Multimodal polymerization process using multiple catalyst systems

Abstract

The present disclosure provides a process for polymerizing olefin monomers to produce a polyolefin, the process comprising reacting ethylene and optionally one or more olefin monomers in the presence of a catalyst system in one or more reactors; the catalysts comprise two or more catalysts wherein at least one catalyst is derived from a bis-phenylphenoxy procatalyst according to formula (I), and wherein at least one catalyst is derived from a phosphinimine procatalyst according to formula (V): # imgabs0 #

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims the benefit of U.S. Provisional Application Serial No. 63 / 401,901, filed on August 29, 2022, the entire disclosure of which is hereby incorporated by reference into this document. Technical Field

[0003] Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and processes, and more particularly to olefin polymerization catalyst systems including a bisphenylphenoxy Group IV transition metal catalyst and a PN catalyst, and polymerization processes incorporating the catalyst system to produce bimodal polymers. Background Art

[0004] Olefin-based polymers such as polyethylene, ethylene-based polymers, polypropylene, and propylene-based polymers are produced by various catalyst systems. The selection of such catalyst systems used in the polymerization process of olefin-based polymers is an important factor contributing to the characteristics and properties of such olefin-based polymers.

[0005] Polymers based on ethylene and polymers based on propylene are manufactured for various articles. Polyethylene and polypropylene polymerization processes can differ in many aspects to produce various resulting polyethylene resins with different physical properties, which make various resins suitable for different applications. Ethylene monomer and optional one or more comonomers are present in a liquid diluent (such as a solvent), such as an alkane or isoalkane, for example isobutylene. Hydrogen can also be added to the reactor. Catalyst systems for producing homopolymers or copolymers based on ethylene can generally include chromium-based catalyst systems, Ziegler-Natta catalyst systems and / or molecular (metallocene or non-metallocene (molecule)) catalyst systems. The reactants in the diluent and catalyst system circulate around the reactor at an elevated polymerization temperature, thereby producing homopolymers or copolymers based on ethylene. Periodically or continuously remove a portion of the reaction mixture containing the polyethylene product dissolved in the diluent and unreacted ethylene and one or more optional comonomers from the reactor. The reaction mixture can be processed to remove the polyethylene product from the diluent and unreacted reactants when removed from the reactor, wherein the diluent and unreacted reactants are typically recycled back into the reactor. Alternatively, the reaction mixture can be sent to a second reactor connected in series with the first reactor, in which a second polyethylene fraction can be produced. Although research is devoted to developing catalyst systems suitable for olefin polymerizations such as polyethylene or polypropylene polymerizations, there is still a need to improve the efficiency of catalyst systems that can produce polymers with adjustable molecular weights during polymerization. Summary of the invention

[0006] There is a continuing need to produce multimodal polyethylene polymers. In particular, to synthesize LLDPE resins using flexible catalyst systems that are compatible with high temperature solution processes.

[0007] By combining catalysts derived from two different classes, such as bisphenylphenoxy metal-ligand complexes (BPP catalysts) and phosphinimine complexes (PN catalysts), advantage of the different properties of the catalysts allows for the production of multimodal polyethylene resins.

[0008] The PN catalyst is more sensitive to hydrogen than the BPP catalyst, so the molecular weight of the polymer produced by the PN catalyst can be changed based on the amount of hydrogen in the reactor system. Therefore, the molecular weight distribution (the difference in molecular weight of the polyethylene produced by the two catalysts) can be easily customized by adjusting the hydrogen level without significantly changing other conditions. Small changes in hydrogen levels result in large differences in the molecular weight of the polymer produced by the PN catalyst. In comparison, the same increase in H2 results in smaller changes in the polymer produced by the BPP catalyst. Figure 1A , Figure 1B and Figure 1C The change in molecular weight of polyethylene produced by the BPP catalyst and the PN catalyst is shown.

[0009] Embodiments of the present disclosure include methods for polymerizing olefin monomers to produce polyolefins. The method includes reacting ethylene and optional one or more olefin monomers in one reactor or multiple reactors in the presence of a catalyst system and optional hydrogen. The catalyst includes two or more catalysts, wherein at least one catalyst is derived from a bisphenylphenoxy procatalyst according to formula (I), and wherein at least one catalyst is derived from a phosphinimine procatalyst according to formula (V). The amount of hydrogen can be adjusted to customize the molecular weight of the polyolefin.

[0010] Formula (I) and Formula (V) have structures according to the following formula:

[0011]

[0012] In formula (I), M1 is titanium, zirconium, hafnium, scandium or yttrium.

[0013] In formula (I) and formula (V), each X is independently selected from (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -CH2Si(R C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C ) Q、-OSi(R C ) 3-Q (OR C ) Q 、-CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q 、-P(R C ) 2-W (OR C ) W 、-P(O)(R C ) 2-W (OR C ) W 、-N(R C )2、-NH(R C )、-N(Si(R C )3)2、-NR C Si(R C )3, -NHSi(R C )3. -OR C 、-SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C 、-S(O)2R C 、-OS(O)2R C 、-N=C(R C )2, -N=CH(R C )、-N=CH2、-N=P(R C )3. -OC(O)R C 、-C(O)OR C 、-N(R C )C(O)R C 、-N(R C )C(O)H、-NHC(O)R C 、-C(O)N(R C )2. -C(O)NHR C 、-C(O)NH2、halogen、B(R Y )4、Al(R Y )4 or Ga(R Y )4 or a monodentate ligand of hydrogen, wherein each R C Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1 or 2; each R Y=–H, (C1-C 30 ) a hydrocarbon group or a halogen atom, wherein two X ligands may be linked to form a metal cyclize ring.

