )(R 7 ) (C); and wherein R 5 to R 7 are as previously in formula (A 1), (B 1 ) or (C 1 ) as defined. To remove all doubts, the ligand R of formula (A), (B) or (C) is respectively obtained from or derived from the kinetic modifier compound of formula (A 1 ), (B 1 ) or (C 1 ). To remove all doubts, each ligand R of formula (A) and (B) contains a carbon-carbon double bond (i.e., an alkenyl group). To remove all doubts, the ligand R has a different structure from the leaving group X, i.e., the definition of the ligand R does not overlap with the definition of the leaving group X.

[0014] Aspect 3. The method according to aspect 1 or 2, wherein in the post-metallocene pre-catalyst of formula (I), each of R 1 to R 4 is H and each X is benzyl, and the post-metallocene pre-catalyst of formula (I) is pre-catalyst (1): ("pre-catalyst 1"), wherein M is Hf or Zr. The pre-catalyst (1) is synthesized by repeating the procedure 2 from line 53 of column 33 to line 9 of column 34 of US6967184B2.

[0015] Aspect 4. The method according to any one of aspects 1 to 3, wherein in the post-metallocene pre-catalyst of formula (I), each of R 1 to R 4 is H and each R H is CH3, and the attenuated post-metallocene catalyst of formula (III) is the ignition-attenuated catalyst (1): wherein A - is an anion (for formally balancing the positive charge of the metal M); and wherein R is respectively of formula (A), (B) or (C): -C(R 5 )=C(X)R 6 (A), -C(R 5 )2-C(X)=C(R 6 )2 (B) or -C(R 5 )(R 7 )-C(X)(R 6 )(R 7 ) (C) ligand; and wherein R 5 to R 7 are respectively as defined in the previous formula (A 1 ), (B 1 ) or (C 1 ). M is Hf or Zr.

[0016] Aspect 5. The method according to any one of aspects 1 to 4, wherein the kinetic modifier compound is described by any one of the limitations (i) to (vi): (i) having the formula (A 1 ), or (B 1 ); (ii) having the formula (A 1 ), or (C 1 ); (iii) having the formula (B 1 ), or (C 1 ); (iv) having the formula (A 1 ); (v) having the formula (B 1 ); or (vi) having the formula (C 1 ). Without being bound by theory, it is believed and has been found that the kinetic modifier compounds of formula (A 1 ) and (B 1 ) produce the R ligands (A) and (B) respectively, and each of the ligands (A) and (B) has a carbon-carbon double bond as a common structural feature between them. In some aspects, the kinetic modifier compound consists of carbon atoms and hydrogen atoms. In other aspects, the kinetic modifier compound consists of carbon atoms, hydrogen atoms, and at least one atom selected from halogen atoms, O, N, and Si; alternatively, the kinetic modifier compound consists of carbon atoms, hydrogen atoms, and at least one halogen atom; alternatively, the kinetic modifier compound consists of carbon atoms, hydrogen atoms, and at least one atom selected from the following: O, N, and Si; alternatively O or N; alternatively O and Si; alternatively N and Si; alternatively O; alternatively N; alternatively Si.

[0017] Aspect 6. The method according to any one of aspects 1 to 5, wherein the kinetic modifier compound has the formula (A 1 ): R 5 -C≡C-R 6 (A 1 ), and the kinetic modifier compound is selected from: phenylacetylene; (substituted phenyl)acetylene; diphenylacetylene; substituted diphenylacetylene; cycloalkylacetylene; the acetylene of the formula HC≡CSi(phenyl) h ((C1-C 20 )alkyl) 3-h , wherein the subscript h is an integer from 0 to 3; and the acetylene of the formula HC≡C-(CH2) m CH3, wherein the subscript m is an integer from 1 to 15, alternatively from 1 to 10, alternatively from 2 to 15. In formula (III) of aspect 2, the corresponding ligand R can be selected from: -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-C20 )(alkyl) 3-h , wherein the subscript h is as defined above; -C(H)=C(X)-(CH2) m CH3, wherein the subscript m is as defined above; or -CH2-C(X)=C(alkyl)2. The subscript m can be an integer from 8 to 15, alternatively from 1 to 7, alternatively from 2 to 6, alternatively from 2 to 4, alternatively from 1 to 3. (Substituted phenyl)acetylene can be (fluorine-substituted phenyl)acetylene or (methyl-substituted phenyl)acetylene; alternatively, 3,4-difluorophenylacetylene, 3,5-difluorophenylacetylene, 3-fluorophenylacetylene, 4-fluorophenylacetylene or 2,4,5-trimethylphenylacetylene.

[0018] Aspect 7. The method according to any one of Aspects 1 to 6, wherein the kinetic modifier compound has the formula (A 1 ): R 5 -C≡C-R 6 (A 1 ), and the kinetic modifier compound of formula (A 1 ) is selected from the group consisting of any one of KMC1 to KMC14: kinetic modifier compound (1) ("KMC1"): phenylacetylene (i.e., (C6H5)C≡CH); kinetic modifier compound (2) ("KMC2"): 4-methylphenyl-acetylene (i.e., (4-CH3-C6H4)C≡CH); kinetic modifier compound (3) ("KMC3"): 2,4,5-trimethylphenyl-acetylene (i.e., (2,4,5-(CH3)3-C6H2)C≡CH); kinetic modifier compound (4) ("KMC4"): 1,3,5-triethynylbenzene (i.e., 1,3,5-tri(HC≡C)3(C6H3)); kinetic modifier compound (5) ("KMC5"): diphenylacetylene (i.e., (C6H5)C≡C(C6H5)); kinetic modifier compound (6) ("KMC6"): 3-fluorophenyl-acetylene (i.e., (3-F-C6H4)C≡CH); kinetic modifier compound (7) ("KMC7"): 4-fluorophenyl-acetylene (i.e., (4-F-C6H4)C≡CH); kinetic modifier compound (8) ("KMC8"): 3,4-difluorophenyl-acetylene (i.e., (3,4-F2-C6H3)C≡CH); kinetic modifier compound (9) ("KMC9"): 3,5-difluorophenyl-acetylene (i.e., (3,5-F2-C6H3)C≡CH); kinetic modifier compound (10) ("KMC10"): cyclohexylacetylene (i.e., C6H 11C≡CH); kinetic modifier compound (11) (“KMC11”): phenyldimethylsilylacetylene (i.e., (C6H5)(CH3)2SiC≡CH); kinetic modifier compound (12) (“KMC12”): 1-pentyne (i.e., CH3(CH2)2C≡CH); kinetic modifier compound (13) (“KMC13”): 1-octyne (i.e., CH3(CH2)5C≡CH); and kinetic modifier compound (14) (“KMC14”): 1,7-octadiyne (i.e., HC≡C(CH2)4C≡CH).

[0019] Aspect 8. The method according to any one of Aspects 1 to 5, wherein the kinetic modifier compound has the formula (B 1 ): (R 5 )2C═C═C(R 6 )2(B 1 ), and the kinetic modifier compound is selected from: cycloalkylallenes; alkylallenes; dialkylallenes; trialkylallenes; trialkylsilylallenes; vinylidenecycloalkanes; and alkyl esters of allenoic acids. The cycloalkylallene can be ((C3-C8) cycloalkyl)allene, alternatively cyclohexylallene. The alkylallene can be methylallene, ethylallene, propylallene, or (1,1-dimethylethyl)allene. The dialkylallene can be 1,1-dialkylallene or 1,3-dialkylallene; alternatively 1,1-dimethylallene. The trialkylallene can be 1,1,3-trimethylallene. The trialkylsilylallene can be trimethylsilylallene, triethylsilylallene, or dimethyl,(1,1-dimethylethyl)silylallene (i.e., tert-butyl-dimethyl-silylallene). The vinylidenecycloalkane can be vinylidenecyclohexane of the formula .

[0020] Aspect 9. The method according to any one of Aspects 1 to 5, wherein the kinetic modifier compound has the formula (B 1 ): (R 5 )2C═C═C(R 6 )2(B 1 ), and the kinetic modifier compound of the formula (B 1 ) is selected from the group consisting of any one of KMC15 to KMC17: kinetic modifier compound (15) (“KMC15”): cyclohexylallene (i.e., (C6H 11)C(H)=C=CH2); kinetic modifier compound (16) ("KMC16"): ethyl 2,3-butadienoate (i.e., H2C=C=CH-C(=O)-O-CH2CH3); and kinetic modifier compound (17) ("KMC17"): 1,1-dimethylallene (i.e., (CH3)2C=C=CH2).

[0021] Aspect 10. The method according to any one of Aspects 1 to 5, wherein the kinetic modifier compound has the formula (C 1 ): (R 5 )(R 7 )C=C(R 6 )(R 7 )(C 1 ), and the kinetic modifier compound of formula (C 1 ) is an internal olefin. Thus, the internal olefin does not have a terminal carbon-carbon double bond or a terminal carbon-carbon triple bond. The internal olefin may 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-diphenylethylene. In formula (III) of Aspect 2, the corresponding ligand R may respectively be derived from or have: the formula -C(H)(CH3)-C(X)CH3, -C(H)(CH3)-C(X)CH2CH3 or -C(H)(phenyl)-C(X)phenyl.

[0022] Aspect 11. The method according to any one of Aspects 1 to 10, further comprising, before the combining step, a step of preparing a faster-starting catalyst by activating the precatalyst of formula (I) with an activator under effective activation conditions, thereby preparing a faster-starting catalyst. In some embodiments, the activator is an alkylaluminoxane, an organoborane compound or an organoborate.

[0023] Aspect 12. The method according to any one of aspects 1 to 11, wherein the method further comprises preparing a mixture of a deactivated post-metallocene catalyst, a support material, and an inert hydrocarbon solvent, and removing the inert hydrocarbon solvent from the mixture so as to obtain the deactivated post-metallocene catalyst disposed on the support material. The mixture may further comprise an excess of an activator, as the activator is typically used in excess to activate the post-metallocene precatalyst. The removing step may be achieved by conventional evaporation of the inert hydrocarbon solvent from the mixture (i.e., a conventional concentration method), which results in an evaporated / loaded deactivated post-metallocene catalyst. Alternatively, the removing step may be achieved by spray drying the mixture. The spray drying embodiment gives a spray dried / loaded deactivated post-metallocene catalyst, which may have improved properties relative to the evaporated / loaded deactivated post-metallocene catalyst. Examples of the support material are alumina and hydrophobic fumed silica; alternatively, the hydrophobic fumed silica. The hydrophobic fumed silica may be prepared by surface treating untreated anhydrous fumed silica with an effective amount of a hydrophobicizing agent. The hydrophobicizing agent may be dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane; alternatively, dimethyldichlorosilane. The hydrophobic fumed silica prepared by surface treating untreated anhydrous fumed silica with dimethyldichlorosilane may be CABOSIL TS-610.

[0024] Aspect 13. A deactivated post-metallocene catalyst prepared by the method according to any one of aspects 1 to 12. The deactivated post-metallocene catalyst may have the previously described formula (III), or be based on the previously described formula (III). In some embodiments, the deactivated post-metallocene catalyst is made from the post-metallocene precatalyst of formula (Ia).

[0025] Aspect 14. A method of feeding a post-metallocene catalyst to a slurry-phase or gas-phase polymerization reactor containing an olefin monomer and a moving bed of a polyolefin polymer, the method comprising preparing a deactivated post-metallocene catalyst outside the reactor and according to the method of any one of aspects 1 to 12, and feeding the deactivated post-metallocene catalyst in pure form (e.g., dry powder) or as a solution or slurry thereof in an inert hydrocarbon liquid to the slurry-phase or gas-phase polymerization reactor through a feed line free of olefin monomer. In some embodiments, the method further comprises transferring the deactivated post-metallocene catalyst or a fully active post-metallocene catalyst prepared in situ in the reactor to a (second) gas-phase polymerization reactor, wherein the catalyst catalyzes a second olefin polymerization reaction.

[0026] Aspect 15. A multimodal (e.g., bimodal or trimodal) catalyst system, the multimodal catalyst system comprising a weakened post-metallocene catalyst according to Aspect 13 and at least one second catalyst selected from the group consisting of: any non-weakened post-metallocene catalyst, a different weakened post-metallocene catalyst, and a metallocene catalyst. In some embodiments, the multimodal catalyst system comprises the weakened post-metallocene catalyst and only one second catalyst, alternatively only two different second catalysts. The multimodal catalyst system may further comprise a support material, and the weakened post-metallocene catalyst and the metallocene catalyst may be disposed (e.g., spray dried) on the support material. The weakened post-metallocene catalyst and the metallocene catalyst of the multimodal catalyst system may have ignition curves measured by an ignition vial test method (described later), wherein the time of their respective peak polymerization temperatures (Temp peak ) is within 60 minutes, alternatively within 45 minutes, alternatively within 30 minutes. When the second catalyst is the metallocene catalyst, the ignition performance of the catalysts of the multimodal catalyst system may be advantageously compatible such that a multimodal (e.g., bimodal or trimodal) polyolefin polymer is prepared by polymerization with the multimodal catalyst system, the multimodal polyolefin polymer comprising a higher molecular weight (HMW) component made from the weakened post-metallocene catalyst and a lower molecular weight (LMW) component, and the multimodal polyolefin polymer does not overproduce the HMW component relative to the LMW component, and thus fewer off-spec multimodal polyolefin polymers are prepared, or no off-spec multimodal polyolefin polymers are prepared.

