Weakened Mixed Catalyst

Abstract

The present invention relates to a method for preparing a mixed catalyst with reduced ignition, which comprises reacting a catalyst with a faster ignition rate with an effective amount of a compound of formula (A) as defined herein under effective reaction conditions. 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 ) to obtain a weakened mixed catalyst, the weakened mixed catalyst exhibiting a weakened ignition kinetic curve (relative to the kinetic curve of the catalyst that ignites faster); wherein the catalyst that ignites faster has been activated by structural formula (I) as defined herein: (Cp)(L) k (X) x (I) Preparation of mixed precatalysts (i.e., unactivated "ligand entities" or "ligand-metal complexes"); and related methods, compositions and uses.

Description

[0001] Olefin polymerization catalysts, processes and polyolefins prepared thereby.

[0002] Preface

[0003] Publications and patents in the field include EP 0 188 914 A2, EP 0 748 823 A1, EP 1 778 738 A1, EP 2 121 776 A1, EP 2 609 123 A1, US 5,624,878, US 5,965,677, US 6,083,339 B2, US 6,967,184 B2, US 7,705,157 B2, US 8,455,601 B2, US 8,609,794 B2, US 8,835,577 B2, US 9,000,108 B2, US 9,029,487 B2, US 9,234,060 B2, US 9,718,900 B2, US 2009 / 0306323 A1, US 2017 / 0081444 A1, US 2017 / 0101494 A1, US 2017 / 0137550 A1, US 2018 / 0002464 A1, US 2018 / 0282452 A1, US 2018 / 0298128 A1, WO 2006 / 066126 A2, WO 2009 / 064404 A2, WO 2009 / 064452 A2, WO 2009 / 064482 A1, WO 2011 / 087520 A1, WO 2012 / 027448, WO 2013 / 070601 A2, WO 2014 / 105411 A1、WO 2016 / 172097 A1, WO 2017 / 058858, WO 2017 / 058981 A1, WO 2018 / 022975 A1, WO 2020 / 055893 A1 and WO 2018 / 183026 A1.

[0004] Among them, US 8,609,794 B2, US 9,000,108 B2, US 9,029,487 B2, US 2017 / 0081444A1, US 2017 / 0101494 A1, US 2017 / 0137550 A1, US 2018 / 0002464 A1, US 2018 / 0282452A1, WO 2017 / 058858 and WO 2018 / 022975 A1 were assigned to Dow Global Technologies LLC, a subsidiary of The Dow Chemical Company, and describe biphenylphenoxy-type (BPP-type) precatalysts and catalysts, their synthesis and their use in olefin polymerization reactions.

[0005] US 6,967,184 B2 was issued to Timothy T. Wenzel ("Wenzel") and US 9,718,900 B2 was issued to Garth R. Giesbrecht ("Giesbrecht"), both of which were assigned to Univation Technologies, LLC, a wholly owned subsidiary of The Dow Chemical Company, Midland, Michigan, USA. Wenzel and Giesbrecht describe HN5-type precatalysts and catalysts, their synthesis and their use in gas-phase olefin polymerization reactions.

[0006] US 6,803,339 B2 was awarded to Richard A. Hall et al. ("Hall") and is listed as assigned to BP Corporation North America Inc. Hall noted the problems with metallocene catalysts when they are fed into a polymerization reactor in an olefin monomer stream. "Metallocene catalysts are difficult to use directly in conventional polymerization processes, and particularly in gas phase processes where the catalyst system is to be dispersed in hydrocarbons or monomers and metered into the reactor via a feed line. Supported metallocene catalysts have optimal activity when preactivated, i.e., when combined with a cocatalyst component before introduction into the reactor. Dispersing such catalysts in an olefin monomer stream for direct feeding into a reactor system results in polymer formation and severe plugging of the feed line. In addition, polymerization is carried out 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 agglomerations and plating. Reactors rapidly foul, thereby reducing catalyst production and requiring frequent shutdowns to clean the reactor." (Column 2, lines 50 to 65; emphasis added.)

[0007] Hall elaborates on solutions that others have tried before. "Temporarily reducing the activity of metallocene catalysts has been described in the art. For example, adding 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, the catalyst activity can only be partially retarded by such treatment. When dispersed in the monomer feed stream, the catalyst treated directly with dialkylborane or dialkylaluminum remains sufficiently active 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 the catalyst is recovered and polymerization is carried out." (Column 3, lines 14-26; emphasis added.)

[0008] Hall seeks a method for temporarily and reversibly deactivating a metallocene catalyst whereby the catalyst activity is reduced to a level that will allow the catalyst to be fed to a reactor in contact with olefin monomer and fully dispersed in the reactor polymer bed prior to reactivation (column 3, lines 49 to 55). That is, Hall seeks a method that will allow a temporarily substantially deactivated metallocene catalyst to be fed to a polymerization reactor in an olefin monomer stream.

[0009] Hall's solution is directed to a metallocene catalyst that can be temporarily and reversibly deactivated by contact with an effective amount of an unsaturated hydrocarbon deactivating compound (Abstract). Hall's solution is also directed to a method of temporarily and reversibly deactivating a metallocene catalyst, wherein a fully activated metallocene catalyst can be temporarily and reversibly deactivated by contact with an effective amount of a deactivating compound (column 3, lines 58 to 62). The temporarily and reversibly deactivated metallocene catalyst is further characterized as a latent olefin polymerization catalyst and will have a substantially reduced activity for polymerizing olefins (column 3, lines 63 to 66).

[0010] Thus, Hall seeks to temporarily substantially deactivate (poison) a metallocene catalyst so that the resulting temporarily substantially deactivated metallocene catalyst can be fed into a reactor in an olefin monomer stream, and the temporarily substantially deactivated metallocene catalyst will not polymerize the olefin monomers in the feed stream or plug a feed line. This will give Hall time to disperse the temporarily substantially deactivated metallocene catalyst in a polymer bed in the reactor, and wherein the temporarily substantially deactivated metallocene catalyst will be reversibly reactivated. Thus, Hall's metallocene catalyst is fully activated or substantially deactivated, and in the presence of olefin monomers in an olefin monomer feed stream, the substantially deactivated metallocene catalyst is fed into a reactor. Summary of the invention

[0011] We find that there is a problem with the separate feeding (that is, separation from monomer and polyolefin polymer particles) of mixed catalyst (that is, catalyst with only one cyclopentadienyl-containing part) into gas phase olefin polymerization reactor. Olefin polymerization is an exothermic reaction that can be carried out in solution phase, slurry phase or gas phase. The essence of gas phase polymerization is to make it have the minimum mass for absorbing the heat of reaction exotherm. We find that even when the active mixed catalyst is separated from the olefin monomer feed (and for that matter, separated from the active polyolefin polymer particles) and fed into the gas phase polymerization reactor containing olefin monomer and polyolefin polymer moving bed, such as when the active mixed catalyst is fed into the reactor as a solution or slurry in an inert hydrocarbon solvent (for example, alkane or xylene), once the active mixed catalyst is in the reactor inside and experiences polymerization conditions (for example, high temperature and high pressure), the active mixed catalyst may light off too fast in the gas phase polymerization reactor. That is, when the mixed catalyst is fed (e.g., injected), and before the "faster-lighting" catalyst can be fully dispersed into the moving resin bed, the catalyst begins to produce polymer particles in the reactor near the catalyst injection site. This locally generates heat faster than it can be absorbed, causing the polymer particles to fuse together, forming aggregates. These aggregates foul reactor components and / or impair the properties of the polyolefin product.

[0012] In addition, when a hybrid 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.

[0013] 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.

[0014] Our technical solution to the problem of "faster light-off" hybrid catalysts is as follows: an effective amount of a kinetic modifier compound is used to modify the molecular structure of the hybrid catalyst so that the resulting structurally modified hybrid catalyst has a new molecular structure and retains activity, but exhibits a characteristic light-off reduced kinetic curve when fed separately from the olefin monomer feed to a gas phase polymerization reactor (a "mixed catalyst with reduced light-off", or more simply "a weakened hybrid catalyst"). For example, the weakened kinetic curve may include a peak reaction temperature (Temperature) of the weakened hybrid 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 mixed catalyst show that the catalytic activity / polymerization productivity (expressed as the grams of the dry polyolefin product prepared / 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 from the prior art.

[0015] A method for preparing a mixed catalyst with reduced light-off ("reduced mixed catalyst"), the method comprising reacting a catalyst with a faster light-off with an effective amount of a compound of formula (A) as defined herein under effective reaction conditions. 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 ) to obtain a weakened mixed catalyst, the weakened mixed catalyst exhibiting a weakened ignition kinetic curve (relative to the kinetic curve of the catalyst that ignites faster); wherein the catalyst that ignites faster has been activated by structural formula (I) as defined herein: (Cp)(L) k (X) x (I) Preparation of a mixed precatalyst (ie, an unactivated "ligand entity" or "ligand-metal complex").

[0016] An attenuated mixed catalyst prepared by a preparation method.

[0017] A method for feeding a mixed catalyst to a gas phase polymerization reactor containing a moving bed of olefin monomer and polyolefin polymer, the method comprising preparing an abated mixed catalyst according to the above method and feeding the abated mixed catalyst into the gas phase polymerization reactor through a feed line free of olefin monomer in a pure state (e.g., dry powder) or as a solution or slurry thereof in an inert hydrocarbon liquid.

[0018] A multimodal (eg, bimodal or trimodal) catalyst system comprising an attenuated mixed catalyst and one or more different olefin polymerization catalysts.

[0019] A method for feeding a multimodal (e.g., bimodal or trimodal) catalyst system to a gas phase polymerization reactor containing a moving bed of olefin monomer and polyolefin polymer, the method comprising preparing an abated mixed catalyst according to the method described above, contacting a solution of the abated mixed catalyst and an activated metallocene catalyst in an inert hydrocarbon solvent with a support material (e.g., fumed silica) so as to prepare a slurry of the multimodal (e.g., bimodal or trimodal) catalyst system, the multimodal catalyst system consisting essentially of the abated mixed catalyst and the activated metallocene catalyst co-supported on the same support material and suspended in an inert hydrocarbon solvent; optionally removing the inert hydrocarbon solvent from the slurry so as 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 or into a gas phase polymerization reactor through a feed line free of olefin monomer.

[0020] A process for preparing polyolefin polymers comprising contacting at least one 1-olefin monomer with an abated mixed catalyst or a multimodal (e.g., bimodal or trimodal) catalyst system under gas phase polymerization conditions in a gas phase polymerization reactor containing a moving bed of polyolefin resin to prepare polyolefin polymers.

[0021] A polyolefin polymer is produced by a preparation method thereof.

[0022] A manufactured product made from polyolefin polymers. DETAILED DESCRIPTION

[0023] The entire content of the Summary section is incorporated herein by reference.Additional embodiments follow; some embodiments are numbered for ease of reference.

[0024] Aspect 1. A method for preparing a weakened mixed catalyst ("mixed 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 compound of formula (A 1 )、(B 1 ) or (C 1 ): R 5 -C≡CR 6 (A 1 )、(R 5 )2C=C=C(R 6 )2(B 1 ) or (R 5 )(R 7 )C=C(R 6 )(R 7 )(C 1 ) in combination with a kinetic modifier compound ("KMC") to obtain a mixed catalyst with reduced light-off, wherein the mixed catalyst with reduced light-off exhibits a kinetic curve of reduced light-off (relative to the kinetic curve of a catalyst with faster light-off); wherein the catalyst with faster light-off has been activated by the structural formula (I): (Cp)(L) k (X) x (I) Preparation of a mixed precatalyst; wherein in formula (A 1 )、(B 1 ) or (C 1 ), R 5 and R 6 Each of which is independently H or R 7 , and each R 7 Independently (C 1 -C 20 )alkyl, -C(=O)-O-(unsubstituted C1-C 20 )alkyl), (C1-C 19 ) heteroalkyl or tri((C1-C 20 )alkyl)silyl, or two R 7 together to form a (C3-C6)alkylene group; provided that each R 7 lacks carbon-carbon double bonds; each (C1-C 20 ) The hydrocarbon groups are independently unsubstituted or substituted by 1 to 4 groups R S Substituted; 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 in formula (I): metal M is Ti, Hf or Zr; subscript k is 0 or 1; subscript x is 1, 2 or 3; Cp group is an unsubstituted cyclopentadienyl group; a cyclopentadienyl group substituted with a hydrocarbon group; or a cyclopentadienyl group substituted with an organic heteroyl group; group L is a monodentate organic heteroyl group; each X is a monodentate group independently selected from the following: a halogen atom; ((C1-C5) alkyl); 20 )alkyl) 3-g -(phenyl) g Si-, wherein the subscript g is 0, 1, 2 or 3; CH3; (C2-C 20 )alkyl-CH2; (C6-C 12 )aryl-((C0-C 10 )alkylene)-CH2 (for example, 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 4-(C1-C 20 )alkyl-substituted 1,3-butadiene molecules, and each of the remaining X, if any, is independently a monodentate group X. Each monodentate group X can provide a tooth number κ of 1 to M, and wherein at least one group X acts as a leaving group during the activation step, and optionally, at least one group X acts as a leaving group during the combination step. In some embodiments, at least one X does not leave but remains coordinated to M). X is 4-(C1-C 20) alkyl-substituted 1,3-butadiene molecules, which can provide M with a Haptor number η (eta) of 2 or 4 2 (“η 2 ”) or eta 4 (“η 4 ”)), and each of the remaining Xs (if any) is independently a monodentate group X. The Cp group may be an unsubstituted cyclopentadienyl group and may provide M with a Haptor number η (eta) of 5 5 (“η 5 ”)) and a tooth number κ of 0; or the Cp group may be a cyclopentadienyl group substituted with a hydrocarbon group consisting of carbon and hydrogen atoms, and may provide a Hapto number η (eta) of 5 to M 5 (“η 5 ”)) and a tooth number κ of 0; or the Cp group may be a cyclopentadienyl group substituted with an organic heteroalkylene group, and may provide a Hapto number η (eta) of 5 to M 5 (“η 5 ”)) and a tooth number κ of 1. The group L is a monodentate organic heteroyl group and can provide a tooth number κ of 1 to M. In some aspects, each R 7 Independently (C1-C 20 ) hydrocarbon group, which independently may be unsubstituted or substituted with 1 to 3 substituents selected from halogen (e.g., F) and alkyl (e.g., CH3), provided that each R 7 Lack of carbon-carbon double bonds. For the removal of all doubts, the monodentate group X does not contain a carbon-carbon double bond or a carbon-carbon triple bond, ie the monodentate group X is not an alkenyl group or an alkynyl group.