[0014] In formulas (I) and (V), each Y is independently a Lewis base; optionally, X and Y may be linked to form a ring. Each subscript m is independently 0, 1 or 2; and each subscript n is independently 0, 1 and 2.

[0015] In formula (I), R 1 and R 16 Independently selected from the group consisting of: –H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-, -N=C(R C 2. R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)-, halogen, a group having the formula (II), a group having the formula (III) and a group having the formula (IV):

[0016]

[0017] In formula (II), (III) and (IV), R 31–35 , R 41–48 and R 51–59 Each of the following is independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、RC OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)- or halogen.

[0018] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)- and halogen.

[0019] In formula (I), L is (C1-C 40 )alkylene or (C2-C 40 ) heteroalkylene.

[0020] In formula (I), each R in formula (I) C , R P and R N Independently (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H.

[0021] In formula (V), M2 is titanium, zirconium or hafnium; R 61 , R 62 , R 63 , R 64 and R 65Independently (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, wherein R 62 , R 63 , R 64 and R 65 Any of are optionally linked to form a ring structure; R 66 , R 67 and R 68 Independently (C1-C 20 ) hydrocarbon group, (C1-C 20 ) heteroalkyl, (C6-C 30 ) aryl, (C5-C 30 ) heteroaryl, wherein R 66 , R 67 and R 68 Two of are optionally linked to form a ring. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1A Two theoretical molecular weight distribution curves are shown for two unimodal polymer compositions produced by a bisphenylphenoxy catalyst and by a phosphinimine catalyst in the absence of hydrogen in the reactor chamber.

[0023] Figure 1B Two theoretical molecular weight distribution curves are shown for two unimodal polymer compositions produced by a bisphenylphenoxy catalyst and by a phosphinimine catalyst with a small amount of hydrogen in the reactor chamber.

[0024] Figure 1C Two theoretical molecular weight distribution curves are shown for two unimodal polymer compositions produced by a bisphenylphenoxy catalyst and by a phosphinimine catalyst with a relatively large amount of hydrogen in the reactor chamber.

[0025] Figure 2 is a graph of the molecular weight of the polymers produced by three different phosphinimine catalysts as a function of the amount of hydrogen (mmol) in the reactor.

[0026] Figure 3 The molecular weight distribution curves of bimodal polymer compositions obtained from gel permeation chromatography (GPC) produced by bisphenylphenoxy catalyst (BPP-1) and phosphinimine catalyst (PN-1) with different amounts of hydrogen in the reactor chamber. The amount of hydrogen is: 0 mmol H2, 5 mmol H2, 20 mmol H2 and 40 mmol H2.

[0027] Figure 4is the GPC trace of the comonomer distribution of polyethylene produced by dual catalysts (BPP-1 and PN-1).

[0028] Figure 5 is the GPC trace of comonomer distribution of PE produced by dual catalysts with PN-1 and BPP-2 at three hydrogen loadings at a temperature of 160°C.

[0029] Figure 6 is the GPC trace of the comonomer distribution of PE produced by dual catalysts.

[0030] Figure 7 The improved comonomer composition distribution (iCCD) data of PE produced by dual catalysts with dual catalysts.

[0031] Figure 8 is the GPC traces of comonomer distribution of PE produced by dual catalysts with PN-1 and BPP-3 at three hydrogen loadings at a temperature of 160°C.

[0032] Fig. 9 is the GPC trace of comonomer distribution of PE produced by dual catalysts with PN-1 and BPP-4 at three hydrogen loadings at a temperature of 160°C.

[0033] Fig.10 is the GPC trace of comonomer distribution of PE produced by dual catalyst with PN-1 and BPP-5 at three hydrogen loadings at a temperature of 160°C. DETAILED DESCRIPTION

[0034] Specific embodiments of the catalyst system will now be described. It should be understood that the catalyst system of the present disclosure can be embodied in different forms and should not be construed as being limited to the specific embodiments set forth in the present disclosure. On the contrary, embodiments are provided so that the present disclosure will be thorough and complete, and the embodiments will fully convey the scope of the subject matter to those skilled in the art.

[0035] The term "independently selected from" is used herein to refer to each of the R groups that precede the term, such as R 1 , R 2 , R 3 , R 4 and R 5 may be the same or different and is not dependent on the identity of any other groups that precede the term.

[0036] The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. The term "activator" refers to a compound that chemically reacts with the procatalyst in a manner that converts the procatalyst into a catalytically active catalyst. As used herein, the terms "procatalyst" and "activator" are interchangeable terms.

