Weakened post-metallocene catalyst

Abstract

A method for preparing a post-metallocene catalyst with reduced light-off, 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≡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 post-metallocene catalyst, the weakened post-metallocene catalyst exhibiting a monomer absorption curve with weakened light-off (relative to the monomer absorption curve of the catalyst with faster light-off); wherein the catalyst with faster light-off has been prepared by activating a post-metallocene precatalyst of structural formula (I) as defined herein; and related methods, compositions and uses.

Description

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

[0002] 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.)

[0003] 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.)

[0004] 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.

[0005] 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).

[0006] 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

[0007] We find that there is a problem with feeding (that is, separate from monomer and polyolefin polymer particles) a post-metallocene catalyst (i.e., a catalyst without cyclopentadienyl ligands) into a gas phase olefin polymerization reactor. Olefin polymerization is an exothermic reaction that can be carried out in a solution phase, a slurry phase, or a gas phase. The essence of gas phase polymerization is to have a minimum mass for absorbing the heat of reaction exotherm. We find that even when the active post-metallocene catalyst is separated from the olefin monomer feed (and for that matter, separated from the active polyolefin polymer particles) and fed into a gas phase polymerization reactor containing an olefin monomer and a moving bed of polyolefin polymer, such as when the active post-metallocene catalyst is fed into the reactor as a solution or slurry in an inert hydrocarbon solvent (e.g., an alkane or xylene), once the active post-metallocene catalyst is inside the reactor and undergoes polymerization conditions (e.g., high temperature and high pressure), the active post-metallocene catalyst may light off too fast in the gas phase polymerization reactor. That is, when the metallocene 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, thereby forming aggregates. These aggregates foul reactor components and / or impair the properties of the polyolefin product.

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

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

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

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

[0012] Aspect 1. A method for preparing a weakened post-metallocene catalyst ("a post-metallocene catalyst with weakened light-off"), the method comprising reacting a catalyst with a faster light-off under effective reaction conditions with an effective amount of a catalyst of formula (A 1 )、(B 1 ) or (C 1 ): R 5 -C≡CR 6(A 1 )、(R 5 ) 2 C=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 post-metallocene catalyst with reduced light-off, the post-metallocene catalyst with reduced light-off exhibiting a monomer absorption curve with reduced light-off (relative to the monomer absorption curve of the catalyst with faster light-off); wherein the catalyst with faster light-off has been prepared by activating a post-metallocene precatalyst of structural formula (I): 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 (C 1 -C 20 ) alkyl), (C 1 -C 19 ) heteroalkyl or tri((C 1 -C 20 )alkyl)silyl, or two R 7 Put together to form (C 3 -C 6 ) alkylene; provided that each R 7 lacks a carbon-carbon double bond; each (C 1 -C 20 ) The hydrocarbon groups are independently unsubstituted or substituted by 1 to 4 groups R S Substituted; wherein each substituent group R S are independently selected from halogen (e.g., F), unsubstituted (C 1 -C 5 ) alkyl (e.g., CH 3 )、-C≡CH、-OH、(C 1 -C 5 )alkoxy, -C(=O)-(unsubstituted (C 1 -C 5 )alkyl), -NH 2 、-N(H)(unsubstituted(C 1 -C5 ) alkyl), -N(unsubstituted(C 1 -C 5 )alkyl) 2 , -COOH, -C(=O)-NH 2 , -C(=O)-N(H)(unsubstituted(C 1 -C 5 ) alkyl), -C(=O)-N(unsubstituted (C 1 -C 5 )alkyl) 2 、-S-(unsubstituted(C 1 -C 5 )alkyl), -S(=O) 2 -(Unsubstituted(C 1 -C 5 )alkyl), -S(=O) 2 -NH 2 、-S(=O) 2 -N(H)(Unsubstituted(C 1 -C 5 )alkyl), -S(=O) 2 -N(unsubstituted(C 1 -C 5 )alkyl) 2 , -C(=)S-(unsubstituted (C 1 -C 5 ) alkyl) and -COO (unsubstituted (C 1 -C 5 ) alkyl); and wherein in formula (I): L is CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 , CH 2 C(R L ) 2 CH 2 , CH 2 CH(R L )CH(R L )CH 2 , CH 2 Ge(R L ) 2 CH 2 or CH 2 Si(R L ) 2 CH 2 , where each R Lare independently unsubstituted (C 1 -C 20 ) alkyl; M is Ti, Zr or Hf; alternatively, M is Zr or Hf; R 1a and R 1b Each of the above is independently a halogen atom (e.g., Cl or F, alternatively F), (C 1 -C 20 )alkyl or Si(CH 3 ) 2 (CH 2 ) q CH 3 , wherein subscript q is an integer from 0 to 20; each subscript r is independently an integer from 0 to 3; R 2a and R 2b Each of which is independently H, F, Cl or unsubstituted (C 1 -C 20 ) alkyl (e.g., CH 3 , ethyl, 1-methylethyl), alternatively H or CH 3 ; Each subscript s is independently an integer from 0 to 3; R 3a and R 3b Each of which is independently halogen, unsubstituted (C 1 -C 20 ) alkyl or (C 1 -C 20 )alkoxy, optionally unsubstituted (C 1 -C 20 ) alkyl or (C 1 -C 20 ) alkoxy; each AR 1a and Ar 1b is independently an unsubstituted or substituted aromatic group selected from the group consisting of phenyl, substituted phenyl, diphenyl, substituted diphenyl, anthracene, substituted anthracene, carbazolyl and substituted carbazolyl, wherein each substituent in the substituted aromatic group is independently an alkyl group; and each X is independently a monodentate group independently selected from a halogen atom, ((C 1 -C 20 )alkyl) 3-g -(phenyl) g Si-, where subscript g is 0, 1, 2 or 3; CH 3 , (C 2 -C 20 )alkyl-CH 2 , (C 6 -C 12 )Aryl-((C 0 -C 10 )alkylene)-CH 2(For example, benzyl when (C 6 -C 12 ) aryl is phenyl and (C 0 -C 10 ) alkylene is (C 0 ) alkylene, benzyl), (C 1 -C 6 )alkyl-substituted (C 6 -C 12 ) aryl, (C 1 -C 6 ) alkoxy-substituted (C 6 -C 12 ) aryl, (C 1 -C 6 ) alkoxy-substituted benzyl, and (C 1 -C 6 )alkyl-substituted benzyl; or one X is 4-(C 1 -C 20 )alkyl-substituted 1,3-butadiene molecules, and each of the remaining X, if any, is independently a monodentate group X. 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 combining step. In some embodiments, at least one X does not leave but remains coordinated to M. In some aspects, at least one X is (C 6 -C 12 )Aryl-((C 0 -C 10 )alkylene)-CH 2 (e.g., benzyl). In some aspects, each X is independently (C 6 -C 12 )Aryl-((C 0 -C 10 )alkylene)-CH 2 Alternatively, one X is (C 6 -C 12 )Aryl-((C 0 -C 10 )alkylene)-CH 2 (e.g., benzyl), and the other X is F, Cl or methyl; alternatively, each X is benzyl. For the removal of all doubts, the monodentate group X does not contain a carbon-carbon double bond or a carbon-carbon triple bond, i.e., the monodentate group X is not an alkenyl group or an alkynyl group. In some aspects, each R 7 Independently (C 1 -C 20 ) hydrocarbon groups, which independently may be unsubstituted or substituted by 1 to 3 groups selected from halogen (e.g., F) and alkyl (e.g., CH 3 ) is substituted by a substituent group, provided that each R7 Lacks carbon-carbon double bonds. In some embodiments, L is a carbon bridging group selected from: CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 , CH 2 C(R L ) 2 CH 2 and CH 2 CH(R L )CH(R L )CH 2 Alternatively, CH 2 CH 2 , CH 2 CH 2 CH 2 and CH 2 CH 2 CH 2 CH 2 Alternatively, CH 2 C(R L ) 2 CH 2 and CH 2 CH(R L )CH(R L )CH 2 , where each R L In some embodiments, L is a heteroatom-containing bridging group selected from: CH 2 Ge(R L ) 2 CH 2 and CH 2 Si(R L ) 2 CH 2 Alternatively, CH 2 Ge(R L ) 2 CH 2 Alternatively, CH 2 Si(R L ) 2 CH 2 ; where each R L In some embodiments, L is selected from CH 2 C(R L ) 2 CH 2 , CH2 CH(R L )CH(R L )CH 2 , CH 2 Ge(R L ) 2 CH 2 and CH 2 Si(R L ) 2 CH 2 R L Substituted bridging group; wherein each R L In some embodiments, M is Zr or Hf, and R 3a and R 3b Each of which is independently unsubstituted (C 1 -C 20 ) alkyl. The post-metallocene precatalyst of formula (I) may be any post-metallocene precatalyst described in any one of WO 2012 / 027448 A1; WO 2014 / 105411 A1; WO 2017 / 058981 A1; WO 2018 / 022975 A1; or WO 2018 / 183026 A1.

[0013] Aspect 2. The method according to aspect 1, wherein the catalyst with faster ignition has formula (II): and wherein the weakened post-metallocene catalyst has formula (III): Where the subscripts are r and s; the group R 1a To R 3a , R 1b To R 3b ,Ar 1a ,Ar 1b , L and X; and metal M 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(R 5 )(R 7 )-C(X)(R 6 )(R 7 )(C); and wherein R 5 To R 7 As in the previous formula (A 1 )、(B1 ) 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.

[0014] Aspect 3. The method according to aspect 1 or 2, wherein the post-metallocene pre-catalyst of formula (I) is a post-metallocene pre-catalyst of formula (Ia): Where L is CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 , CH 2 C(R L ) 2 CH 2 , CH 2 CH(R L )CH(R L )CH 2 , CH 2 Ge(R L ) 2 CH 2 or CH 2 Si(R L ) 2 CH 2 , where each R L are independently unsubstituted (C 1 -C 20 ) alkyl; M is Zr or Hf; R 1a and R 1b Each of the above is independently a halogen atom (e.g., Cl or F, alternatively F), (C 1 -C 20 )alkyl or Si(CH 3 ) 2 (CH 2 ) q CH 3 , wherein the subscript q is an integer from 0 to 9; R 2a and R 2b Each of which is independently H, Cl or unsubstituted (C1 -C 20 ) alkyl (e.g., CH 3 , ethyl, 1-methylethyl, alternatively CH 3 ), alternatively H or CH 3 ; R 3a and R 3b Each of which is independently unsubstituted 1,1-dimethyl-(C 2 To C 8 ) alkyl; R 4a , R 4b , R 5a , R 5b Each of which is independently H, unsubstituted (C 1 -C 20 ) alkyl (e.g., CH 3 , ethyl, 1-methylethyl or 1,1,3,3-tetramethylbutyl), ((C 1 -C 20 )alkyl) 3-g -(phenyl) g Si-(wherein the subscript g is 0, 1, 2, or 3) (e.g., the subscript g is 0 and the resulting ((C 1 -C 20 )alkyl) 3 Si- is dimethyl-octyl-silyl), or unsubstituted 1,1-dimethyl-(C 2 To C 6 )alkyl (e.g., 1,1,3,3-tetramethylbutyl), alternatively H or unsubstituted 1,1-dimethyl-(C 2 To C 4 )alkyl; and each X is independently defined as in formula (I).