[0025] Aspect 2. The method according to aspect 1, wherein the catalyst with faster ignition has the formula (II): (Cp)(L) k (X) x-1 A - (II), wherein the subscripts k and x, the metal M, and the ligand L and the leaving group X are as defined in formula (I); and wherein the attenuated mixed catalyst has the formula (III): (Cp)(L) k (X) x-2 (R)A - (III); wherein the subscripts k and x, the metal M, and the ligand L are as defined in formula (I); each X is a monodentate group as defined in formula (I); wherein A - is an anion (used to formally balance 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(R5 )(R 7 )-C(X)(R 6 )(R 7 )(C); and wherein R 5 To R 7 As in the previous formula (A 1 )、(B 1 ) or (C 1 ). To remove all doubts, the ligand R of formula (A), (B) or (C) is obtained or derived from formula (A) 1 )、(B 1 ) or (C 1 ). For the removal of all doubts, each ligand R of formula (A) and (B) contains a carbon-carbon double bond (i.e., an alkenyl group). For the removal of all doubts, the ligand R is structurally different from the leaving group X, i.e., the definition of the ligand R does not overlap with the definition of the leaving group X.

[0026] Aspect 3. The method according to aspect 1 or 2, wherein the mixed precatalyst has formula (Ia): CpM(X) x (Ia), wherein the metal M is Ti, Hf or Zr; the subscript x is 1, 2 or 3; Cp is a cyclopentadienyl group substituted with the organic heteroylene group; and each X is as defined in formula (I). Without being bound by theory, it is believed that the structure of the catalyst with faster ignition made from the mixed precatalyst of formula (Ia) has the formula (IIa): CpM(X) x-1 A - (IIa), and wherein the attenuated mixed catalyst has the formula (IIIa): CpM(X) x-2 (R)(IIIa); wherein the subscript x, the metal M, and the ligand Cp are as defined in formula (Ia), and X is as defined in formula (I); wherein A - As defined in formula (II); and wherein R is as defined in formula (III).

[0027] Aspect 4. The method according to aspect 3, wherein the mixed precatalyst of formula (I) has formula (Ia)-1 Each group R a1 and R a2 Independently (C1-C 20 )alkyl (e.g., (C2-C5)alkyl, e.g., 1,1-dimethylethyl); and each group R a3 are independently H or (C1-C 20)alkyl (e.g., (C1-C4)alkyl, for example, each is 1,1-dimethylethyl); each subscript 1-5 is independently 0, 1, 2, 3, 4 or 5; and M, X and subscript x are as defined in formula (I). Without being bound by theory, it is believed that the structure of the catalyst with faster ignition made from the mixed precatalyst of formula (Ia)-1 has formula (IIa)-1: And wherein the weakened mixed catalyst has formula (IIIa)-1: Wherein the metal M, and each subscript 1-5 and the group R a1 To R a3 and subscript x is as defined in formula (Ia)-1; X is as defined in formula (I); wherein A - As defined in formula (II); and wherein R is as defined in formula (III). In some embodiments, the hybrid precatalyst has formula (Ia)-1a: Among them, each group R a1 , R a2 and R a3 and M and subscripts 1-5 are as defined above. In some embodiments, M is Ti. The mixed precatalyst of formula (Ia)-1 may be any one of those described in US 5,624,878.

[0028] Aspect 5. The method according to aspect 4, wherein in the mixed precatalyst of formula (Ia)-1, the group R a1 is 1,1-dimethylethyl; and the group R a2 and R a3 Each is methyl; M is Ti; the subscript x is 1 and X is the molecule 1,3-pentadiene; and the mixed precatalyst of formula (Ia)-1 is precatalyst (1) ("PreCat 1"). Precatalyst (1) was synthesized according to the general procedure of US 5,624,878 (eg, Example 17). Another embodiment of the invention is the precatalyst (1) itself.

[0029] Aspect 6. The method according to aspect 1 or 2, wherein the mixed precatalyst of formula (I) has formula (Ib): (Cp)(L)(X) x (Ib); wherein M, L, X and subscript x are as defined in formula (I); and Cp is an unsubstituted cyclopentadienyl group or a hydrocarbyl-substituted cyclopentadienyl group. In some embodiments, the hybrid precatalyst has formula (Ib)-1: Each group R b1 Independently (C1-C 20 )alkyl (e.g., (C2-C5)alkyl, e.g., 1,1-dimethylethyl); and each group Rb2 are independently H or (C1-C 20 )alkyl (e.g., (C1-C4)alkyl, for example, each is 1,1-dimethylethyl); each subscript 1-5 is independently 0, 1, 2, 3, 4 or 5; and M and X are as defined in formula (I). Without being bound by theory, it is believed that the structure of the catalyst with faster ignition made from the mixed precatalyst of formula (Ib)-1 has formula (IIb)-1: And wherein the weakened mixed catalyst has formula (IIIb)-1: wherein each subscript 1-5 and groups Rb1 to Rb2 are as defined in formula (Ib)-1; and M and X are as defined in formula (I); wherein A - As defined in formula (II); and wherein R is as defined in formula (III). The mixed precatalyst of formula (Ib)-1 may be any one of those described in US 5,965,677.

[0030] Aspect 7. The method according to aspect 6, wherein in the mixed precatalyst of formula (Ib)-1, M is Hf, each X is methyl; and the mixed precatalyst of formula (Ib)-1 is precatalyst (2): ("PreCat2"); wherein Me is methyl. Precatalyst (2) was synthesized according to the procedure of US 5,965,677 (eg, Example 8);. Another embodiment of the present invention is precatalyst (2) itself.

[0031] Aspect 8. The method according to any one of aspects 1 to 7, wherein the kinetic modifier compound is described by any one of 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 ); (vi) having the formula (C 1 Without being bound by theory, it is believed that formula (A 1 ) and (B 1) produces R ligands (A) and (B), respectively, each of which 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 atom selected from halogen atoms, O, N and Si; alternatively O or N; alternatively O and Si; alternatively N and Si; alternatively O; alternatively N; alternatively Si.

[0032] Aspect 9. The method according to any one of aspects 1 to 8, wherein the kinetic modifier compound has the formula (A 1 ): R 5 -C≡CR 6 (A 1 ), the kinetic modifier compound is selected from: phenylacetylene; (substituted phenyl)acetylene; diphenylacetylene; substituted diphenylacetylene; cycloalkylacetylene; HC≡CSi(phenyl) h ((C1-C 20 )alkyl) 3-h Acetylene, wherein the subscript h is an integer from 0 to 3; and the formula HC≡C-(CH2) m CH3 acetylene, wherein the subscript m is an integer from 1 to 15, alternatively from 1 to 10, alternatively from 2 to 15. In the 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-C 20 )alkyl) 3-h , wherein the subscript h is as defined above; -C(H)=C(X)-(CH2) m CH3, wherein subscript m is as defined above; or -CH2-C(X)=C(alkyl)2. Subscript m may 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.

[0033] Aspect 10. The method according to any one of aspects 1 to 9, wherein the kinetic modifier compound has the formula (A 1 ): R 5 -C≡CR 6 (A 1). The (substituted phenyl)acetylene may 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.

[0034] Aspect 11. The method according to any one of aspects 1 to 10, wherein the kinetic modifier compound has the formula (A 1 ): R 5 -C≡CR 6 (A 1 ), and 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-tris(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 11 C≡CH); kinetic modifier compound (11) ("KMC11"): phenyldimethylsilyl acetylene (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-octanediyne (i.e., HC≡C(CH2)4C≡CH).

[0035] Aspect 12. The method according to any one of aspects 1 to 8, 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: cycloalkyl propadiene; alkyl propadiene; dialkyl propadiene; trialkyl propadiene; trialkylsilyl propadiene; vinylidene cycloalkanes; and alkyl esters of propadiene carboxylic acids. The cycloalkyl propadiene may be ((C3-C8)cycloalkyl)propadiene, alternatively cyclohexylpropadiene. The alkyl propadiene may be methylpropadiene, ethylpropadiene, propylpropadiene, or (1,1-dimethylethyl)propadiene. The dialkyl propadiene may be 1,1-dialkylpropadiene or 1,3-dialkylpropadiene; alternatively 1.1-dimethylpropadiene. The trialkyl propadiene may be 1,1,3-trimethylpropadiene. The trialkylsilyl propadiene may be trimethylsilyl propadiene, triethylsilyl propadiene, or dimethyl, (1,1-dimethylethyl) silyl propadiene (ie, tert-butyl-dimethyl-silyl propadiene). The vinylidene cycloalkane may be of the formula of vinylidenecyclohexane.

[0036] Aspect 13. The method according to any one of aspects 1 to 8 and 12, wherein the kinetic modifier compound has the formula (B 1 ):(R 5 )2C=C=C(R 6 )2(B 1 ), and formula (B 1 ) is selected from the group consisting of any one of KMC15 to KMC17: Kinetic modifier compound (15) ("KMC15"): cyclohexyl propadiene (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-dimethylpropadiene (i.e., (CH3)2C=C=CH2).

[0037] Aspect 14. The method according to any one of aspects 1 to 8, wherein the kinetic modifier compound has the formula (C 1 ):(R 5 )(R 7 )C=C(R 6 )(R 7 )(C 1 ), and formula (C 1) is an internal olefin. Therefore, the internal olefin does not have a terminal carbon-carbon double bond or a terminal carbon-carbon triple bond. The internal olefin can be selected from KMC18 to KMC20: kinetic modifier compound (18) ("KMC18"): 2-butene; kinetic modifier compound (19) ("KMC19"): 2-pentene and kinetic modifier compound (20) ("KMC20"): 1,2-diphenylethylene. In formula (III) of aspect 2, the corresponding ligand R can 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, respectively.

[0038] Aspect 15. The method according to any one of aspects 1 to 14 further comprises, before the combining step, a step of preparing a catalyst with faster ignition by activating a pre-catalyst of formula (I) with an activator under effective activation conditions, thereby preparing a catalyst with faster ignition. In some embodiments, the activator is an alkylaluminoxane, an organic borane compound, or an organic borate.

[0039] Aspect 16. A method according to any one of aspects 1 to 15, wherein the method further comprises preparing a mixture of the weakened mixed catalyst, a support material and an inert hydrocarbon solvent, and removing the inert hydrocarbon solvent from the mixture to obtain the weakened mixed catalyst disposed on the support material. The mixture may also include an excess of an activator, since the activator is typically used in excess to activate the mixed precatalyst. The removal step may be achieved by conventionally evaporating the inert hydrocarbon solvent from the mixture (i.e., a conventional concentration method), which produces an evaporated / supported weakened mixed catalyst. Alternatively, the removal step may be achieved by spray drying the mixture. The spray drying embodiment provides a spray-dried / supported weakened mixed catalyst that may have improved performance relative to the evaporated / supported weakened mixed 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 hydrophobic agent. The hydrophobic 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.

[0040] Aspect 17. A weakened hybrid catalyst prepared by a method according to any one of aspects 1 to 16. The weakened hybrid catalyst may have the previously described formula (III), or be based on the previously described formula (III). In some embodiments, the weakened hybrid catalyst is prepared from a mixed precatalyst of formula (Ia)-1, (Ia)-1a or (Ib)-1, alternatively formula (Ia)-1, alternatively formula (Ia)-1a, alternatively formula (Ib)-1.

[0041] Aspect 18. A method for feeding a mixed catalyst to a slurry phase or gas phase polymerization reactor containing a moving bed of olefin monomers and polyolefin polymers, the method comprising preparing the weakened mixed catalyst outside the reactor and according to any one of aspects 1 to 16, and feeding the weakened mixed catalyst into the slurry phase or gas phase polymerization reactor in a pure state (e.g., dry powder) or as a solution or slurry thereof in an inert hydrocarbon liquid through a feed line that does not contain olefin monomers. In an embodiment, the method also includes transferring the weakened mixed catalyst or the fully active mixed catalyst prepared in situ from the reactor to a (second) gas phase polymerization reactor, wherein the catalyst catalyzes a second olefin polymerization reaction.

[0042] Aspect 19. A multimodal (e.g., bimodal or trimodal) catalyst system comprising an attenuated mixed catalyst according to Aspect 17 and at least one second catalyst selected from the group consisting of: an unattenuated mixed catalyst as described herein, a different attenuated mixed catalyst, a post-metallocene catalyst, and a metallocene catalyst. In some embodiments, the multimodal catalyst system comprises an attenuated post-metallocene catalyst according to Aspect 17 and only one second catalyst, alternatively only two different second catalysts. The multimodal catalyst system may also include a support material, and the attenuated mixed catalyst and the metallocene catalyst may be disposed (e.g., spray dried) on the support material. The attenuated mixed catalyst and the metallocene catalyst of the multimodal catalyst system may have an ignition curve measured by the ignition vial test method (described later), wherein their respective peak polymerization temperatures (Temp peak) within 60 minutes, alternatively within 45 minutes, alternatively within 30 minutes. When the second catalyst is the metallocene catalyst, the light-off properties of the catalysts of the multimodal catalyst system may advantageously be compatible, so that polymerisation with the multimodal catalyst system to produce a multimodal (e.g. bimodal or trimodal) polyolefin polymer comprising a higher molecular weight (HMW) component and a lower molecular weight (LMW) component made from the attenuated mixed catalyst does not produce an excessive amount of the HMW component relative to the LMW component and thus produces less off-spec multimodal polyolefin polymer, or does not produce off-spec multimodal polyolefin polymer.

[0043] Aspect 20. A method for feeding a multimodal (e.g., bimodal or trimodal) catalyst system to a slurry phase or gas phase polymerization reactor containing a moving bed of olefin monomer and polyolefin polymer, the method comprising preparing the abated mixed catalyst outside the reactor and according to the method of any one of Aspects 1 to 16, contacting a solution of the abated mixed 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 essentially consisting of the abated mixed catalyst and the activated metallocene catalyst co-supported on the same support material and suspended in the 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.

[0044] Aspect 21. A method for preparing a polyolefin polymer, the method comprising contacting at least one 1-olefin monomer with an abated mixed catalyst prepared by the method according to any one of aspects 1 to 16, or a multimodal catalyst system according to aspect 19, in a slurry phase or gas phase polymerization reactor containing a moving bed of polyolefin resin, respectively, under slurry phase or gas phase polymerization conditions, thereby preparing the polyolefin polymer. The method may include a step before the contacting step, the step comprising: feeding the abated mixed catalyst prepared by the method according to any one of aspects 1 to 16, or the multimodal catalyst system according to aspect 18, into a slurry phase or gas phase polymerization reactor containing a moving bed of polyolefin resin and at least one 1-olefin monomer, respectively, under slurry phase or gas phase polymerization conditions, so as to allow abated ignition of the abated mixed catalyst and subsequent polymerization of the at least one 1-olefin monomer, thereby preparing the 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 an embodiment, 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 these polymerization conditions may be slurry phase polymerization conditions. In some such embodiments, the method may also include transferring active polymer particles prepared in the first gas phase polymerization reactor under first gas phase polymerization conditions or prepared in the slurry phase polymerization reactor under slurry phase polymerization conditions, and in either case containing (in the particles) an active mixed catalyst to a (second) gas phase polymerization reactor under (second) gas phase polymerization conditions (these gas phase polymerization conditions are 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), thereby preparing a multimodal (e.g., bimodal or trimodal) polyolefin polymer (i.e., having a multimodal (e.g., bimodal or trimodal) molecular weight distribution (M) in the (second) gas phase polymerization reactor). w / M n ) of polyolefin polymers).