[0037] When used to describe certain chemical groups containing carbon atoms, the form "(C x -C y )" means that the unsubstituted form of the chemical group has from x to y carbon atoms (including x and y). For example, (C1-C 50 ) alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be replaced by, for example, R S etc. is substituted with one or more substituents. x -C y )" The chemical group defined in brackets is R S The substitution pattern may be based on any group R S The property contains more than y carbon atoms. For example, "exactly one group R S Substituted (C1-C 50 ) alkyl, wherein R S The phenyl group (-C6H5)" may contain from 7 to 56 carbon atoms. Therefore, in general, when the parenthetical phrase "(C x -C y )" is replaced by one or more carbon-containing substituents R S When substituted, both x and y are added to the substituent R from all carbon atoms. S The combined sum of the number of carbon atoms is used to determine the minimum and maximum total number of carbon atoms in a chemical group.

[0038] The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S The term "fully substituted" means that each hydrogen atom (H) bonded to a carbon atom or heteroatom of the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S ) replacement. The term "polysubstituted" means that at least two but less than all hydrogen atoms bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group are replaced by substituents. The term "-H" means a hydrogen or hydrogen group covalently bonded to another atom. "Hydrogen" and "-H" are interchangeable and have the same meaning unless expressly specified.

[0039] The term "(C1-C 50)alkyl" means a hydrocarbon group having 1 to 50 carbon atoms, and the term "(C1-C 50 )alkylene group" means a hydrocarbon diradical having 1 to 50 carbon atoms, wherein each hydrocarbon group and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight chain or branched, cyclic (having three carbons or more, and including monocyclic and polycyclic, fused and non-fused polycyclic and bicyclic) or acyclic, and is substituted by one or more R S Replaced or not replaced.

[0040] In the present disclosure, (C1-C 50 The hydrocarbon group may be unsubstituted or substituted (C1-C 50 )alkyl, (C3-C 50 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 ) alkylene, (C6-C 40 )aryl or (C6-C 20 )aryl-(C1-C 20 ) alkylene (such as benzyl (-CH2-C6H5)).

[0041] The term "(C1-C 50 )alkyl" and "(C1-C 18 )alkyl" means unsubstituted or substituted with one or more R S Substituted saturated straight chain or branched hydrocarbon groups having 1 to 50 carbon atoms and saturated straight chain or branched hydrocarbon groups having 1 to 18 carbon atoms. 50 Examples of alkyl groups are unsubstituted (C1-C 20 ) alkyl; unsubstituted (C1-C 10 )alkyl; unsubstituted (C1-C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and 1-decyl. Substituted (C1-C5)alkyl 40 Examples of alkyl groups are substituted (C1-C 20 ) alkyl, substituted (C1-C 10 ) alkyl, trifluoromethyl and [C 45 ] alkyl. The term "[C 45 "] alkyl" means that there are up to 45 carbon atoms in the group (including substituents), and is, for example, (C 27 -C 40 ) alkyl, each of which is replaced by an R S(which is a (C1-C5) alkyl) substituted. Each (C1-C5) alkyl may be a methyl group, a trifluoromethyl group, an ethyl group, a 1-propyl group, a 1-methylethyl group or a 1,1-dimethylethyl group.

[0042] The term "(C6-C 50 ) aryl means an unsubstituted or (substituted by one or more R S )-substituted monocyclic, bicyclic or tricyclic aromatic hydrocarbon groups, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms. Monocyclic aromatic hydrocarbon groups include one aromatic ring; bicyclic aromatic hydrocarbon groups have two rings; and tricyclic aromatic hydrocarbon groups have three rings. Unsubstituted (C6-C 50 Examples of aryl groups include: unsubstituted (C6-C 20 ) aryl, unsubstituted (C6-C 18 )aryl; 2-(C1-C5)alkyl-phenyl; phenyl; fluorenyl; tetrahydrofluorenyl; dicyclopentadienylphenyl; hexahydrodicyclopentadienylphenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; and phenanthrene. Substituted (C6-C 40 Examples of aryl groups include: substituted (C1-C 20 ) aryl; substituted (C6-C 18 )aryl; 2,4-bis([C 20 ] alkyl)-phenyl; polyfluorophenyl; pentafluorophenyl; and fluoren-9-on-1-yl.

[0043] The term "(C3-C 50 "Cycloalkyl" means a saturated cyclic hydrocarbon group having 3 to 50 carbon atoms, which is unsubstituted or substituted by one or more R S Other cycloalkyl groups (e.g., (C x -C y )cycloalkyl) is defined in a similar manner as having x to y carbon atoms and being unsubstituted or substituted with one or more R S replaced.

[0044] (C1-C 50 Examples of the alkylene group include unsubstituted or substituted (C6-C 50 ) arylene, (C3-C 50 )cycloalkylene and (C1-C 50 ) alkylene (e.g., (C1-C 20) alkylene). The diradicals can be on the same carbon atom (e.g., -CH2-) or on adjacent carbon atoms (i.e., 1,2-diradicals), or separated by one, two, or more than two intermediate carbon atoms (e.g., 1,3-diradicals, 1,4-diradicals, etc.). Some diradicals include 1,2-diradicals, 1,3-diradicals, 1,4-diradicals, or α,ω-diradicals and other 1,2-diradicals. α,ω-diradicals are diradicals with the largest carbon backbone spacing between the radical carbons. (C2-C 20 Some examples of alkylene α,ω-diyl radicals include ethane-1,2-diyl (ie, -CH2CH2-), propane-1,3-diyl (ie, -CH2CH2CH2-), 2-methylpropane-1,3-diyl (ie, -CH2CH(CH3)CH2-). (C6-C 50 Some examples of arylene α,ω-diradicals include phenyl-1,4-diyl, naphthalene-2,6-diyl, or naphthalene-3,7-diyl.