[0015] Aspect 4. The method according to aspect 1 or 3, wherein the precatalyst of formula (I) or (Ia) is defined by any one of limitations (i) to (vi): (i) R 1a and R 1b Each of R is the same; (ii) R 2a and R 2b Each of the R 3a and R 3b are the same; (iv) R 4a and R 4b Each of the two is the same; (v) R 5a and R 5bIn some aspects, the combination restriction (vi) is any one of the combination restrictions (vii) to (xviii): (vii) (i) and (ii) both; (viii) (i) and (iii) both; (ix) (i) and (iv) both; (x) (i) and (v) both; (xi) (ii) and (iii) both; (xii) (ii) and (iv) both; (xiii) (ii) and (v) both; (xiv) (iii) and (iv) both; (xv) (iii) and (v) both; (xvi) (iv) and (v) both; (xvii) any four of the restrictions (i) to (v); and (xviii) each of the restrictions (i) to (v). In some embodiments, R 4a , R 4b , R 5a , R 5b Each of is H; alternatively, R 4a and R 4b Each of is H, and R 5a and R 5b Each of which is an unsubstituted 1,1-dimethyl-(C 2 To C 6 ) alkyl; alternatively, R 4a and R 4b Each of which is an unsubstituted 1,1-dimethyl-(C 2 To C 6 ) alkyl, and R 5a and R 5b Each of is H.

[0016] Aspect 5. The method according to aspect 1, 3 or 4, wherein the precatalyst of formula (I) or (Ia) is defined by any one of limitations (i) to (vi): (i) L is CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 or CH 2 Si(CH(CH 3 ) 2 ) 2 CH 2 , alternatively L is CH 2 CH 2 CH 2 or CH 2 CH 2 CH 2 CH 2, alternatively L is CH 2 CH 2 CH 2 or CH 2 Si(CH(CH 3 ) 2 ) 2 CH 2 , alternatively L is CH 2 CH 2 CH 2 CH 2 or CH 2 Si(CH(CH 3 ) 2 ) 2 CH 2 , alternatively L is CH 2 CH 2 CH 2 , alternatively L is CH 2 CH 2 CH 2 CH 2 , alternatively L is CH 2 Si(CH(CH 3 ) 2 ) 2 CH 2 ; (ii) M is Zr; (iii) M is Hf; (iv) each X is independently (C 7 -C 20 ) aralkyl (e.g., each X is benzyl); (v) one X is (C 7 -C 20 ) aralkyl (e.g., benzyl) and the other X is F, Cl or methyl; and (vi) a combination of any two or more of the restrictions (i) to (v). In some aspects, the combination restriction (vi) is any one of the combination restrictions (vii) to (xviii): (vii) (i) and (ii) both; (viii) (i) and (iii) both; (ix) (i) and (iv) both; (x) (i) and (v) both; (xi) (ii) and (iii) both; (xii) (ii) and (iv) both; (xiii) (ii) and (v) both; (xiv) (iii) and (iv) both; (xv) (iii) and (v) both; (xvi) (iv) and (v) both; (xvii) any four of the restrictions (i) to (v); and (xviii) each of the restrictions (i) to (v). In some aspects, each X is F; alternatively, each X is Cl; alternatively, each X is benzyl; alternatively, each X is methyl.

[0017] Aspect 6. The method according to any one of aspects 3 to 5, wherein the catalyst with faster light-off has formula (IIa): And wherein the light-off-reduced catalyst has formula (IIIa): Among them, L, M; R 1a To R 5a ; R 1b To R 5b ;Ar 1a and Ar 1b and X is defined as formula (Ia); wherein A - As defined in formula (II); and wherein R is as defined in formula (III).

[0018] Aspect 7. The method according to any one of aspects 3 to 6, wherein the post-metallocene precatalyst of (Ia) is any one of the post-metallocene precatalysts (1) to (5): ("Precatalyst 1"); ("Precatalyst 2"); ("Precatalyst 3"); ("Precatalyst 4"); and ("Precatalyst 5").

[0019] Precatalyst (1) was synthesized according to the procedure of WO2014105411 A1. Precatalyst (2) was synthesized according to the procedure of WO2017058981 A1. Precatalyst (3) was synthesized according to the procedure of WO2012027448 A1. Precatalyst (4) was synthesized according to the procedure of WO 2018 / 022975 A1 (e.g., Example E-19). Precatalyst (5) was synthesized according to the procedure of WO 2018 / 183026 A1 (e.g., Example 26).

[0020] 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 and has been found that: 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 S; alternatively O; alternatively N; alternatively Si.

[0021] 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 ((C 1 -C 20 )alkyl) 3-h acetylene, wherein the subscript h is an integer from 0 to 3; and the formula HC≡C-(CH 2 ) m CH 3 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 may be selected from: -C(H)=C(X)-phenyl; -C(H)=C(X)-(substituted phenyl); -CH 2 -C(X)=C(H)-cycloalkyl; -CH 2 -C(X)=C(H)-Si(phenyl) h ((C 1 -C 20 )alkyl) 3-h , wherein the subscript h is as defined above; -C(H)=C(X)-(CH 2 ) m CH 3 , wherein the subscript m is as defined above; or -CH 2 -C(X)=C(alkyl) 2The 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. (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.

[0022] 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 ), and formula (A 1 ) wherein the kinetic modifier compound is selected from the group consisting of any one of KMC1 to KMC14: Kinetic modifier compound (1) ("KMC1"): phenylacetylene (i.e., (C 6 H 5 )C≡CH); Kinetic modifier compound (2) ("KMC2"): 4-methylphenyl-acetylene (i.e., (4-CH 3 -C 6 H 4 )C≡CH); Kinetic modifier compound (3) ("KMC3"): 2,4,5-trimethylphenyl-acetylene (i.e., (2,4,5-(CH 3 ) 3 -C 6 H 2 )C≡CH); Kinetic modifier compound (4) ("KMC4"): 1,3,5-triethynylbenzene (i.e., 1,3,5-tris(HC≡C) 3 (C 6 H 3 )); Kinetic modifier compound (5) ("KMC5"): diphenylacetylene (ie, (C 6 H 5 )C≡C(C 6 H 5 )); Kinetic modifier compound (6) ("KMC6"): 3-fluorophenyl-acetylene (ie, (3-FC 6 H 4 )C≡CH); Kinetic modifier compound (7) ("KMC7"): 4-fluorophenyl-acetylene (ie, (4-FC 6 H 4 )C≡CH); Kinetic modifier compound (8) ("KMC8"): 3,4-difluorophenyl-acetylene (i.e., (3,4-F 2 -C 6 H 3)C≡CH); Kinetic modifier compound (9) ("KMC9"): 3,5-difluorophenyl-acetylene (i.e., (3,5-F 2 -C 6 H 3 )C≡CH); Kinetic modifier compound (10) ("KMC10"): cyclohexyl acetylene (i.e., C 6 H 11 C≡CH); Kinetic modifier compound (11) ("KMC11"): phenyldimethylsilyl acetylene (i.e., (C 6 H 5 )(CH 3 ) 2 SiC≡CH); kinetic modifier compound (12) ("KMC12"): 1-pentyne (i.e., CH 3 (CH 2 ) 2 C≡CH); Kinetic modifier compound (13) ("KMC13"): 1-octyne (i.e., CH 3 (CH 2 ) 5 C≡CH); and a kinetic modifier compound (14) ("KMC14"): 1,7-octanediyne (i.e., HC≡C(CH 2 ) 4 C≡CH).

[0023] Aspect 11. The method according to any one of aspects 1 to 8, wherein the kinetic modifier compound has the formula (B 1 ):(R 5 ) 2 C=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. The cycloalkyl propadiene may be ((C 3 -C 8 )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 trimethylsilylpropadiene, triethylsilylpropadiene, or dimethyl, (1,1-dimethylethyl)silylpropadiene (i.e., tert-butyl-dimethyl-silylpropadiene). The vinylidene cycloalkane may be of the formula of vinylidenecyclohexane.

[0024] 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 ) 2 C=C=C(R 6 ) 2 (B 1 ), and formula (B 1 ) wherein the kinetic modifier compound is selected from the group consisting of any one of KMC15 to KMC17: Kinetic modifier compound (15) ("KMC15"): cyclohexyl propadiene (i.e., (C 6 H 11 )C(H)=C=CH 2 ); Kinetic modifier compound (16) ("KMC16"): ethyl 2,3-butadienoate (ie, H 2 C=C=CH-C(=O)-O-CH 2 CH 3 ); and a kinetic modifier compound (17) ("KMC17"): 1,1-dimethylpropadiene (ie, (CH 3 ) 2 C=C=CH 2 ).

[0025] Aspect 13. 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. Thus, the internal olefin does not have a terminal carbon-carbon double bond or a terminal carbon-carbon triple bond. The internal olefin may be selected from KMC18 to KMC20: kinetic modifier compound (18) ("KMC18"): 2-butene; kinetic modifier compound (19) ("KMC19"): 2-pentene and kinetic modifier compound (20) ("KMC20"): 1,2-diphenylethylene. In formula (III) of aspect 2, the corresponding ligand R may be derived from or have the formula: -C(H)(CH 3 )-C(X)CH 3 、-C(H)(CH 3 )-C(X)CH 2 CH 3 or -C(H)(phenyl)-C(X)phenyl.

[0026] Aspect 14. The method according to any one of aspects 1 to 13, further comprising, before the combining step, a step of preparing the catalyst with faster ignition by activating the precatalyst of formula (I) with the activator under effective activation conditions, thereby preparing the catalyst with faster ignition. In some embodiments, the activator is an alkylaluminoxane, an organic borane compound, or an organic borate.

[0027] Aspect 15. A method according to any one of aspects 1 to 14, wherein the method further comprises preparing a mixture of the weakened post-metallocene catalyst, a support material and an inert hydrocarbon solvent, and removing the inert hydrocarbon solvent from the mixture to obtain the weakened post-metallocene catalyst disposed on the support material. The mixture may also include an excess of an activator, since the activator is typically used in excess to activate the post-metallocene 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 post-metallocene catalyst. Alternatively, the removal step may be achieved by spray drying the mixture. The spray drying embodiment provides a spray-dried / supported weakened post-metallocene catalyst that may have improved performance relative to an evaporated / supported weakened post-metallocene catalyst. Examples of the support material are alumina and hydrophobic fumed silica; alternatively, the hydrophobic fumed silica. The hydrophobic fumed silica may be prepared by surface treating untreated anhydrous fumed silica with an effective amount of a 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, which is a fumed silica surface treated with dimethyldichlorosilane.