[0027] Aspect 16. A method of feeding a multimodal (e.g., bimodal or trimodal) catalyst system to a slurry-phase or gas-phase polymerization reactor containing an olefin monomer and a moving bed of polyolefin polymer, the method comprising preparing a weakened post-metallocene catalyst outside the reactor according to the method of any one of Aspects 1 to 12, contacting a solution of the weakened post-metallocene catalyst and an activated metallocene catalyst in an inert hydrocarbon solvent with a support material (e.g., fumed silica) outside the reactor to prepare a slurry of the multimodal (e.g., bimodal or trimodal) catalyst system, the multimodal catalyst system consisting essentially of the weakened post-metallocene catalyst and the activated metallocene catalyst co-loaded on the same support material and suspended in an inert hydrocarbon solvent; optionally removing the inert hydrocarbon solvent from the slurry to render the multimodal catalyst system in a pure (dry powder) state; and feeding the slurry of the multimodal catalyst system or the pure state of the multimodal catalyst system to the slurry-phase or gas-phase polymerization reactor through a feed line free of olefin monomer.

[0028] Aspect 17. A method for preparing a polyolefin polymer, the method comprising contacting at least one 1-olefin monomer with a weakened post-metallocene catalyst prepared by the method according to any one of Aspects 1 to 12 or a multimodal catalyst system according to Aspect 15 in a slurry-phase or gas-phase polymerization reactor containing a moving bed of polyolefin resin under slurry-phase or gas-phase polymerization conditions to prepare a polyolefin polymer. The method may include a step before the contacting step, the step comprising: feeding a weakened post-metallocene catalyst prepared by the method according to any one of Aspects 1 to 12 or feeding a multimodal catalyst system according to Aspect 16 into a slurry-phase or gas-phase polymerization reactor containing a moving bed of polyolefin resin and at least one 1-olefin monomer under slurry-phase or gas-phase polymerization conditions to allow the ignition of the weakening of the weakened post-metallocene catalyst and the subsequent polymerization of at least one 1-olefin monomer to prepare a polyolefin polymer. The moving bed may be a stirred bed or a fluidized bed. The at least one 1-olefin monomer may be ethylene or a combination of ethylene and a comonomer selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene. In some 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 particles containing (in the particles) an active post-metallocene catalyst prepared in the first gas-phase polymerization reactor under first gas-phase polymerization conditions or in the slurry-phase polymerization reactor under slurry-phase polymerization conditions, and in either case, to a (second) gas-phase polymerization reactor under (second) gas-phase polymerization conditions (the gas-phase polymerization conditions being different from the first gas-phase polymerization conditions used in the first gas-phase polymerization reactor or the slurry-phase polymerization conditions used in the slurry-phase polymerization reactor, as the case may be) to prepare a multimodal (e.g., bimodal or trimodal) polyolefin polymer (i.e., a polyolefin polymer having a multimodal (e.g., bimodal or trimodal) molecular weight distribution (M w / M n ) in the (second) gas-phase polymerization reactor).

[0029] Aspect 18. A polyolefin polymer prepared by the preparation method according to Aspect 17. The polyolefin polymer obtained in original form from the slurry-phase or gas-phase polymerization reactor may be in particulate form and has a lower amount of aggregates (fused particles) than a comparative polyolefin polymer obtained in original form from the slurry-phase or gas-phase polymerization reactor, except where the weakened post-metallocene catalyst is replaced by a catalyst with faster ignition, and the polyolefin polymer is run under the same polymerization conditions.

[0030] Aspect 19. A manufactured article (eg, a blown film or a cast film) made from the polyolefin polymer according to aspect 18. The manufactured article may have a lower gel number than a comparative manufactured article made from a comparative polyolefin polymer.

[0031] Aspect 20. The embodiment of the invention according to any one of aspects 1 to 19, wherein the abated post-metallocene catalyst is free of support material, for example, free of fumed silica or alumina.

[0032] Aspect 21. A post-metallocene precatalyst selected from the group consisting of the aforementioned post-metallocene precatalysts of formula (1).

[0033] Aspect 22. A post-metallocene catalyst prepared by contacting the post-metallocene pre-catalyst according to aspect 21 with an activator.

[0034] A method for preparing a weakened post-metallocene catalyst. The method comprises reacting a catalyst with a relatively fast ignition rate with an effective amount of a catalyst of formula (A 1 )、(B 1 ) or (C 1 ) is combined with a kinetic modifier compound to prepare a weakened post-metallocene catalyst. The catalyst that ignites faster may have formula (II), and the weakened post-metallocene catalyst may have formula (III). The combination step may be performed in the absence of a pre-catalyst of formula (I). If an activator is used in excess in the activation step, the combination step may be performed in the presence of unreacted activator. The catalyst that ignites faster contains a leaving group X bonded to a metal atom M. In the combination step, the kinetic modifier compound reacts with the catalyst that ignites faster in such a way that the leaving group X from the catalyst that ignites faster is replaced, and the leaving group is replaced with a ligand R derived from the kinetic modifier compound and the leaving group X. The ligand is bonded to the metal atom M in the resulting weakened post-metallocene catalyst. In some aspects, the weakened post-metallocene catalyst has formula (III), and the catalyst that ignites faster has formula (II), and the pre-catalyst has formula (I), wherein all M are Zr and each X is benzyl.

[0035] In some embodiments, the metal M is Zr or Hf; alternatively, M is Zr or Ti; alternatively, M is Ti or Hf; alternatively, M is Zr; alternatively, M is Hf; alternatively, M is Ti.

[0036] The embodiment of the preparation method may include any one of Synthesis Schemes 1 to 12.

[0037] Synthesis Scheme 1: Step (a) late metallocene pre-catalyst + excess activator → intermediate mixture of activated late metallocene catalyst + remaining activator. Step (b) intermediate mixture + effective amount of kinetic modifier compound → attenuated late metallocene catalyst + remaining activator.

[0038] Synthesis Scheme 2: Step (a) late metallocene pre-catalyst + effective amount of kinetic modifier compound → intermediate late metallocene pre-catalyst (unreacted mixture or reaction product of late metallocene pre-catalyst + kinetic modifier compound). Step (b) intermediate late metallocene pre-catalyst + activator (e.g., alkylaluminoxane such as methylaluminoxane (“MAO”)) → attenuated late metallocene catalyst.

[0039] Synthesis Scheme 3: Step (a) late metallocene pre-catalyst + activator (e.g., alkylaluminoxane such as methylaluminoxane (“MAO”)) → activated late metallocene catalyst (catalyst with faster ignition). Step (b) activated late metallocene catalyst + effective amount of kinetic modifier compound → attenuated late metallocene catalyst.

[0040] 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 + late metallocene pre-catalyst → late metallocene catalyst with attenuated ignition.

[0041] Synthesis Scheme 5: Step (a) activator → late metallocene pre-catalyst ← effective amount of kinetic modifier compound (adding activator and kinetic modifier to late metallocene pre-catalyst simultaneously but separately) → attenuated late metallocene catalyst. Step (b): None.

[0042] Synthesis Scheme 6: Step (a) late metallocene pre-catalyst + support material → supported late metallocene pre-catalyst. (b) Supported late metallocene pre-catalyst + certain amount of activator → intermediate mixture of activated late metallocene catalyst + remaining activator is disposed on (or in equilibrium with) the support material. Step (c) intermediate mixture + effective amount of kinetic modifier compound → attenuated late metallocene catalyst is disposed on (or in equilibrium with) the support material. In some aspects, Step (a) further includes an inert hydrocarbon solvent and the deposition on the support material is carried out by evaporating the solvent (alternatively by spray drying). The amount of activator can be a stoichiometric amount relative to the metal M of the late metallocene catalyst (e.g., a molar ratio of 1.0 to 1.0); alternatively, less than a stoichiometric amount relative to the metal M of the late metallocene catalyst (e.g., a molar ratio of 0.1 to 0.94); alternatively, an excess amount relative to the metal M of the late metallocene catalyst (e.g., a molar ratio of 1.1 to 10,000).

[0043] Synthesis Scheme 7: Step (a) Post-metallocene pre-catalyst + effective amount of kinetic modifier compound + support material → Set the intermediate mixture of the post-metallocene pre-catalyst and the kinetic modifier compound on the support material (or equilibrate with the support material). Step (b) Intermediate mixture + activator (e.g., alkylaluminoxane such as methylaluminoxane (“MAO”)) → Set the attenuated post-metallocene catalyst on the support material (or equilibrate with the support material). In some aspects, step (a) also includes an inert hydrocarbon solvent, and the deposition on the support material is carried out by evaporating the solvent (alternatively by spray drying).

[0044] Synthesis Scheme 8: Step (a) Post-metallocene pre-catalyst + support material + activator (e.g., alkylaluminoxane such as methylaluminoxane (“MAO”)) → Set the activated post-metallocene catalyst (a catalyst with faster ignition) on the support material (or equilibrate with the support material). Step (b) Supported activated post-metallocene catalyst + effective amount of kinetic modifier compound → Set the attenuated post-metallocene catalyst on the support material (or equilibrate with the support material). In some aspects, step (a) also includes an inert hydrocarbon solvent, and the deposition on the support material is carried out by evaporating the solvent (alternatively by spray drying).

[0045] 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 + post-metallocene pre-catalyst + support material → Set the post-metallocene catalyst with attenuated ignition on the support material (or equilibrate with the support material). In some aspects, step (b) also includes an inert hydrocarbon solvent, and the deposition on the support material is carried out by evaporating the solvent (alternatively by spray drying).

[0046] Synthesis Scheme 10: Step (a) Activator → Post-metallocene pre-catalyst + support material ← Effective amount of kinetic modifier compound (add the activator and the kinetic modifier compound simultaneously but separately to the mixture of the post-metallocene pre-catalyst + support material) → Set the attenuated post-metallocene catalyst on the support material (or equilibrate with the support material). Step (b): None. In some aspects, step (a) also includes an inert hydrocarbon solvent, and the deposition on the support material is carried out by evaporating the solvent (alternatively by spray drying).

[0047] Scheme 11: Step (a): Activator (e.g., alkylaluminoxane such as methylaluminoxane (“MAO”)) + support material (e.g., hydrophobic fumed silica) + inert hydrocarbon solvent → Set the slurry of the supported activator on the support material (or equilibrate with the support material). Step (b): Spray-dry the slurry of step (a) → Set the spray-dried supported activator in dry powder form on the support material (e.g., spray-dried MAO (“SDMAO” or “sdMAO”) on hydrophobic fumed silica in dry powder form). Step (c): Mix the post-metallocene pre-catalyst + the spray-dried supported activator of step (b) + inert hydrocarbon solvent → Set the suspension of the supported post-metallocene catalyst with faster ignition on the support material (or equilibrate with the support material). Step (d): Mix the suspension from step (c) with an effective amount of a kinetic modifier compound → Set the suspension of the supported attenuated post-metallocene catalyst in an inert hydrocarbon solvent on the support material (or equilibrate with the support material). Optional step (e): Remove the inert hydrocarbon solvent from the suspension of the supported attenuated post-metallocene catalyst → Set the supported attenuated post-metallocene catalyst in dry powder form on the support material. Step (e) can be carried out by conventional evaporation of the inert hydrocarbon solvent from the suspension from step (d) or by spray-drying the suspension from step (d).

[0048] Scheme 12: Prepare a multimodal catalyst system comprising an attenuated post-metallocene catalyst and a spray-dried non-attenuated metallocene catalyst on a silica support: Step (a) Post-metallocene pre-catalyst + support material + activator (e.g., alkylaluminoxane such as methylaluminoxane (“MAO”)) → Set the activated post-metallocene catalyst (faster-igniting catalyst) on the support material (or equilibrate with the support material). Step (b) Supported activated post-metallocene catalyst + effective amount of a kinetic modifier compound → Set the attenuated post-metallocene catalyst on the support material (e.g., spray-dried non-attenuated metallocene catalyst / support material) (or equilibrate with the support material). Step (c) Add the non-attenuated metallocene catalyst to the attenuated post-metallocene catalyst set on the support material (or equilibrated with the support material) to obtain a multimodal catalyst system. In some aspects, step (a) also includes an inert hydrocarbon solvent and the deposition on the support material is carried out by evaporating the solvent (alternatively by spray-drying). For example, MAO in a slurry of the support material (e.g., fumed silica) and a solvent (e.g., toluene). Then add the faster-igniting post-metallocene catalyst. Mix for a period of time (e.g., 1 hour). Then add the kinetic modifier compound. Mix for another period of time (e.g., 1 hour). Then add the second non-attenuated metallocene catalyst. Spray-dry the resulting mixture.

[0049] A multimodal catalyst system can be prepared and fed into a gas-phase polymerization reactor. If desired, an additional amount of a deactivated post-metallocene catalyst or an additional amount of a second catalyst (e.g., a metallocene catalyst) can be fed separately into the reactor as a solution thereof in an inert hydrocarbon solvent, where it contacts the multimodal catalyst system in the reactor. Such a separate catalyst solution is sometimes referred to as a tuning catalyst. Alternatively, the multimodal catalyst system can be contacted with the tuning catalyst feed in the feed line before entering the reactor. In other embodiments, the multimodal catalyst system can be prepared in situ in the gas-phase polymerization reactor by separately adding a deactivated post-metallocene catalyst and at least one second catalyst into the reactor, where these catalysts contact each other, thereby preparing the multimodal catalyst system in situ in the reactor.