[0045] The term "(C1-C 50 ) Alkylene means a group having 1 to 50 carbon atoms which is unsubstituted or substituted with one or more R S Substituted saturated straight or branched chain diradicals (i.e., the groups are not on ring atoms). Unsubstituted (C1-C 50 Examples of alkylene groups are unsubstituted (C1-C 20 )alkylene, including unsubstituted -CH2CH2-, -(CH2)3-, -(CH2)4-, -(CH2)5-, -(CH2)6-, -(CH2)7-, -(CH2)8-, -CH2C*HCH3, and -(CH2)4C*(H)(CH3), wherein "C*" represents a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl group. Substituted (C1-C 50 Examples of alkylene groups are substituted (C1-C 20 )alkylene, -CF2-, -C(O)- and -(CH2) 14 C(CH3)2(CH2)5- (i.e., 6,6-dimethyl-substituted n-1,20-eicosene). As mentioned above, the two R S can form together (C1-C 18 ) alkylene, substituted (C1-C 50 Examples of the alkylene group also include 1,2-bis(methylene)cyclopentane, 1,2-bis(methylene)cyclohexane, 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane, and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0046] The term "(C3-C 50) Cycloalkylene means a cycloalkylene group having 3 to 50 carbon atoms which is unsubstituted or substituted with one or more R S Substituted cyclic diradicals (ie, the groups are on ring atoms).

[0047] The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more heteroatoms include O, S, S(O), S(O)2, Si(R C ) 2、 P(R P )、N(R N )、-N=C(R C )2、-Ge(R C )2- or -Si(R C )-, where each R C and each R P For unsubstituted (C1-C 18 )alkyl or -H, and each R N For unsubstituted (C1-C 18 ) hydrocarbon group. The term "heterohydrocarbon" refers to a molecule or molecular skeleton in which one or more carbon atoms of a hydrocarbon are replaced by a heteroatom. 50 )heteroalkyl" means a heteroalkyl group having 1 to 50 carbon atoms, and the term "(C1-C 50 "Heteroalkylene" means a heterohydrocarbon diradical having 1 to 50 carbon atoms. (C1-C 50 )heteroalkyl or (C1-C 50 ) The heteroalkylene group has one or more heteroatoms. The radicals of the heteroalkylene group can be on carbon atoms or heteroatoms. The two radicals of the heteroalkylene group can be on a single carbon atom or on a single heteroatom. In addition, one of the two radicals of the diradical can be on a carbon atom and the other can be on a different carbon atom; one of the two radicals can be on a carbon atom and the other can be on a heteroatom; or one of the two radicals can be on a heteroatom and the other can be on a different heteroatom. Each (C1-C 50 ) heteroalkyl and (C1-C 50 ) heteroalkylene may be unsubstituted or (substituted by one or more R S ) substituted, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

[0048] (C1-C 50 )Heteroalkyl may be unsubstituted or substituted. (C1-C 50 Non-limiting examples of heteroalkyl groups include (C1-C 50 ) heteroalkyl, (C1-C 50)alkyl-O-, (C1-C 50 )alkyl-S-, (C1-C 50 )alkyl-S(O)-, (C1-C 50 )alkyl-S(O)2-, (C1-C 50 )alkyl-Si(R C )2-、(C l -C 50 )alkyl-N(R N )-、(C l -C 50 )alkyl-P(R P )-、(C2-C 50 )heterocycloalkyl, (C2-C 19 )heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 )cycloalkyl-(C1-C 19 )heteroalkylene, (C2-C 19 )heterocycloalkyl-(C1-C 20 )heteroalkylene, (C1-C 50 )heteroaryl, (C1-C 19 )heteroaryl-(C1-C 20 ) alkylene, (C6-C 20 )aryl-(C1-C 19 )heteroalkylene or (C1-C 19 )heteroaryl-(C1-C 20 ) heteroalkylene.

[0049] The term "(C4-C 50 ) heteroaryl" means an unsubstituted or (substituted by one or more R S ) substituted monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon groups. Monocyclic heteroaromatic hydrocarbon groups include one heteroaromatic ring; bicyclic heteroaromatic hydrocarbon groups have two rings; and tricyclic heteroaromatic hydrocarbon groups have three rings. When a bicyclic heteroaromatic hydrocarbon group or a tricyclic heteroaromatic hydrocarbon group is present, at least one of the rings in the group is heteroaromatic. The other one or more rings of the heteroaromatic group may independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., typically (C x -C y ) heteroaryl, such as (C4-C 12 )heteroaryl) is defined as having x to y carbon atoms (such as 4 to 12 carbon atoms) and is unsubstituted or substituted by one or more than one R SThe monocyclic heteroaromatic hydrocarbon group is a 5-membered ring or a 6-membered ring. The 5-membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms and can be 1, 2, 3 or 4, and each heteroatom can be O, S, N or P.