[0028] Aspect 16. An attenuated post-metallocene catalyst prepared by the method according to any one of aspects 1 to 15. The attenuated post-metallocene catalyst may have the previously described formula (III), or be based on the previously described formula (III). In some embodiments, the attenuated post-metallocene catalyst is made from the post-metallocene precatalyst of formula (Ia).

[0029] Aspect 17. A method for feeding a post-metallocene 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 post-metallocene catalyst outside the reactor, and preparing the weakened post-metallocene catalyst according to the method described in any one of Aspects 1 to 15, and feeding the weakened post-metallocene catalyst in a pure state (e.g., dry powder) or as a solution or slurry thereof in an inert hydrocarbon liquid to the slurry phase or gas phase polymerization reactor through a feed line that does not contain olefin monomers. In some embodiments, the method also includes transferring the weakened post-metallocene catalyst or a fully active post-metallocene catalyst prepared in situ from the reactor to a (second) gas phase polymerization reactor, wherein the catalyst catalyzes a second olefin polymerization reaction.

[0030] Aspect 18. A multimodal (e.g., bimodal or trimodal) catalyst system comprising a weakened post-metallocene catalyst according to Aspect 16 and at least one second catalyst selected from the group consisting of an unweakened post-metallocene catalyst, a different weakened post-metallocene catalyst, and a metallocene catalyst. In some embodiments, the multimodal catalyst system comprises the weakened post-metallocene catalyst and only one second catalyst, alternatively only two different second catalysts. The multimodal catalyst system may also include a support material, and the weakened post-metallocene catalyst and the metallocene catalyst may be disposed (e.g., spray dried) on the support material. The weakened post-metallocene catalyst and the metallocene catalyst of the multimodal catalyst system may have 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 post-metallocene 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.

[0031] Aspect 19. A method of 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 post-metallocene catalyst outside the reactor and contacting a solution of the abated post-metallocene catalyst and the activated metallocene catalyst in an inert hydrocarbon solvent with a support material (e.g., fumed silica) outside the reactor according to the method of any one of aspects 1 to 15 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 post-metallocene 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.

[0032] Aspect 20. A method for preparing a polyolefin polymer, the method comprising contacting at least one 1-olefin monomer with the abated post-metallocene catalyst prepared by the method according to any one of aspects 1 to 15, or the method of feeding the 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 post-metallocene catalyst prepared by the method according to any one of aspects 1 to 15, or the multimodal catalyst system according to aspect 19, to 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 light-off of the abated post-metallocene 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 propylene, 1-butene, 1-hexene, and 1-octene. In some embodiments, the reactor is a first gas phase polymerization reactor and is under first gas phase polymerization conditions. Alternatively, the reactor may be a slurry phase polymerization reactor, and the polymerization conditions may be slurry phase polymerization conditions. In some such embodiments, the process may further comprise transferring the active polymer particles produced in the first gas phase polymerization reactor under first gas phase polymerization conditions or produced in the slurry phase polymerization reactor under slurry phase polymerization conditions and in either case containing (in the particles) an active post-metallocene 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 producing 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).

[0033] Aspect 21. A polyolefin polymer prepared by the preparation method according to aspect 20. 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 post-metallocene catalyst is replaced by the faster light-off catalyst.

[0034] Aspect 22. A manufactured article (eg, a blown film or a cast film) made from the polyolefin polymer according to aspect 21. The manufactured article may have a lower gel number than a comparative manufactured article made from a comparative polyolefin polymer.

[0035] Aspect 23. The embodiment of the invention according to any one of aspects 1 to 22, wherein the abated post-metallocene catalyst is free of support material, for example, free of fumed silica or alumina.

[0036] Aspect 24. The post-metallocene precatalyst is selected from the group consisting of the aforementioned post-metallocene precatalysts of formula (1) to (5), alternatively selected from any four precatalysts of precatalysts (1) to (5). In some embodiments, the post-metallocene precatalyst is a metallocene precatalyst of formula (5).

[0037] Aspect 25. Prepare a post-metallocene catalyst by contacting the post-metallocene pre-catalyst according to aspect 24 with an activator.

[0038] A method for preparing an attenuated post-metallocene catalyst. The method comprises: reacting a catalyst with a relatively fast ignition rate with an effective amount of a compound of formula (A) under effective reaction conditions. 1 )、(B 1 ) or (C 1 ) is combined with a kinetic modifier compound to prepare a weakened post-metallocene catalyst. The catalyst that ignites faster may have formula (II), and the weakened post-metallocene catalyst may have formula (III). The combination step may be performed in the absence of a pre-catalyst of formula (I). If an activator is used in excess in the activation step, the combination step may be performed in the presence of unreacted activator. The catalyst that ignites faster contains a leaving group X bonded to a metal atom M. In the combination step, the kinetic modifier compound reacts with the catalyst that ignites faster in such a way that the leaving group X from the catalyst that ignites faster is replaced, and the leaving group is replaced with a ligand R derived from the kinetic modifier compound and the leaving group X. The ligand is bonded to the metal atom M in the resulting weakened post-metallocene catalyst. In some aspects, the weakened post-metallocene catalyst has formula (III), and the catalyst that ignites faster has formula (II), and the pre-catalyst has formula (I), wherein all M are Zr and each X is benzyl.

[0039] 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.

[0040] The embodiment of the preparation method may include any one of Synthesis Schemes 1 to 12.

[0041] Synthesis Scheme 1: Step (a) post-metallocene precatalyst + excess activator → activated post-metallocene catalyst + residual activator intermediate mixture. Step (b) intermediate mixture + effective amount of kinetic modifier compound → weakened post-metallocene catalyst + residual activator.

[0042] Synthesis Scheme 2: Step (a) post-metallocene precatalyst + effective amount of kinetic modifier compound → intermediate post-metallocene precatalyst (unreacted mixture or reaction product of post-metallocene precatalyst + kinetic modifier compound). Step (b) intermediate post-metallocene precatalyst + activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) → weakened post-metallocene catalyst.

[0043] Synthesis Scheme 3: Step (a) post-metallocene precatalyst + activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) → activated post-metallocene catalyst (faster light-off catalyst). Step (b) activated post-metallocene catalyst + effective amount of kinetic modifier compound → weakened post-metallocene catalyst.

[0044] Synthesis Scheme 4: Step (a) Activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) + effective amount of kinetic modifier compound → intermediate solution. Step (b) Intermediate solution + post-metallocene precatalyst → post-metallocene catalyst with reduced light-off.

[0045] Synthesis Scheme 5: Step (a) Activator → post-metallocene pre-catalyst ← effective amount of kinetic modifier compound (activator and kinetic modifier are added to post-metallocene pre-catalyst simultaneously but separately) → attenuated post-metallocene catalyst. Step (b): None.

[0046] Synthesis Scheme 6: Step (a) post-metallocene precatalyst + support material → supported post-metallocene precatalyst. (b) supported post-metallocene precatalyst + a certain amount of activator → the intermediate mixture of activated post-metallocene catalyst + remaining activator is disposed on the support material (or balanced with the support material). Step (c) intermediate mixture + effective amount of kinetic modifier compound → the weakened post-metallocene catalyst is disposed 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 the activator may be a stoichiometric amount relative to the metal M of the post-metallocene 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 post-metallocene catalyst (e.g., a molar ratio of 0.1 to 0.94); alternatively, an excess amount relative to the metal M of the post-metallocene catalyst (e.g., a molar ratio of 1.1 to 10,000).

[0047] Synthesis Scheme 7: Step (a) post-metallocene precatalyst + effective amount of kinetic modifier compound + support material → intermediate mixture of post-metallocene precatalyst and kinetic modifier compound is disposed on (or balanced with) a support material. Step (b) intermediate mixture + activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) → attenuated post-metallocene catalyst is disposed on (or balanced 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).

[0048] Synthesis Scheme 8: Step (a) post-metallocene precatalyst + support material + activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) → the activated post-metallocene catalyst (the catalyst that ignites faster) is disposed on the support material (or balanced with the support material). Step (b) supported activated post-metallocene catalyst + effective amount of kinetic modifier compound → the weakened post-metallocene catalyst is disposed 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).

[0049] Synthesis Scheme 9: Step (a) activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) + effective amount of kinetic modifier compound → intermediate solution. Step (b) intermediate solution + post-metallocene precatalyst + support material → the post-metallocene catalyst with reduced light-off is disposed on the support material (or in equilibrium with the support material). In some aspects, step (b) also includes an inert hydrocarbon solvent, and the deposition on the support material is performed by evaporating the solvent (alternatively by spray drying).

[0050] Synthesis Scheme 10: Step (a) Activator → Post-metallocene precatalyst + support material ← effective amount of kinetic modifier compound (adding activator and kinetic modifier compound simultaneously but separately to the mixture of post-metallocene precatalyst + support material) → disposing the weakened post-metallocene catalyst on the support material (or equilibrating with the support material). Step (b): None. In some aspects, step (a) further comprises an inert hydrocarbon solvent, and the deposition on the support material is performed by evaporating the solvent (alternatively by spray drying).

[0051] 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): post-metallocene precatalyst + spray-dried supported activator of step (b) + inert hydrocarbon solvent are mixed → a suspension of a supported post-metallocene 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 supported attenuated post-metallocene catalyst on (or equilibrating with) a support material in an inert hydrocarbon solvent. Optional step (e): removing the inert hydrocarbon solvent from the suspension of the supported attenuated post-metallocene catalyst → disposing the supported attenuated post-metallocene 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).

[0052] Scheme 12: Preparation of a multimodal catalyst system comprising an attenuated post-metallocene catalyst and a spray-dried non-attenuated metallocene catalyst on a silica support: Step (a) post-metallocene precatalyst + support material + activator (e.g., alkylaluminoxane, such as methylaluminoxane ("MAO")) → the activated post-metallocene catalyst (the catalyst that ignites faster) is disposed on the support material (or balanced with the support material). Step (b) supported activated post-metallocene catalyst + effective amount of kinetic modifier compound → the attenuated post-metallocene catalyst is disposed on the support material (e.g., spray-dried non-attenuated metallocene catalyst / support material) (or balanced with the support material). Step (c) the non-attenuated metallocene catalyst is added to the attenuated post-metallocene catalyst disposed on the support material (or balanced with the support material) to obtain a multimodal catalyst system. In some aspects, step (a) also includes an inert hydrocarbon solvent, and the deposition on the support material is performed by evaporating the solvent (alternatively by spray drying). For example, slurry support material (e.g., fumed silica) and MAO in a solvent (e.g., toluene). Then add a post-metallocene catalyst that ignites faster. Mix for a period of time (e.g., 1 hour). Then add a kinetic modifier compound. Mix for another period of time (e.g., 1 hour). Then add a second unabated post-metallocene catalyst. Spray dry the resulting mixture.

[0053] 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.

[0054] The method according to any of the above aspects may further comprise the step of transferring polymer particles prepared in a gas phase or slurry phase polymerization reactor to a (second) gas phase polymerization reactor, and these polymer particles contain fully active post-metallocene catalyst in the particles.