[0050] The method according to any of the above aspects can further include the step of transferring polymer particles prepared in a gas-phase or slurry-phase polymerization reactor to a (second) gas-phase polymerization reactor, and these polymer particles contain fully active post-metallocene catalyst in the particles.

[0051] Kinetic modifier compound (“KMC”). The kinetic modifier compound of formula (A 1 ) is R 5 -C≡C-R 6 (A 1 ). The kinetic modifier compound of formula (B 1 ) is (R 5 )2C=C=C(R 6 )2(B 1 ). The kinetic modifier compound of formula (C 1 ) is (R 5 )(R 7 )C=C(R 6 )(R 7 )(C 1 ). The kinetic modifier compounds of formula (A 1 ), (B 1 ) or (C 1 ) do not advantageously poison the post-metallocene catalyst, or may act at most slightly. The compound of formula (A 1 ) is an alkyne, the compound of formula (B 1 ) is allene, and the compound of formula (C 1 ) is an internal olefin. The kinetic modifier compound does not contain a vinyl functional group (i.e., lacks a group of the formula -C(H)=CH2).

[0052] In some embodiments, the kinetic modifier compound is defined as in any of the numbered aspects described above.

[0053] In formula (A1 ), (B 1 ) or (C 1 ), in some embodiments of the kinetic modifier compounds, the (C1-C 20 ) hydrocarbyl group is a (C2-C6) alkyl group, a (C3-C8) cycloalkyl group, or a phenyl group. In some embodiments, -C(=O)-O-(unsubstituted C1-C 20 ) hydrocarbyl group) is -C(=O)-O-(unsubstituted C1-C5) alkyl group), alternatively -C(=O)-O-ethyl.

[0054] 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, alternatively where the subscript g is 0 or 1, alternatively 0, alternatively 1. In some aspects, at least one X is (C6-C 12 ) aryl-((C0-C 10 ) alkylene)-CH2 (e.g., benzyl). In some aspects, each X is independently (C6-C 12 ) aryl-((C0-C 10 ) alkylene)-CH2; alternatively, one X is (C6-C 12 ) aryl-((C0-C 10 ) alkylene)-CH2 (e.g., benzyl), and the other X is F, Cl, or methyl; alternatively, each X is benzyl. In some aspects, each X is benzyl; alternatively, one X is benzyl, and the other X is F, Cl, or methyl. In some embodiments, at least one X, alternatively each X, is a (C1-C6) alkoxy-substituted (C6-C 12 ) aryl, or a (C1-C6) alkoxy-substituted benzyl. Without being bound by theory, it is believed that except for the replacement of one of the leaving groups X in the leaving group of the catalyst with a faster ignition by the weakened leaving group R in the weakened post-metallocene catalyst, the structure of the weakened post-metallocene catalyst is similar to the structure of the catalyst with a faster ignition, where R is defined later and is derived from the kinetic modifier compound. The weakened leaving group R of the weakened post-metallocene catalyst is structurally different from the leaving group X of the catalyst with a faster ignition and leaves more slowly than the leaving group of the catalyst with a faster ignition.

[0055] The ligand R derived from the kinetic modifier compound and the leaving group X. The ligand derived from the kinetic modifier compound in the attenuated post-metallocene catalyst can be the group R (“ligand R”). Without being bound by theory, it is believed that ligand R is mainly responsible for the improved monomer absorption profile of the attenuated post-metallocene catalyst (e.g., of formula (II)) relative to the faster-starting catalyst from which it is prepared (e.g., of formula (III)). Ligand R can have the formula (A), (B), or (C): -C(R 5 )=C(X)R 6 (A), -C(R 5 )2-C(X)=C(R 6 )2 (B), or -C(R 5 )(R 7 )-C(X)(R 6 )(R 7 )(C); where each of X and R 5 to R 7 is as previously described. In some embodiments, R is a ligand of formula (A) or (B), alternatively R is a ligand of formula (A) or (C), alternatively R is a ligand of formula (B) or (C), alternatively R is a ligand of formula (A), alternatively R is a ligand of formula (B), alternatively R is a ligand of formula (C). The ligands of both formula (A) and (B) contain carbon-carbon double bonds, and it is believed that these ligands polymerize extremely slowly under gas-phase polymerization conditions.

[0056] Without wishing to be bound by theory, it is believed that the reaction of an olefin monomer (e.g., ethylene, propylene, 1-butene, 1-hexene, 1-octene, etc.) with the slower-starting catalyst proceeds by inserting the olefin monomer into the bond between the M metal center and the attenuated leaving group R. This insertion may be much slower than the corresponding insertion reaction of the olefin monomer into the bond between the M metal center and the leaving group X of the faster-starting catalyst. The slower reaction of the present invention can delay the start of polymerization. After the first (or few) olefin monomer insertion reactions, the attenuated leaving group R is no longer bonded to the metal center, such that all subsequent insertions occur at a rate similar to that of the faster-starting catalyst. Since only the first (or few) insertion reactions out of the thousands or millions of insertion reactions carried out by the catalyst are slowed down, the overall catalyst productivity may not be significantly reduced. In fact, the slower-starting catalyst may have increased productivity because its exotherm is reduced relative to that of the faster-starting catalyst. This is because exothermic reactions raise the temperature experienced by the catalyst, thereby accelerating the deactivation of the catalyst, which can reduce the productivity of some catalysts (such as some post-metallocene catalysts).

[0057] In the ligand R of formula (A), (B), or (C), R 5 and R 6Each of which is independently H or R 7 and wherein each R 7 is independently a (C1-C 20 ) hydrocarbyl or a (C1-C 17 ) heterohydrocarbyl, provided that each R 7 is devoid of a carbon-carbon double bond. A (C1-C 20 ) hydrocarbyl may be unsubstituted and composed of carbon and hydrogen atoms, or a (C1-C 20 ) hydrocarbyl may be substituted and composed of carbon, hydrogen, and one or more halogen atoms. Each halogen atom is independently selected from F, Cl, Br, and I; alternatively selected from F, Cl, and Br; alternatively selected from F and Cl; alternatively selected from F; alternatively selected from Cl. An unsubstituted (C1-C 20 ) hydrocarbyl may be an unsubstituted (C1-C 20 ) alkyl, an unsubstituted (C3-C 20 ) cycloalkyl, an unsubstituted (C6-C 12 ) aryl, an unsubstituted ((C1-C4)alkyl) 1-3 -phenyl, or an unsubstituted (C6-C 12 ) aryl-(C1-C6)alkyl. A substituted (C1-C 20 ) hydrocarbyl may be a monofluoro derivative or a difluoro derivative of the aforementioned unsubstituted (C1-C 20 ) hydrocarbyl, such as 2-(3,4-difluorophenyl)-ethen-1-yl (having formula (A)).

[0058] R 5 to each (C1-C 7 ) heterohydrocarbyl of the embodiments of R 19 contains the same heterohydrocarbyl, which may be unsubstituted and composed of carbon, hydrogen, and at least one heteroatom selected from N and O, or a (C1-C 17 ) heterohydrocarbyl may be substituted and composed of carbon, hydrogen, at least one heteroatom selected from N and O, and one or more halogen atoms. An unsubstituted (C1-C 17 ) heterohydrocarbyl may be a (C1-C 19 ) heteroalkyl, a (C3-C 19 ) heterocycloalkyl, a (C6-C 12 ) heteroaryl, ((C1-C4)alkoxy) 1-3 -phenyl, or (C6-C 12 ) heteroaryl-(C1-C6)alkyl. A substituted (C1-C 17 ) heterohydrocarbyl may be the aforementioned unsubstituted (C1-C 17)Mono- or difluoro derivatives of heterohydrocarbyls such as 2-(3,4-dimethoxyphenyl)-vinyl-1-yl (having formula (A)).

[0059] The structure of ligand R is different from the structure of ligand X and, for this substance, the structure of ligand R is different from that of anion A - of the structure.

[0060] A deactivated post-metallocene catalyst. According to the method, a deactivated post-metallocene catalyst such as of formula (III) is made from a faster-starting catalyst such as of formula (II). The deactivated post-metallocene catalyst is a post-metallocene catalyst containing a ligand (e.g., R) bonded to its metal atom M (e.g., Ti, Zr or Hf), the ligand being derived from a kinetic modifier compound. The deactivated post-metallocene catalyst is a new post-metallocene catalyst. In some embodiments, the deactivated post-metallocene catalyst is a deactivated post-metallocene catalyst of formula (III).

[0061] It is believed that, all other conditions being the same, a deactivated post-metallocene catalyst such as of formula (III) may function without a significant reduction in the overall catalytic activity relative to the overall catalytic activity of the faster-starting catalyst (e.g., of formula (II)) from which it is prepared. That is, although the start is delayed, the activity / polymerization productivity of the catalyst (expressed as grams of dry polyolefin product prepared / grams of catalyst added to the reactor per hour (gPE / gcat-hr)) may not be significantly less than the catalytic activity / polymerization productivity of the faster-starting post-metallocene catalyst and, in some embodiments, may be greater than the catalytic activity / polymerization productivity of the faster-starting post-metallocene catalyst. For example, the deactivated post-metallocene catalyst may have a productivity greater than 200%, alternatively 30.0% to 180.0%, alternatively 50.0% to 180%, alternatively 30.0% to 70.0%, alternatively 70.0% to 180.0%, alternatively 70.0% to 150.0%, alternatively 70.0% to 120%, alternatively 80.0% to 120%, alternatively 90.0% to 120%, alternatively 100.0% to 120%, alternatively 110% to 120%, alternatively 70.0% to 110%, alternatively 80.0% to 110%, alternatively 90.0% to 110%, alternatively 100.0% to 110%, alternatively 70.0% to ≤100%, alternatively 80.0% to ≤100%, alternatively 90.0% to ≤100% of the productivity of the faster-starting catalyst from which it is prepared.

[0062] It is believed that the attenuated post-metallocene catalyst of formula (III) can inhibit catalyst ignition and advantageously improve the operability of a gas phase reactor by reducing the fouling rate and increasing the time between reactor shutdowns relative to a faster-igniting catalyst (such as of formula (II)) from which it is prepared.

[0063] It is believed that the attenuated post-metallocene catalyst (such as of formula (III)) may exhibit an improved monomer absorption profile compared to the faster-igniting catalyst of formula (II) from which it is prepared. This improved monomer absorption profile will advantageously increase the compatibility of the attenuated post-metallocene catalyst (such as of formula (III)) with slower-igniting olefin polymerization catalysts (such as some metallocene catalysts), and the resulting ignition-compatible multimodal (such as bimodal or trimodal) catalyst system has improved performance relative to the faster-igniting catalyst (such as of formula (II)) from which it is prepared.

[0064] Additionally, if storage and / or transportation of the catalyst is desired, it is believed that the attenuated post-metallocene catalyst (such as of formula (III)) can be stored and transported at ambient temperature, rather than under refrigerated storage and refrigerated transportation conditions desired for the faster-igniting catalyst (such as of formula (II)) from which it is prepared, until the attenuated post-metallocene catalyst is available for use in a chemical process. It is believed that the attenuated post-metallocene catalyst (such as of formula (III)) can achieve any one of such benefits, or a combination of any two or more of such benefits.

[0065] In some embodiments, the method of the attenuated post-metallocene catalyst (such as of formula (III)) and polymerizing an olefin monomer does not contain an excess of a kinetic modifier compound (KMC) of formula (A 1 )、(B 1 ) or (C 1 ). In other embodiments, the attenuated post-metallocene catalyst and method have an excess of a kinetic modifier compound. Such embodiments of the attenuated post-metallocene catalyst (such as of formula (III)) can be prepared by combining a faster-igniting catalyst (such as of formula (II)) having a molar ratio of the number of moles of the kinetic modifier compound to the number of moles of metal M of formula (II) of greater than 0 to 1.0, alternatively 1.1 to 50, alternatively 0.5 to 40, alternatively 0.5 to 30, alternatively 0.5 to 20, alternatively 0.5 to 10, alternatively 0.5 to 2, alternatively 0.8 to 1.2, alternatively 0.9 to 1.1 (such as 1.0). In such embodiments, formula (A 1 )、(B 1 ) or (C 1) The kinetic modifier compound is used in a stoichiometric amount (molar ratio 1.0) or less than a stoichiometric amount (molar ratio >0 to 0.99). When the kinetic modifier compound is used in less than a stoichiometric amount, the resulting attenuated post-metallocene catalyst (e.g., of formula (III)) has a partially attenuated ignition activity relative to the faster-igniting catalyst (e.g., of formula (II)) from which it is prepared. This partially attenuated ignition activity can be helpful when the faster-igniting catalyst (e.g., of formula (III)) is only slightly overactivated. Generally, the higher the molar ratio of the moles of the kinetic modifier compound to the moles of metal M (e.g., of formula (II)), the greater the attenuation of the overactivity of the faster-igniting catalyst (e.g., of formula (II)) that will result.