[0050] The term "(C1-C 50 ) heteroalkyl" means a saturated straight or branched chain group containing one to fifty carbon atoms or less and one or more heteroatoms. The term "(C1-C 50 ) "heteroalkylene" means a saturated straight chain or branched diradical containing 1 to 50 carbon atoms and one or more heteroatoms. The heteroatoms of heteroalkyl or heteroalkylene may include Si(R C )3、Ge(R C )3、Si(R C )2、Ge(R C 2. P(R P 2. P(R P )、N(R N )2、N(R N )、N、O、OR C , S, SR C , S(O) and S(O)2, wherein each of the heteroalkyl and heteroalkylene groups is unsubstituted or substituted with one or more R S replace.

[0051] The term "halogen atom" or "halogen" refers to a radical of a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), or an iodine atom (I). The term "halide" refers to the anionic form of a halogen atom: a fluoride ion (F - ), chloride ion (Cl - ), bromide ion (Br - ) or iodide ion (I - ).

[0052] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in groups containing heteroatoms) carbon-nitrogen double bonds, carbon-phosphorus double bonds, and carbon-silicon double bonds. S In the case of substitution, one or more double bonds and / or triple bonds may or may not be present in the substituent R S The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds or (in a group containing heteroatoms) one or more carbon-nitrogen double bonds, carbon-phosphorus double bonds or carbon-silicon double bonds, excluding those that may be present in the substituent R S double bonds in aromatic rings (if any) or (hetero)aromatic rings (if any).

[0053] Embodiments of the present disclosure include methods for polymerizing olefin monomers to produce polyolefins. The method includes reacting ethylene and optional one or more olefin monomers in one reactor or multiple reactors in the presence of a catalyst system. The catalyst includes two or more catalysts, wherein at least one catalyst is derived from a bisphenylphenoxy procatalyst according to formula (I), and wherein at least one catalyst is derived from a phosphinimine procatalyst according to formula (V). The amount of hydrogen is adjusted to customize the molecular weight of the polyolefin.

[0054] Hydrogen can be added to the polymerization process. At any given time during the polymerization reaction, the amount of hydrogen in the reactor can be 0 mmol. The amount of hydrogen can increase or decrease as the reaction proceeds. In a semi-batch polymerization process, the amount of hydrogen may decrease when the polymerization reactants consume hydrogen and no additional hydrogen is added.

[0055] The catalyst comprises one or more bisphenylphenoxy procatalysts according to formula (I) and one or more phosphinimine procatalysts according to formula (V).

[0056] Embodiments of the present disclosure include catalyst systems comprising one or more bisphenylphenoxy procatalysts according to formula (I):

[0057]

[0058] In formula (I), M1 is titanium, zirconium, hafnium, scandium or yttrium.

[0059] In formula (I), each X is independently selected from (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -CH2Si(R C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C ) Q 、-OSi(R C ) 3-Q (OR C ) Q 、-CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q 、-P(R C ) 2-W (OR C )W 、-P(O)(R C ) 2-W (OR C ) W 、-N(R C )2、-NH(R C )、-N(Si(R C )3)2、-NR C Si(R C )3, -NHSi(R C )3. -OR C 、-SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C 、-S(O)2R C 、-OS(O)2R C 、-N=C(R C )2, -N=CH(R C )、-N=CH2、-N=P(R C )3. -OC(O)R C 、-C(O)OR C 、-N(R C )C(O)R C 、-N(R C )C(O)H、-NHC(O)R C 、-C(O)N(R C )2. -C(O)NHR C 、-C(O)NH2、halogen、B(R Y )4、Al(R Y )4 or Ga(R Y )4 or a monodentate ligand of hydrogen, wherein each R C Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1 or 2; each R Y =–H, (C1-C 30 ) a hydrocarbon group or a halogen atom, wherein two X ligands may be linked to form a metal cyclize ring.

[0060] In formula (I), each Y is independently a Lewis base; optionally, X and Y may be linked to form a ring. Subscript m is 1 or 2; and subscript n is 0, 1, and 2.

[0061] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7, R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)- and halogen.

[0062] In formula (I), R 1 and R 16 Independently selected from the group consisting of: –H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-, -N=C(R C 2. R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)-, halogen, a group having the formula (II), a group having the formula (III) and a group having the formula (IV):

[0063]

[0064] In formula (II), R 31 , R32 , R 33 , R 34 , R 35 are independently selected from -H, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)- or halogen.

[0065] In formula (III), R 41 , R 42 , R 43 , R 44 , R 45 , R 46 , R 47 , R 48 are independently selected from -H, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)- or halogen.

[0066] In formula (IV), R 51 , R 52 , R 53 , R54 , R 55 , R 56 , R 57 , R 58 and R 59 are independently selected from -H, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)- or halogen.