[0055] 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 ) 2 C=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 post-metallocene catalyst, or may at most have a slight effect. 1 ) is an alkyne, formula (B 1 ) is propadiene, and the compound of formula (C 1 The kinetic modifier compound does not contain a vinyl functional group (i.e., lacks a olefin of the formula -C(H)=CH 2 of groups).

[0056] In some embodiments, the kinetic modifier compound is as defined in any of the numbered aspects described above.

[0057] In the formula (A 1 )、(B 1 ) or (C 1 ) in some embodiments of the kinetic modifier compound, (C 1 -C 20 ) The hydrocarbon group is (C 2 -C 6 ) alkyl, (C 3 -C 8 )cycloalkyl, or phenyl. In some embodiments, -C(=O)-O-(unsubstituted C 1 -C 20 )alkyl) is -C(=O)-O-(unsubstituted C 1 -C 5 )alkyl), alternatively -C(=O)-O-ethyl.

[0058] In some embodiments, at least one X is ((C 1 -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 (C 6 -C 12 )Aryl-((C 0 -C 10 )alkylene)-CH 2 (e.g., benzyl). In some aspects, each X is independently (C 6 -C 12 )Aryl-((C 0 -C 10 )alkylene)-CH 2 Alternatively, one X is (C 6 -C 12 )Aryl-((C 0 -C 10 )alkylene)-CH 2 (e.g., benzyl), and the other X is F, Cl or methyl; alternatively, each X is benzyl. In some aspects, each X is benzyl; alternatively, one X is benzyl and the other X is F, Cl or methyl. In some embodiments, at least one X, alternatively each X is (C 1 -C 6 ) alkoxy-substituted (C 6 -C 12 ) aryl, or (C 1 -C 6) alkoxy-substituted benzyl. Without being bound by theory, it is believed that the structure of the weakened post-metallocene catalyst is similar to that of the catalyst that lighted off faster, except that one of the leaving groups X of the catalyst that lighted off faster has been replaced by the weakened leaving group R in the weakened post-metallocene catalyst, wherein R is defined later and is derived from the kinetic modifier compound. The weakened leaving group R of the weakened post-metallocene catalyst is structurally different from the leaving group X of the catalyst that lighted off faster, and leaves more slowly than the leaving group of the catalyst that lighted off faster.

[0059] The ligand R is derived from the kinetic modifier compound and the leaving group X. The ligand derived from the kinetic modifier compound in the weakened post-metallocene 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 monomer absorption profile of the weakened post-metallocene 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.

[0060] 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 deactivation of the catalyst, which can reduce the productivity of some catalysts (such as some post-metallocene catalysts).

[0061] 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 (C 1 -C 20 ) alkyl or (C 1 -C 17 ) heteroalkyl, provided that each R 7 Lack of carbon-carbon double bonds. 1 -C 20 ) The hydrocarbon group may be unsubstituted and consist of carbon atoms and hydrogen atoms, or (C 1 -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. Unsubstituted (C 1 -C 20 ) The hydrocarbon group may be unsubstituted (C 1 -C 20 ) alkyl, unsubstituted (C 3 -C 20 )cycloalkyl, unsubstituted (C 6 -C 12 ) aryl, unsubstituted ((C 1 -C 4 )alkyl) 1-3 -phenyl, or unsubstituted (C6 -C 12 )Aryl-(C 1 -C 6 ) alkyl. Substituted (C 1 -C 20 ) The hydrocarbon group may be the aforementioned unsubstituted (C 1 -C 20 ) a mono- or di-fluoro derivative of a hydrocarbon group, such as 2-(3,4-difluorophenyl)-ethen-1-yl (having formula (A)).

[0062] R 5 To R 7 Each of the embodiments (C 1 -C 19 ) heteroalkyl contains 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 (C 1 -C 17 ) heteroalkyl 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. 1 -C 17 ) heteroalkyl may be (C 1 -C 19 ) heteroalkyl, (C 3 -C 19 ) heterocycloalkyl, (C 6 -C 12 ) heteroaryl, ((C 1 -C 4 )alkoxy) 1-3 -phenyl, or (C 6 -C 12 )heteroaryl-(C 1 -C 6 ) alkyl. Substituted (C 1 -C 17 ) heteroalkyl may be the aforementioned unsubstituted (C 1 -C 17 ) a mono- or di-fluoro derivative of a heteroalkyl group, such as 2-(3,4-dimethoxyphenyl)-ethen-1-yl (having formula (A)).

[0063] 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.

[0064] Weakened post-metallocene catalyst.According to the method, a weakened post-metallocene catalyst (e.g., of formula (III)) is prepared from a catalyst (e.g., of formula (II)) that ignites faster. The weakened post-metallocene catalyst is a post-metallocene catalyst containing a ligand (e.g., R) bonded to its metal atom M (e.g., Ti, Zr or Hf), the ligand being derived from a kinetic modifier compound. The weakened post-metallocene catalyst is a new post-metallocene catalyst. In some embodiments, the weakened post-metallocene catalyst is a weakened post-metallocene catalyst of formula (III).

[0065] It is believed that, all other conditions being equal, the weakened post-metallocene catalyst (e.g., of formula (III)) may work without significantly reducing the total catalytic activity relative to the total catalytic activity of the catalyst (e.g., of formula (II)) that ignites faster to prepare it. 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 post-metallocene catalyst that ignites faster, and in some embodiments may be greater than the catalytic activity / polymerization productivity of the post-metallocene catalyst that ignites faster. For example, the attenuated post-metallocene catalyst may have a catalyst content of greater than 200%, alternatively from 30.0% to 180.0%, alternatively from 50.0% to 180%, alternatively from 30.0% to 70.0%, alternatively from 70.0% to 180.0%, alternatively from 70.0% to 150.0%, alternatively from 70.0% to 120%, alternatively from 80.0% to 120%, alternatively from 90.0% to 120%, alternatively from 100.0% to 150. ... The productivity of the catalyst having faster ignition speed for preparing the catalyst is 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%.

[0066] It is believed that the attenuated post-metallocene 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.

[0067] It is believed that the weakened post-metallocene catalyst (e.g., of formula (III)) can exhibit an improved polymerization monomer absorption curve compared to the faster light-off catalyst of formula (II) from which it is prepared. This improved polymerization monomer absorption curve will advantageously increase the compatibility of the weakened post-metallocene catalyst (e.g., of formula (III)) with slower light-off olefin polymerization catalysts (such as some metallocene catalysts), and 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.

[0068] In addition, if it is desired to store and / or transport the catalyst, it is believed that the weakened post-metallocene catalyst (e.g., of formula (III)) can be stored and transported at ambient temperature, rather than under refrigerated storage and refrigerated transport conditions for the faster-lighting catalyst (e.g., of formula (II)) that is desired to be used to prepare it, until the weakened post-metallocene catalyst can be used in a chemical process. It is believed that the weakened post-metallocene catalyst (e.g., of formula (III)) can achieve any one of such benefits, or a combination of any two or more such benefits.

[0069] In some embodiments, the attenuated post-metallocene catalyst (e.g., of formula (III)) and the method for polymerizing olefin monomers do not contain a catalyst of formula (A 1 )、(B 1 ) or (C 1 ) of excess kinetic modifier compound (KMC). In other embodiments, the weakened post-metallocene catalyst and method have an excess of kinetic modifier compound. Such embodiments of weakened post-metallocene catalysts (e.g., of formula (III)) can be prepared by combining a catalyst (e.g., of formula (II)) with a faster light-off ratio of the number of moles of kinetic modifier compound to the number of moles of metal M of formula (II) 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 a less than stoichiometric amount (molar ratio>0 to 0.99). When the kinetic modifier compound is used in a less than stoichiometric amount, the resulting attenuated post-metallocene catalyst (e.g., of formula (III)) has a partially attenuated light-off activity relative to the faster light-off catalyst (e.g., of formula (II)) from which it is prepared. This partially attenuated light-off activity may be helpful when the faster light-off catalyst (e.g., of formula (III)) 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., of formula (II)), the greater the attenuation of the overactivity of the faster light-off catalyst (e.g., of formula (II)) will result.

[0070] In some embodiments, the attenuated post-metallocene 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 post-metallocene 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 kinetic modifier compound to moles of 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 post-metallocene catalyst (e.g., of formula (III)) and / or the productivity of the gas phase polymerization reaction using it may not be significantly reduced 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 post-metallocene catalyst (e.g., of formula (III)) and / or the productivity of the gas phase polymerization reaction using it may be significantly reduced relative to the catalytic activity and productivity of the 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.

[0071] Monomer absorption curve with reduced ignition. The weakened post-metallocene catalyst (e.g., of formula (III)) exhibits a monomer absorption curve with weakened light-off. For example, the weakened monomer absorption curve may include a peak reaction temperature (T ) of the weakened post-metallocene catalyst relative to a catalyst with faster light-off from which it is prepared. max ) is longer and / or T max The value of is lower. 0 )) The reactor containing olefin monomer but no catalyst is heated to the peak polymerization temperature (Temp peak ) is a longer time of at least 0.65 minutes. peak A higher value of indicates a greater delay in catalyst light-off.

[0072] 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.

[0073] An effective amount of a kinetic modifier compound (KMC). Amount of 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.

[0074] 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 M of the post-metallocene 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 effective amount of KMC can be expressed as the inverse molar ratio of the number of moles of metal M to the number of moles of kinetic modifier compound ("M mol / KMC mol”) to describe the aforementioned embodiment, the inverse molar ratios are 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. Generally, 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.

[0075] In terms of weakened light-off performance, the effective amount of the kinetic modifier compound (KMC) can be represented by the results measured by the light-off vial test method described later. For example, as measured separately by the light-off vial test method described later, a post-metallocene catalyst with a weakened and 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) a time delay in the onset of the exotherm, i.e., the reaction temperature rise (i.e., from the addition time zero (Time 0)) 0 ) to the start time of temperature exotherm (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 Time 0 From the time of addition 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 Time 0 From the time of addition to the 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).

[0076] Weakened post-metallocene 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.

[0077] In some embodiments, the monomer absorption curve of the weakened post-metallocene catalyst is Temp. max (℃) can be characterized as peak temperature (Temp peak ) is reduced. In the light-off batch reactor test method, the reduced Temp max Temp of the catalyst that can be prepared to ignite faster max 1°C to 30.0°C lower, alternatively 1°C to 16°C, alternatively 2°C to 15°C, alternatively 3°C to 14°C lower. In some embodiments, the post-metallocene catalyst with faster light-off is made from any of the post-metallocene precatalysts (1) to (10) described previously.

[0078] In some embodiments, the monomer absorption curve of the weakened post-metallocene catalyst can be characterized as ethylene (C 2 ) absorption and C after 0.1 hour 2 Absolute weight / weight ratio of absorption (C 2 (1h) / C 2 (0.1 h)). In some embodiments, the reduced C of the post-metallocene catalyst 2 (1h) / C 2 The (0.1h) ratio may 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 faster light-off post-metallocene catalyst is made from any of the post-metallocene pre-catalysts (1) to (10) described previously.