[0066] In some embodiments, the method of attenuated post-metallocene catalyst (e.g., of formula (III)) and polymerizing an olefin monomer comprises an excess of a kinetic modifier compound (KMC) of formula (A 1 ), (B 1 ) or (C 1 ). Such embodiments of the attenuated post-metallocene catalyst (e.g., of formula (III)) can be prepared by combining a faster-igniting catalyst (e.g., of formula (II)) having a molar ratio of the moles of the kinetic modifier compound to the moles of metal M of formula (II) greater than 1.0, e.g., a KMC / M molar ratio of 1.1 to 50, alternatively 1.1 to 40, alternatively 1.1 to 30, alternatively 1.1 to 20, alternatively 1.1 to 10, alternatively 2 to 20, alternatively greater than 20. Notably, in some embodiments, even when the kinetic modifier compound is used in an excess amount within the foregoing range (KMC / M molar ratio up to about 50), the catalytic activity of the attenuated post-metallocene catalyst (e.g., of formula (III)) and / or the productivity of the gas-phase polymerization reaction using it may not be significantly reduced, and may even increase, relative to the catalytic activity and productivity of the faster-igniting catalyst (e.g., of formula (II)) from which it is prepared. In other embodiments, when the kinetic modifier compound is used in an excess amount, the catalytic activity of the attenuated post-metallocene catalyst (e.g., of formula (III)) and / or the productivity of the gas-phase polymerization reaction using it may be significantly reduced relative to the catalytic activity and productivity of the faster-igniting catalyst (e.g., of formula (II)) from which it is prepared. Although the reason for the reduction is not clear, the excess kinetic modifier compound may compete with the olefin monomer and displace the attenuated leaving group R of formula (III) in a balanced manner. When the exact molar amount of metal M of the faster-igniting catalyst (e.g., of formula (II)) is not precisely known or may vary from batch to batch, using an excess of the kinetic modifier compound may be helpful.

[0067] Monomer absorption curve with reduced ignition. A reduced post-metallocene catalyst (e.g., of formula (III)) exhibits a monomer absorption curve with reduced ignition. For example, the reduced monomer absorption curve may include a longer length of time for the reduced post-metallocene catalyst to reach the peak reaction temperature T peak compared to the faster-igniting catalyst from which it was prepared and / or a lower value of T peak . The time from injecting the catalyst (time zero (Time0)) into a reactor containing an olefin monomer but no catalyst until the peak polymerization temperature (Temp peak ) is reached is at least 0.65 minutes. The higher the value of Temp peak , the greater the delay in catalyst ignition.

[0068] To compare the ignition times of different catalysts, the same olefin monomer (e.g., 1-octene) and the same reactor are used. To rapidly screen catalysts, a 40 mL glass vial is used as the reactor and the ignition vial test method described later is used as the test method.

[0069] Effective amount of kinetic modifier compound (KMC). An amount of kinetic modifier compound (KMC) sufficient to reduce the ignition of the catalyst. The effective amount of KMC can be expressed as an absolute value compared to the amount of (pre)catalyst metal M or as a relative value compared to the reduced ignition performance or a combination thereof.

[0070] In some embodiments, the absolute value of the effective amount of the kinetic modifier compound can be expressed as the molar ratio of the moles of the kinetic modifier compound to the moles of metal M (“KMC mol / M mol ”), where M is the M of the post-metallocene precatalyst of formula (I), e.g., M is a Group 4 metal. In some embodiments, the effective amount of KMC is expressed as KMC mol / M mol≥0.50 / 1.0, alternatively ≥0.9 / 1.0, alternatively ≥1.0 / 1.0, alternatively ≥1.5 / 1.0, alternatively ≥1.9 / 1.0, alternatively ≥3 / 1.0, alternatively ≥5 / 1.0, alternatively ≥6 / 1.0, alternatively ≥9 / 1.0, alternatively ≥10.0 / 1.0, alternatively ≤10.0 / 1.0, alternatively ≤20.0 / 1.0, alternatively ≤30.0 / 1.0, alternatively ≤40.0 / 1.0, alternatively ≤50.0 / 1.0. In other words, the foregoing embodiments can be described as follows by expressing the effective amount of KMC as the inverse molar ratio of the number of moles of metal M to the number of moles of the kinetic modifier compound (“Mmol / KMCmol”): respectively ≤1.0 / 0.5, alternatively ≤1.0 / 0.9, alternatively ≤1.0 / 1.0, alternatively ≤1.0 / 1.5, alternatively ≤1.0 / 1.9, alternatively ≤1.0 / 3.0, alternatively ≤1.0 / 5.0, alternatively ≤1.0 / 6.0, alternatively ≤1.0 / 9.0, alternatively ≤1.0 / 10.0, alternatively ≤1.0 / 20.0, alternatively ≤1.0 / 30.0, alternatively ≤1.0 / 40.0, alternatively ≤1.0 / 50.0. Generally, it is believed that KMC mol / M mol above about 50 / 1.0 may undesirably prevent the ignition or functionality of the post-metallocene catalyst containing it. However, in some embodiments, for practical reasons (e.g., the cost of KMC and / or post-polymerization processing operations / costs (e.g., stripping excess KMC from the polyolefin resin)), KMC mol / M mol should not be higher than at most 40 / 1, alternatively at most 30 / 1, alternatively at most 20 / 1, alternatively at most 10.0, alternatively at most 6.0, alternatively at most 5.0.

[0071] In terms of the attenuated ignition performance, the effective amount of the kinetic modifier compound (KMC) can be represented by the results measured by the ignition vial test method described later. For example, as measured separately by the ignition vial test method described later, using an attenuated post-metallocene catalyst and a faster-igniting post-metallocene catalyst prepared therewith having a kinetic modifier compound; the effective amount of the kinetic modifier compound (KMC) can have any one of the characteristics (i) to (xii) observed after catalyst injection: (i) a time delay at the start of exotherm, i.e., the reaction temperature rises (i.e., from the addition time zero point (Time0) to the temperature exotherm start time (Time exo); (ii) a slower rate of increase in degrees Celsius per minute (°C / min) at the reaction temperature (e.g., a lower maximum slope in a graph of reaction temperature on the y-axis versus time after catalyst injection on the x-axis); (iii) reaching a lower peak reaction temperature in °C (Temp peak ); (iv) a longer time of at least 0.65 minutes from the addition time at Time0 to the time of peak temperature (Time peakT ); (v) both (i) and (ii), but not including (iii) or (iv); (vi) both (i) and (iii), but not including (ii) or (iv); (vii) both (ii) and (iii), but not including (i) or (iv); (viii) both (i) and (iv), but not including (ii) and (iii); (ix) both (ii) and (iv), but not including (i) or (iii); (x) both (iii) and (iv), but not including (i) or (ii); (xi) any three of (i) to (iv); and (xii) each of (i) to (iv). In some embodiments, the light-off attenuation and effective amount of the KMC are characterized by at least feature (iv), alternatively only by feature (iv). In some embodiments, the longer time of feature (iv) is a time of at least 0.65 minutes (39 seconds or longer) from the addition time at Time0 to the time of peak temperature (Time peakT ), and the time of peak temperature is at least 0.65 minutes; alternatively at least 1.0 minute; alternatively at least 1.5 minutes; alternatively 1.5 minutes to 55 minutes; alternatively 1.6 minutes to 100 minutes; alternatively 1.6 minutes to 55 minutes; alternatively 1.6 minutes to 10.0 minutes; alternatively 10.1 minutes to 20.0 minutes; alternatively 20.1 minutes to 30.0 minutes; alternatively 30.1 minutes to 40.0 minutes; alternatively 40.1 minutes to 50.0 minutes; alternatively 50.1 minutes to 55 minutes; alternatively 2.0 minutes to 29 minutes; alternatively 30.1 minutes to 50.4 minutes; all measured according to the light-off vial test method described later. In some embodiments, the light-off attenuation and effective amount of the KMC are characterized by feature (viii). In some embodiments, the light-off attenuation is characterized by feature (ix). In some embodiments, the light-off attenuation and effective amount of the KMC are characterized by feature (x). In some embodiments, the light-off attenuation is characterized by feature (xi).

[0072] The post-metallocene catalyst with attenuation reaches Temp max at a time relative to the catalyst with faster light-off reaching Temp maxThe delay in time can be from 0.70 minutes to 500 minutes (e.g., an example is 293 minutes), alternatively from 0.70 minutes to 120 minutes, alternatively from 1.0 minutes to 120 minutes, alternatively from 5 minutes to 90 minutes, alternatively from 10 minutes to 70 minutes.

[0073] In some embodiments, when run under the same polymerization conditions according to the ignition batch reactor test method described later, the monomer absorption curve of the attenuated post-metallocene catalyst relative to the faster-igniting catalyst from which it is prepared max (°C) can be characterized by a decrease in the peak temperature (Temp peak ). In the ignition batch reactor test method, the Temp max of the attenuated post-metallocene catalyst can be max 1 °C to 30.0 °C lower, alternatively 1 °C to 16 °C lower, alternatively 2 °C to 15 °C lower, alternatively 3 °C to 14 °C lower than that of the faster-igniting catalyst from which it is prepared. In some embodiments, the faster-igniting post-metallocene catalyst is made from any one of the post-metallocene precatalysts (1) to (10) described previously.

[0074] In some embodiments, the monomer absorption curve of the attenuated post-metallocene catalyst can be characterized by the absolute weight / weight ratio of ethylene (C2) absorption after 1 hour (h) to C2 absorption after 0.1 hour (C2(1h) / C2(0.1h)). In some embodiments, the C2(1h) / C2(0.1h) ratio of the attenuated post-metallocene catalyst can be from 2.1 to 11, alternatively from 2.2 to 10.4, alternatively from 2.4 to 10.0, alternatively from 3 to 9.9. In some embodiments, the faster-igniting post-metallocene catalyst is made from any one of the post-metallocene precatalysts (1) to (10) described previously.

[0075] In some embodiments, when run under the same polymerization conditions according to the ignition batch reactor test method described later, the monomer absorption curve of the attenuated post-metallocene catalyst can be characterized by the relative C2(1h) / C2(0.1h) ratio of the C2(1h) / C2(0.1h) ratio of the attenuated post-metallocene catalyst to the C2(1h) / C2(0.1h) ratio of the faster-igniting catalyst from which it is prepared. This relative C2(1h) / C2(0.1h) ratio can be from 1.05 to 6, alternatively from 1.1 to 6, alternatively from 1.2 to 5.4, alternatively from 1.5 to 5.0.

[0076] An alternative or additional way of expressing an effective amount of a kinetic modifier compound (KMC) with respect to reduced light-off performance, as measured by the Light-off Vial Test Method described later, may be a sufficient amount of KMC such that the reduced post-metallocene catalyst and the faster light-off catalyst prepared therefrom may have a light-off curve as measured by the Light-off Vial Test Method (described later) wherein their respective peak polymerization temperatures (Temp peak ) is at least 0.7 minutes, alternatively greater than 1.0 minutes, alternatively greater than 5 minutes, alternatively greater than 10.0 minutes, alternatively greater than 20.0 minutes, alternatively greater than 30.0 minutes, alternatively greater than 40.0 minutes, alternatively greater than 50.0 minutes of each other. The weakened post-metallocene catalyst and the catalyst that ignites faster therefrom can have a light-off curve measured by the light-off vial test method (described later), wherein their corresponding peak polymerization temperatures (Temp peak ) within 60 minutes, alternatively within 45 minutes, alternatively within 30 minutes of each other. The kinetic modifier compound has a delayed effect on the peak polymerization temperature (Temp) of the post-metallocene catalyst. peak ) time relative to the time Temp of the post-metallocene catalyst with faster light-off prepared from the weakened post-metallocene catalyst peak , may vary depending on: (a) the structural class (e.g., Formula (I)) or structural subclass (e.g., Formula (Ia)) of the attenuated post-metallocene catalyst; and / or (b) the structural class (e.g., acetylene, propadiene, or internal olefin) or structural subclass (e.g., aryl acetylene versus alkyl acetylene; or monoacetylene versus diacetylene or triacetylene; or acyclic propadiene versus cycloalkyl propadiene versus vinylidene propadiene; or aryl-type internal olefin versus alkyl-type internal olefin). In some aspects, the Temp of the attenuated post-metallocene catalyst is peak The post-metallocene catalyst Temp with faster ignition speed peak Any of the end values ​​within the range of the time difference between the two values ​​can be based on data given later in the Examples.

[0077] In some embodiments, the monomer absorption profile of the weakened post-metallocene catalyst can be characterized as a combination of any two of the foregoing embodiments, alternatively all but any one, alternatively each of the foregoing embodiments.

[0078] Comparative Examples or Examples not according to the invention do not contain any kinetic modifier compound or contain less than an effective amount of a kinetic modifier compound.

[0079] Catalyst Activity. The peak polymerization temperature (Temp) in degrees Celsius (°C) of a post-metallocene catalyst, as measured by the light-off vial test method, is the maximum temperature of the catalyst after the catalyst is reduced. peak) The difference from the Temp of the faster-igniting catalyst peak reaches within ±5 °C, alternatively within ±4 °C, alternatively within ±3 °C, alternatively within ±2 °C, alternatively within ±1 °C, then it is determined that the catalytic activity of the attenuated post-metallocene catalyst (e.g., of formula (III)) is substantially the same as that of the faster-igniting catalyst. Or under all other identical conditions, the catalytic activity is determined such that the activity / polymerization productivity of this catalyst (expressed as grams of dry polyolefin product prepared / grams of catalyst added to the reactor per hour (gPE / gcat-hr)) may not be significantly less than the catalytic activity / polymerization productivity of the faster-igniting post-metallocene catalyst, and in some embodiments may be greater than the catalytic activity / polymerization productivity of this faster-igniting post-metallocene catalyst.