[0067] The group R in the metal-ligand complex of formula (I) 1 and R 16 are chosen independently of each other. For example, R 1 can be selected from groups having formula (II), (III) or (IV), and R 16 It can be (C4-C 50 ) heteroaryl; or R 1 can be selected from a group having formula (II), (III) or (IV), and R 16 Can be selected from R 1 The same or different groups have formula (II), (III) or (IV). In an embodiment, R 1 and R 16 Both are radicals of formula (II) in which the radical R 31-35 In R 1 and R 16 In some embodiments, R 1 and R 16 Both are groups of formula (III) in which the group R 41-48 In R 1 and R 16 In other embodiments, R 1 and R 16 Both are radicals of formula (IV) in which the radical R 51-59 In R1 and R 16 The same or different.

[0068] In an embodiment, R 1 and R 16 At least one of them is a group having formula (II), wherein R 32 and R 34 In some embodiments, when R 1 or R 16 When at least one of them is a group having formula (III), R 43 and R 46 One or both of them are tert-butyl, and R 41-42 , R 44-45 and R 47-48 is -H. In some embodiments, R 42 and R 47 One or both of them are tert-butyl, and R 41 , R 43-46 and R 48 is -H. In some embodiments, R 42 and R 47 Both are -H. In some embodiments, R 41-48 Yes – H.

[0069] In formula (I), R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are independently selected from -H, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R COC(O)-、R C C(O)N(R)-、(R C )2NC(O)- and halogen.

[0070] In some embodiments, R 5 , R 6 , R 7 and R 8 At least one of is a halogen atom; and R 9 , R 10 , R 11 and R 12 At least one of is a halogen atom. 5 , R 6 , R 7 and R 8 At least two of are halogen atoms; and R 9 , R 10 , R 11 and R 12 At least two of are halogen atoms. In various embodiments, R 5 , R 6 , R 7 and R 8 At least three of are halogen atoms; and R 9 , R 10 , R 11 and R 12 At least three of them are halogen atoms.

[0071] In an embodiment, R 3 and R 14 Yes (C1-C 24 ) alkyl. In various embodiments, R 3 and R 14 is (C1-C 20 In some embodiments, R 3 and R 14 (C4-C 24 ) alkyl. In one or more embodiments, R 3 and R 14 (C8-C 12 In some embodiments, R 3 and R 14 is 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl, and decyl. In an embodiment, R 3 and R 14For-OR C , where R C is (C1-C 20 ) hydrocarbon, and in some embodiments, R C It is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl) or 1,1-dimethylethyl.

[0072] In an embodiment, R 3 and R 14 In other embodiments, R 3 and R 14 Yes (C4-C 24 In some embodiments, R 8 and R 9 are 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methyl-1-butyl, hexyl, 4-methyl-1-pentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl and decyl.

[0073] In some embodiments, R 6 and R 11 is halogen. In other embodiments, R 6 and R 11 Yes (C1-C 24 In some embodiments, R 6 and R 11 R is independently selected from methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpentan-2-yl), nonyl, and decyl. In some embodiments, R 6 and R 11 In the embodiment, R 6 and R 11 For-OR C , where R C is (C1-C 20 ) alkyl, and in some embodiments, R C is methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl) or 1,1-dimethylethyl. In other embodiments, R 6 and R 11 -SiR C 3, where each R C Independently (C1-C 20 ) alkyl, and in some embodiments, R CIt is methyl, ethyl, 1-propyl, 2-propyl (also called isopropyl) or 1,1-dimethylethyl.

[0074] In some embodiments, R 3 and R 14 is methyl; and R 6 and R 11 is halogen. In other embodiments, R 6 and R 11 In other embodiments, R 3 and R 14 It is tert-octyl or n-octyl.

[0075] In one or more embodiments, in formula (I), R 1 and R 16 In some embodiments, when R 1 and R 16 When one of them is a group having formula (III), R 42 and R 47 is (C1-C 20 )alkyl or -Si[(C1-C 20 )alkyl]3. In various embodiments, when R 1 and R 16 When one of them is a group having formula (III), R 43 and R 46 is (C1-C 20 )alkyl or -Si[(C1-C 20 )hydrocarbon group]3.

[0076] In some embodiments, in Formula (I), R 1 and R 16 At least one of them is a group having formula (II), and R 32 and R 34 is (C1-C 12 )alkyl or –Si[(C1-C 20 )hydrocarbon group]3.

[0077] In various embodiments, in Formula (I), R 1 and R 16 When at least one of them is a group having formula (IV), and R 52 , R 53 , R 55 , R 57 and R 58 At least two of them are (C1-C 20 )alkyl or –Si[(C1-C 20 )hydrocarbon group]3.

[0078] In one or more embodiments, R 8 and R 9 are independently (C1-C4)alkyl.

[0079] In some embodiments, R 3 and R 14 Yes (C1-C 20 ) alkyl. In various embodiments, R 3 and R 14 is methyl; R 6 and R 11 In one or more embodiments, R 6 and R 11 In some embodiments, R 3 and R 14 It is tert-octyl or n-octyl.