[0079] In some embodiments, the monomer absorption curve of the weakened post-metallocene catalyst can be characterized as the weakened post-metallocene catalyst C when operated under the same polymerization conditions according to the Light-off Batch Reactor Test Method described later. 2 (1h) / C 2 (0.1h) than the C of the catalyst that ignites faster than the one used to prepare it 2 (1h) / C 2 (0.1h) Ratio of relative C 2 (1h) / C 2 (0.1h) ratio. 2 (1h) / C 2 The (0.1 h) ratio may be 1.05 to 6, alternatively 1.1 to 6, alternatively 1.2 to 5.4, alternatively 1.5 to 5.0.

[0080] An alternative or additional way of expressing an effective amount of a kinetic modifier compound (KMC) with respect to reduced light-off performance, as measured by the Light-off Vial Test Method described later, may be a sufficient amount of KMC such that the reduced post-metallocene catalyst and the faster light-off catalyst prepared therefrom may have a light-off curve as measured by the Light-off Vial Test Method (described later) wherein their respective peak polymerization temperatures (Temp peak ) is at least 0.7 minutes, alternatively greater than 1.0 minutes, alternatively greater than 5 minutes, alternatively greater than 10.0 minutes, alternatively greater than 20.0 minutes, alternatively greater than 30.0 minutes, alternatively greater than 40.0 minutes, alternatively greater than 50.0 minutes of each other. The weakened post-metallocene catalyst and the catalyst that ignites faster therefrom can have a light-off curve measured by the light-off vial test method (described later), wherein their corresponding peak polymerization temperatures (Temp peak ) within 60 minutes, alternatively within 45 minutes, alternatively within 30 minutes of each other. The kinetic modifier compound has a delayed effect on the peak polymerization temperature (Temp) of the post-metallocene catalyst. peak ) time relative to the time Temp of the post-metallocene catalyst with faster light-off prepared from the weakened post-metallocene catalyst peak , may vary depending on: (a) the structural class (e.g., Formula (I)) or structural subclass (e.g., Formula (Ia)) of the attenuated post-metallocene catalyst; and / or (b) the structural class (e.g., acetylene, propadiene, or internal olefin) or structural subclass (e.g., aryl acetylene versus alkyl acetylene; or monoacetylene versus diacetylene or triacetylene; or acyclic propadiene versus cycloalkyl propadiene versus vinylidene propadiene; or aryl-type internal olefin versus alkyl-type internal olefin). In some aspects, the Temp of the attenuated post-metallocene catalyst is peak The post-metallocene catalyst Temp with faster ignition speed peak Any of the end values ​​within the range of the time difference between the two values ​​can be based on data given later in the Examples.

[0081] In some embodiments, the monomer absorption profile of the weakened post-metallocene catalyst can be characterized as a combination of any two of the foregoing embodiments, alternatively all but any one, alternatively each of the foregoing embodiments.

[0082] 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.

[0083] Catalyst activity. If the peak polymerization temperature (Temp) of the weakened post-metallocene catalyst in degrees Celsius (°C) as measured by the light-off vial test methodpeak ) and the Temp of the catalyst with faster ignition peak The difference between the catalyst activity of the post-metallocene catalyst (e.g., of formula (III)) and the catalyst activity of the catalyst with a faster light-off is determined to be substantially the same as the catalyst activity of the catalyst with a faster light-off. Alternatively, when all other conditions are the same, 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 post-metallocene catalyst with a faster light-off, and in some embodiments may be greater than the catalytic activity / polymerization productivity of the post-metallocene catalyst with a faster light-off.

[0084] Catalyst that ignites faster. For the reasons described above, embodiments of catalysts (e.g., of formula (II)) that light off faster may require attenuation of monomer absorption for slurry phase and / or gas phase polymerization of 1-olefin monomers. The same or other embodiments of catalysts (e.g., of formula (II)) that light off faster may require ligands R for different reasons, such as for modifying the solubility of the catalyst in alkane solvents, or for NMR studies of post-metallocene catalyst structure and improved catalyst structure design.

[0085] Anion A - . The post-metallocene catalyst with a faster light-off (e.g., of formula (II)) and the post-metallocene catalyst with a weakened light-off (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 post-metallocene catalyst with a faster ignition rate from a post-metallocene pre-catalyst of formula (I). The activator is used to activate the post-metallocene pre-catalyst of formula (I) by extracting the leaving group X from the post-metallocene pre-catalyst of formula (I) to obtain a post-metallocene catalyst with a faster ignition rate (for example, a post-metallocene catalyst of formula (II)) and an anion A - The resulting activated post-metallocene catalyst (i.e., the post-metallocene 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 post-metallocene catalysts (eg, of formula (II)) with a faster light-off and the post-metallocene catalysts (eg, of formula (III)) with a weakened light-off made therefrom are neutral overall.

[0086] Anion A -The nature of X is not considered important in the post-metallocene catalysts with faster light-off (e.g., formula (II)) and the post-metallocene catalysts with reduced light-off (e.g., 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 late metallocene catalyst (e.g., of formula (II)) which ignites faster - The combined steps generate an anion A in the post-metallocene 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 post-metallocene catalyst (e.g., of formula (III)) - Anions A in the post-metallocene catalyst (e.g., of formula (II)) that can ignite faster - The same or different. For example, the anion A in the post-metallocene catalyst (e.g., of formula (II)) that ignites faster - It may be an anionic derivative of the activator, and for example, the anion A in the weakened post-metallocene catalyst of formula (III) - Can be X - .

[0087] Catalyst structure. Without being bound by theory, it is believed that the molecular structure of the faster light-off post-metallocene catalyst of formula (II) and the molecular structure of the weakened post-metallocene catalyst of formula (III) can be determined by conventional analytical methods such as nuclear magnetic resonance (NMR) spectroscopy or gas chromatography / mass spectrometry (GC / MS). The structure of the ligand R in formula (III) can be determined by using a protic solvent such as isopropanol, CH 3 OH or H 2 O), partially deuterated protic solvents (such as isopropyl-OD, CH 3 OD or HDO) or a perdeuterated protic solvent such as perdeuterated isopropanol ((CD 3 ) 2C(D)OD), fully deuterated methanol (CD 3 OD) or D 2 O) quenching the weakened post-metallocene catalyst of formula (III) to obtain a by-product 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.

[0088] Activation step. In some embodiments, the method for preparing a weakened post-metallocene catalyst (e.g., of formula (III)) further comprises an activation step as a preliminary step, which can be completed before the combining step begins. The activation step comprises contacting a pre-catalyst of formula (I) with an activator under effective activation conditions for preparing a post-metallocene catalyst that ignites faster. The activation step can be performed in the absence of a kinetic modifier compound.

[0089] Activator. The activator for activating the post-metallocene 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.

[0090] Alkylaluminoxane: Also known as alkylalumoxane. A partial hydrolysis product of a trialkylaluminum compound. The embodiment may be (C 1 -C 10 ) alkylaluminoxane, alternatively (C 1 -C 6 ) alkylaluminoxane, alternatively (C 1 -C 4 ) alkylaluminoxane, alternatively (C 1 -C 3 ) alkylaluminoxane, alternatively (C 1 -C 2) 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). Alkylaluminoxanes can be obtained from commercial suppliers or prepared by any suitable method. Suitable methods for preparing alkylaluminoxanes are well known. Examples of such preparation methods are described in U.S. Patents 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; 5,248,8 01; 5,235,081; 5,157,137; 5,103,031; 5,391,793; 5,391,529; and 5,693,838; and are described in European publications EP-A-0-561-476; EP-B1-0-279-586; and EP-A-0-594-218; and are described in PCT publication WO 94 / 10180.

[0091] 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.

[0092] Organoborane compounds. Tri(fluoro-functional organo)borane compounds ((fluoro-organo) 3 B), such as tris(pentafluorophenyl)borane ((C 6 F 5 ) 3 B), tris[3,5-bis(trifluoromethyl)phenyl]borane ((3,5-(CF 3 ) 2 -C 6 H 3 ) 3 B), or a mixture of any two or more thereof.

[0093] Organic borate compounds. Tetra(fluoro-functional organo)borate compounds 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-tetrakis(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.) and HCl and Li[B(C 6 F 5 ) 4 ] by reaction. Such preparation is disclosed in US 5,919,983. Example 2. Organic borate compounds can be used herein without (further) purification. In addition, bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyl)borate amine.

[0094] 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.

[0095] 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.

[0096] Without being bound by theory, it is believed that the selection of an activator for activating the faster light-off post-metallocene catalyst does not affect the structure of the weakened post-metallocene catalyst made from the faster light-off post-metallocene catalyst. That is, only the cationic portion of formula (III) is considered (i.e., ignoring the anionic A - ), it is expected that the structures of the weakened post-metallocene catalysts prepared using different activators are the same. The structure of the non-supported weakened post-metallocene catalyst may be easier to determine by NMR than the structure of the supported weakened post-metallocene catalyst, which is attributed to the heterogeneity of the latter (typical support materials are insoluble in NMR solvents).

[0097] In some embodiments, A - The choice of A may have an additional effect on the monomer absorption profile of the weakened post-metallocene catalyst. - Any such effect will not completely eliminate the beneficial effect of the kinetic modifier compound on the monomer uptake profile of the weakened post-metallocene catalyst.

[0098] Valid conditions. The reactions described herein (e.g., combination steps, activation steps, polymerization) are independently carried out in the case of allowing the 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 combination step of the post-metallocene catalyst for the preparation of the weakened catalyst may include: reaction temperature of -50°C to 80°C, alternatively 0°C to 50°C, alternatively -50°C to 50°C, alternatively -50°C to 30°C; inert atmosphere (e.g., nitrogen, helium, or water-free and O 2 of argon); does not contain water and O 2 and reactants with a purity of 90% to 100%; an amount of reactants to minimize waste / maximize product yield; stirring or mixing the reactants; and a reaction time period of 1 minute to 24 hours.

[0099] Effective reaction conditions for the post-metallocene precatalyst for preparing 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.

[0100] A post-metallocene precatalyst of formula (I). The precatalyst of formula (I) can be synthesized according to methods known in the art, including those mentioned above. Alternatively, the post-metallocene precatalyst can be obtained from a precatalyst supplier such as Boulder Scientific.

[0101] Polyolefin polymers are prepared by a polymerization process.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 of 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.

[0102] 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.

[0103] Multimodal (eg bimodal or trimodal) catalyst systems. Bimodal catalyst systems include a weakened post-metallocene catalyst and at least one other olefin polymerization catalyst selected from the following items: different weakened post-metallocene catalysts, post-metallocene catalysts and metallocene catalysts. Multimodal catalyst systems prepare multimodal polyethylene compositions comprising HMW polyethylene components and LMW polyethylene components 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 changes in the sedimentation of catalyst particles of different sizes. In some aspects, the variability of melt index (I 2 ) can be measured based on particle size rather than using a gel measurement.