[0045] Aspect 22. A polyolefin polymer prepared by the preparation method according to aspect 21. The polyolefin polymer obtained from the slurry phase or gas phase polymerization reactor as raw form may be in the form of particles, and the polyolefin polymer has a lower amount of aggregates (fused particles) than a comparative polyolefin polymer obtained in raw form from a slurry phase or gas phase polymerization reactor, respectively, operating under the same polymerization conditions except that the weakened mixed catalyst is replaced by the faster-lighting catalyst.

[0046] Aspect 23. A manufactured article (eg, a blown film or cast film) made from the polyolefin polymer according to aspect 22. The manufactured article may have a lower gel number than a comparative manufactured article made from a comparative polyolefin polymer.

[0047] Aspect 24. The embodiment of the present invention according to any one of aspects 1 to 23, wherein the abated mixed catalyst does not contain a support material, for example, does not contain fumed silica or alumina.

[0048] Aspect 25. A hybrid precatalyst selected from the group consisting of the aforementioned hybrid precatalysts of formulas (1) to (2).

[0049] Aspect 26. Prepare a hybrid catalyst by contacting the hybrid precatalyst according to aspect 25 with an activator.

[0050] 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.

[0051] Unsubstituted cyclopentadienyl group. Formula [C5H5] - of carbon anions.

[0052] Hydrocarbyl-substituted cyclopentadienyl groups. The carbanion is formally obtained by replacing one or more hydrogen atoms of an unsubstituted cyclopentadienyl group with one or more hydrocarbyl groups and / or replacing two hydrogen atoms on adjacent ring carbon atoms with one or two hydrocarbylene groups. Examples of such hydrocarbyl groups are (C1-C 10 ) alkyl groups such as methyl, ethyl, 1-methylethyl, propyl and butyl. Examples of such alkylene groups are -C(H)=C(H)-C(H)=C(H)- (e.g., as in an indenyl group, or when two such groups are used, in a fluorenyl group); -C(CH3)=C(H)-C(H)=C(H)-; -C(H)=C(CH3)-C(H)=C(H)-; -C(H)=C(H)-C(CH3)=C(H)-; -C(H)=C(H)-C(H)=C(CH3)-; and -C(H)=C(CH3)-C(H)=C(CH3)-C(H)=C(CH3)- (e.g., as in a 1,5-dimethylindenyl group (in which one methyl group is on a 5-membered ring and one methyl group is on a 6-membered ring) and a 4,6-dimethylindenyl group (in which both methyl groups are on the 6-membered ring)).

[0053] Cyclopentadienyl groups substituted with organic heteroylene groups. Cyclopentadienyl groups substituted with organic heteroylene groups, which are defined later and are divalent heteroatom-containing organic groups, have groups on carbon atoms and groups on heteroatoms (e.g., N). For example, the formula -(R a1 )N(Ra2 )2Si-organic heteroarylene group (as used in formula (Ia)-1), such as tert-(C4-C8)alkylamino-dimethylsilyl group.

[0054] A method for preparing a weakened mixed catalyst. The method comprises mixing a catalyst with a faster ignition speed with an effective amount of a compound of formula (A 1 )、(B 1 ) or (C 1 ) is combined with a kinetic modifier compound to prepare a weakened mixed catalyst. The catalyst that ignites faster may have formula (II), and the weakened mixed catalyst may have formula (III). The combination step may be performed in the absence of a pre-catalyst of formula (I). If the 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 the 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. The ligand is bonded to the metal atom M in the resulting weakened mixed catalyst. In some aspects, the weakened mixed catalyst has formula (III), and the catalyst that ignites faster has formula (II), and the pre-catalyst has formula (I), wherein all M are Ti and each X is methyl or one X is 1,3-pentadiene.

[0055] The embodiment of the preparation method may include any one of Synthesis Schemes 1 to 11.

[0056] Synthesis Scheme 1: Step (a) mixed precatalyst + excess activator → activated mixed catalyst + intermediate mixture of remaining activator. Step (b) intermediate mixture + effective amount of kinetic modifier compound → attenuated mixed catalyst.

[0057] Synthesis Scheme 2: Step (a) mixed precatalyst + effective amount of kinetic modifier compound → intermediate mixed precatalyst (unreacted mixture or reaction product of mixed precatalyst + kinetic modifier compound). Step (b) intermediate mixed precatalyst + activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) → attenuated mixed catalyst.

[0058] Synthesis Scheme 3: Step (a) mixed precatalyst + activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) → activated mixed catalyst (faster light-off catalyst). Step (b) activated mixed catalyst + effective amount of kinetic modifier compound → weakened mixed catalyst.

[0059] Synthesis Scheme 4: Step (a) Activator (eg, alkylaluminoxane, such as methylaluminoxane ("MAO")) + effective amount of kinetic modifier compound → intermediate solution. Step (b) Intermediate solution + mixed precatalyst → light-off reduced mixed catalyst.

[0060] Synthesis Scheme 5: Step (a) Activator → mixed precatalyst ← effective amount of kinetic modifier compound (activator and kinetic modifier are added to mixed precatalyst simultaneously but separately) → attenuated mixed catalyst. Step (b): None.

[0061] Synthesis Scheme 6: Step (a) mixed precatalyst + support material → supported mixed precatalyst. (b) supported mixed precatalyst + a certain amount of activator → the intermediate mixture of activated mixed catalyst + remaining activator is set on the support material (or balanced with the support material). Step (c) intermediate mixture + effective amount of kinetic modifier compound → the weakened mixed catalyst is set on the support material (or balanced with the support material). In some aspects, step (a) also includes an inert hydrocarbon solvent, and the deposition on the support material is performed by evaporating the solvent (alternatively by spray drying). The amount of activator can be a stoichiometric amount relative to the metal M of the mixed catalyst (e.g., a molar ratio of 1.0 to 1.0); alternatively, less than the stoichiometric amount relative to the metal M of the mixed catalyst (e.g., a molar ratio of 0.1 to 0.94); alternatively, an excess amount relative to the metal M of the mixed catalyst (e.g., a molar ratio of 1.1 to 10,000).

[0062] Synthesis Scheme 7: Step (a) mixed precatalyst + effective amount of kinetic modifier compound + support material → intermediate mixture of mixed precatalyst and kinetic modifier compound is disposed on (or equilibrated with) a support material. Step (b) intermediate mixture + activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) → attenuated mixed catalyst is disposed on (or equilibrated with) a support material. In some aspects, step (a) further comprises an inert hydrocarbon solvent, and deposition on the support material is performed by evaporating the solvent (alternatively by spray drying).

[0063] Synthesis Scheme 8: Step (a) mixed precatalyst + support material + activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) → the activated mixed catalyst (the catalyst that ignites faster) is disposed on the support material (or in equilibrium with the support material). Step (b) supported activated mixed catalyst + effective amount of kinetic modifier compound → the weakened mixed catalyst is disposed on the support material (or in equilibrium with the support material). In some aspects, step (a) also includes an inert hydrocarbon solvent, and the deposition on the support material is performed by evaporating the solvent (alternatively by spray drying).

[0064] 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 + mixed precatalyst + support material → the light-off-reduced mixed catalyst is disposed on (or equilibrated with) a support material. In some aspects, step (b) further comprises an inert hydrocarbon solvent, and the deposition on the support material is performed by evaporating the solvent (alternatively by spray drying).

[0065] Synthesis Scheme 10: Step (a) Activator → Mixed Precatalyst + Support Material ← Effective Amount of Kinetic Modifier Compound (Adding Activator and Kinetic Modifier Compound Simultaneously but Separately to Mixed Precatalyst + Support Material Mixture) → Disposing the Attenuated Mixed Catalyst on (or in Equilibrium with) Support Material. Step (b): None. In some aspects, step (a) further comprises an inert hydrocarbon solvent, and deposition on the support material is performed by evaporating the solvent (alternatively by spray drying).

[0066] Scheme 11: Step (a): activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) + support material (e.g., hydrophobic fumed silica) + inert hydrocarbon solvent → a slurry of the supported activator is disposed on the support material (or balanced with the support material). Step (b): spray-dried slurry of step (a) → the spray-dried supported activator is disposed on the support material in dry powder form (e.g., spray-dried MAO ("SDMAO" or "sdMAO") on hydrophobic fumed silica in dry powder form). Step (c): mixed precatalyst + spray-dried supported activator of step (b) + inert hydrocarbon solvent → a suspension of the supported mixed catalyst with faster ignition is disposed on the support material (or balanced with the support material). Step (d): mixing the suspension from step (c) with an effective amount of a kinetic modifier compound → disposing the suspension of the attenuated supported mixed catalyst on (or equilibrated with) a support material in an inert hydrocarbon solvent. Optional step (e): removing the inert hydrocarbon solvent from the suspension of the attenuated supported mixed catalyst → disposing the attenuated supported mixed catalyst on a support material in dry powder form. Step (e) may be performed by conventional evaporation of the inert hydrocarbon solvent from the suspension from step (d) or by spray drying the suspension from step (d).

[0067] A multimodal catalyst system can be prepared to be fed into a gas phase polymerization reactor. If desired, an additional amount of a weakened post-metallocene catalyst or an additional amount of a second catalyst (e.g., a metallocene catalyst) can be fed separately to the reactor as a solution thereof in an inert hydrocarbon solvent, where it contacts the multimodal catalyst system. Such separate catalyst solutions are sometimes referred to as fine-tuning catalysts. Alternatively, the multimodal catalyst system can be contacted with a fine-tuning catalyst feed in a feed line before entering the reactor. In other embodiments, the multimodal catalyst system can be prepared in situ in a gas phase polymerization reactor by adding a weakened post-metallocene catalyst and at least one second catalyst separately to the reactor, where these catalysts contact each other, thereby preparing the multimodal catalyst system in situ in the reactor.

[0068] The method according to any of the above aspects may further comprise the step of transferring polymer particles produced in a gas phase or slurry phase polymerization reactor to a (second) gas phase polymerization reactor, and these polymer particles contain fully active mixed catalyst in the particles.

[0069] Kinetic modifier compound ("KMC"). Formula (A 1 ) is a kinetic modifier compound R 5 -C≡CR 6 (A 1 ). Formula (B 1) is a kinetic modifier compound (R 5 )2C=C=C(R 6 )2(B 1 ). Formula (C 1 ) is a kinetic modifier compound (R 5 )(R 7 )C=C(R 6 )(R 7 )(C 1 ). Formula (A 1 )、(B 1 ) or (C 1 The kinetic modifier compound of formula (A) advantageously has no poisoning effect on the mixed catalyst, or may have at most a slight effect. 1 ) is an alkyne, formula (B 1 ) is propadiene, and the compound of formula (C 1 ) are internal olefins. The kinetic modifier compound does not contain vinyl functionality (ie, lacks a group of the formula -C(H)=CH2).

[0070] In some embodiments, the kinetic modifier compound is as defined in any of the numbered aspects described above.

[0071] In the formula (A 1 )、(B 1 ) or (C 1 In some embodiments of the kinetic modifier compound of (C1-C 20 )alkyl is (C2-C6)alkyl, (C3-C8)cycloalkyl, or phenyl. In some embodiments, -C(=O)-O-(unsubstituted C1-C 20 )alkyl) is -C(=O)-O-(unsubstituted C1-C5)alkyl), alternatively -C(=O)-O-ethyl.

[0072] In some embodiments, at least one X is ((C1-C 20 )alkyl) 3-g -(phenyl) g Si-, wherein the subscript g is 0, 1, 2 or 3, alternatively wherein 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 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 10In some aspects, at least one X, and alternatively each X is (C1-C6)alkoxy-substituted (C6-C 12 )aryl, or (C1-C6)alkoxy-substituted benzyl. Without being bound by theory, it is believed that the structure of the weakened hybrid catalyst is similar to that of the catalyst that ignites faster, except that one of the leaving groups X of the catalyst that ignites faster has been replaced by the weakened leaving group R in the weakened hybrid catalyst, where R is defined later and is derived from the kinetic modifier compound. The weakened leaving group R of the weakened hybrid catalyst is structurally different from the leaving group X of the catalyst that ignites faster and leaves more slowly than the leaving group of the catalyst that ignites faster.

[0073] Ligand R derived from a kinetic modifier compound. The ligand derived from a kinetic modifier compound in the attenuated hybrid catalyst can be a group R ("ligand R"). Without being bound by theory, it is believed that the ligand R is primarily responsible for the improved kinetic profile of the attenuated hybrid catalyst (e.g., of formula (II)) relative to the catalyst (e.g., of formula (III)) from which it is prepared with a faster light-off. The ligand R can have 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 X and R 5 To R 7 Each of which 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 formulas (A) and (B) contain carbon-carbon double bonds, and it is believed that these ligands polymerize extremely slowly under gas phase polymerization conditions.

[0074] Without wishing to be bound by theory, it is believed that the reaction of olefin monomers (e.g., ethylene, propylene, 1-butene, 1-hexene, 1-octene, etc.) with the catalyst that light-off weakens is carried out by inserting the olefin monomer into the bond between the M metal center and the leaving group R that weakens. This insertion may be much slower than the corresponding insertion reaction of olefin monomers in the bond between the M metal center and the leaving group X of the catalyst that light-off is faster. The slower reaction of the present invention can delay the start of polymerization. After the first (or a few) olefin monomer insertion reaction, the weakened leaving group R is no longer bonded to the metal center, so that all subsequent insertions occur at a rate similar to the rate of the catalyst that light-off is faster. Because of the thousands or millions of insertion reactions that the catalyst carries out, only the first (or a few) insertion reaction is slowed down, so the total catalyst productivity may not be significantly reduced. In fact, the catalyst that light-off weakens may have an increased productivity because its heat release is reduced relative to the heat release of the catalyst that light-off is faster. This is because the exothermic reaction increases the temperature experienced by the catalyst, thereby accelerating the deactivation of the catalyst, which can reduce the productivity of some catalysts (such as some mixed catalysts).