[0080] In some embodiments, L is selected from -CH2(CH2) m CH2-、-CH2Si(R C )(R D )CH2-、-CH2Ge(R C )(R D )CH2-, -CH2(CH3)CH2CH*(CH3), bis(methylene)cyclohexane-1,2-diyl; -CH2CH(R C )CH2-,-CH2C(R C )2CH2-, where each R in L C is (C1-C 20 ) alkyl and R in L D is (C1-C 20 ) hydrocarbon group.

[0081] Embodiments of the present disclosure include catalyst systems comprising one or more phosphinimine procatalysts according to formula (V):

[0082]

[0083] In formula (V), M2 is titanium, zirconium or hafnium.

[0084] In formula (V), each X is independently selected from (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -CH2Si(R C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C )Q 、-OSi(R C ) 3-Q (OR C ) Q 、-CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q 、-P(R C ) 2-W (OR C ) W 、-P(O)(R C ) 2-W (OR C ) W 、-N(R C )2、-NH(R C )、-N(Si(R C )3)2、-NR C Si(R C )3, -NHSi(R C )3. -OR C 、-SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C 、-S(O)2R C 、-OS(O)2R C 、-N=C(R C )2, -N=CH(R C )、-N=CH2、-N=P(R C )3. -OC(O)R C 、-C(O)OR C 、-N(R C )C(O)R C 、-N(R C )C(O)H、-NHC(O)R C 、-C(O)N(R C )2. -C(O)NHR C 、-C(O)NH2、halogen、B(R Y )4、Al(R Y )4 or Ga(R Y )4 or a monodentate ligand of hydrogen, wherein each R C Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1 or 2; each RY =–H, (C1-C 30 ) a hydrocarbon group or a halogen atom, wherein two X ligands may be linked to form a metal cyclize ring.

[0085] In formula (V), each Y is independently a Lewis base; optionally, X and Y may be linked to form a ring. Subscript m is 1 or 2; and subscript n is 0, 1, and 2.

[0086] In formula (V), R 61 , R 62 , R 63 , R 64 and R 65 Independently (C1-C 50 ) alkyl, wherein R 61 and R 62 Optionally connected to form a ring, or R 62 and R 63 Optionally connected to form a ring, R 63 and R 64 Optionally connected to form a ring, R 64 and R 65 optionally linked to form a ring;

[0087] In formula (V), R 66 , R 67 and R 68 Independently (C1-C 20 ) hydrocarbon group, (C1-C 20 ) heteroalkyl, (C6-C 30 ) aryl, (C5-C 30 ) heteroaryl, wherein R 66 , R 67 and R 68 Two of are optionally linked to form a ring; and

[0088] In formula (I), (II), (III), (IV) and (V), each R in formula (I) C , R P and R N Independently (C1-C 30 ) hydrocarbon group, (C1-C 30 ) heteroalkyl or -H.

[0089] In one or more embodiments, in Formula (V), R 66 , R 67 , R 68 Independently (C1-C 20 )alkyl.

[0090] In some embodiments, in Formula (V), R 66 , R67 , R 68 are independently selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl and decyl.

[0091] In various embodiments, in Formula (V), wherein R 64 and R 65 connected to form an aromatic ring.

[0092] In some embodiments, the monodentate ligands X and Y of formula (I) and formula (V) can be monoanionic ligands. The net formal oxidation state of the monoanionic ligand is -1. Each monoanionic ligand can independently be a hydride, (C1-C 40 ) Hydrocarbyl carbon anion, (C1-C 40 ) Heteroalkyl carbon anions, halides, nitrates, carbonates, phosphates, sulfates, HC(O)O - 、HC(O)N(H) - 、(C1-C 40 )C(O)O - 、(C1-C 40 )alkylC(O)N((C1-C 20 )alkyl) - 、(C1-C 40 )C(O)N(H) - , R K R L B - , R K R L N - , R K O - , R K S - , R K R L P - or R M R K R L Si - , where each R K , R L and R M are independently hydrogen, (C1-C 40 )alkyl or (C1-C 40 ) heteroalkyl, or R K and R L Together they form (C2-C 40 )alkylene or (C1-C20 )heteroalkylene, and R M As defined above.

[0093] In other embodiments, at least one of the monodentate ligands X and Y can be a neutral ligand, independent of any other ligand X and other ligands Y. In a specific embodiment, the neutral ligand is a neutral Lewis base group, such as R Q NR K R L , R K OR L , R K SR L or R Q PR K R L , where each R Q are independently hydrogen, [(C1-C 10 )alkyl]3Si(C1-C 10 ) hydrocarbon group, (C1-C 40 )alkyl, [(C1-C 10 )alkyl]3Si or (C1-C 40 ) heteroalkyl, and each R K and R L Independently as defined previously.

[0094] In the metal-ligand complex according to formula (I), each Y is bonded to M by a coordination bond or an ionic bond. In one or more embodiments, Y is a Lewis base. A Lewis base can be a compound or an ionic substance that can donate an electron pair to an acceptor compound. For the purposes of this embodiment, the acceptor compound is M, which is the metal of the metal-ligand complex of formula (I). The Lewis base can be neutral or anionic. In some embodiments, the Lewis base can be a heterohydrocarbon or an unsaturated hydrocarbon. Examples of neutral heterohydrocarbon Lewis bases include, but are not limited to, amines, trialkylamines, ethers, cyclic ethers, or sulfides. Examples of anionic hydrocarbons include, but are not limited to, cyclopentadienyl. Examples of neutral hydrocarbon Lewis bases include, but are not limited to, 1,3-butadiene.