[0080] Faster-igniting catalyst. For the reasons described above, embodiments of the faster-igniting catalyst (e.g., of formula (II)) may require attenuation of monomer absorption in the slurry phase and / or gas phase polymerization of 1-olefin monomers. The same or other embodiments of the faster-igniting catalyst (e.g., of formula (II)) may require ligand R for different reasons, such as for changing the solubility of the catalyst in alkane solvents, or for NMR studies of the post-metallocene catalyst structure and improving the catalyst structure design.

[0081] Anion A - . The faster-igniting post-metallocene catalyst (e.g., of formula (II)) and the attenuated post-metallocene catalyst (e.g., of formula (III)) may each contain anion A derived from an activator or from leaving group X - , the activator being used to prepare the faster-igniting post-metallocene catalyst from the post-metallocene precatalyst of formula (I). The activator is used to activate the post-metallocene precatalyst of formula (I) by extracting leaving group X from the post-metallocene precatalyst of formula (I) to obtain the faster-igniting post-metallocene catalyst (e.g., of formula (II)) and anion A - . The resulting activated post-metallocene catalyst (i.e., the faster-igniting post-metallocene catalyst of formula (II)) is drawn in a conventional manner, showing the metal atom M with a positive charge. This positive charge indicates the catalytic site where olefin monomers may bond during the polymerization reaction. Anion A - formally balances the positive charge such that the faster-igniting post-metallocene catalyst (e.g., of formula (II)) and the attenuated post-metallocene catalyst (e.g., of formula (III)) made therefrom are overall neutral.

[0082] Anion A -The property is considered unimportant in the faster-igniting post-metallocene catalysts (e.g., of formula (II)) and the attenuated post-metallocene catalysts (e.g., of formula (III)). As mentioned, it can be an anionic derivative of X (i.e., X - ) or an anionic derivative of the activator. When the activator is an alkylaluminoxane and the anion A - is its anionic derivative, the anion A - can be an alkylaluminoxane anion; alternatively, when the activator is an organoborane compound and the anion A - is its anionic derivative, the anion A - can be an organoborane anion; alternatively, when the activator is an organic borate compound and the anion A - is its anionic derivative, the anion A - can be an organic borate anion. The anion A - is formed during the activation step according to aspect 1. It is believed that the anion A - in the faster-igniting post-metallocene catalysts (e.g., of formula (II)) is produced by the combination step such that the anion A - in the attenuated post-metallocene catalysts (e.g., of formula (III)) can be the same as the anion A - in the faster-igniting catalyst. However, the anion A - in the attenuated post-metallocene catalysts (e.g., of formula (III)) can be the same as or different from the anion A - in the faster-igniting post-metallocene catalysts (e.g., of formula (II)). For example, the anion A - in the faster-igniting post-metallocene catalysts (e.g., of formula (II)) can be an anionic derivative of the activator, and for example, the anion A - in the attenuated post-metallocene catalysts (of formula (III)) can be X - .

[0083] Catalyst Structure. Without being bound by theory, it is believed that the molecular structure of the faster light-off post-metallocene catalyst of formula (II) and the molecular structure of the attenuated post-metallocene catalyst of formula (III) can be determined by conventional analytical methods such as nuclear magnetic resonance (NMR) spectroscopy or gas chromatography / mass spectrometry (GC / MS). The structure of the ligand R in formula (III) can be determined by quenching the NMR sample of the attenuated post-metallocene catalyst of formula (III) with a proton solvent such as isopropanol, CH3OH or H2O, a partially deuterated proton solvent such as isopropyl-OD, CH3OD or HDO, or a fully deuterated proton solvent such as fully deuterated isopropanol ((CD3)2C(D)OD), fully deuterated methanol (CD3OD) or D2O) to obtain a by-product of formula H-R or D-R, and analyzing the structure of the by-product by NMR such as proton NMR ( 1 H-NMR)) or gas chromatography / mass spectrometry (GC / MS).

[0084] Activation Step. In some embodiments, the method for preparing an attenuated post-metallocene catalyst (e.g., of formula (III)) further includes an activation step as a preparatory step, which can be completed before the combination step begins. The activation step includes contacting a pre-catalyst of formula (I) with an activator under effective activation conditions for preparing a faster light-off post-metallocene catalyst. The activation step can be carried out in the absence of a kinetic modifier compound.

[0085] Activator. The activator for activating the post-metallocene pre-catalyst of formula (I) can be an alkylaluminoxane, an organoborane compound, an organoborate compound or a trialkylaluminum compound. The activator can also be a combination of any two or more of them. For example, the activator can include an alkylaluminoxane (such as methylaluminoxane) and an organoborate compound, such as an organoborate having the CAS name bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyl)borate amine, bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyl)borate(1-)amine. The activator for activating a cyclopentadienyl ligand-metal (Ti, Zr or Hf) complex to obtain a metallocene catalyst can be a trialkylaluminum compound.

[0086] Alkylaluminoxane: Also known as alkylalumoxane. A partial hydrolysis product of a trialkylaluminum compound. Embodiments can be (C1-C 10)Alkylaluminoxanes, alternatively (C1-C6)alkylaluminoxanes, alternatively (C1-C4)alkylaluminoxanes, alternatively (C1-C3)alkylaluminoxanes, alternatively (C1-C2)alkylaluminoxanes, alternatively methylaluminoxane (MAO), alternatively modified methylaluminoxane (MMAO). In some aspects, the alkylaluminoxane is MAO. In some embodiments, the alkylaluminoxane is supported on untreated silica (such as fumed silica). The alkylaluminoxane can be obtained from commercial suppliers or prepared by any suitable method. Suitable methods for preparing alkylaluminoxanes are well known. Examples of such preparation methods are described in U.S. Patent Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, and 5,693,838; and European Publications EP-A-0 561 476, EP-B1-0 279 586, and EP-A-0 594-218; and PCT Publication WO 94 / 10180.

[0087] Based on the molar ratio of the number of moles of Al metal atoms in the aluminoxane to the number of moles of metal atom M (e.g., Ti, Zr, or Hf) in the precatalyst, the maximum amount of alkylaluminoxane can be selected as a 5,000-fold molar excess of the precatalyst. The minimum amount of activator to precatalyst can be a 1:1 molar ratio (Al / M). The maximum value of the molar ratio of Al / M can be 150, alternatively 124.

[0088] Organoborane compounds. Tris(fluoro-functional organic)borane compounds ((fluoro-organic)3B), such as tris(pentafluorophenyl)borane ((C6F5)3B), tris[3,5-bis(trifluoromethyl)phenyl]borane ((3,5-(CF3)2-C6H3)3B), or a mixture of any two or more thereof.

[0089] Organoborate compounds. Tetrakis(fluoro-functional organic)borate compounds ((fluoro-organic)4B), such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or a mixture of any two or more thereof. The organoborate compound can be the methyl bis((C14 -C 18 )alkyl)ammonium salts, or by reacting a long-chain trialkylamine (Armeen TM M2HT, available from Akzo Nobel, Inc.) with HCl and Li[B(C6F5)4]. Such a preparation is disclosed in Example 2 of US 5,919,983. The organoborate compound can be used herein without (further) purification. In addition, bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyl)borate ammonium.

[0090] Trialkylaluminum compounds can be used as activators (metallocene pre-catalysts) or as scavengers to remove residual water therefrom before starting up a polymerization reactor. Examples of suitable alkylaluminum compounds are trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, and tri-n-octylaluminum.

[0091] Activators, also known as co-catalysts, can affect the molecular weight, degree of branching, comonomer content, or other properties of polyolefin polymers. Activators can enable coordination polymerization or cationic polymerization.

[0092] Without being bound by theory, it is believed that the choice of activator for activating a faster-igniting post-metallocene catalyst will not affect the structure of the attenuated post-metallocene catalyst made from the faster-igniting post-metallocene catalyst. That is, only considering the cationic part of formula (III) (i.e., ignoring the anion A - ), it is expected that the structures of the attenuated post-metallocene catalysts prepared using different activators are the same. The structure of the non-supported attenuated post-metallocene catalyst may be easier to determine by NMR than that of the supported attenuated post-metallocene catalyst, which is attributed to the heterogeneity of the latter (typical support materials are insoluble in NMR solvents).

[0093] In some embodiments, the choice of A - may have an additional effect on the monomer absorption curve of the attenuated post-metallocene catalyst. However, any such effect of A - will not completely eliminate the beneficial effect of the kinetic modifier compound on the monomer absorption curve of the attenuated post-metallocene catalyst.

[0094] Effective conditions. The reactions described herein (e.g., combination steps, activation steps, polymerization) are carried out independently under conditions that permit the reactions to proceed. Examples of effective conditions are reaction temperature, type of atmosphere (e.g., inert atmosphere), reactant purity, stoichiometry of the reactants, agitation / mixing of the reactants, and reaction time period. Conditions effective for the activation step and the polymerization step can be those described in the art and well-known to one of ordinary skill in the art. For example, effective activation conditions can include techniques for manipulating the catalyst, such as an in-line mixer, a catalyst preparation reactor, and a polymerization reactor. The activation temperature can be from 20 °C to 800 °C, alternatively from 300 °C to 650 °C. The reaction time can be from 10 minutes to 2 hours. Examples of gas phase polymerization conditions are described later herein. Effective conditions for the combination step for preparing the attenuated metallocene catalyst can include: a reaction temperature of -50 °C to 80 °C, alternatively 0 °C to 50 °C, alternatively -50 °C to 50 °C, alternatively -50 °C to 30 °C; an inert atmosphere (e.g., nitrogen, helium, or argon free of water and O2); reactants free of water and O2 and having a purity of 90% to 100%; the amount of reactants for minimizing waste / maximizing product yield; agitation or mixing of the reactants; and a reaction time period of 1 minute to 24 hours.

[0095] Effective reaction conditions for preparing the metallocene pre-catalyst of formula (IV). Such conditions can include techniques for manipulating air-sensitive and / or moisture-sensitive reagents and reactants, such as Schlenk-line techniques and an inert gas atmosphere (e.g., nitrogen, helium, or argon). Effective reaction conditions can also include sufficient reaction time, sufficient reaction temperature, and sufficient reaction pressure. Each reaction temperature can independently be from -78 °C to 120 °C, alternatively from -30 °C to 30 °C. Each reaction pressure can independently be from 95 kPa to 105 kPa, alternatively from 99 kPa to 103 kPa. The progress of any particular reaction step can be monitored by analytical methods such as nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry to determine the reaction time that effectively maximizes the yield of the desired product. Alternatively, each reaction time can independently be from 30 minutes to 48 hours.

[0096] The metallocene pre-catalyst of formula (I). The pre-catalyst of formula (I) can be synthesized according to methods known in the art, including those mentioned above. Alternatively, the metallocene pre-catalyst can be obtained from a pre-catalyst supplier such as Boulder Scientific Company.

[0097] Polyolefin polymers are prepared by polymerization methods. When the 1-olefin monomer is a combination of ethylene and propylene, the polyolefin polymer made therefrom is an ethylene / propylene copolymer. When the 1-olefin monomer is ethylene alone, the polyolefin polymer made therefrom is a polyethylene homopolymer. When the 1-olefin monomer is a combination of ethylene and 1-butene, 1-hexene, or 1-octene, the polyolefin polymer made 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 made from the 1-olefin monomer is a vinyl polymer having the following components: 50 weight percent to 100 weight percent (wt%) of the repeating units are derived from ethylene, and 50 wt% to 0 wt% of the repeating units are derived from the 1-olefin monomer selected from propylene, 1-butene, 1-hexene, 1-octene, and combinations of any two or more thereof.

[0098] In some embodiments, the polymerization method uses a 1-olefin monomer and a comonomer that is a diene monomer (e.g., 1,3-butadiene). When the 1-olefin monomer is a combination of ethylene and propylene and the polymerization also uses a diene monomer, the polyolefin polymer is an ethylene / propylene / diene monomer (EPDM) copolymer. The EPDM copolymer can be an ethylene / propylene / 1,3-butadiene copolymer.

[0099] Multimodal (e.g., bimodal or trimodal) catalyst systems. A bimodal catalyst system includes a attenuated post-metallocene catalyst and at least one other olefin polymerization catalyst selected from: a different attenuated post-metallocene catalyst, a post-metallocene catalyst, and a metallocene catalyst. The multimodal catalyst system prepares a multimodal polyethylene composition comprising a HMW polyethylene component and a LMW polyethylene component in a single reactor. Some problems relate to unwanted gels in multimodal (e.g., bimodal or trimodal) polyethylene compositions that are melt blended in a supplementary reactor. Other problems relate to the transitional complexity and stability of multimodal (e.g., bimodal or trimodal) catalyst systems. Even in the absence of gels, problems can exist due to settling variations of catalyst particles of different sizes. In some aspects, the variability of the melt index (I2) can be measured according to particle size rather than using gels.

[0100] The method for preparing the attenuated post-metallocene catalyst can be carried out in the presence of a metallocene catalyst or a metallocene precatalyst. When carried out in the presence of a metallocene precatalyst, the method for activating the precatalyst of formula (I) with an activator further includes activating the metallocene precatalyst with the same or a different activator. Generally, the method for preparing the attenuated post-metallocene catalyst is carried out in the absence of a metallocene (pre)catalyst.