[0075] In the ligand R of formula (A), (B) or (C), R 5 and R 6 Each of which is independently H or R 7 , and each R 7 Independently (C1-C 20 )alkyl or (C1-C 17 ) heteroalkyl, provided that each R 7 Lack of carbon-carbon double bonds. (C1-C 20 The hydrocarbon group may be unsubstituted and composed of carbon atoms and hydrogen atoms, or (C1-C 20 The hydrocarbon group may be substituted and consists of carbon atoms, hydrogen atoms 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. 20 ) The hydrocarbon group may be unsubstituted (C1-C 20 ) alkyl, unsubstituted (C3-C 20 )cycloalkyl, unsubstituted (C6-C 12 )aryl, unsubstituted ((C1-C4)alkyl) 1-3 -phenyl, or unsubstituted (C6-C 12 )aryl-(C1-C6)alkyl. 20 ) The hydrocarbon group may be the aforementioned unsubstituted (C1-C 20) a mono- or di-fluoro derivative of a hydrocarbon group, such as 2-(3,4-difluorophenyl)-ethen-1-yl (having formula (A)).

[0076] R 5 To R 7 Each of the embodiments (C1-C 19 ) heteroalkyl includes the same heteroalkyl group, which may be unsubstituted and consists of carbon atoms, hydrogen atoms and at least one heteroatom selected from N and O, or (C1-C 17 The heteroalkyl group may be substituted and consists of carbon atoms, hydrogen atoms, at least one heteroatom selected from N and O, and one or more halogen atoms. 17 ) heteroalkyl may be (C1-C 19 ) heteroalkyl, (C3-C 19 )heterocycloalkyl, (C6-C 12 )heteroaryl, ((C1-C4)alkoxy) 1-3 -phenyl, or (C6-C 12 )heteroaryl-(C1-C6)alkyl. 17 ) heteroalkyl may be the aforementioned unsubstituted (C1-C 17 ) a mono- or di-fluoro derivative of a heteroalkyl group, such as 2-(3,4-dimethoxyphenyl)-ethen-1-yl (having formula (A)).

[0077] The structure of ligand R is different from that of ligand X, and for this substance, the structure of ligand R is different from that of anion A. - structure.

[0078] Weakened mixed catalyst. According to the method, a weakened mixed catalyst (e.g., of formula (III)) is made from a catalyst (e.g., of formula (II)) that ignites faster. The weakened mixed catalyst is a mixed catalyst containing a ligand (e.g., R) bonded to its metal atom M (e.g., Ti, Zr or Hf), and the ligand is derived from a kinetic modifier compound. The weakened mixed catalyst is a new mixed catalyst. In some embodiments, the weakened mixed catalyst is a weakened mixed catalyst of formula (III).

[0079] It is believed that, all other conditions being equal, the attenuated hybrid catalyst (e.g., of formula (III)) may function without significantly reducing the overall catalytic activity relative to the overall catalytic activity of the faster-lighting catalyst (e.g., of formula (II)) from which it is prepared. That is, despite the delayed start, 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 hybrid catalyst that ignites faster, and in some embodiments may be greater than the catalytic activity / polymerization productivity of the hybrid catalyst that ignites faster. For example, the attenuated mixed catalyst may have a productivity of greater than 200%, alternatively 70.0% to 180%, 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 catalyst to prepare it with faster ignition.

[0080] It is believed that the attenuated mixed catalyst of formula (III) can suppress catalyst light-off and advantageously improve the operability of the gas phase reactor by reducing the fouling rate and increasing the time between reactor shutdowns relative to the catalyst from which it is prepared (e.g., of formula (II)) which light-off faster.

[0081] It is believed that the weakened mixed catalyst (e.g., of formula (III)) can exhibit improved polymerization kinetics compared to the faster light-off catalyst of formula (II) from which it is prepared. Such improved polymerization kinetics will advantageously increase the compatibility of the weakened mixed catalyst (e.g., of formula (III)) with slower light-off olefin polymerization catalysts (such as some metallocene catalysts), and the resulting light-off compatible multimodal (e.g., bimodal or trimodal) catalyst system has improved performance relative to the faster light-off catalyst (e.g., of formula (II)) from which it is prepared.

[0082] In addition, it is believed that the weakened hybrid catalyst (e.g., of formula (III)) can be stored and transported at ambient temperature, rather than under refrigerated storage and refrigerated transportation conditions that are expected to be used to prepare the faster-igniting catalyst (e.g., of formula (II)), until the weakened hybrid catalyst can be used in a chemical process. It is believed that the weakened hybrid catalyst (e.g., of formula (III)) can achieve any one of such benefits, or a combination of any two or more such benefits.

[0083] In some embodiments, the attenuated mixed catalyst (e.g., of formula (III)) and the method for polymerizing olefin monomers do not contain a 1 )、(B 1 ) or (C 1 ) of excess kinetic modifier compound. In other embodiments, the attenuated post-metallocene catalyst and method has an excess of kinetic modifier compound. Such embodiments of the attenuated mixed catalyst (e.g., of formula (III)) can be prepared by combining a faster ignition catalyst (e.g., of formula (II)) having a molar ratio of the number of moles of 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 (e.g., 1.0). In such embodiments, formula (A 1 )、(B 1 ) or (C 1 ) is used in a stoichiometric amount (molar ratio 1.0) or in an amount less than stoichiometric (molar ratio>0 to 0.99). When the kinetic modifier compound is used in an amount less than stoichiometric, the resulting (e.g., formula (III)) weakened mixed catalyst has a partially weakened ignition activity relative to the (e.g., formula (II)) faster ignition catalyst prepared therefrom. This partially weakened ignition activity may be helpful when the (e.g., formula (III)) faster ignition catalyst is only slightly overactivated. Generally, the higher the molar ratio of the number of moles of the kinetic modifier compound to the number of moles of the metal M (e.g., formula (II)), the greater the weakening of the overactivity of the (e.g., formula (II)) faster ignition catalyst.

[0084] In some embodiments, the attenuated mixed catalyst (e.g., of formula (III)) and the method for polymerizing olefin monomers contain formula (A 1 )、(B 1 ) or (C 1). Such embodiments of the attenuated mixed catalyst (e.g., of formula (III)) can be prepared by combining a faster light-off catalyst (e.g., of formula (II)) having a molar ratio of moles of the kinetic modifier compound to moles of the metal M of formula (II) greater than 1.0, such as 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. It is noteworthy that in some embodiments, even when the kinetic modifier compound is used in an excess amount within the aforementioned range (KMC / M molar ratio of up to about 50), the catalytic activity of the weakened mixed catalyst (e.g., of formula (III)) and / or the productivity of the gas phase polymerization reaction using it may not be significantly reduced relative to the catalytic activity and productivity of the catalyst (e.g., of formula (II)) that ignites faster to prepare it, and may also be increased. In other embodiments, when the kinetic modifier compound is used in an excess amount, the catalytic activity of the weakened mixed 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 catalyst (e.g., of formula (II)) that ignites faster to prepare it. Although the reason for the reduction is not clear, the excess kinetic modifier compound may compete with the olefin monomer to replace the weakened leaving group R of formula (III) in a balanced manner. When the exact molar amount of the metal M of the faster light-off catalyst (eg, of formula (II)) is not precisely known or may vary from batch to batch, it may be helpful to use an excess of the kinetic modifier compound.

[0085] Kinetic curve of reduced light-off. The reduced mixed catalyst (e.g., of formula (III)) exhibits a kinetic curve of reduced light-off. For example, the reduced kinetic curve may include a peak reaction temperature Temp of the reduced mixed catalyst relative to a catalyst from which it is prepared that has a faster light-off. peak The length of time is longer and / or T max The value of is lower. From the time the catalyst is injected (time zero (Time0)) into the reactor containing olefin monomer but no catalyst until the polymerization reaction peak temperature (Temp peak ) is a longer time of at least 0.65 minutes. peak The larger the value of , the greater the delay in catalyst light-off.

[0086] To compare the light-off time of different catalysts, the same olefin monomer (e.g., 1-octene) and the same reactor were used. For rapid catalyst screening, a 40 mL glass vial was used as the reactor and the light-off vial test method described later was used as the test method.

[0087] An effective amount of a kinetic modifier compound (KMC). An amount of a kinetic modifier compound (KMC) sufficient to reduce the light-off of the catalyst. The effective amount of KMC can be expressed as an absolute value compared to the amount of (pre)catalyst metal M or as a relative value compared to the reduced light-off performance or a combination thereof.

[0088] In some embodiments, the absolute value of the effective amount of the kinetic modifier compound can be expressed as a molar ratio of the number of moles of the kinetic modifier compound to the number of moles of the metal M ("KMC mol / M mol ”), wherein M is the M of the mixed precatalyst of formula (I), for example, M is a Group 4 metal. In some embodiments, the effective amount of KMC is represented by 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 may be described 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 ("M mol / KMC mol") as follows: ≤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, respectively. In general, it is believed that KMC mol / M mol Above about 50 / 1.0 may undesirably prevent light-off or function of a post-metallocene catalyst containing it. However, in some embodiments, for practical reasons (e.g., cost of KMC and / or post-polymerization processing operations / costs (e.g., stripping excess KMC from polyolefin resins)), KMC is preferably 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.

[0089] In terms of weakened 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, a mixed catalyst with weakened ignition and a mixed catalyst with a kinetic modifier compound prepared therefrom that ignites faster; the effective amount of the kinetic modifier compound (KMC) can have any one of the characteristics (i) to (xii) observed after catalyst injection: (i) the time delay in the onset of the exotherm, that is, the reaction temperature rise (i.e., from the addition time zero (Time0) to the temperature exotherm start time (Time exo ) for a longer period of time (in minutes)); (ii) a slower rate of increase in reaction temperature in degrees Celsius per minute (°C / min) (e.g., a lower maximum slope in a plot of reaction temperature on the y-axis versus time after catalyst injection on the x-axis); (iii) a lower peak reaction temperature in °C (Temperature) is reached. peak ); (iv) from the addition time at Time0 to the peak temperature (Time peakT ) is a longer time of at least 0.65 minutes; (v) both of (i) and (ii), but not including (iii) or (iv); (vi) both of (i) and (iii), but not including (ii) or (iv); (vii) both of (ii) and (iii), but not including (i) or (iv); (viii) both of (i) and (iv), but not including (ii) and (iii); (ix) both of (ii) and (iv), but not including (i) or (iii); (x) both of (iii) and (iv), but not including (i) or (ii); any three of (xi) to (iv); and each of (xii) to (iv). In some embodiments, the ignition reduction and effective amount of KMC are characterized by at least feature (iv), alternatively only by feature (iv). In some embodiments, the longer time of feature (iv) is from the addition time at Time0 to the time peak temperature (Time peakT) is at least 0.65 minutes (39 seconds or more), the time peak temperature is at least 0.65 minutes; alternatively at least 1.0 minutes; 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 ignition vial test method described later. In some embodiments, the ignition reduction and effective amount of KMC are characterized by feature (viii). In some embodiments, the light-off reduction is characterized by feature (ix). In some embodiments, the light-off reduction and effective amount of KMC are characterized by feature (x). In some embodiments, the light-off reduction is characterized by feature (xi).

[0090] Weakened mixed catalyst reaches Temp max The time it takes for the catalyst with faster ignition to reach Temp max The time delay may be 0.70 minutes to 500 minutes (eg, 293 minutes is an example), alternatively 0.70 minutes to 120 minutes, alternatively 1.0 minutes to 120 minutes, alternatively 5 minutes to 90 minutes, alternatively 10 minutes to 70 minutes.

[0091] In some embodiments, the kinetic curve of the weakened hybrid catalyst is relative to the Temp of the faster light-off catalyst prepared therefrom when operated under the same polymerization conditions according to the Light-off Batch Reactor Test Method described later. max (℃) can be characterized as peak temperature (Temp peak ) is reduced. In the light-off batch reactor test method, the reduced mixed catalyst Temp max Temp of the catalyst that can be prepared to ignite faster max 1° C. to 16° C. lower, alternatively 2° C. to 15° C. lower, alternatively 3° C. to 14° C. lower. In some embodiments, the hybrid catalyst with faster light-off is made from any of the hybrid precatalysts (1) to (2) described previously.

[0092] In some embodiments, the kinetic curve of the weakened mixed 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 weakened mixed catalyst can be 2.1 to 11, alternatively 2.2 to 10.4, alternatively 2.4 to 10.0, alternatively 3 to 9.9. In some embodiments, the mixed catalyst with faster ignition is made of any one of the mixed precatalysts (1) to (2) described previously.

[0093] In some embodiments, when operated under the same polymerization conditions according to the Light-off Batch Reactor Test Method described later, the kinetic curve of the weakened mixed catalyst can be characterized as the relative C2(1h) / C2(0.1h) ratio of the weakened mixed catalyst C2(1h) / C2(0.1h) ratio to the C2(1h) / C2(0.1h) ratio of the faster light-off catalyst from which it is prepared. The relative C2(1h) / C2(0.1h) ratio can be 1.05 to 6, alternatively 1.1 to 6, alternatively 1.2 to 5.4, alternatively 1.5 to 5.0.

[0094] An alternative or additional way of expressing an effective amount of a kinetic modifier compound (KMC) with respect to attenuated light-off performance, as measured by the Light-off Vial Test Method described later, may be a sufficient amount of KMC such that the attenuated hybrid 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 attenuated mixed catalyst and the faster light-off catalyst prepared therefrom may 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 peak polymerization temperature Temp of the mixed catalyst with delayed attenuation of the kinetic modifier compound peak The influence of the time of the mixed catalyst with faster light-off is compared with the time of the mixed catalyst prepared by the weakened mixed catalyst. peak, may vary depending on: (a) the structural class (e.g., Formula (Ia) or (Ib)) or structural subclass (e.g., Formula (Ia)-1 vs. (Ia)-1a, or Formula (Ia)-1 vs. (Ib)-1) of the attenuated mixed catalyst, and / or (b) the structural class (e.g., acetylene, propadiene, or internal olefin) or structural subclass (e.g., aryl acetylene vs. alkyl acetylene; or monoacetylene vs. diacetylene or triacetylene; or acyclic propadiene vs. cycloalkyl propadiene vs. vinylidene propadiene; or aromatic type internal olefin vs. alkyl type internal olefin). In some aspects, the Temp of the attenuated mixed catalyst is peak Mixed 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.

[0095] In some embodiments, the weakened mixed catalyst kinetic profile can be characterized as a combination of any two of the foregoing embodiments, alternatively all but any one, alternatively each of the foregoing embodiments.

[0096] 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.

[0097] Catalyst Activity. The peak polymerization temperature (Temp) in degrees Celsius (°C) of the weakened mixed catalyst as measured by the light-off vial test method. peak ) and the Temp of the catalyst with faster ignition peak If the difference between the catalyst activity and the catalyst activity of the attenuated mixed catalyst (e.g., of formula (III)) is within ±5°C, alternatively within ±4°C, alternatively within ±3°C, alternatively within ±2°C, alternatively within ±1°C, then the catalyst activity of the attenuated mixed catalyst (e.g., of formula (III)) is determined to be substantially the same as the catalyst activity of the catalyst that ignites faster. Alternatively, under all other conditions being equal, the catalyst activity is determined as 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)) which may not be significantly less than the catalytic activity / polymerization productivity of the mixed catalyst that ignites faster, and in some embodiments may be greater than the catalytic activity / polymerization productivity of the mixed catalyst that ignites faster.