[0104] The method for preparing the weakened post-metallocene catalyst can be carried out in the presence of a metallocene catalyst or a metallocene pre-catalyst. When carried out in the presence of a metallocene pre-catalyst, the method for activating the pre-catalyst of formula (I) with an activator also includes activating the metallocene pre-catalyst with the same or different activators. Typically, the method for preparing the weakened post-metallocene catalyst is carried out in the absence of a metallocene (pre) catalyst.

[0105] 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 materials 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.

[0106] Unsupported or supported catalysts. The post-metallocene precatalyst of formula (I), the post-metallocene catalyst with a faster light-off (such as the catalyst with a faster light-off of formula (II)), the attenuated post-metallocene catalyst (such as the attenuated post-metallocene catalyst of formula (III)) and the multimodal catalyst system may independently be unsupported or disposed on a solid particulate support material. In the absence of a support material, the post-metallocene precatalyst of formula (I), the post-metallocene catalyst with a faster light-off (such as the catalyst with a faster light-off of formula (II)), the attenuated post-metallocene catalyst (such as the attenuated post-metallocene catalyst of formula (III)) and / or the multimodal catalyst system may be injected into a slurry phase or gas phase polymerization reactor as a solution in a hydrocarbon solvent. When the post-metallocene precatalyst of formula (I), the faster light-off post-metallocene catalyst (such as the faster light-off catalyst of formula (II)), the attenuated post-metallocene catalyst (such as the attenuated post-metallocene catalyst of formula (III)) and / or the multimodal catalyst system are disposed on a support material, they can be injected into a slurry phase or gas phase polymerization reactor as a slurry suspended in a hydrocarbon solvent or as a dry powder (i.e., a dry particulate solid).

[0107] A post-metallocene catalyst (e.g., of formula (II)) with a faster light-off and / or a post-metallocene catalyst (e.g., of formula (III)) with a weakened light-off can be prepared in the absence of a support material and later disposed on a support material. Alternatively, a post-metallocene precatalyst of formula (I) or a post-metallocene catalyst (e.g., of formula (II)) with a faster light-off can be disposed on a support material, and then a post-metallocene catalyst (e.g., of formula (II)) with a faster light-off and / or a post-metallocene catalyst (e.g., of formula (III)) with a weakened light-off can be prepared in situ on the support material.

[0108] The supported post-metallocene precatalyst of formula (I), supported post-metallocene catalyst (for example, supported catalyst of formula (II)) that ignites faster and / or supported post-metallocene catalyst (for example, supported catalyst of formula (III)) that weakens can be prepared by concentration method, and the concentration method is by evaporating hydrocarbon solvent from the suspension of the support material in the solution of the precatalyst of formula (I) in hydrocarbon solvent, the catalyst (for example, supported catalyst of formula (II)) that ignites faster and / or supported post-metallocene catalyst (for example, supported catalyst of formula (III)). Alternatively, the supported precatalyst of formula (I), supported post-metallocene catalyst (for example, supported catalyst of formula (II)) that ignites faster and / or supported post-metallocene catalyst (for example, supported catalyst of formula (III)) that weakens can be prepared by the spray drying method of spray drying suspension or solution. In some embodiments, spray drying method is used.

[0109] Carrier 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.

[0110] 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 polymeric beads as disclosed in PCT Publication WO 99 / 50311.

[0111] The carrier material may have a thickness of about 10 m 2 / g to about 700m 2 Surface area in the range of / g, 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.

[0112] 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.

[0113] The metallocene precatalyst may be spray dried according to the general method described in US 5648310. The support used with the post metallocene 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.

[0114] Solution phase polymerization and / or slurry phase polymerization of olefin monomers is well known. See, for example, US Pat. No. 8,291,115 B2.

[0115] 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 dimethylbenzene. 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 acyclic or cyclic independently. Each acyclic alkane can be straight or branched independently. Acyclic 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 (C 5 -C 12 ) alkane composition.

[0116] Gas Phase Polymerization (GPP).The polymerization uses a GPP reactor, such as a stirred bed gas phase polymerization reactor (SB-GPP reactor) or a fluidized bed gas phase polymerization reactor (FB-GPP reactor). Such reactors and methods are generally well known. For example, the FB-GPP reactor / method may be a method as described in any of the following documents: 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; US5,541,270; US 2018 / 0079836 A1; EP-A-0-802-202; and Belgian Patent 839,380. These SB-GPP and FB-GPP polymerization reactors and methods mechanically stir or fluidize the polymerization medium inside the reactor by 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.

[0117] 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; feed gas (such as H 2 ), the molar ratio of feed gas to reactant, interfering materials (e.g., H 2 O and / or O 2 ), the absence or concentration of induced condensing agents (ICAs), the average polymer residence time in the reactor, the partial pressures of the components, the feed rate of the monomers, the reactor bed temperature (e.g., fluidized bed temperature), the nature or sequence of the process steps, the transition time periods between steps. Variables other than those variables described or varied by the process or use may be held constant.

[0118] In the GPP method, ethylene (“C 2 ”), hydrogen (“H 2 ”) and 1-hexene (“C 6 " 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 / C2 , for example C 6 / C 2 ), a constant hydrogen to ethylene gas molar ratio or feed mass ratio (“H 2 / C 2 ”), and a constant ethylene (“C 2 ") partial pressure. Gas concentrations were measured by online gas chromatography to understand and maintain the composition of the recycle gas stream. The reaction bed of growing polymer particles was maintained in a fluidized state by continuous flow of make-up feed and recycle gas through the reaction zone. A superficial gas velocity of 0.49 to 0.79 m / sec (1.6 to 2.6 ft / sec) was used. 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 The FB-GPP reactor is operated under the described first reactor bed temperature RBT. By withdrawing a part of the bed at a rate equal to the production rate of the polyolefin polymer composition in particle form, the fluidized bed is maintained at a constant height, and the production rate can be 5,000 kilograms per hour (kg / h) to 150,000 kilograms per hour. Via a series of valves, the product polyolefin polymer composition is semi-continuously moved into a fixed volume chamber, wherein the multimodal (for example, bimodal or trimodal) ethylene-to-1-hexene copolymer composition of this removal is purged to remove entrained hydrocarbons and is purged with moist nitrogen (N 2 ) gas stream to deactivate any traces of residual catalyst.

[0119] 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.

[0120] Induced Condensation Agent (ICA). An inert liquid that can be used to cool the material in the GPP reactor. Its use is optional. ICA is (C 3 -C 20 ) alkane, alternatively (C 5 -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%.

[0121] 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 those described in US 4,988,783 and may include chloroform, CFCl 3 , trichloroethane and difluorotetrachloroethane. A scavenger may be used to react with moisture before 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 (not intentionally added) a scavenger. 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 polyethyleneimine. Static control agents may be added to the FB-GPP reactor to inhibit the formation or accumulation of static charge therein.

[0122] 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.

[0123] 1-Olefin monomers. 1-Olefin monomer is of formula H 2 C=C(H)(CH 2 ) n R 8 The compound wherein the subscript n is an integer from 0 to 19, and the group R 8 H or CH 3 An example is ethylene (subscript n is 0 and R 8 H), propylene (subscript n is 0 and R 8 CH 3 ) and (C 4 -C 20)α-olefin (subscript n is an integer from 1 to 19 and R 8 H or CH 3 ). 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.

[0124] Polyolefin polymers. The product of at least one 1-olefin monomer and a weakened post-metallocene 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.

[0125] 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 post-metallocene catalyst that is weakened by it (e.g., formula (III)), and the LMW polyolefin polymer component can be prepared by its metallocene catalyst.

[0126] 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.

[0127] 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; alternatively, undetectable. IUPAC refers to 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 not present (or excluded), alternatively present (or included). Properties can be measured using standard test methods and conditions. In addition to the integer range that does not include fractional values, the range includes end values, sub-ranges, and integers and / or fractional values ​​included therein. Room temperature: 23°C ± 1°C

[0128] 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.

[0129] Example

[0130] Additional embodiments of the present invention are the aforementioned aspects and the claims described later, which describe a range of processing conditions and / or a range of material properties, wherein in the additional embodiments of the present invention, the end values ​​of the range of processing conditions and / or the end values ​​of the range of material properties are modified to any exemplary processing condition value and / or any exemplary material property value described below in this section for any example of the present invention, respectively.

[0131] Activator 1 (also referred to as co-catalyst 1): bis(hydrogenated tallow alkyl)methyltetrakis(pentafluorophenyl)borate (1-)amine.

[0132] Mineral oil: HYDROBRITE 380PO paraffin oil available from Sonneborn.

[0133] 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.

[0134] 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.

[0135] Preparation 2: Preparation of Spray-dried Metallocene Using Activator Formulation Preparations 1A and 1B were repeated except that 1.5 kg of treated fumed silica (CABOSIL TS-610) was slurried in 16.8 kg of toluene and then a 10 wt % (11.1 kg) solution of MAO in toluene and sufficient (MeCp)(1,3-dimethyl-4,5,6,7-tetrahydroindenyl)ZrMe 2, wherein Me is methyl, Cp is cyclopentadienyl, and MeCp is methylcyclopentadienyl, to give a loading of 40 micromoles of Zr per gram of solids, to prepare an activator formulation. The resulting powder was slurried to give an activator formulation of 22 wt% solids in 10 wt% isoparaffin fluid and 68 wt% mineral oil.

[0136] Preparation Example 2A: Prepare a supported catalyst used 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 post-metallocene precatalyst (e.g., any of the precatalysts 1 to 5 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: a set temperature of 185°C, an outlet temperature of 100°C, an aspirator of 95%, and a pump speed of 150 revolutions per minute (rpm).

[0137] Preparation Example 3: Synthesis of a post-metallocene catalyst with a faster ignition rate: Prepared by the following method: In an inert N 2 Under atmosphere, 40 milliliters (mL) of glass vials containing a magnetic stirring bar coated with poly (tetrafluoroethylene) (PTFE) are loaded into a glove box and capped with a rubber septum with 200 milligrams (mg) of spray-dried methylaluminoxane (SDMAO, prepared according to Preparation Example 1A). Then add slurries of 10 micromoles (μmol) of post-metallocene precatalysts (for example, any precatalyst in precatalyst 1 to precatalyst 5) in 0.2mL mineral oil. Stir the resulting mixture for 5 minutes to obtain the mineral oil slurries of the post-metallocene catalyst that is supported on the treated aerosil. Repeat this procedure to prepare the mineral oil slurries of the post-metallocene catalyst that is ignited faster in multiple batches, and each post-metallocene catalyst that is ignited faster is supported on a separate treated aerosil. The post-metallocene catalyst that is ignited faster can be made to have a mol 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.

[0138] Preparation Example 4: Synthesis of a weakened post-metallocene catalyst: A solution of 10 μmol of a kinetic modifier compound in 0.20 mL of toluene was added to a certain amount of slurry to contain 10 μmol of the faster ignition catalyst of Preparation Example 3 supported on treated fumed silica. The resulting mixture was stirred for 5 minutes to obtain a mineral oil / toluene slurry of a weakened post-metallocene catalyst supported on treated fumed silica.