[0101] Metallocene catalysts. The metallocene catalysts can be made from any of the metallocene pre-catalyst components described in columns 11, line 17 to column 22, line 21 of US7873112B2. In some aspects, the metallocene catalysts are made from the metallocene pre-catalyst substances named in column 18, line 51 to column 22, line 5 of US7873112B2. In some aspects, the metallocene pre-catalysts are selected from: 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(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 aspects, the metallocene catalysts are the products of the activation reaction of an activator with any of the foregoing metallocene pre-catalysts.

[0102] Non-supported or supported catalysts. The post-metallocene pre-catalysts of formula (I), the faster-starting post-metallocene catalysts (such as the faster-starting catalysts of formula (II)), the attenuated post-metallocene catalysts (such as the attenuated post-metallocene catalysts of formula (III)), and the multi-modal catalyst systems can be independently non-supported or disposed on a solid particulate carrier material. When no carrier material is present, the post-metallocene pre-catalysts of formula (I), the faster-starting post-metallocene catalysts (such as the faster-starting catalysts of formula (II)), the attenuated post-metallocene catalysts (such as the attenuated post-metallocene catalysts of formula (III)), and / or the multi-modal catalyst systems can be injected into a slurry-phase or gas-phase polymerization reactor as a solution in a hydrocarbon solvent. When the post-metallocene pre-catalysts of formula (I), the faster-starting post-metallocene catalysts (such as the faster-starting catalysts of formula (II)), the attenuated post-metallocene catalysts (such as the attenuated post-metallocene catalysts of formula (III)), and / or the multi-modal catalyst systems are disposed on a carrier material, they can be injected into a slurry-phase or gas-phase polymerization reactor as a slurry suspended in a hydrocarbon solvent or as a dry powder (i.e., dry particulate solid).

[0103] A faster-starting post-metallocene catalyst (e.g., of formula (II)) and / or a weakened post-metallocene catalyst (e.g., of formula (III)) can be prepared in the absence of a support material and later set onto a support material. Alternatively, a post-metallocene precatalyst of formula (I) or a faster-starting post-metallocene catalyst (e.g., of formula (II)) can be set onto a support material, and then a faster-starting post-metallocene catalyst (e.g., of formula (II)) and / or a weakened post-metallocene catalyst (e.g., of formula (III)) can be prepared in situ on the support material.

[0104] Supported post-metallocene precatalysts of formula (I), supported faster-starting post-metallocene catalysts (e.g., supported catalysts of formula (II)), and / or supported weakened post-metallocene catalysts (e.g., supported catalysts of formula (III)) can be prepared by a concentration method that evaporates a hydrocarbon solvent from a suspension or solution of the support material in a solution of a precatalyst of formula (I), a faster-starting catalyst, and / or a weakened post-metallocene catalyst in a hydrocarbon solvent. Alternatively, supported precatalysts of formula (I), supported faster-starting catalysts (e.g., supported catalysts of formula (II)), and / or supported weakened post-metallocene catalysts (e.g., supported catalysts of formula (III)) can be prepared by a spray drying method of a suspension or solution. In some embodiments, the spray drying method is used.

[0105] Support material. The support material is a particulate solid, which can be non-porous, semi-porous, or porous. The support material is a porous support material. Examples of the support material are talc, inorganic oxides, inorganic chlorides, zeolites, clays, resins, and mixtures of any two or more thereof. Examples of suitable resins are polystyrene, functionalized or crosslinked organic supports such as polystyrene divinylbenzene polyolefins. The support material can independently be untreated silica, alternatively calcined untreated silica, alternatively silica treated with a hydrophobic agent, alternatively silica treated with calcination and a hydrophobic agent. The hydrophobic agent can be dichlorodimethylsilane.

[0106] Inorganic oxide support materials include Group 2, 3, 4, 5, 13, or 14 metal oxides. Preferred supports include silica, fumed silica, alumina (see, e.g., PCT Publication WO 99 / 60033), silica-alumina, and mixtures thereof, which may or may not be dehydrated. Other useful supports include magnesia, titania, zirconia, magnesium chloride (U.S. Patent 5,965,477), montmorillonite (EP 0 511 665), phyllosilicate, zeolite, talc, clay (U.S. Patent 6,034,187), etc. In addition, combinations of these support materials may be used, such as silica-chromium, silica-alumina, silica-titania, etc. Additional support materials may include those porous acrylic polymers described in EP 0767 184, which is incorporated herein by reference. Other support materials include nanocomposites as disclosed in PCT Publication WO 99 / 47598, aerogels as disclosed in PCT Publication WO 99 / 48605, pellets as disclosed in U.S. Patent No. 5,972,510, and polymer beads as disclosed in PCT Publication WO 99 / 50311.

[0107] The support material may 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 may be silica (e.g., fumed silica), alumina, clay, or talc. The fumed silica may be hydrophilic (untreated), alternatively hydrophobic (treated). In some aspects, the support is hydrophobic fumed silica, which may be prepared by treating untreated fumed silica with a hydrophobizing agent such as dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane. In some aspects, the treating agent is dimethyldichlorosilane. In one embodiment, the support is Cabosil TM TS-610, which is fumed silica surface-treated with dimethyldichlorosilane.

[0108] One or more precatalysts and / or one or more activators may be deposited on, contacted with, vaporized with, bonded to, or incorporated into one or more supports or carrier materials, adsorbed or absorbed onto or into them.

[0109] Metallocene precatalysts may be spray-dried according to the general methods described in US5648310. Supports used with post-metallocene precatalysts may be functionalized as generally described in EP 0 802 203, or at least one substituent or leaving group may be selected as described in US5688880.

[0110] Solution-phase polymerization and / or slurry-phase polymerization of olefin monomers are well known. See, for example, US8291115B2.

[0111] Inert hydrocarbon solvents. Alkanes, aromatic hydrocarbons, or alkyl aromatic hydrocarbons (i.e., arylalkanes). Examples of inert hydrocarbon solvents are alkanes such as mineral oil, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, etc., and toluene and xylene. In one embodiment, the inert hydrocarbon solvent is an alkane or a mixture of alkanes, where each alkane independently has 5 to 20 carbon atoms, alternatively 5 to 12 carbon atoms, alternatively 5 to 10 carbon atoms. Each alkane can be independently acyclic or cyclic. Each acyclic alkane can be independently straight-chain or branched. The acyclic alkanes can be pentane, 1-methylbutane (isopentane), hexane, 1-methylpentane (isohexane), heptane, 1-methylhexane (isoheptane), octane, nonane, decane, or a mixture of any two or more thereof. The cyclic alkanes can be cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, methylcyclopentane, methylcyclohexane, dimethylcyclopentane, or a mixture of any two or more thereof. Additional examples of suitable alkanes include Isopar-C, Isopar-E, and mineral oils such as paraffin oil. In some aspects, the inert hydrocarbon solvent is free of mineral oil. The inert hydrocarbon solvent can consist of one or more (C5-C 12 ) alkanes.

[0112] Gas-phase polymerization (GPP). The polymerization uses a GPP reactor, such as a stirred-bed gas-phase polymerization reactor (SB-GPP reactor) or a fluidized-bed gas-phase polymerization reactor (FB-GPP reactor). Such reactors and methods are generally well known. For example, the FB-GPP reactor / method can be as described in any one of US3,709,853, US 4,003,712, US 4,011,382, US 4,302,566, US 4,543,399, US4,882,400, US 5,352,749, US 5,541,270, US 2018 / 0079836 A1, EP-A-0802202, and Belgian Patent No. 839,380. These SB-GPP and FB-GPP polymerization reactors and methods mechanically agitate or fluidize the polymerization medium inside the reactor through the continuous flow of gaseous monomers and diluents. Other useful reactors / methods under consideration include tandem or multistage polymerization methods such as those described in US5,627,242, US 5,665,818, US 5,677,375, EP-A-0 794 200, EP-B1-0 649992, EP-A-0 802 202, and EP-B-634421.

[0113] Gas phase polymerization operating conditions are any variable or combination of variables that can affect the polymerization reaction in a GPP reactor or the composition or properties of the polyolefin polymer composition product prepared therefrom. Variables can include: reactor design and size; pre-catalyst composition and amount; reactant composition and amount; molar ratio of two different reactants; presence or absence of a feed gas (such as H2), molar ratio of the feed gas to the reactant, absence or concentration of interfering materials (e.g., H2O and / or O2), absence or presence of an induced condensing agent (ICA), average polymer residence time in the reactor, partial pressure of components, feed rate of monomers, reactor bed temperature (e.g., fluidized bed temperature), nature or order of method steps, transition time period between steps. Variables other than the one / ones described or varied by the method or use can be kept constant.

[0114] In the GPP process, the individual flow rates of ethylene (“C2”), hydrogen (“H2”), and 1 - hexene (“C6” or “C x ”, where x is 6) are controlled to maintain a fixed comonomer to ethylene monomer gas molar ratio or feed mass ratio (C x / C2, e.g., C6 / C2) equal to the described value (e.g., 0.00560 or 0.00703), a constant hydrogen to ethylene gas molar ratio or feed mass ratio (“H2 / C2”) equal to the described value (e.g., 0.00229 or 0.00280), and a constant ethylene (“C2”) partial pressure equal to the described value (e.g., 1,000 kPa). Gas concentrations are measured by on - line gas chromatography to understand and maintain the composition in the recycle gas stream. The reaction bed of growing polymer particles is maintained in a fluidized state by continuously flowing make - up feed and recycle gas through the reaction zone. An apparent gas velocity of 0.49 meters per second (m / sec) to 0.79 meters per second (1.6 feet per second (ft / sec) to 2.6 feet per second) is used. The FB - GPP reactor is operated at a total pressure of about 2068 kilopascals (kPa) to about 2758 kilopascals (about 300 pounds per square inch - gauge (psig) to about 400 pounds per square inch - gauge) and at the described first reactor bed temperature RBT. The fluidized bed is maintained at a constant height by withdrawing a portion of the bed at a rate equal to the production rate of the polyolefin polymer composition in particulate form, which production rate can be 5,000 kilograms per hour (kg / h) to 150,000 kilograms per hour. The product polyolefin polymer composition is semi - continuously transferred into a fixed - volume chamber via a series of valves, where the removed multimodal (e.g., bimodal or trimodal) ethylene - co - 1 - hexene copolymer composition is purged to remove entrained hydrocarbons and treated with a humid nitrogen (N2) gas stream to deactivate any trace of residual catalyst.

[0115] The catalyst system can be fed to the polymerization reactor in a "dry mode" or a "wet mode", alternatively the dry mode, alternatively the wet mode. The dry mode is dry powder or granules. The wet mode is a suspension in an inert liquid (such as mineral oil).

[0116] Induced Condensing Agent (ICA). An inert liquid that can be used to cool the materials in the GPP reactor. Its use is optional. ICA is a (C3 - C 20 ) alkane, alternatively a (C5 - C 20 ) alkane, such as 2 - methylbutane (i.e., isopentane). See US 4,453,399, US 4,588,790, US 4,994,534, US 5,352,749, US 5,462,999 and US 6,489,408. The ICA concentration in the reactor can be 0.1 mol% to 25 mol%, alternatively 1 mol% to 16 mol%, alternatively 1 mol% to 10 mol%.

[0117] The GPP conditions can also include one or more additives, such as a chain transfer agent or a promoter. Chain transfer agents are well - known and can be organometals, such as diethyl zinc. Promoters are known from, for example, US 4,988,783 and can include chloroform, CFCl3, trichloroethane and dichlorotetrafluoroethane. Before reactor startup, a scavenger can be used to react with moisture, and during reactor conversion, a scavenger can be used to react with excess activator. The scavenger can be trialkylaluminum. GPP can be operated without (non - intentionally added) scavenger. The GPP reactor / method can also include a certain amount (e.g., 0.5 ppm to 200 ppm based on all feeds entering the reactor) of one or more electrostatic control agents and / or one or more continuity additives, such as aluminum stearate or polyethyleneimine. The electrostatic control agent can be added to the FB - GPP reactor to inhibit the formation or accumulation of static charge therein.

[0118] The GPP reactor can be a commercial - scale FB - GPP reactor, such as the UNIPOL TM reactor or the UNIPOL TM II reactor, which can be purchased from Univation Technologies, LLC, a subsidiary of The Dow Chemical Company, Midland, Michigan, USA.

[0119] 1 - olefin monomer. The 1 - olefin monomer has the formula H2C=C(H)(CH2) n R 8A compound wherein the subscript n is an integer from 0 to 19, and the group R 8 is H or CH3. Examples are ethylene (subscript n is 0 and R 8 is H), propylene (subscript n is 0 and R 8 is CH3), and (C4-C 20 ) α-olefins (subscript n is an integer from 1 to 19 and R 8 is H or CH3). In some embodiments, the 1-olefin monomer is ethylene, propylene, 1-butene, 1-hexene, 1-octene, or a combination of any two or more thereof. In some embodiments, the 1-olefin monomer is a combination of ethylene and propylene. In other embodiments, the 1-olefin monomer is ethylene alone, or a combination of ethylene and 1-butene, 1-hexene, or 1-octene.