[0098] Faster catalysts. For the reasons described above, embodiments of catalysts (e.g., of formula (II)) that light up faster may require the ignition kinetics of slurry phase and / or gas phase polymerization of 1-olefin monomers to be weakened. The same or other embodiments of catalysts (e.g., of formula (II)) that light up faster may require ligands R for different reasons, such as for changing the solubility of the catalyst in an alkane solvent, or for NMR studies that mix the catalyst structure and improve the catalyst structure design.

[0099] Anion A - The mixed catalyst with faster ignition (e.g., of formula (II)) and the mixed catalyst with weaker ignition (e.g., of formula (III)) may each contain an anion A derived from an activator or from a leaving group X. - The activator is used to prepare a mixed catalyst with a faster ignition rate from a mixed precatalyst of formula (I). The activator is used to activate the mixed precatalyst of formula (I) by extracting the leaving group X from the mixed precatalyst of formula (I) to obtain a mixed catalyst with a faster ignition rate (for example, a mixed catalyst of formula (II)) and an anion A - The resulting activated hybrid catalyst (i.e., the hybrid catalyst of formula (II) with a faster light-off) is drawn in a conventional manner, showing the metal atom M with a positive charge. The positive charge indicates the catalytic site to which the olefin monomer may bond during the polymerization reaction. Anion A - The positive charges are formally balanced so that the mixed catalysts (eg, of formula (II)) with a faster ignition and the mixed catalysts (eg, of formula (III)) with a weaker ignition made therefrom are neutral overall.

[0100] Anion A - The nature of X is not considered important in mixed catalysts with faster ignition (e.g., those of formula (II)) and weaker ignition (e.g., those of formula (III)). As mentioned, it can be an anionic derivative of X (i.e., X - ) or an anionic derivative of an activator. When the activator is an alkylaluminoxane and the anionic - When it is an anionic derivative, anion A - may be an alkylaluminoxane anion; alternatively, when the activator is an organoborane compound and the anion A - When it is an anionic derivative, anion A - Alternatively, when the activator is an organic borate compound and the anion A - When it is an anionic derivative, anion A - It can be an organic borate anion. Anion A - is formed during the activation step according to aspect 1. It is believed that the anion A in the mixed catalyst (e.g., of formula (II)) which ignites faster -The combined steps produce an anion A in the mixed catalyst (e.g., of formula (III)) that is weakened. - Can react with anion A in the catalyst with faster ignition - However, the anion A in the weakened mixed catalyst (e.g., of formula (III)) - The anion A in the mixed catalyst (e.g., of formula (II)) which can ignite faster - For example, the anion A in the mixed catalyst (e.g., of formula (II)) that ignites faster - It can be an anionic derivative of the activator, and for example, the anion A in the attenuated mixed catalyst (of formula (III)) - Can be X - .

[0101] Catalyst structure. Without being bound by theory, it is believed that the molecular structure of the faster-ignited mixed catalyst of formula (II) and the molecular structure of the weakened mixed catalyst of formula (III) can be determined by conventional analytical methods (such as nuclear magnetic resonance (NMR) spectroscopy or gas chromatography / mass spectrometry (GC / MS)). The structure of the ligand R in formula (III) can be determined by quenching an NMR sample of the weakened post-metallocene catalyst of formula (III) with a protic solvent (such as isopropanol, CH3OH or H2O), a partially deuterated protic solvent (such as isopropyl-OD, CH3OD or HDO) or a fully deuterated protic solvent (such as fully deuterated isopropanol ((CD3)2C(D)OD), fully deuterated methanol (CD3OD) or D2O) to obtain a byproduct of formula HR or DR, and by NMR (such as proton NMR ( 1 H-NMR)) or gas chromatography / mass spectrometry (GC / MS) to analyze the structure of the by-product.

[0102] Activation step. In some embodiments, the method of preparing a weakened hybrid catalyst (e.g., of formula (III)) further includes an activation step as a preliminary step, which can be completed before the combining step begins. The activation step includes contacting the precatalyst of formula (I) with an activator under effective activation conditions to prepare a hybrid catalyst that ignites faster. The activation step can be performed in the absence of a kinetic modifier compound.

[0103] Activator. The activator for activating the mixed precatalyst of formula (I) may be an alkylaluminoxane, an organic borane compound, an organic borate compound or a trialkylaluminum compound. The activator may also be a combination of any two or more thereof. For example, the activator may include an alkylaluminoxane (such as methylaluminoxane) and an organic borate compound, such as an organic borate having the CAS name of bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)borate amine, bis(hydrogenated tallow alkyl)methyltetra(pentafluorophenyl)borate (1-)amine. The activator for activating the ligand-metal (Ti, Zr or Hf) complex containing a cyclopentadienyl group to obtain a metallocene catalyst may be a trialkylaluminum compound.

[0104] Alkylaluminoxane: also known as alkylalumoxane. A partial hydrolysis product of a trialkylaluminum compound. The embodiment may be (C1-C 10 ) alkylaluminoxane, alternatively (C1-C6) alkylaluminoxane, alternatively (C1-C4) alkylaluminoxane, alternatively (C1-C3) alkylaluminoxane, alternatively (C1-C2) alkylaluminoxane, 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 a commercial supplier or prepared by any suitable method. Suitable methods for preparing alkylaluminoxanes are well known. Examples of such preparation methods are described in U.S. Pat. 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.

[0105] The maximum amount of alkylaluminoxane can be selected to be a 5,000-fold molar excess of the precatalyst based on the molar ratio of the number of moles of Al metal atoms in the aluminoxane to the number of moles of metal atoms M (e.g., Ti, Zr, or Hf) in the precatalyst. The minimum amount of activator to precatalyst can be a 1:1 molar ratio (Al / M). The maximum value of the molar ratio of Al / M can be 150, alternatively 124.

[0106] Organoborane compounds. Tri(fluoro-functional organo)borane compounds ((fluoro-organo)3B), such as tri(pentafluorophenyl)borane ((C6F5)3B), tri[3,5-bis(trifluoromethyl)phenyl]borane ((3,5-(CF3)2-C6H3)3B), or mixtures of any two or more thereof.

[0107] Organic borate compound. Tetrakis(fluoro-functional organic) borate compound ((fluoro-organic) 4B), such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, triphenylcarbonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or triphenylcarbonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, or a mixture of any two or more thereof. The organic borate compound may be methyl di((C 2-(pentafluorophenyl))borate available from Boulder Scientific. 14 -C 18 ) alkyl) ammonium salts, or by long chain trialkylamine (Armeen TM M2HT, available from Akzo Nobel, Inc.) is prepared by reaction with HCl and Li[B(C6F5)4]. Such preparation is disclosed in Example 2 of US 5,919,983. The organic borate compound can be used herein without (further) purification. In addition, bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyl)borate amine.

[0108] The trialkylaluminum compound can be used as an activator for the precatalyst (metallocene precatalyst) or as a scavenger to remove residual water from the polymerization reactor before start-up. Examples of suitable alkylaluminum compounds are trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum.

[0109] Activators, also called cocatalysts, can affect the molecular weight, degree of branching, comonomer content or other properties of polyolefin polymers. Activators can achieve coordination polymerization or cationic polymerization.

[0110] Without being bound by theory, it is believed that the selection of an activator for activating the faster light-off hybrid catalyst does not affect the structure of the weakened hybrid catalyst made from the faster light-off hybrid catalyst. That is, only the cationic portion of formula (III) is considered (i.e., ignoring the anionic A - ), the structures of the attenuated hybrid catalysts prepared using different activators are expected to be the same. The structure of the unsupported attenuated hybrid catalyst may be easier to determine by NMR than the structure of the supported attenuated hybrid catalyst due to the heterogeneity of the latter (typical support materials are insoluble in NMR solvents).

[0111] In some embodiments, A - The choice of A may have an additional effect on the kinetic profile of the attenuated mixed catalyst. - Any such effect will not completely eliminate the beneficial effect of the kinetic modifier compound on the attenuated kinetic profile of the hybrid catalyst.

[0112] Effective conditions. The reactions described herein (e.g., combination steps, activation steps, polymerization) are independently carried out under conditions that allow the expected reaction to proceed. Examples of effective conditions are reaction temperature, atmosphere type (e.g., inert atmosphere), reactant purity, stoichiometry of reactants, stirring / mixing of reactants, and reaction time period. The conditions effective for the activation step and polymerization step may be those conditions described in the art and well known to those of ordinary skill. For example, effective activation conditions may include techniques for manipulating catalysts, such as online mixers, catalyst preparation reactors, and polymerization reactors. The activation temperature may be 20°C to 800°C, alternatively 300°C to 650°C. The reaction time may be 10 minutes to 2 hours. Examples of gas phase polymerization conditions are described later herein. Effective conditions for the combined steps of preparing the attenuated mixed catalyst may include: a reaction temperature of -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%; amounts of reactants to minimize waste / maximize product yield; stirring or mixing the reactants; and a reaction time period of 1 minute to 24 hours.

[0113] Effective reaction conditions for preparing the mixed precatalyst of formula (IV). Such conditions may include techniques for manipulating air sensitivity and / or moisture sensitivity reagents and reactants, such as Schlenk-line technology and inert gas atmosphere (e.g., nitrogen, helium or argon). Effective reaction conditions may also include sufficient reaction time, sufficient reaction temperature and sufficient reaction pressure. Each reaction temperature may be independently -78°C to 120°C, alternatively -30°C to 30°C. Each reaction pressure may be independently 95kPa to 105kPa, alternatively 99kPa to 103kPa. The progress of any particular reaction step may be monitored by analytical methods such as nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry to determine the reaction time that effectively maximizes the yield of the desired product. Alternatively, each reaction time may be independently 30 minutes to 48 hours.

[0114] Hybrid precatalysts of formula (I). The precatalysts of formula (I) can be synthesized according to methods known in the art, including those mentioned above. Alternatively, the hybrid precatalysts can be obtained from precatalyst suppliers such as Boulder Scientific.

[0115] Prepare polyolefin polymer by polymerization method.When 1-olefin monomer is the combination of ethylene and propylene, the polyolefin polymer made therefrom is ethylene / propylene copolymer.When 1-olefin monomer is ethylene alone, the polyolefin polymer made therefrom is polyethylene homopolymer.When 1-olefin monomer is the combination of ethylene and 1-butene, 1-hexene or 1-octene, the polyolefin polymer made therefrom is poly(ethylene-to-1-butene) copolymer, poly(ethylene-to-1-hexene) copolymer or poly(ethylene-to-1-octene) copolymer.In some embodiments, the polyolefin polymer made therefrom by 1-olefin monomer is a vinyl polymer with following components: 50 weight percent to 100 weight percent (wt%) repeating units are derived from ethylene, and 50 weight % to 0 weight % repeating units are derived from 1-olefin monomer, and the 1-olefin monomer is selected from propylene, 1-butene, 1-hexene, 1-octene and any two or more combinations thereof.

[0116] In some embodiments, the polymerization process 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.

[0117] Multimodal (e.g., bimodal or trimodal) catalyst systems. The bimodal catalyst system comprises a weakened mixed catalyst and at least one other olefin polymerization catalyst selected from the following items: different weakened mixed catalysts, mixed catalysts and metallocene catalysts. 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 undesirable gels in multimodal (e.g., bimodal or trimodal) polyethylene compositions melt blended in supplementary reactors. Other problems relate to transition complexity and stability of multimodal (e.g., bimodal or trimodal) catalyst systems. Even in the absence of gel, there may be problems due to the sedimentation changes of catalyst particles of different sizes. In some aspects, the variability (I2) of the melt index can be measured according to particle size, rather than using gel measurement.

[0118] The method for preparing the weakened mixed 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 also includes activating the metallocene precatalyst with the same or different activators. Typically, the method for preparing the weakened mixed catalyst is carried out in the absence of a metallocene (pre)catalyst.

[0119] Metallocene catalyst. The metallocene catalyst can be made from any of the metallocene precatalyst components described in US7873112B2, column 11, line 17 to column 22, line 21. In some aspects, the metallocene catalyst is made from the metallocene precatalyst material named in US7873112B2, column 18, line 51 to column 22, line 5. In some aspects, the metallocene precatalyst is selected from: bis(η 5 -tetramethylcyclopentadienyl)zirconium dichloride; bis(η 5 -tetramethylcyclopentadienyl)zirconium dimethyl; bis(η 5 -pentamethylcyclopentadienyl)zirconium dichloride; bis(η 5 dimethyl zirconium; (1,3-dimethyl-4,5,6,7-tetrahydroindenyl)(1-methylcyclopentadienyl) dimethyl zirconium; bis(1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride; bis(1-methyl-3-n-butylcyclopentadienyl) dimethyl zirconium; bis(n-propylcyclopentadienyl) hafnium dichloride; bis(n-propylcyclopentadienyl) dimethyl hafnium; bis(n-butylcyclopentadienyl) zirconium dichloride; (cyclopentadienyl)(1,5-dimethylindenyl) dimethyl zirconium; (methylcyclopentadienyl)(1,5-dimethylindenyl) dimethyl zirconium; (cyclopentadienyl)(1,4-dimethylindenyl) dimethyl zirconium; (methylcyclopentadienyl)(1,4-dimethylindenyl) dimethyl zirconium; and bis(n-butylcyclopentadienyl) dimethyl zirconium. In some aspects, the metallocene catalyst is the product of an activation reaction of an activator with any of the aforementioned metallocene precatalysts.

[0120] Unsupported or supported catalysts. The mixed precatalyst of formula (I), the mixed catalyst with a faster ignition rate (such as the catalyst with a faster ignition rate of formula (II)), the weakened mixed catalyst (such as the weakened mixed catalyst of formula (III)) and the multimodal catalyst system can independently be unsupported or arranged on a solid particulate support material. When there is no support material, the mixed precatalyst of formula (I), the mixed catalyst with a faster ignition rate (such as the catalyst with a faster ignition rate of formula (II)), the weakened mixed catalyst (such as the weakened mixed catalyst of formula (III)) and / or the multimodal catalyst system can be injected into a slurry phase or gas phase polymerization reactor as a solution in a hydrocarbon solvent. When the mixed precatalyst of formula (I), the faster light-off mixed catalyst (such as the faster light-off catalyst of formula (II)), the attenuated mixed catalyst (such as the attenuated mixed catalyst of formula (III)) and / or the multimodal catalyst system are arranged on a support material, they can be injected into a slurry phase or gas phase polymerization reactor as a slurry suspended in a hydrocarbon solvent or as a dry powder (i.e., a dry particulate solid).