[0139] Embodiments (A1) to (A20) of the present invention (IE(A1) to IE(A20)): According to Preparation Example 2A or Preparation Examples 3 and 4, twenty weakened post-metallocene catalysts were prepared separately using precatalyst 1 and different kinetic modifier compounds among kinetic modifier compounds (1) to (20), respectively.

[0140] Embodiments (B1) to (B20) of the present invention (IE(B1) to IE(B20)): According to Preparation Example 2A or Preparation Examples 3 and 4, twenty weakened post-metallocene catalysts were prepared separately using precatalyst 2 and different kinetic modifier compounds among kinetic modifier compounds (1) to (20), respectively.

[0141] Embodiments (C1) to (C20) of the present invention (IE(C1) to IE(C20)): According to Preparation Example 2A or Preparation Examples 3 and 4, twenty weakened post-metallocene catalysts were prepared separately using precatalyst 3 and different kinetic modifier compounds among kinetic modifier compounds (1) to (20), respectively.

[0142] Embodiments (D1) to (D20) of the present invention (IE(D1) to IE(D20)): According to Preparation Example 2A or Preparation Examples 3 and 4, twenty weakened post-metallocene catalysts were prepared separately using precatalyst 4 and different kinetic modifier compounds among kinetic modifier compounds (1) to (20), respectively.

[0143] Embodiments (E1) to (E20) of the present invention (IE(E1) to IE(E20)): According to Preparation Example 2A or Preparation Examples 3 and 4, twenty weakened post-metallocene catalysts were prepared separately using precatalyst 5 and different kinetic modifier compounds among kinetic modifier compounds (1) to (20), respectively.

[0144] Ignition vial test method: A mineral oil slurry of the faster light-off catalyst supported on treated fumed silica or a mineral oil / toluene slurry of the attenuated post-metallocene catalyst supported 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 time of addition was recorded as T 0(0.00 min). Manually shake (do not stir) the vial to prevent clumping. Then place the shaken vial in different wells of a foam block on a hot plate / stirrer. Immediately insert a thermocouple through the septum cap below the liquid level in the vial and place at T 0 To T 0 The temperature (°C) of the vial contents was recorded every 5 seconds for 300 minutes after addition. The temperature and time data were downloaded to a spreadsheet and thermodynamic curves were plotted for analysis. The results of these runs can be graphically depicted as the reaction temperature of the batch reactor contents on the y-axis versus the time from addition on the x-axis. 0 A graph of the time of start.

[0145] 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 post-metallocene catalysts with a faster light-off to obtain the attenuated post-metallocene catalysts of the Inventive Examples. The Comparative Examples met one of three criteria (1) to (3): (1) containing a post-metallocene catalyst but no kinetic modifier compound, (2) containing a post-metallocene catalyst and 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 post-metallocene catalysts with a faster light-off and the Inventive Examples were tested with polyoctenes according to the Light-Off Vial Test Method to compare their relative activities. In a separate vial, (a) 1-octene-free mineral oil, (b) post-metallocene precatalyst example, and (c) spray-dried methylaluminoxane (SDMAO) without kinetic modifier compounds were premixed for 10 minutes to obtain a slurry of a post-metallocene catalyst with a faster light-off without 1-octene and kinetic modifier compounds. In other vials, (a) 1-octene-free mineral oil, (b) post-metallocene precatalyst, (c) SDMAO, and (d) kinetic modifier compounds were premixed for 10 minutes to obtain a slurry of a post-metallocene catalyst with a weakened 1-octene-free catalyst. 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, an increase in the temperature of the mixture 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) is observed as evidence of activation of the corresponding catalyst.One of the following four sets of conditions can be used: Condition (A): 5.5 mL Isopar-E; 8 μmol M; the amount of SDMAO is such that the molar ratio Al / M=120 is given; 0 μmol (CE) or 2 μmol (IE) kinetic modifier compound; 11 mL 1-octene; Condition (B): 5.5 mL Isopar-E; 10 μmol M; the amount of SDMAO is such that the molar ratio Al / M=120 is given; 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 1): 5.5 mL Isopar-E; 20 μmol M; the amount of SDMAO is such that the molar ratio Al / M=120 is given; the amount of kinetic modifier compound is 0 μmol (CE) or such that the indicated molar ratio M / KMC (IE) is given; 5.5 mL 1-octene; Condition (D) (used in Table 2): 5.5 mL Isopar-E; 2 μmol M; the amount of SDMAO is to give a molar ratio Al / M=120; the amount of the kinetic modifier compound is 0 μmol (CE) or an amount to give the indicated molar ratio M / KMC (IE); 5.5 mL 1-octene.

[0146] Table 1: Conditions of use (C) and formula of Results of the light-off vial test method performed on the precatalyst (1).

[0147]

[0148] As shown in Table 1, depending on the post-metallocene precatalyst and kinetic modifier compound used, longer or shorter delays in activation time are achieved, and greater or lesser reductions in peak reaction temperature are achieved.

[0149] Table 2: Usage conditions (D) and formula of Results of the light-off vial test method performed on the precatalyst (2).

[0150]

[0151]

[0152] As shown in Table 2, depending on the post-metallocene precatalyst and kinetic modifier compound used, longer or shorter delays in activation time are achieved, and greater or lesser reductions in peak reaction temperature are achieved.

[0153] Light-off batch reactor test method .

[0154] The relative kinetics of the faster ignition catalyst and the slower post-metallocene 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 the batch reactor, hydrogen (H 2 ) was used to copolymerize ethylene with 1-hexene. The ethylene (“C 2 ”), 1-hexene (“C 6 ”) and H 2 C was added continuously throughout the 3 h polymerization run. 6 and H 2 components to maintain their concentrations at steady state, but without adding more C 2 The monomer uptake is measured versus time to give a relative representation of the catalyst kinetics curve.

[0155] The batch reactor was dried and loaded. Before each run, the batch reactor was dried for 1 hour. Then 200 g of NaCl was loaded into the dried batch reactor. 2 The batch reactor and its contents were heated for 30 minutes under an atmosphere to further dry the batch reactor. 3 g of silica-loaded methylaluminoxane (SMAO) was then added to purge the residue, the batch reactor was sealed, and the contents were stirred. 3.04 L of H 2 and 1-hexene are charged into the obtained dry batch reactor to obtain 1-hexene and ethylene (C 6 / C 2 ) molar ratio was 0.004. The batch reactor was pressurized to 1.52 megapascals (MPa) with ethylene. The resulting system was allowed to reach steady state.

[0156] The catalyst (faster ignition catalyst or weakened post-metallocene catalyst) is then loaded into the batch reactor to initiate polymerization. The time of catalyst addition is recorded as time zero (Time 0 ). Raise the reactor temperature to the target temperature T target (e.g., 90°C, 93°C, or 100°C), and the reactor is maintained at this temperature for 0.5 to 5 hours, alternatively 1 to 5 hours (e.g., 1 hour). The reactor is cooled, vented, opened, and the resulting polyolefin product is washed with water, methanol, and dried to obtain a dry polyolefin product. For a post-metallocene catalyst with a faster ignition, the peak temperature (T max , also known as T peak ) and target temperature T target (T max -T targetThe difference between the peak temperature (T) and the peak temperature (T) indicates the extent to which the post-metallocene catalyst with a faster light-off exceeds the target temperature. max ) and target temperature T target (T max -T target The difference between the values ​​of (°C) and (°C) indicates how much of an attenuation effect the kinetic modifier compound has on the attenuated post-metallocene catalyst made therewith.

[0157] For each batch reactor run, the catalyst activity / polymerization productivity was calculated as grams of dry polyolefin product produced / grams of catalyst added to the reactor per hour (gPE / gcat-hr). Higher values ​​of gPE / gcat-hr indicate higher catalyst activity / polymerization productivity. The monomer uptake after 0.1 hour (C 2 Absorption 0.1h) (6 minutes) and monomer absorption after 1.0 hour (C 2 Absorption 1h) (60 minutes) and recorded as (C 2 Absorption 1h) / (C 2 Absorption 0.1h). Under all other conditions being the same, (C 2 Absorption 1 hour) / (C 2 A higher ratio of T (0.1 hour absorption) indicates a more weakened catalyst. For each run, T max is a measure of the reduction in light-off between pairs of inventive and comparative examples.

[0158] The melting temperature of the dried polyolefin product was determined using differential scanning calorimetry (DSC) according to ASTM D3418-08 using a scan rate of 10°C / minute for a 10 mg sample and using a second heating cycle. Some embodiments of the polyolefin products of the present invention prepared by an attenuated post-metallocene catalyst may have a higher melting point than the melting point of a comparative polyolefin product prepared by its corresponding catalyst having a faster light-off.

[0159] From the light-off batch reactor operation with a catalyst that light-off is relatively fast, most of the monomer uptake may occur within the first few minutes after the start of polymerization (e.g., Time 0 The monomer uptake was more evenly spread throughout the 3 hour long polymerization run compared to the weakened post-metallocene catalyst. The results of these comparative examples and inventive runs can be graphically depicted as the reaction temperature of the batch reactor contents on the y-axis or the ethylene monomer ("C 2 ”) Absorption and the time from the time of addition on the x-axis 0 A graph of the time of start.

[0160] Table 3: Catalysts used in the light-off batch reactor test method.

[0161]

[0162]

[0163] The results of running a batch reactor using the catalyst of Table 3 are shown in Tables 4 and 5.

[0164] Table 4: Polymerization results for the Light-off Batch Reactor Test Method.

[0165]

[0166] * When CE1 is used under conditions for preparing HDPE and when CE3 is used under all conditions, polymer aggregates (lumps) are undesirably produced. As shown in the data in Table 4, the catalyst activity of the catalyst with reduced light-off may not be significantly reduced, and in some embodiments, the catalyst activity of the catalyst with reduced light-off may be improved relative to the catalyst with faster light-off from which it is prepared.

[0167] Table 5. Polyolefin product characteristics.

[0168]

[0169] N / t means untested. As shown in the data in Table 5, the polyolefin product prepared by the catalyst with weakened light-off has a higher melting point and a lower molecular weight distribution compared with the melting point and molecular weight distribution of the polyolefin product prepared by the catalyst with faster light-off. The polymer data in Table 5 show that, in some embodiments, the weakened post-metallocene catalyst prepares a polyethylene polymer with higher molecular weight compared with the faster post-metallocene catalyst with faster light-off of the post-metallocene catalyst prepared by the weakened post-metallocene catalyst. Without being bound by theory, this improvement may be at least partially attributed to the fact that the faster post-metallocene catalyst with light-off produces too much heat (higher exotherm), which in turn may cause the chain termination reaction to increase relative to the rate of chain growth, and therefore reduce the total molecular weight.

[0170] The relative monomer uptake profile of the catalyst with reduced light-off is represented by a plot of monomer uptake over time. Most of the monomer uptake by the catalyst with faster light-off occurs within the first few minutes after catalyst addition. In contrast, the monomer uptake of the catalyst with reduced light-off is more evenly spread over the 3 hour polymerization run.

[0171] Comparative Example Using Metallocene Precatalyst .