[0120] A polyolefin polymer. A product of polymerization of at least one 1-olefin monomer with a late metallocene catalyst or a multimodal catalyst system. A macromolecule or a collection of macromolecules having constituent units derived from at least one 1-olefin monomer. For example, when at least one 1-olefin monomer consists of ethylene, the polyolefin polymer consists of a polyethylene homopolymer. When at least one 1-olefin monomer consists of ethylene and propylene, the polyolefin polymer consists of an ethylene / propylene copolymer. When at least one 1-olefin monomer consists of ethylene and a comonomer selected from 1-butene, 1-hexene, and 1-octene, the polyolefin polymers are respectively selected from poly(ethylene-co-1-butene) copolymers, poly(ethylene-co-1-hexene) copolymers, and poly(ethylene-co-1-octene) copolymers.

[0121] The polyolefin polymer can be a homopolymer or a copolymer. The polyolefin polymer can have a unimodal molecular weight distribution or a multimodal molecular weight distribution. A polyolefin polymer made from a multimodal catalyst system has a multimodal (e.g., bimodal or trimodal) molecular weight distribution and includes a higher molecular weight (HMW) polyolefin polymer component and a lower molecular weight (LMW) polyolefin polymer component. The HMW polyolefin polymer component can be prepared by its (e.g., of formula (III)) late metallocene catalyst, and the LMW polyolefin polymer component can be prepared by its metallocene catalyst.

[0122] Any compound, composition, formulation, material, mixture, or reaction product herein may be free of any chemical element selected from the group consisting of the following chemical elements: H, Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, the lanthanide elements, and the actinide elements; provided that the chemical elements required for the compound, composition, formulation, material, mixture, or reaction product (e.g., Zr for a zirconium compound, or C and H for polyethylene, or C, H, and O for an alcohol) are not counted.

[0123] Alternatively, prior to different embodiments. ASTM is a standards organization, ASTM International, West Conshohocken, Pennsylvania, USA. Any comparative example is for illustrative purposes only and should not be prior art. Free of or lacking means completely absent; or undetectable. IUPAC is the International Union of Pure and Applied Chemistry (IUPAC Secretariat, Research Triangle Park, North Carolina, USA). The periodic table is the IUPAC version released on May 1, 2018. An option may be granted, rather than being essential. Operable means functionally capable or effective. Optional (ly) means absent (or excluded) or present (or included). Properties may be measured using standard test methods and conditions. A range includes endpoints, sub-ranges, and integral and / or fractional values contained therein, except for integer ranges excluding fractional values. Room temperature: 23 °C ± 1 °C

[0124] Unless otherwise specified, the term definitions used herein are taken from the 2.3.3 version of the "IUPAC Compendium of Chemical Technology" ("Gold Book") on February 24, 2014. For convenience, some definitions are given below.

[0125] Example

[0126] Additional embodiments of the present invention are the foregoing aspects and the claims described hereinafter, which describe ranges of processing conditions and / or ranges of material properties, wherein in the additional embodiments of the present invention, the end values of the ranges of processing conditions and / or the end values of the ranges of material properties are respectively modified to any of the exemplary processing condition values and / or any of the exemplary material property values described hereinafter for any example of the present invention.

[0127] Activator 1 (also known as cocatalyst 1): bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyl)borate(1-) amine.

[0128] Mineral oil: HYDROBRITE 380PO paraffin oil purchased from Sonneborn.

[0129] Preparation Example 1A: Preparation of an activator formulation comprising spray-dried methylaluminoxane / treated fumed silica (SDMAO) in hexane / mineral oil. 1.6 kg of treated fumed silica (CABOSIL TS-610) in 16.8 kg of toluene was slurried, and then a toluene solution of 10 wt% (11.6 kg) MAO was added to obtain a mixture. Using a spray dryer set at 160 °C and an outlet temperature of 70 °C to 80 °C, the mixture was introduced into the atomizing device of the spray dryer to produce droplets of the mixture, and then the mixture was contacted with a hot nitrogen stream to evaporate the liquid from the mixture to obtain a powder. The powder was separated from the gas mixture in a cyclone separator and the separated powder was discharged into a container to obtain SDMAO as a fine powder.

[0130] Preparation Example 1B: Preparation of a slurry of the activator formulation of Preparation Example 1A. The SDMAO powder of Preparation Example 1A in a mixture of 10 wt% n-hexane and 78 wt% mineral oil was slurried to obtain an activator formulation having 12 wt% SDMAO / treated fumed silica solids in hexane / mineral oil.

[0131] Preparation Example 2: Preparation of spray-dried metallocene using the activator formulation. Preparation Examples 1A and 1B were repeated, except that an activator formulation was prepared by slurrying 1.5 kg of treated fumed silica (CABOSIL TS-610) in 16.8 kg of toluene, then adding a toluene solution of 10 wt% (11.1 kg) MAO and a sufficient amount of (MeCp)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)ZrMe2, where Me is methyl, Cp is cyclopentadienyl, and MeCp is methylcyclopentadienyl, to obtain a loading of 40 μmol Zr per gram of solid. The resulting powder was slurried to obtain an activator formulation having 22 wt% solids in 10 wt% isoparaffinic fluid and 68 wt% mineral oil.

[0132] Preparation Example 2A: Preparation of a supported catalyst used in the light-off batch reactor test method described later. In a nitrogen-purged glove box, in an oven-dried glass bottle, 2.65 g of Cabosil TS-610 fumed silica in 62.5 g of toluene was slurried until well dispersed. Then, 22 grams (g) of a toluene solution of 10 weight percent (wt%) methylaluminoxane (MAO) was added. The mixture was stirred for 15 minutes, and then a post-metallocene precatalyst (e.g., precatalyst 1 described previously) and any one of the kinetic modifier compounds KMC1 to KMC20 described previously were added. The resulting mixture was stirred for 30 minutes to 60 minutes. The stirred mixture was spray-dried using a Büchi Mini Spray Dryer B-290 with the following parameters to produce a dry sample: set temperature of 185 °C, outlet temperature of 100 °C, aspirator at 95%, and pump speed of 150 revolutions per minute (rpm).

[0133] Preparation Example 3: Synthesis of a post-metallocene catalyst with faster light-off: Prepared by the following method: A 40 milliliter (mL) glass vial containing a magnetic stir bar coated with poly(tetrafluoroethylene) (PTFE) was placed in a glove box under an inert N2 atmosphere and capped with a rubber septum having 200 milligrams (mg) of spray-dried methylaluminoxane (SDMAO, prepared according to Preparation Example 1A). Then, a slurry of 10 micromoles (μmol) of a post-metallocene precatalyst (e.g., precatalyst 1) in 0.2 mL of mineral oil was added. The resulting mixture was stirred for 5 minutes to obtain a mineral oil slurry of the corresponding post-metallocene catalyst with faster light-off supported on the treated fumed silica. This procedure was repeated to prepare multiple batches of mineral oil slurries of post-metallocene catalysts with faster light-off, each post-metallocene catalyst with faster light-off being supported on a separate treated fumed silica. The post-metallocene catalyst with faster light-off can have a molar ratio of aluminum to metal atoms (Al / M) of 120. The foregoing procedure is generally used to prepare the catalysts used in the light-off vial test method described later.

[0134] Preparation Example 4: Synthesis of a weakened post-metallocene catalyst: A solution of 10 μmol of a kinetic modifier compound in 0.20 mL of toluene was added to a certain amount of slurry containing 10 μmol of the post-metallocene catalyst with faster light-off of Preparation Example 3 supported on treated fumed silica. The resulting mixture was stirred for 5 minutes to obtain a mineral oil / toluene slurry of the weakened post-metallocene catalyst supported on treated fumed silica.

[0135] Preparation Example 5: Synthesis of HN5 precatalyst (1): HN5 precatalyst (1) is a precatalyst of formula (I), where M is Zr; R1 to R 4 each of which is H; and each X is benzyl. Repeat the procedure of US6967184B2, column 33, line 53 to column 34, line 9, to obtain the HN5 precatalyst (1).

[0136] Examples (A1) to (A20) (IE(A1) to IE(A20)) of the present invention: Twenty attenuated post-metallocene catalysts were separately prepared according to Preparation Example 2A or Preparation Examples 3 and 4, using different kinetic modifier compounds among the precatalyst 1 and the kinetic modifier compounds (1) to (20).

[0137] Ignition vial test method: Add the mineral oil slurry of the faster-igniting catalyst supported on treated fumed silica or the mineral oil / toluene slurry of the attenuated 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 minutes). Manually shake (without stirring) the vial to prevent caking. Then place the shaken vial in different holes of a foam block located on a hot plate / stirrer. Immediately insert a thermocouple through the septum cap below the liquid level in the vial and record the temperature (°C) of the vial contents every 5 seconds from T0 to 300 minutes after T0. Download the temperature and time data into a spreadsheet and plot a thermokinetic curve for analysis. The results of these runs can be graphically depicted as a plot of the reaction temperature of the batch reactor contents on the y-axis versus the time starting from Time0 at the time of addition on the x-axis.

[0138] The examples of the present invention ("IE") and comparative examples ("CE") were prepared by the ignition vial test method. An effective amount of certain kinetic modifier compounds ("KMC") was combined with certain faster-igniting post-metallocene catalysts to obtain the attenuated post-metallocene catalysts of the examples of the present invention. The comparative examples satisfied one of three criteria (1) to (3): (1) containing a post-metallocene catalyst but no kinetic modifier compound, (2) containing a post-metallocene catalyst and less than an effective amount of a kinetic modifier compound (e.g., CE1a), or (3) containing a metallocene catalyst and a kinetic modifier compound. According to the ignition vial test method, the ignition effects of the faster-igniting post-metallocenes and the examples of the present invention were tested with polyoctene to compare their relative activities. In separate vials, (a) mineral oil without 1-octene, (b) an example of a post-metallocene precatalyst, and (c) spray-dried methylaluminoxane (SDMAO) without a kinetic modifier compound were premixed for 10 minutes to obtain a slurry of the faster-igniting post-metallocene catalyst without 1-octene and a kinetic modifier compound. In other vials, (a) mineral oil without 1-octene, (b) a post-metallocene precatalyst, (c) SDMAO, and (d) a kinetic modifier compound were premixed for 10 minutes to obtain a slurry of the attenuated post-metallocene catalyst without 1-octene. After 10 minutes of premixing (the time under all conditions except (B)*), the same amount of 1-octene was added to each vial. After the addition of 1-octene, at the temperature of the mixture, as evidence of the activation of the corresponding catalyst, an increase in temperature from 5 °C to 120 °C, alternatively from 10 °C to 110 °C, alternatively an increase in temperature in any of its ten-degree cycles (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) was observed.One of the following four sets of conditions can be used: Condition (A): 5.5 mL of Isopar-E; 8 μmol of M; the amount of SDMAO is the amount that gives a molar ratio of Al / M = 120; 0 μmol (CE) or 2 μmol (IE) of the kinetic modifier compound; 11 mL of 1-octene; Condition (B) (predictive): 5.5 mL of Isopar-E; 10 μmol of M; the amount of SDMAO is the amount that gives a molar ratio of Al / M = 120; 0 μmol (CE) or 2 μmol (IE) of the kinetic modifier compound; 5.5 mL of 1-octene, where premixing is for 5 minutes instead of 10 minutes*; Condition (C): 5.5 mL of Isopar-E; 20 μmol of M; the amount of SDMAO that gives a molar ratio of Al / M = 120; the amount of the kinetic modifier compound is 0 μmol (CE) or the amount that gives the indicated molar ratio of M / KMC (IE); 5.5 mL of 1-octene; Condition (D): 5.5 mL of Isopar-E; 2 μmol of M; the amount of SDMAO that gives a molar ratio of Al / M = 120; the amount of the kinetic modifier compound is 0 μmol (CE) or the amount that gives the indicated molar ratio of M / KMC (IE); 5.5 mL of 1-octene.

[0139] Table 1: Results of the ignition vial test method using condition (B) and the pre-catalyst of formula (1), where M is Zr (1), where M is Zr 。

[0140]

[0141] As seen in Table 1, the kinetic modifier compound has modified the structure of the catalyst with a faster light-off to prepare a catalyst with a weakened light-off starting with a delayed peak reaction temperature.

[0142] Examples 2a to 2j and Comparative Example 2 of the present invention: Alternative procedure for the vial light-off test method: In a glove box under a nitrogen atmosphere, a 40 mL glass vial with a magnetic stir bar coated with poly(tetrafluoroethylene) was charged with spray-dried MAO (SDMAO, 200 mg) and 10 μmol of precatalyst 1 (as a slurry in 0.2 mL of mineral oil). The mixture was stirred for 5 minutes. 10 μmol portions of KMC (50 μmol / mL in toluene) were added. The resulting mixture was stirred for 5 minutes. Then 1-octene (5.5 mL) was added at time T0, and the vial and its contents were briefly shaken manually (to prevent caking). Then the shaken vial was placed in a hole of a 4-hole foam block on a hot plate / stirrer. A thermocouple was inserted through the septum into the vial below the liquid level, and the temperature was recorded at 5-second intervals until at least the maximum temperature (T max), i.e., the peak temperature. Plot the thermokinetic curve data in Excel. Conduct four separate polymerization reactions simultaneously in four separate vials according to this procedure. The results are reported in Table 2 below.

[0143] Table 2. Results of alternative ignition vial test methods for pre-catalyst 1 (CE2 and IE2a to IE2j) (conditions: 10 μ mol Zr; for SDMAO, Al / Zr = 120; 11 mL 1-octene) .