[0121] A mixed catalyst (e.g., of formula (II)) with a faster ignition and / or a mixed catalyst (e.g., of formula (III)) with a weakened ignition can be prepared in the absence of a support material and later disposed on the support material. Alternatively, a mixed precatalyst of formula (I) or a mixed catalyst (e.g., of formula (II)) with a faster ignition can be disposed on a support material, and then a mixed catalyst (e.g., of formula (II)) with a faster ignition and / or a mixed catalyst (e.g., of formula (III)) with a weakened ignition can be prepared in situ on the support material.

[0122] The supported mixed precatalyst of formula (I), the supported mixed catalyst (e.g., the supported catalyst of formula (II)) and / or the supported mixed catalyst (e.g., the supported catalyst of formula (III)) that is weakened can be prepared by a concentration method, which is prepared by evaporating the hydrocarbon solvent from a suspension or solution of the support material in the solution of the precatalyst of formula (I), the supported catalyst (e.g., the supported catalyst of formula (II)) and / or the supported mixed catalyst (e.g., the supported catalyst of formula (III)) that is weakened from the solution of the supported precatalyst, the supported catalyst (e.g., the supported catalyst of formula (II)) that is weakened from the solution of the supported mixed catalyst from the hydrocarbon solvent. Alternatively, the supported precatalyst of formula (I), the supported catalyst (e.g., the supported catalyst of formula (II)) that is weakened from the solution of the supported mixed catalyst (e.g., the supported catalyst of formula (III)) that is weakened can be prepared by a spray drying method of spray drying the suspension or solution. In some embodiments, a spray drying method is used.

[0123] Support material. The support material is a granular solid which may be non-porous, semi-porous or porous. The support material is a porous support material. Examples of support materials are talc, inorganic oxides, inorganic chlorides, zeolites, clays, resins and mixtures of any two or more thereof. Examples of suitable resins are polystyrene, functionalized or cross-linked organic supports such as polystyrene divinyl benzene polyolefins. The support material may independently be untreated silica, alternatively calcined untreated silica, alternatively silica treated with a hydrophobic agent, alternatively silica treated with a calcined and hydrophobic agent. The hydrophobic agent may be dichlorodimethylsilane.

[0124] Inorganic oxide support materials include Group 2, 3, 4, 5, 13 or 14 metal oxides. Preferred supports include dehydrated or non-dehydrated silica, fumed silica, alumina (see, e.g., PCT Publication WO 99 / 60033), silica-alumina, and mixtures thereof. Other useful supports include magnesium oxide, titanium dioxide, zirconium oxide, magnesium chloride (U.S. Pat. No. 5,965,477), montmorillonite (EP 0 511 665), phyllosilicates, zeolites, talc, clay (U.S. Pat. No. 6,034,187), and the like. In addition, combinations of these support materials may be used, such as silica-chromium, silica-alumina, silica-titania, and the like. Additional support materials may include those porous acrylic polymers described in EP 0 767 184, 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, spheroids as disclosed in US Pat. No. 5,972,510, and polymer beads as disclosed in PCT Publication WO 99 / 50311.

[0125] The carrier material may have a thickness of about 10 m 2 / g to about 700m 2 / g range, about 0.1cm 3 / g to about 4.0cm 3 The carrier 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 carrier is a hydrophobic fumed silica, which may be prepared by treating untreated fumed silica with a hydrophobic agent such as dimethyldichlorosilane, polydimethylsiloxane fluid, or hexamethyldisilazane. In some aspects, the treating agent is dimethyldichlorosilane. In one embodiment, the carrier is Cabosil. TM TS-610.

[0126] The one or more precatalysts and / or one or more activators may be deposited on, contacted with, vaporized with, bonded with, incorporated into, adsorbed or absorbed into or onto one or more carrier or support materials.

[0127] The metallocene precatalyst may be spray dried according to the general method described in US 5648310. The support used with the hybrid precatalyst 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 US 5688880.

[0128] Solution phase polymerization and / or slurry phase polymerization of olefin monomers is well known. See, for example, US Pat. No. 8,291,115 B2.

[0129] Inert hydrocarbon solvent. Alkanes, aromatic hydrocarbons or alkyl aromatic hydrocarbons (i.e., aryl alkanes). 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, wherein 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 noncyclic alkane can be independently straight or branched. Noncyclic alkane can be pentane, 1-methylbutane (isopentane), hexane, 1-methylpentane (isohexane), heptane, 1-methylhexane (isoheptane), octane, nonane, decane or any two or more mixtures thereof. The cyclic alkane can be cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, methylcyclopentane, methylcyclohexane, dimethylcyclopentane or a mixture of any two or more thereof. Additional examples of suitable alkanes include Isopar-C, Isopar-E and mineral oils such as paraffin oil. In some aspects, the inert hydrocarbon solvent does not contain mineral oil. The inert hydrocarbon solvent can be composed of one or more (C5-C 12 ) alkane composition.

[0130] Gas phase polymerization (GPP). Polymerization uses a GPP reactor, such as a stirred bed gas phase polymerization reactor (SB-GPP reactor) or a fluidized bed gas phase polymerization reactor (FB-GPP reactor). Such reactors and methods are generally well known. For example, FB-GPP reactors / methods can be as described in any of US 3,709,853, US 4,003,712, US 4,011,382, US 4,302,566, US 4,543,399, US 4,882,400, US 5,352,749, US 5,541,270, US 2018 / 0079836 A1, EP-A-0 802 202 and Belgian Patent No. 839,380. These SB-GPP and FB-GPP polymerization reactors and methods mechanically stir or fluidize the polymerization medium inside the reactor by the continuous flow of gaseous monomers and diluents, respectively. Other useful reactors / processes contemplated include tandem or multistage polymerization processes such as described in US 5,627,242, US 5,665,818, US 5,677,375, EP-A-0 794 200, EP-B1-0 649 992, EP-A-0 802 202, and EP-B-634 421.

[0131] Gas phase polymerization operating conditions are any variable or combination of variables that may affect the polymerization reaction in the GPP reactor or the composition or properties of the polyolefin polymer composition product produced therefrom. Variables may include: reactor design and size; precatalyst composition and amount; reactant composition and amount; molar ratio of two different reactants; presence or absence of feed gas (such as H2), molar ratio of feed gas to reactant, absence or concentration of interfering materials (e.g., H2O and / or O2), absence or presence of induced condensing agent (ICA), average polymer residence time in the reactor, partial pressure of ingredients, feed rate of monomers, reactor bed temperature (e.g., fluidized bed temperature), nature or sequence of process steps, transition time periods between steps. Variables other than that / those variables described or varied by the process or use may be kept constant.

[0132] In the GPP process, the production of ethylene ("C2"), hydrogen ("H2"), and 1-hexene ("C6" or "C x ”, where x is 6) to maintain a fixed comonomer to ethylene monomer gas molar ratio or feed mass ratio (C) equal to the described value (e.g., 0.00560 or 0.00703) x The reactor is controlled to have a constant hydrogen to ethylene gas mole ratio or feed mass ratio ("H2 / C2") equal to a stated value (e.g., 0.00229 or 0.00280), and a constant ethylene ("C2") partial pressure equal to a stated value (e.g., 1,000 kPa). The gas concentrations are measured by online 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. A superficial gas velocity of 0.49 to 0.79 meters per second (m / sec) (1.6 to 2.6 feet per second (ft / sec)) 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 first reactor bed temperature RBT as described. 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 particle form, which can be from 5,000 kilograms per hour (kg / h) to 150,000 kilograms per hour. The product polyolefin polymer composition is semi-continuously moved into a fixed volume chamber via a series of valves, wherein the removed multimodal (e.g., bimodal or trimodal) ethylene-to-1-hexene copolymer composition is purged to remove entrained hydrocarbons and treated with a humid nitrogen (N2) gas stream to deactivate any traces of residual catalyst.

[0133] The catalyst system can be fed into the polymerization reactor in "dry mode" or "wet mode", alternatively dry mode, alternatively wet mode. The dry mode is a dry powder or granules. The wet mode is a suspension in an inert liquid such as mineral oil.

[0134] Induced Condensing Agent (ICA). An inert liquid that can be used to cool materials in a GPP reactor. Its use is optional. ICA is (C3-C 20 ) alkane, alternatively (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 may be 0.1 mol% to 25 mol%, alternatively 1 mol% to 16 mol%, alternatively 1 mol% to 10 mol%.

[0135] The GPP conditions may also include one or more additives, such as chain transfer agents or promoters. Chain transfer agents are well known and may be metal alkyls, such as diethyl zinc. Promoters are known, such as in US 4,988,783, and may include chloroform, CFCl3, trichloroethane, and difluorotetrachloroethane. A scavenger may be used to react with moisture prior to reactor startup, and a scavenger may be used to react with excess activator during reactor conversion. The scavenger may be a trialkylaluminum. The GPP may be operated without (non-intentionally added) scavengers. The GPP reactor / process may also include an amount (e.g., 0.5 ppm to 200 ppm based on all feeds entering the reactor) of one or more static control agents and / or one or more continuity additives, such as aluminum stearate or polyethylene imine. Static control agents may be added to the FB-GPP reactor to inhibit the formation or accumulation of static charge therein.

[0136] The GPP reactor may be a commercial scale FB-GPP reactor, such as the UNIPOL 1000 reactor available from Univation Technologies, LLC, a subsidiary of The Dow Chemical Company, Midland, Michigan, USA. TM Reactor or UNIPOL TM II reactor.

[0137] 1-Olefin monomer. 1-Olefin monomer has the formula H2C=C(H)(CH2) n R 8The compound wherein the subscript n is an integer from 0 to 19, and the group R 8 is H or CH3. An example is ethylene (subscript n is 0 and R 8 H), propylene (subscript n is 0 and R 8 CH3) and (C4-C 20 )α-olefin (subscript n is an integer from 1 to 19 and R 8 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.

[0138] Polyolefin polymer. The product of at least one 1-olefin monomer and a weakened mixed catalyst or multimodal catalyst system polymerization. A macromolecule or a collection of macromolecules having a constituent unit derived from at least one 1-olefin monomer. For example, when at least one 1-olefin monomer is composed of ethylene, the polyolefin polymer is composed of a polyethylene homopolymer. When at least one 1-olefin monomer is composed of ethylene and propylene, the polyolefin polymer is composed of an ethylene / propylene copolymer. When at least one 1-olefin monomer is composed of ethylene and a comonomer selected from 1-butene, 1-hexene and 1-octene, the polyolefin polymer is selected from poly(ethylene-to-1-butene) copolymers, poly(ethylene-to-1-hexene) copolymers and poly(ethylene-to-1-octene) copolymers, respectively.

[0139] 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. The polyolefin polymer made by a multimodal catalyst system has a multimodal (e.g., bimodal or trimodal) molecular weight distribution, and comprises 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 a mixed catalyst that is weakened by it (e.g., formula (III)), and the LMW polyolefin polymer component can be prepared by its metallocene catalyst.

[0140] Any compound, composition, formulation, material, mixture or reaction product herein may not contain any one of the chemical elements selected from the group consisting of: H, Li, Be, B, C, N, O, F, Na, Mg, Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, I, Cs, Ba, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, lanthanides and actinides; provided that the chemical elements required for the compound, composition, formulation, material, mixture or reaction product (e.g., Zr required for the zirconium compound, or C and H required for polyethylene, or C, H and O required for the alcohol) are not counted.

[0141] Alternatively, before different embodiments. ASTM is a standards organization, ASTM International, West Conshohocken, Pennsylvania, USA. Any comparative examples are for illustrative purposes only and should not be prior art. Containing 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. Permitted options can be given, but not essential. Operability means functionally capable or effective. Optional (ground) means absence (or exclusion) or presence (or inclusion). Properties can be measured using standard test methods and conditions. Ranges include endpoints, subranges, and integers and / or fractional values ​​contained therein, except for integer ranges that do not include fractional values. Room temperature: 23°C ± 1°C

[0142] Unless otherwise indicated, the definitions of terms used herein are taken from the "IUPAC Compendium of Chemical Technology" ("Gold Book"), version 2.3.3, February 24, 2014. For convenience, some definitions are given below.

[0143] Alkane (solvent). One or more compounds of formula C n H 2n+2Acyclic, linear or branched compounds and / or one or more compounds of formula C m H 2m wherein the subscripts n and m are independently integers of 5 to 50 (eg, 6). It does not contain a carbon-carbon double bond (C=C) and a terminal carbon-carbon triple bond (C≡C).

[0144] Alkyl (unsubstituted). A monovalent group consisting of a hydrogen atom and at least one carbon atom and formally prepared by removing a hydrogen atom from an alkane. Contains no carbon-carbon double bond (C=C) and terminal carbon-carbon triple bond (C≡C).

[0145] Alkyl (substituted). Formally, by using a substituent (e.g., R s ) replacing at least one hydrogen atom of an unsubstituted alkyl group.

[0146] Alkaryl (unsubstituted) or alkyl-substituted aryl. A monovalent group consisting of a hydrogen atom and at least seven carbon atoms and formally prepared by removing a hydrogen atom from the aromatic hydrocarbon portion of an alkyl-aromatic hydrocarbon. For example, 4-methylphenyl.

[0147] Alkaryl (substituted) or alkyl substituted aryl. Formally, by using a substituent (e.g., R s ) replacing at least one hydrogen atom of an unsubstituted alkylaryl group.

[0148] Aralkyl (unsubstituted). A monovalent group consisting of hydrogen atoms and at least seven carbon atoms and formally prepared by removing hydrogen atoms from the alkane portion of an aralkyl-alkane. For example, benzyl. Contains no carbon-carbon double bonds (C=C) and terminal carbon-carbon triple bonds (C≡C).

[0149] Aralkyl (substituted). Formally, by using a substituent (e.g., R s ) replacing at least one hydrogen atom of an unsubstituted aralkyl group.

[0150] Aryl (unsubstituted). A monovalent group consisting of hydrogen atoms and at least six carbon atoms and formally prepared by removing hydrogen atoms from aromatic hydrocarbons. For example, phenyl, naphthyl. Contains no carbon-carbon double bonds (C=C) and terminal carbon-carbon triple bonds (C≡C).

[0151] Aryl (substituted). Formally, by using a substituent (e.g., R s ) is a monovalent group prepared by replacing at least one hydrogen atom of an unsubstituted aryl group.

[0152] 4-(C1-C 20 ) alkyl-substituted 1,3-butadiene molecule. Formula H2C=C(H)-C(H)=C(H)-(C1-C 20 ) alkyl compounds.

[0153] (C # -C # ) (as a modifying functional group). # or a numeric symbol indicates the range of carbon atoms in the unsubstituted form of the functional group. For example, (C1-C6) has 1 to 6 carbon atoms, (C7-C 20 ) has 7 to 20 carbon atoms, (C6-C 12 ) has 6 to 12 carbon atoms, and (C1-C 20 ) has 1 to 20 carbon atoms.