[0172] Table 6: Usage conditions (A) and formula Comparison of Metallocene Precatalyst 1 ("MCN1") Comparative polymerization results for the Light-off Vial Test Method, where n-Bu is n-butyl.

[0173]

[0174] As shown in Table 6, phenylacetylene has essentially no attenuating effect on the kinetics of the comparative metallocene catalyst made from MCN1.

[0175] Table 7: Usage conditions (A) and formula Comparison of Metallocene Precatalyst 1 ("MCN1") Comparative polymerization results for the Light-off Batch Reactor Test Method, where n-Bu is n-butyl.

[0176]

[0177] As shown in Table 7, the kinetic modifier compounds had essentially no debilitating effect on the kinetics of the comparative metallocene catalyst made from MCN1.

[0178] Table 8: Usage conditions (A) and formula Comparison of Metallocene Precatalyst 2 ("MCN2") Comparative polymerization results for the Fired Batch Reactor Test Method where n-Pr is n-propyl.

[0179]

[0180] As shown in Table 8, 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.

[0181] Table 9: Usage conditions (A) and formula Comparison of Metallocene Precatalyst 3 ("MCN3") Comparative polymerization results of the light-off batch reactor test method.

[0182]

[0183] As shown in Table 9, the kinetic modifier compounds had essentially no attenuating effect on the catalytic activity of the comparative metallocene catalyst made from MCN3.

Claims

1. A method for preparing a post-metallocene catalyst with reduced ignition, the method comprising reacting a catalyst with a faster ignition rate with an effective amount of a catalyst of formula (A 1 ) or (B 1 ): R 5 -C≡CR 6 (A 1 ) or (R 5 ) 2 C=C=C(R 6 ) 2 (B 1 ) in combination with a kinetic modifier compound KMC to obtain a post-metallocene catalyst with reduced light-off, wherein the post-metallocene catalyst with reduced light-off exhibits a monomer absorption curve with reduced light-off; wherein the catalyst with faster light-off has been prepared by activating a post-metallocene precatalyst of structural formula (I): 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 (C 1 -C 20 )alkyl, -C(=O)-O-(unsubstituted (C 1 -C 20 ) alkyl), (C 1 -C 19 ) heteroalkyl or tri((C 1 -C 20 )alkyl)silyl, or two R 7 Put together to form (C 3 -C 6 ) alkylene; provided that each R 7 lacks a carbon-carbon double bond; each (C 1 -C 20 ) The hydrocarbon groups are independently unsubstituted or substituted by 1 to 4 groups R S Substituted; wherein each substituent group R S are independently selected from halogen, unsubstituted (C 1 -C 5 )alkyl, -C≡CH, -OH, (C 1 -C 5 )alkoxy, -C(=O)-(unsubstituted (C 1 -C 5 )alkyl), -NH 2 、-N(H)(unsubstituted(C 1 -C 5 ) alkyl), -N(unsubstituted(C 1 -C 5 )alkyl) 2 , -COOH, -C(=O)-NH 2 , -C(=O)-N(H)(unsubstituted(C 1 -C 5 ) alkyl), -C(=O)-N(unsubstituted (C 1 -C 5 )alkyl) 2 、-S-(unsubstituted(C 1 -C 5 )alkyl), -S(=O) 2 -(Unsubstituted(C 1 -C 5 )alkyl), -S(=O) 2 -NH 2 、-S(=O) 2 -N(H)(Unsubstituted(C 1 -C 5 )alkyl), -S(=O) 2 -N(unsubstituted(C 1 -C 5 )alkyl) 2 , -C(=)S-(unsubstituted (C 1 -C 5 ) alkyl) and -COO (unsubstituted (C 1 -C 5 ) alkyl); and wherein in formula (I): L is CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 , CH 2 C(R L ) 2 CH 2 , CH 2 CH(R L )CH(R L )CH 2 , CH 2 Ge(R L ) 2 CH 2 or CH 2 Si(R L ) 2 CH 2 , where each R L are independently unsubstituted (C 1 -C 20 ) alkyl; M is Ti, Zr or Hf; R 1a and R 1b Each of which is independently a halogen atom, (C 1 -C 20 )alkyl or Si(CH 3 ) 2 (CH 2 ) q CH 3 , wherein subscript q is an integer from 0 to 20; each subscript r is independently an integer from 0 to 3; R 2a and R 2b Each of which is independently H, F, Cl or unsubstituted (C 1 -C 20 ) alkyl; each subscript s is independently an integer from 0 to 3; R 3a and R 3b Each of which is independently halogen, unsubstituted (C 1 -C 20 ) alkyl or (C 1 -C 20 ) alkoxy; each AR 1a and Ar 1b is independently an unsubstituted or substituted aromatic group selected from the group consisting of phenyl, substituted phenyl, diphenyl, substituted diphenyl, anthracene, substituted anthracene, carbazolyl, and substituted carbazolyl, wherein each substituent in the substituted aromatic group is independently an alkyl group; and each X is independently a monodentate group, the monodentate group being independently selected from the group consisting of halogen atoms, ((C 1 -C 20 )alkyl) 3-g -(phenyl) g Si-, where subscript g is 0, 1, 2 or 3; CH 3 , (C 2 -C 20 )alkyl-CH 2 , (C 6 -C 12 )Aryl-((C 0 -C 10 )alkylene)-CH 2 , (C 1 -C 6 )alkyl-substituted (C 6 -C 12 ) aryl, (C 1 -C 6 ) alkoxy-substituted (C 6 -C 12 ) aryl, (C 1 -C 6 ) alkoxy-substituted benzyl and (C 1 -C 6 )alkyl-substituted benzyl; or one X is 4-(C 1 -C 20 ) an alkyl-substituted 1,3-butadiene molecule, and each of the remaining Xs, if present, is independently a monodentate group X, The effective reaction conditions include a reaction temperature of -50°C to 80°C, an inert atmosphere, and no water and O 2 and reactants with 90% to 100% purity, amounts of reactants to minimize waste / maximize product yield, stirring or mixing the reactants, and reaction times ranging from 1 minute to 24 hours, The effective amount refers to the amount of the kinetic modifier compound KMC that is sufficient to reduce the light-off of the catalyst, and The monomer absorption curve with reduced light-off includes the peak reaction temperature T of the post-metallocene catalyst with reduced light-off relative to the catalyst with faster light-off from which it is prepared. max The length of time is longer and / or T max The value of is lower.

2. The method according to claim 1, wherein the catalyst having a faster light-off has formula (II): A - (II); and wherein the post-metallocene catalyst with reduced light-off has the formula (III): A - (III); wherein the subscripts r and s; the group R 1a To R 3a , R 1b To R 3b ,Ar 1a ,Ar 1b , L and X; and metal M as defined in formula (I); wherein A - is an anion; and wherein R is respectively of formula (A) or (B): -C(R 5 )=C(X)R 6 (A) or -C(R 5 ) 2 -C(X)=C(R 6 ) 2 (B) ligand; And where R 5 To R 7 As shown in formula (A 1 ) or (B 1 ) as defined in the Regulations.

3. The method according to claim 1, wherein the post-metallocene pre-catalyst of formula (I) is a post-metallocene pre-catalyst of formula (Ia): (Ia); wherein L is CH 2 CH 2 , CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 , CH 2 C(R L ) 2 CH 2 , CH 2 CH(R L )CH(R L )CH 2 , CH 2 Ge(R L ) 2 CH 2 or CH 2 Si(R L ) 2 CH 2 , where each R L are independently unsubstituted (C 1 -C 20 ) alkyl; M is Zr or Hf; R 1a and R 1b Each of which is independently F, (C 1 -C 20 )alkyl or Si(CH 3 ) 2 (CH 2 ) q CH 3 , wherein the subscript q is an integer from 0 to 9; R 2a and R 2b Each of 3 ; R 3a and R 3b Each of which is independently unsubstituted 1,1-dimethyl-(C 2 To C 8 ) alkyl; R 4a , R 4b , R 5a , R 5b Each of which is independently H, unsubstituted (C 1 -C 20 )alkyl, unsubstituted 1,1-dimethyl-(C 2 To C 6 ) alkyl, or ((C 1 -C 20 )alkyl) 3-g -(phenyl) g Si-, wherein the subscript g is 0, 1, 2 or 3; and each X is independently defined as in formula (I).

4. The method according to claim 1 or 3, wherein the precatalyst of formula (I) or (Ia) is defined by any one of limitations (i) to (vi), respectively: (i) R 1a and R 1b Each of R is the same; (ii) R 2a and R 2b Each of the R 3a and R 3b are the same; (iv) R 4a and R 4b Each of the two is the same; (v) R 5a and R 5b Each of them is the same; and (vi) a combination of any two or more of restrictions (i) to (v).

5. The method according to claim 1 or 3, wherein the precatalyst of formula (I) or (Ia) is defined by any one of limitations (i) to (vi): (i) L is CH 2 CH 2 CH 2 , CH 2 CH 2 CH 2 CH 2 or CH 2 Si(CH(CH 3 ) 2 ) 2 CH 2 ; (ii) M is Zr; (iii) M is Hf; (iv) each X is independently (C 7 -C 20 ) aralkyl; (v) one X is (C 7 -C 20 ) aralkyl, and another X is F, Cl or methyl; and (vi) limiting the combination of any two or more of (i) to (v).

6. The method of 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 ((C 1 -C 20 )alkyl) 3-h acetylene, wherein the subscript h is an integer from 0 to 3; and the formula HC≡C-(CH 2 ) m CH 3 wherein the subscript m is an integer from 1 to 15.

7. The method of claim 1 or 2, wherein the kinetic modifier compound has the formula (B 1 ):(R 5 ) 2 C=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.

8. The method according to claim 1 or 2 further comprises, before the combining step, a step of preparing the catalyst with faster ignition by activating the pre-catalyst of formula (I) with an activator under effective activation conditions, thereby preparing the catalyst with faster ignition.

9. The method according to claim 8, wherein the activator is an alkylaluminoxane, an organic borane compound or an organic borate.

10. The method according to claim 1 or 2, wherein the method further comprises preparing a mixture of the post-metallocene catalyst with reduced light-off, a carrier material and an inert hydrocarbon solvent, and removing the inert hydrocarbon solvent from the mixture to obtain the post-metallocene catalyst with reduced light-off disposed on the carrier material.

11. A post-metallocene catalyst with light-off reduction, the post-metallocene catalyst being prepared by the method according to any one of claims 1 to 10.

12. A method for feeding a post-metallocene 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 light-off weakened post-metallocene catalyst outside the reactor, preparing the weakened post-metallocene catalyst according to the method of any one of claims 1 to 10, and feeding the weakened post-metallocene catalyst in a pure state or as a solution or slurry thereof in an inert hydrocarbon liquid to the slurry phase or gas phase polymerization reactor through a feed line free of olefin monomers.

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

14. A method for preparing a polyolefin polymer, the method comprising contacting at least one 1-olefin monomer with the post-metallocene catalyst with reduced light-off prepared by the method according to any one of claims 1 to 10, or the multimodal catalyst system according to claim 13, 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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