[0144]

[0145] As shown by the results in Table 2, relative to CE2 without the kinetic modifier compound (KMC), the KMCs of IE2a to IE2j attenuated the 1-octene (monomer) absorption of the supported catalyst prepared from the precatalyst (1). This attenuation was shown by delaying the peak temperature relative to those values of CE2 (i.e., by extending the time from T0 to reach the peak temperature) and by decreasing the peak temperature (i.e., by decreasing T max ).

[0146] Ignition batch reactor test method .

[0147] The relative kinetic curves of the faster-starting catalyst and the attenuated post-metallocene catalyst are typically observed in separate polymerization runs, with each run being carried out in a 2-liter (L) semi-batch autoclave polymerization reactor equipped with a mechanical stirrer. In the batch reactor, ethylene is copolymerized with 1-hexene 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 the 3-hour polymerization run to maintain their concentrations at a steady state, but no more C2 is added. Ethylene absorption is measured versus time to obtain a relative representation of the catalyst kinetic curve.

[0148] The batch reactor is dried and loaded. Before each run, the batch reactor is dried for 1 hour. Then 200 g of NaCl is loaded into the dried batch reactor. The batch reactor is further dried by heating the batch reactor and its contents in an N2 atmosphere at 100 °C for 30 minutes. Then 3 g of silica-supported methylaluminoxane (SMAO) is added to scavenge residues, the batch reactor is sealed, and the contents are stirred. Then 3.04 liters (L) of H2 and 1-hexene are loaded into the resulting dried batch reactor so as to obtain a molar ratio of 1-hexene to ethylene (C6 / C2) of 0.004. The batch reactor is pressurized with ethylene to 1.52 megapascals (MPa). The resulting system is allowed to reach a steady state.

[0149] Then load the catalyst (a catalyst with a faster ignition or a weakened post-metallocene catalyst) into a batch reactor to initiate polymerization. Record the time of adding the catalyst as time zero (Time0). Raise the reactor temperature to the target temperature T target (e.g., 90 °C, 93 °C, or 100 °C), and maintain the reactor at this temperature for 0.5 to 5 hours, alternatively 1 to 5 hours (e.g., 1 hour). Cool, vent, and open the reactor, wash the resulting polyolefin product with water and methanol, and dry it to obtain a dry polyolefin product. For a post-metallocene catalyst with a faster ignition, the difference between the peak temperature reached (T max , also known as T peak ) and the target temperature T target (T max - T target (°C)) indicates the extent to which the post-metallocene catalyst with a faster ignition exceeds the target temperature. The difference between the peak temperature reached (T max ) and the target temperature T target for the weakened post-metallocene catalyst (T max – T target (°C)) shows how much weakening effect the kinetic modifier compound has in the weakened post-metallocene catalyst prepared with it.

[0150] For each batch reactor run, calculate the catalyst activity / polymerization productivity as the grams of dry polyolefin product prepared per gram of catalyst added to the reactor per hour (gPE / gcat-hr). A higher value of gPE / gcat-hr indicates a higher catalyst activity / polymerization productivity. Record the ethylene uptake at 0.1 hour (C2 uptake 0.1h) (6 minutes) and the ethylene uptake at 1.0 hour (C2 uptake 1h) (60 minutes), and record the ratio as (C2 uptake 1h) / (C2 uptake 0.1h). All other conditions being the same, a higher ratio of (C2 uptake 1 hour) / (C2 uptake 0.1 hour) indicates more weakening of the catalyst ignition. For each run, T max is a measure of the ignition weakening between the examples and comparative examples of the present invention. The results are reported in Table 3 below.

[0151] Determine the melting temperature of the dry polyolefin product using differential scanning calorimetry (DSC) according to ASTM D3418-08 on a 10 mg sample using a scan rate of 10 °C / minute and using the second heating cycle. Some embodiments of the polyolefin products of the present invention prepared with a weakened post-metallocene catalyst may have a higher melting point than the comparative polyolefin products prepared with their corresponding catalysts with a faster ignition. These results are shown in Table 4 below.

[0152] From the start-up batch reactor runs with catalysts having faster light-off, most of the ethylene uptake likely occurs within the first few minutes after polymerization begins (e.g., within 10 minutes of Time 0). Compared to the attenuated post-metallocene catalysts, the ethylene uptake is more evenly spread throughout the 3-hour long polymerization runs. The results of these comparative examples and the runs of the present invention can be graphically depicted as a plot (not shown) of the reaction temperature of the batch reactor contents on the y-axis or the ethylene monomer (“C2”) uptake on the y-axis versus time starting from Time 0 at addition on the x-axis.

[0153] Table 3: Polymerization results of the ignition batch reactor test method based on pre-catalyst (1) 。

[0154]

[0155] N / t means not tested. *The data for IE1k and IE1I are from 3-hour polymerization runs. The data for CE1 and IE1a to IE1g are from 1-hour polymerization runs. Thus, the yields of IE1k and IE1l are one-third of the yields expected based on the polymer production of 9795 g PE / g catalyst. As shown by the data in Table 3, the catalyst activity of the attenuated light-off catalysts may not be significantly reduced relative to the catalyst activity of the faster light-off catalysts used to prepare them, and may increase in some embodiments.

[0156] Table 4: Polyolefin product properties 。

[0157] Example number Melting point (DSC, °C) Mn Mw Mw / Mn CE1 129.17 65,718 369,511 5.6 IE1a 130.01 68,726 366,755 5.3 IE1b 130.41 72,517 356,492 4.9 IE1c N / t N / t N / t N / t IE1d 129.5 67,425 374,069 5.5 IE1e 129.01 73,676 386,577 5.2 IE1f N / t N / t N / t N / t IE1g 131.01 86,555 427,368 4.9 IE1h 130.1 79,548 406,159 5.1 IE1i N / t N / t N / t N / t IE1j 129.43 71,074 384,384 5.4 IE1k N / t 77,153 441,024 5.7 IE1l 129.17 78,458 434,070 5.5

[0158] N / t means not tested. As shown by the data in Table 4, the polyolefin products prepared from the attenuated light-off catalysts have higher melting points than the polyolefin products prepared from the faster light-off catalysts used to make them.

[0159] Comparative example using metallocene pre-catalyst 。

[0160] Table 5: Comparative polymerization results of the ignition vial test method using condition (A) and the comparative metallocene pre-catalyst 1 ("MCN1") of formula (1), where n-Bu is n-butyl (1), where n-Bu is n-butyl 。

[0161]

[0162] As shown in Table 5, phenylacetylene has substantially no attenuating effect on the kinetics of the comparative metallocene catalyst made from MCN1.

[0163] Table 6: Comparative polymerization results of the ignition batch reactor test method using condition (A) and the comparative metallocene pre-catalyst 1 ("MCN1") of formula (1), where n-Bu is n-butyl (1), where n-Bu is n-butyl 。

[0164]

[0165] As shown in Table 6, the kinetic modifier compound has substantially no attenuating effect on the kinetics of the comparative metallocene catalyst made from MCN1.

[0166] Table 7: Comparative polymerization results of the ignition batch reactor test method using condition (A) and the comparative metallocene pre-catalyst 2 ("MCN2") of formula (1), where n-Pr is n-propyl (1), where n-Pr is n-propyl 。

[0167]

[0168] As shown in Table 7, the kinetic modifier compound reduces the polymerization productivity and has substantially no attenuating effect on the catalytic activity of the comparative metallocene catalyst made from MCN2.

[0169] Table 8: Comparative polymerization results of the ignition batch reactor test method using condition (A) and the comparative metallocene pre-catalyst 3 ("MCN3") of formula (1) (1) 。

[0170]

[0171] As shown in Table 8, the kinetic modifier compound has substantially no attenuating effect on the catalytic activity of the comparative metallocene catalyst made from MCN3.

Claims

1. A method for preparing a post-metallocene catalyst with reduced ignition, said method comprising reacting a catalyst with a relatively fast ignition with an effective amount 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 )(R 7 )(C 1 ) power A kinetic modifier compound KMC is combined to obtain a post-metallocene catalyst with reduced ignition, and the post-metallocene catalyst with reduced ignition exhibits a monomer absorption curve with reduced ignition; In formula (A 1 ), (B 1 ), or (C 1 ), each of R 5 and R 6 is independently H or R 7 , and each R 7 is independently a (C1-C 20 ) hydrocarbyl, -C(=O)-O-(unsubstituted (C1-C 20 ) hydrocarbyl), (C1-C 19 ) heterohydrocarbyl, or tris((C1-C 20 ) hydrocarbyl)silyl, or two R 7 together form a (C3-C6) alkylene; provided that each R 7 lacks a carbon-carbon double bond; wherein each (C1-C 20 ) hydrocarbyl is independently unsubstituted or substituted with 1 to 4 substituent groups R S ; wherein each substituent group R S is independently selected from 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 (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); wherein the catalyst with faster ignition has the formula (II): and wherein said post-metallocene catalyst with reduced ignition has the formula (III): wherein each of the groups R 1 to R 4 is H, each R H is CH3, and each X is benzyl; wherein A - is an anion for formally balancing the positive charge of the metal M; where M is Hf or Zr; wherein said formula R 5 -C≡C-R 6 (A 1 ) the kinetic modifier compounds are selected from phenylacetylene; substituted phenyl-acetylene; diphenylacetylene; substituted diphenylacetylene; cycloalkylacetylene; formula HC≡CSi(phenyl) h ((C1-C 20 )alkyl) 3-h acetylene, wherein the subscript h is an integer from 0 to 3; and formula HC≡C-(CH2) m CH3 acetylene, wherein the subscript m is an integer from 1 to 15, wherein said formula (R 5 )2C=C=C(R 6 )2(B 1 ) the kinetic modifier compounds are selected from cycloalkylallene; alkylallene; dialkylallene; trialkylallene; trialkylsilylallene; vinylidenecycloalkane; and alkyl esters of allenoic acid, wherein the kinetic modifier compound of the formula (R 5 )(R 7 )C═C(R 6 )(R 7 )(C 1 ) is an internal olefin, and wherein each R is of formula (A), (B) or (C): -C(R 5 )=C(X)R 6 (A), -C(R 5 )2-C(X)=C(R 6 )2 (B) or -C(R 5 )(R 7 )-C(X)(R 6 )(R 7 )(C), a ligand obtained from or derived from a kinetic modifier compound of formula (A 1 ), (B 1 ) or (C 1 ); and wherein R 5 to R 7 are as previously defined in formula (A 1 ), (B 1 ) or (C 1 ), and X is as defined in formula (II); and Before the combining step, the method further includes the step of preparing the catalyst with faster ignition by activating a post-metallocene precatalyst of formula (I) with an activator under effective activation conditions: Thereby, the catalyst with relatively fast ignition is prepared, wherein R 1 to R 4 , R H , M and X are as defined in the previous formula (II), and wherein the activator is an alkylaluminoxane, an organoborane compound or an organoborate.

2. The method according to claim 1, wherein the kinetic modifier compound is selected from: (C6H5)C≡CH; (4-CH3-C6H4)C≡CH; (2,4,5-(CH3)3-C6H2)C≡CH; 1,3,5-(HC≡C)3(C6H3); (C6H5)C≡C(C6H5); (3-F-C6H4)C≡CH; (4-F- C6H4)C≡CH; (3,4-F2-C6H3)C≡CH; (3,5-F2-C6H3)C≡CH; C6H11C≡CH; (C6H5)(CH3)2SiC≡CH; CH3(CH2)2C≡CH; CH3(CH2)5C≡CH; HC≡C(CH2)4C≡CH.

3. The method according to claim 1, wherein the kinetic modifier compound is selected from: (C6H11)C(H)=C=CH2; H2C=C=CH-C(=O)-O-CH2CH3; and (CH3)2C=C=CH2.

4. The method according to claim 1, wherein the kinetic modifier compound is 2-butene, 2-pentene or 1,2-diphenylethylene.

5. The method according to any one of claims 1 to 4, wherein the method further includes preparing a mixture of the post-metallocene catalyst with reduced ignition, a support material and an inert hydrocarbon solvent, and removing the inert hydrocarbon solvent from the mixture to obtain the post-metallocene catalyst with reduced ignition disposed on the support material.

6. A post-metallocene catalyst with reduced ignition, which is prepared by the method according to any one of claims 1 to 5.

7. A method for feeding a post-metallocene catalyst into a slurry-phase or gas-phase polymerization reactor containing an olefin monomer and a moving bed of a polyolefin polymer, the method including preparing the post-metallocene catalyst with reduced ignition outside the reactor according to any one of claims 1 to 5, and feeding the post-metallocene catalyst with reduced ignition in pure form or as a solution or slurry thereof in an inert hydrocarbon liquid into the slurry-phase or gas-phase polymerization reactor through a feed line free of olefin monomers.

8. A multimodal catalyst system, which includes the post-metallocene catalyst with reduced ignition according to claim 6 and at least one second catalyst selected from the group consisting of: the catalyst with faster ignition described in claim 1 and a metallocene catalyst.

9. A method for preparing a polyolefin polymer, the method comprising contacting at least one 1-olefin monomer with the ignition-attenuated post-metallocene catalyst prepared by the method according to any one of claims 1 to 5 or the multimodal catalyst system according to claim 8 in a slurry-phase or gas-phase polymerization reactor containing a moving bed of polyolefin resin under slurry-phase or gas-phase polymerization conditions to prepare the polyolefin polymer.

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