[0154] -C(=O)-O-(unsubstituted C1-C 20 ) Hydrocarbyl). A monovalent group consisting of a hydrogen atom, two oxygen atoms and 2 to 21 carbon atoms and formally prepared by removing a hydrogen atom from a carbonyl carbon atom of a formate. For example, -C(=O)-O-phenyl or C(=O)-O-ethyl. Contains no carbon-carbon double bond (C=C) and terminal carbon-carbon triple bond (C≡C).

[0155] Coordination Entity. An aggregate consisting of a central atom (the metal atom) attached (bonded) to a surrounding array of other atomic groups (ligands).

[0156] Coordination number. For a given atom in a chemical species (e.g., M), the number of other atoms that are directly connected or bonded to the given atom in the chemical species. For example, in titanium tetrachloride, the coordination number of the titanium atom is 4.

[0157] Denticity. In a coordination entity, the number of donor groups, kappa (κ), from the same ligand attached to the same central atom (eg, to M).

[0158] Bidentate organic hetero groups. A monovalent group that serves as a ligand for a metal M and is composed of a carbon atom, a hydrogen atom, and at least one heteroatom selected from N, O, S, and P, and may be selected so that the monovalent group is di-coordinated with the metal M via a carbon atom and one such heteroatom or via two such heteroatoms. The monovalent ligand may provide a tooth number κ of 2 to M. The bidentate organic hetero group may be free of a terminal carbon-carbon double bond (>C=CH2) and a terminal carbon-carbon triple bond (-C≡CH); alternatively, it may be free of any carbon-carbon double bond (C=C) and any terminal carbon-carbon triple bond (C≡C).

[0159] Bidentate organic heteroylene. A divalent group, which serves as a ligand for a metal atom M and is composed of a carbon atom, a hydrogen atom, and at least one heteroatom selected from N, O, S, and P, and may be selected so that the divalent group is double coordinated with the metal M via a carbon atom and one such heteroatom or via two such heteroatoms. The divalent group may provide a tooth number κ of 2 to M. Bidentate organic heteroylene may be free of a terminal carbon-carbon double bond (>C=CH2) and a terminal carbon-carbon triple bond (-C≡CH); alternatively, it may be free of any carbon-carbon double bond (C=C) and any terminal carbon-carbon triple bond (C≡C).

[0160] Dry. Typically, the moisture content is 0 to less than 5 parts per million by weight. The material fed to the reactor during the polymerization reaction is dry.

[0161] Effective Amount: An amount sufficient to achieve a result.

[0162] Halogen atoms. An atom selected from the group consisting of F, Cl, Br and I; alternatively selected from the group consisting of F, Cl and Br; alternatively selected from the group consisting of F and Cl; alternatively selected from the group consisting of F and Br; alternatively selected from the group consisting of Cl and Br; alternatively selected from F; alternatively selected from Cl.

[0163] Hapto number. In a coordination entity, the number of atoms n in a continuous or uninterrupted series of two or more atoms from the same ligand attached to a central atom (e.g., M). For example, a cyclopentadienyl group has five continuous or uninterrupted carbon atoms coordinated to M and thus may have a Hapto number n (eta) of 5. 5 ("η5")). 4-(C1-C 20 ) alkyl-substituted 1,3-butadiene molecules can be substituted via one of their two carbon-carbon double bonds (which can provide M with a Haptor number η (eta) of 2 2 ("η2")) or via both of its carbon-carbon double bonds (which can provide M with a Haptor number η (eta 4) 4 ("η4")) is coordinated with M.

[0164] Heteroalkyl. A monovalent group consisting of carbon atoms, hydrogen atoms and at least one heteroatom selected from N, O, S, Si and P, and which is therefore organic, but whose free valence is a carbon atom. The heteroalkyl group may be free of terminal carbon-carbon double bonds (>C=CH2) and terminal carbon-carbon triple bonds (-C≡CH); alternatively free of any carbon-carbon double bonds (C=C) and any terminal carbon-carbon triple bonds (C≡C). In some embodiments, at least one heteroatom is selected from the group consisting of: N, O and Si; alternatively N and O; alternatively N and Si; alternatively O and Si; alternatively N; alternatively O; alternatively Si; alternatively S; alternatively P. In some embodiments, the R-type group is not a heteroalkyl group.

[0165] Higher molecular weight (HMW) component. A subgroup of macromolecules having a higher molecular weight peak in a GPC plot of dW / dLog(MW) on the y-axis versus Log(MW) on the x-axis.

[0166] Hydrocarbyl. A monovalent group formally obtained by removing H atoms from carbon atoms of a hydrocarbon compound consisting of C and H atoms. In some embodiments, each hydrocarbyl is independently an alkyl, alkaryl, aryl, or aralkyl.

[0167] Hydrocarbylene. A divalent radical formally derived by removing two H atoms from different carbon atoms of a hydrocarbon compound consisting of C and H atoms.

[0168] Inert. Typically, it does not (appreciably) react or interfere (appreciably) in the polymerization reaction of the present invention. The term "inert" as applied to the purge gas or ethylene feed means that the molecular oxygen (O2) content is from 0 to less than 5 parts per million, based on the total weight of the purge gas or ethylene feed.

[0169] Inert hydrocarbon solvents. Liquid materials at 25°C, consisting of carbon and hydrogen atoms and optionally one or more halogen atoms, and free of carbon-carbon double bonds and carbon-carbon triple bonds.

[0170] Leaving group. A group X that coordinates to the metal M in the precatalyst (MX) and removes one such group from the precatalyst when the precatalyst is contacted with an activator to convert the precatalyst into an active catalyst (M + ) and byproduct anion X - In some aspects, the above A in the catalyst with faster light-off and the catalyst with weaker light-off - Can be X - Each monodentate X is a leaving group which can provide M with a denticity κ of 1.

[0171] Ligand. A molecule or group derived therefrom by removal of a hydrogen atom capable of coordinating with a transition metal atom M, such as a Group 4 metal atom Ti, Hf or Zr.

[0172] The ligands Cp and L differ from the leaving group X in that Cp and L, if any, remain coordinated to the metal atom M in the precatalyst, the faster light-off catalyst prepared from the precatalyst, and the weakened mixed catalyst prepared from the faster light-off catalyst, while at least one leaving group X present in the precatalyst is not present in the faster light-off catalyst, and at least one leaving group X present in the faster light-off catalyst is replaced by a weakened leaving group R in the weakened mixed catalyst.

[0173] Lower molecular weight (LMW) component. A subgroup of macromolecules having a lower molecular weight peak in a GPC plot of dW / dLog(MW) on the y-axis versus Log(MW) on the x-axis.

[0174] Metallocene catalysts. Homogeneous or heterogeneous materials that enhance olefin polymerization reaction rates and comprise a ligand-metal complex having two (substituted or unsubstituted)-cyclopentadienyl groups (unbridged or bridged). Substantially single site or double site. Each metal is a transition metal Ti, Zr or Hf.

[0175] Minute (one). A unit of time equal to 60.0 seconds. 0.1 minute equals 6.0 seconds.

[0176] Organic heteroradical. A monovalent group consisting of carbon atoms, hydrogen atoms and at least one heteroatom selected from N, O, S, Si and P, and which is therefore organic, but has a free valence on one heteroatom. The organic heteroradical may be free of terminal carbon-carbon double bonds (>C=CH2) and terminal carbon-carbon triple bonds (-C≡CH); alternatively free of any carbon-carbon double bonds (C=C) and any terminal carbon-carbon triple bonds (C≡C).

[0177] Organic heteroylene. A divalent group consisting of carbon atoms, hydrogen atoms and at least one heteroatom selected from N, O, S, Si and P, and which is therefore organic, but has one of its two free valencies on one of the heteroatoms and the other free valency on a carbon atom or a different heteroatom. The organic heteroylene may be free of terminal carbon-carbon double bonds (>C=CH2) and terminal carbon-carbon triple bonds (-C≡CH); alternatively free of any carbon-carbon double bonds (C=C) and any terminal carbon-carbon triple bonds (C≡C).

[0178] Post-metallocene catalyst. Homogeneous or heterogeneous ligand-metal complex, which is neither a metallocene catalyst nor a mixed catalyst. Non-metallocene molecular catalyst. Post-metallocene catalyst lacks ligands containing (substituted or unsubstituted)-cyclopentadienyl groups and enhances the rate of olefin polymerization. Essentially single-site or dual-site catalyst. Prepared by activating a post-metallocene precatalyst, which also lacks (substituted or unsubstituted)-cyclopentadienyl ligands. Each metal is a transition metal Ti, Zr or Hf.

[0179] Precatalyst (cf. mixed precatalyst). An unactivated coordination entity or ligand-metal complex containing only one ligand containing a (substituted or unsubstituted)-cyclopentadienyl group.

[0180] R-type groups. The groups in the structural formula are written as "R" or "R 上标 ”, where “superscript” is a number, letter, or both. “R 上标 Examples of "groups" are R 1, R a1 , R a2 , R b1 wait.

[0181] C1-C 20 )alkyl)silyl. Bonded to three independently selected (C1-C 20 ) is a monovalent group consisting of a silicon atom of a hydrocarbyl group and having its free valences at the silicon atom.

[0182] Unsubstituted (C1-C5) alkyl. An alkyl group selected from the group consisting of methyl, ethyl, propyl, butyl and pentyl. The propyl group may be n-propyl or 1-methylethyl. The butyl group may be n-butyl; 1-methylpropyl; 2-methylpropyl; or 1,1-dimethylethyl. The pentyl group may be n-pentyl; 1-methylbutyl; 2-methylbutyl; 3-methylbutyl; 1,1-dimethylpropyl; 2,2-dimethylpropyl; or 2,3-dimethylpropyl.

[0183] Ziegler-Natta catalyst. A heterogeneous material that enhances the rate of olefin polymerization reactions and is prepared by contacting an inorganic titanium compound (such as a titanium halide) supported on a magnesium halide support (eg, a magnesium chloride support) with an activator.

[0184] Example

[0185] Activator 1 (also referred to as co-catalyst 1): bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyl)borate (1-)amine.

[0186] Mineral oil: HYDROBRITE 380PO paraffin oil available from Sonneborn.

[0187] Preparation Example 1A: An activator formulation containing spray-dried methylaluminoxane / treated fumed silica (SDMAO) in hexane / mineral oil was prepared. 1.6 kg of treated fumed silica (CABOSIL TS-610) in 16.8 kg of toluene was slurried, and then a 10 wt % (11.6 kg) toluene solution of 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.

[0188] Preparative Example 1B: Preparation of a slurry of the activator formulation of Preparative Example 1A. The SDMAO powder of Preparative Example 1A was slurried in a mixture of 10 wt% n-hexane and 78 wt% mineral oil to give an activator formulation having 12 wt% SDMAO / treated fumed silica solids in hexane / mineral oil.

[0189] Preparation Example 2: Preparation of Spray-dried Metallocene Using Activator Formulation. Preparation Examples 1A and 1B were repeated except that the activator formulation was prepared by slurrying 1.5 kg of treated fumed silica (CABOSIL TS-610) in 16.8 kg of toluene and then adding a 10 wt % (11.1 kg) toluene solution of MAO and sufficient (MeCp)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)ZrMe2, wherein Me is methyl, Cp is cyclopentadienyl, and MeCp is methylcyclopentadienyl, to give a loading of 40 micromoles of Zr per gram of solids. The resulting powder was slurried to give an activator formulation of 22 wt % solids in 10 wt % isoparaffin fluid and 68 wt % mineral oil.

[0190] Preparation Example 2A: Prepare a supported catalyst for use in the light-off batch reactor test method described later. In a nitrogen-purged glove box, 2.65 g of Cabosil TS-610 fumed silica in 62.5 g of toluene was slurried in an oven-dried glass bottle until fully dispersed. Then 22 grams (g) of a 10 weight percent (wt%) toluene solution of methylaluminoxane (MAO) was added. The mixture was stirred for 15 minutes, and then a mixed precatalyst (e.g., any of PreCat1 to PreCat2 described previously) and any of the kinetic modifier compounds KMC1 to KMC20 described previously were added. The resulting mixture was stirred for 30 to 60 minutes. The stirred mixture was spray dried using a Büchi micro spray dryer B-290 with the following parameters to produce a dry sample: set temperature of 185°C, outlet temperature of 100°C, aspirator of 95%, and pump speed of 150 revolutions per minute (rpm).

[0191] Mixed catalysts with faster ignition: Prepared by the following method: A 40 milliliter (mL) glass vial containing a magnetic stirring bar coated with poly(tetrafluoroethylene) (PTFE) is 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 add a slurry of 10 micromoles (μmol) of a mixed precatalyst (e.g., any one of PreCat1 to PreCat2) in 0.2 mL of mineral oil. Stir the resulting mixture for 5 minutes to obtain a mineral oil slurry of a corresponding mixed catalyst with faster ignition supported on treated fumed silica. Repeat this procedure to prepare multiple batches of mineral oil slurries of mixed catalysts with faster ignition, each mixed catalyst with faster ignition being supported on a separate treated fumed silica. The mixed catalyst can have a molar ratio of aluminum to metal atoms (Al / M) of 120. The foregoing procedure is generally used to prepare catalysts for use in the light-off vial test method described later.

[0192] Attenuated hybrid catalyst: In a separate run, a solution of 10 μmol of the kinetic modifier compound (8), (3) or (15) in 0.20 mL of toluene was added to a quantity of slurry to contain 10 μmol of the faster light-off catalyst (1) or (2) supported on treated fumed silica. The resulting mixture was stirred for 5 minutes to obtain a mineral oil / toluene slurry of the attenuated hybrid catalyst supported on treated fumed silica having KMC (8), (3) or (15), respectively.

[0193] Light-off vial test method: A mineral oil slurry of a catalyst with a faster light-off on treated fumed silica or a mineral oil / toluene slurry of a weakened post-metallocene catalyst on treated fumed silica was added to a dry 40 mL glass vial. 5.5 mL or 11 mL of 1-octene was added to the vial and the vial was sealed with a septum cap. The addition time was recorded as T0 (0.00 minutes). The vial was manually shaken (without stirring) to prevent caking. The shaken vial was then placed in different holes of a foam block located on a hot plate / stirrer. The thermocouple was immediately inserted through the septum cap below the liquid level in the vial, and the temperature (°C) of the contents of the vial was recorded every 5 seconds from T0 to 300 minutes after T0. The temperature and time data were downloaded into a spreadsheet and thermodynamic curves were plotted for analysis. The results of these runs can be graphically depicted as a graph of the reaction temperature of the contents of the batch reactor on the y-axis and the time from Time0 when added on the x-axis.

[0194] Inventive Examples ("IE") and Comparative Examples ("CE") were prepared by the Light-off Vial Test Method. An effective amount of certain kinetic modifier compounds ("KMC") were combined with certain faster-igniting hybrid catalysts to obtain the attenuated hybrid catalysts of the Inventive Examples. The Comparative Examples met one of three criteria (1) to (3): (1) containing a hybrid catalyst but no kinetic modifier compound, (2) containing a hybrid catalyst and containing less than an effective amount of a kinetic modifier compound (e.g., CE1a), or (3) containing a metallocene catalyst and a kinetic modifier compound. The light-off effects of the faster-igniting hybrid and Inventive Examples were tested with polyoctenes according to the Light-off Vial Test Method to compare their relative activities. In separate vials, (a) mineral oil without 1-octene, (b) the examples of the mixed precatalyst, and (c) spray-dried methylaluminoxane (SDMAO) without the kinetic modifier compound were premixed for 10 minutes to obtain a slurry of the faster-igniting hybrid catalyst without 1-octene and the kinetic modifier compound. In other vials, (a) 1-octene-free mineral oil, (b) mixed precatalyst, (c) SDMAO and (d) kinetic modifier compound were premixed for 10 minutes to obtain a slurry of a weakened mixed catalyst without 1-octene. After premixing for 10 minutes (time under all conditions except (B)*), the same amount of 1-octene was added to each vial. After adding 1-octene, at the temperature of the mixture, as evidence of activation of the corresponding catalyst, an increase of 5°C to 120°C, alternatively 10°C to 110°C, alternatively an increase in temperature in any decade thereof (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 was used: Condition (A) (used in Tables 1 to 4): 5.5 mL Isopar-E; 8 μmol M; the amount of SDMAO was such that a molar ratio Al / M=120 was obtained; 0 μmol (CE) or 2 μmol (IE) kinetic modifier compound; 11 mL 1-octene; Condition (B) (used in Table 5): 5.5 mL Isopar-E; 10 μmol M; the amount of SDMAO was such that a molar ratio Al / M=120 was obtained; 0 μmol (CE) or 2 μmol (IE) kinetic modifier compound; 5.5 mL 1-octene, with premixing for 5 minutes instead of 10 minutes*; Condition (C) (used in Table 6): 5.5 mL Isopar-E; 20 μmol M; the amount of SDMAO that gave a molar ratio Al / M=120; the amount of kinetic modifier compound was 0 μmol (CE) or such that an indicated molar ratio M / KMC (IE) was obtained; 5.5 mL 1-octene; Condition (D) (used in Table 7): 5.5 mL Isopar-E; 2 μmol M; an amount of SDMAO that gives a molar ratio Al / M=120; an amount of the kinetic modifier compound of 0 μmol (CE) or an amount that gives the indicated molar ratio M / KMC (IE); 5.5 mL 1-octene.

[0195] Table 1: (Indicative) Conditions of Use (A) and Formulas Expected results of the light-off vial test method performed on the precatalyst (1).

[0196]

[0197] Table 2: (Indicative) Conditions of Use (A) and Formulas Expected results of the light-off vial test method performed on the precatalyst (2).

[0198]

[0199] Embodiments (A1) to (A20) of the present invention (IE(A1) to IE(A20)): (Prophetic) According to Preparation Example 2A, twenty weakened mixed catalysts were prepared separately using PreCat1 and different kinetic modifier compounds among the kinetic modifier compounds (1) to (20).

[0200] Embodiments (B1) to (B20) of the present invention (IE(B1) to IE(B20)): (Prophetic) According to Preparation Example 2A, twenty weakened mixed catalysts were prepared separately using PreCat2 and different kinetic modifier compounds among the kinetic modifier compounds (1) to (20).

[0201] Light-off batch reactor test method.

[0202] The relative kinetic profiles of the faster igniting catalyst and the weakened mixed catalyst are usually observed in separate polymerization runs, each run being conducted in a 2 liter (L) semi-batch autoclave polymerization reactor equipped with a mechanical stirrer. In a 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 added continuously 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 profiles.

[0203] The batch reactor is dried and loaded. Before each run, the batch reactor is dried for 1 hour. Then 200g NaCl is loaded into the dried batch reactor. The batch reactor is further dried by heating the batch reactor and its contents under an N2 atmosphere at 100°C for 30 minutes. Then 3g of methylaluminoxane (SMAO) loaded with silica is added to remove 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 that the 1-hexene and ethylene (C6 / C2) molar ratio is 0.004. The batch reactor is pressurized to 1.52 MPa (MPa) with ethylene. The resulting system is allowed to reach a steady state.

[0204] The catalyst (the catalyst with faster ignition or the mixed catalyst with weakening) is then loaded into the batch reactor to initiate polymerization. The time of adding the catalyst is recorded as time zero (Time 0). The reactor temperature is brought to 93°C and maintained at this temperature for 1 to 5 hours. The reactor is cooled, vented, opened, and the resulting polyolefin product is washed with water and methanol and dried to obtain a dry polyolefin product.

[0205] For each batch reactor run, the catalyst activity / polymerization productivity is calculated as the grams of dry polyolefin product prepared / grams of catalyst added to the reactor per hour (gPE / gcat-hr). The higher the number of gPE / gcat-hr, the higher the catalyst activity / polymerization productivity. Record the ethylene absorption after 0.1 hour (C2 absorption 0.1h) (6 minutes) and the ethylene absorption after 1.0 hour (C2 absorption 1h) (60 minutes), and record it as the ratio of (C2 absorption 1h) / (C2 absorption 0.1h). Under the same conditions for all other conditions, the higher the ratio of (C2 absorption 1 hour) / (C2 absorption 0.1 hour), the more the catalyst ignition is weakened.

[0206] The melting temperature of the dried polyolefin product was determined according to ASTM D3418-08 using differential scanning calorimetry (DSC) using a scan rate of 10°C / minute for 10 mg samples and using a second heating cycle. Some embodiments of the polyolefin products of the present invention prepared by the attenuated mixed catalyst may have a higher melting point than the melting point of the comparative polyolefin product prepared by its corresponding catalyst with a faster light-off.

[0207] From the light-off batch reactor runs with the faster light-off catalyst, most of the ethylene absorption may occur within the first few minutes after the start of polymerization (e.g., within 10 minutes of Time 0). Compared to the weakened mixed catalyst, the ethylene absorption is more evenly spread throughout the 3 hour long polymerization run. The results of these comparative examples and inventive runs can be graphically depicted as a graph of the reaction temperature of the batch reactor contents on the y-axis or the ethylene monomer ("C2") absorption on the y-axis versus the time from the addition Time 0 on the x-axis.

[0208] Comparative Example using a metallocene precatalyst.

[0209] Table 3: Usage conditions (A) and formula Comparative polymerization actual results of the light-off vial test method performed on Metallocene Precatalyst 1 ("MCN1"), wherein n-Bu is n-butyl.

[0210]

[0211] As shown in Table 3, phenylacetylene has essentially no dampening effect on the kinetics of the comparative metallocene catalyst made from MCN1.

[0212] Table 4: Usage conditions (A) and formula Comparative polymerization results for the Light-off Batch Reactor Test Method performed with Comparative Metallocene Precatalyst 1 ("MCN1"), wherein n-Bu is n-butyl.

[0213]

[0214] As shown in Table 4, the kinetic modifier compounds had essentially no debilitating effect on the kinetics of the comparative metallocene catalyst made from MCN1.

[0215] Table 5: Usage conditions (A) and formula Comparative polymerization results for the Light-off Batch Reactor Test Method performed with Comparative Metallocene Precatalyst 2 ("MCN2"), wherein n-Pr is n-propyl.

[0216]

[0217] As shown in Table 5, the kinetic modifier compounds reduced the polymerization productivity and had essentially no attenuating effect on the catalytic activity of the comparative metallocene catalyst made from MCN2.

[0218] Table 6: Usage conditions (A) and formula Comparative polymerization actual results of the light-off batch reactor test method conducted with Comparative Metallocene Precatalyst 3 ("MCN3").

[0219]

[0220] As shown in Table 6, the kinetic modifier compounds have essentially no attenuating effect on the catalytic activity of the comparative metallocene catalyst made from MCN3.

Claims

1. A method for preparing a weakened mixed catalyst, the method comprising: mixing a catalyst with a faster ignition speed with an effective amount of a formula (A 1 )、(B 1 ) or (C 1 ): R 5 -C≡CR 6 (A 1 )、(R 5 )2C=C=C(R 6 )2(B 1 ) or (R 5 )(R 7 )C=C(R 6 )(R 7 )(C 1 ) in combination with a kinetic modifier compound KMC to obtain a mixed catalyst with reduced light-off, wherein the mixed catalyst with reduced light-off exhibits a kinetic curve of reduced light-off relative to the kinetic curve of the catalyst with faster light-off; wherein the catalyst with faster light-off has been activated by formula (Ia)-1: A mixed precatalyst is prepared in which each group R a1 and R a2 Independently (C1-C 20 ) alkyl; and each group R a3 are independently H or (C1-C 20 )alkyl; each subscript 1-5 is independently 0, 1, 2, 3, 4 or 5, wherein the metal M is Ti, Hf or Zr; the subscript x is 1, 2 or 3, and each X is a monodentate group independently selected from the following: a halogen atom, a ((C1-C 20 )alkyl) 3-g -(phenyl) g Si-, CH3, (C2-C 20 )alkyl-CH2, (C6-C 12 )aryl-((C0-C 10 )alkylene)-CH2, (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; In the formula (A 1 )、(B 1 ) or (C 1 ), R 5 and R 6 Each of which is independently H or R 7 , and each R 7 Independently (C 1 -C 20 )alkyl, -C(=O)-O-(unsubstituted C1-C 20 )alkyl), (C1-C 19 ) heteroalkyl or tri((C1-C 20 )alkyl)silyl, or two R 7 together to form a (C3-C6)alkylene group; provided that each R 7 lacks carbon-carbon double bonds; each (C1-C 20 ) The hydrocarbon groups are independently unsubstituted or substituted by 1 to 4 groups R S Substituted; wherein each substituent group R S 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 -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).

2. The method according to claim 1, wherein the catalyst having a faster light-off has formula (IIa)-1: And wherein the weakened mixed catalyst has formula (IIIa)-1: wherein the subscript x, the metal M, and the ligands L and X are as defined in formula (Ia)-1; wherein A- is an anion used to formally balance 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); and wherein R 5 To R 7 As shown in formula (A 1 )、(B 1 ) or (C 1 ) as defined in the Regulations.

3. The method according to claim 1 or 2, wherein the kinetic modifier compound has the formula (A 1 ): R 5 -C≡CR 6 (A 1 ), wherein the kinetic modifier compound is selected from: phenylacetylene; (substituted phenyl)acetylene; diphenylacetylene; substituted diphenylacetylene; cycloalkylacetylene; a compound of the formula HC≡CSi(phenyl) h ((C1-C 20 )alkyl) 3-h Acetylene, wherein the subscript h is an integer from 0 to 3; and the formula HC≡C-(CH2) m CH3 acetylene, wherein the subscript m is an integer from 1 to 15.

4. The method of claim 1 or 2, 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 the group consisting of: cycloalkyl propadiene; alkyl propadiene; dialkyl propadiene; trialkyl propadiene; trialkylsilyl propadiene; vinylidene cycloalkanes; and alkyl esters of propadiene carboxylic acids.

5. The method of claim 1 or 2, wherein the kinetic modifier compound has the formula (C 1 )(R 5 )(R 7 )C=C(R 6 )(R 7 )(C 1 ), and formula (C 1 ) wherein the kinetic modifier compound is an internal olefin.

6. The method of claim 1 or 2, wherein the method further comprises preparing a mixture of the weakened hybrid catalyst, a support material, and an inert hydrocarbon solvent, and removing the inert hydrocarbon solvent from the mixture to obtain the weakened hybrid catalyst disposed on the support material.

7. The method according to claim 1 or 2, wherein the mixed precatalyst of formula (Ia)-1 is 8. A method for preparing a weakened mixed catalyst, the method comprising: mixing a catalyst with a faster ignition speed with an effective amount of a compound of formula (A 1 ) or (B 1 ): R 5 -C≡CR 6 (A 1 ) or (R 5 )2C=C=C(R 6 )2(B 1 ) in combination with a kinetic modifier compound KMC to obtain a mixed catalyst with reduced light-off, wherein the mixed catalyst with reduced light-off exhibits a kinetic curve of reduced light-off relative to the kinetic curve of the catalyst with faster light-off; wherein the catalyst with faster light-off has been activated by formula (Ib)-1: A mixed precatalyst is prepared in which each group R b1 Independently (C1-C 20 ) alkyl; and each group R b2 are independently H or (C1-C 20 )alkyl; each subscript 1-5 is independently 0, 1, 2, 3, 4 or 5; wherein the metal M is Ti, Hf or Zr; each X is a monodentate group independently selected from the following: a halogen atom, a ((C1-C 20 )alkyl) 3-g -(phenyl) g Si-, CH3, (C2-C 20 )alkyl-CH2, (C6-C 12 )aryl-((C0-C 10 )alkylene)-CH2, (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; In the formula (A 1 ) or (B 1 ), R 5 and R 6 Each of which is independently H or R 7 , and each R 7 Independently (C1-C 20 )alkyl, -C(=O)-O-(unsubstituted C1-C 20 )alkyl), (C1-C 19 ) heteroalkyl or tri((C1-C 20 )alkyl)silyl, or two R 7 together to form a (C3-C6)alkylene group; provided that each R 7 lacks carbon-carbon double bonds; each (C1-C 20 ) The hydrocarbon groups are independently unsubstituted or substituted by 1 to 4 groups R S Substituted; wherein each substituent group R S 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 -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).

9. An abated mixed catalyst prepared by the method according to any one of claims 1 to 8.

10. A method of feeding a mixed catalyst to a slurry phase or gas phase polymerization reactor containing a moving bed of olefin monomer and polyolefin polymer, the method comprising preparing the abated mixed catalyst outside the reactor and according to the method of any one of claims 1 to 8, and feeding the abated mixed catalyst into the slurry phase or gas phase polymerization reactor through a feed line free of olefin monomer in a neat state or as a solution or slurry thereof in an inert hydrocarbon liquid.

11. A multimodal catalyst system comprising the abated mixed catalyst according to claim 9 and at least one second catalyst selected from the group consisting of: an unabated mixed catalyst, a different abated mixed catalyst, a post-metallocene catalyst and a metallocene catalyst.

12. A process for preparing a polyolefin polymer, the process comprising contacting at least one 1-olefin monomer with the abated mixed catalyst prepared by the process according to any one of claims 1 to 8, or the multimodal catalyst system according to claim 11, under slurry phase or gas phase polymerization conditions in a slurry phase or gas phase polymerization reactor containing a moving bed of polyolefin resin, thereby preparing the polyolefin polymer.

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