[0095] In some embodiments, the Lewis base is an unsaturated (C1-C 20 ) hydrocarbon. In some embodiments, the Lewis base is cyclopentadiene or 1,3-butadiene. In various embodiments, the Lewis base is (C1-C 20 ) heterohydrocarbon, wherein the heteroatom of the heterohydrocarbon is oxygen. In some embodiments, Y is tetrahydrofuran, diethyl ether or methyl tert-butyl ether (MTBE).

[0096] In addition, each X and each Y can be a monodentate ligand, which is independent of any other ligands X and Y and is a halogen, an unsubstituted (C1-C 20) alkyl, unsubstituted (C1-C 20 )C(O)O– or R K R L N-, where R K and R L Each of which is independently unsubstituted (C1-C 20 In some embodiments, each monodentate ligand X is a chlorine atom, (C1-C 10 ) hydrocarbon group (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10 )C(O)O– or R K R L N-, where R K and R L Each of which is independently unsubstituted (C1-C 10 In one or more embodiments of formula (I) and (V), X is benzyl, chloro, -CH2SiMe3 or phenyl.

[0097] In some embodiments, m+n is 2 or 3.

[0098] In other embodiments, each X and / or each Y is independently selected from: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; or chlorine. In some embodiments, each X is the same. In other embodiments, at least two X are different from each other. In an embodiment, when m is 3, at least two X groups are different from at least one X, and X is a different one of the following: methyl; ethyl; 1-propyl; 2-propyl; 1-butyl; 2,2-dimethylpropyl; trimethylsilylmethyl; phenyl; benzyl; and chlorine. In other embodiments, the X ligand is 2,2-dimethyl-2-dimethylsilane-1,3-diyl or 1,3-butadiene.

[0099] In some embodiments, the chemical groups (e.g., X and R) of the metal-ligand complex of formula (I) 1 -R 4 ) may be unsubstituted. In other embodiments, the chemical groups X and R of the metal-ligand complex of formula (I) 1 -R 4 None, any, or all of them may be represented by one or more R S When two or more R S When the same chemical group of the metal-ligand complex of formula (I) is bonded, each R S The chemical groups X and R may be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms.1 -R 4 None, any, or all of them can be R S Completely replaced. S In a fully substituted chemical group, each R S May all be the same or may be independently selected.

[0100] In some embodiments, the ratio of the hydrogen chain transfer constant of the procatalyst of formula (V) to the procatalyst of formula (I) is greater than or equal to 3 at 160°C. In other embodiments, the ratio of the hydrogen chain transfer constant of the procatalyst of formula (V) to the procatalyst of formula (I) is greater than or equal to 5 at 160°C; greater than or equal to 7 at 160°C; or greater than or equal to 10 at 160°C; or greater than or equal to 20 at 160°C.

[0101] In an exemplary embodiment, the catalyst system may include a metal-ligand complex according to formula (I) having the structure of any one of the procatalysts BPP-1 to BPP-10 and a metal-ligand complex according to formula (V) having the structure of any one of the procatalysts PN-1 to PN-3:

[0102]

[0103]

[0104] Co-catalyst component

[0105] Catalyst systems comprising the metal-ligand complex of formula (I) may be rendered catalytically active by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, the primary catalyst of the metal-ligand complex of formula (I) may be rendered catalytically active by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. In addition, the metal-ligand complex according to formula (I) comprises both a neutral primary catalyst form and a catalytic form that may be positively charged due to the loss of a monomeric ionic ligand (such as a benzyl or phenyl group). Activating cocatalysts suitable for use herein include alkylaluminums; polymeric or oligomeric aluminoxanes (also known as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the aforementioned activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means a monoalkylaluminum dihydride or a monoalkylaluminum dihalide, a dialkylaluminum hydride or a dialkylaluminum halide, or a trialkylaluminum. Examples of polymeric or oligomeric aluminoxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

[0106] In some embodiments, the catalyst system does not include additives. Additives are chemical reagents present during the polymerization reaction that do not prevent olefin growth. In one or more embodiments, the catalyst system also includes additives. In some embodiments, the additive is used as a co-catalyst. In other embodiments, the additive is used as a scavenger or a scavenger. A co-catalyst is a reagent that reacts in coordination with the catalyst to catalyze the reaction or improve the catalytic activity of the catalyst. Without being bound by theory, when M of formula (I) is scandium or yttrium, the ligand Y dissociates in the absence of a co-catalyst. However, it is also believed that a co-catalyst can promote the dissociation of any Lewis base present and coordinated to the metal center of the metal-ligand complex.

[0107] Scavengers can sequester impurities in the reactor and thus may not constitute an activator. In some cases, lower loadings of aluminoxanes are not used as cocatalysts, instead, they are used as scavengers.

[0108] Suitable additives may include, but are not limited to, aluminum alkyls; polymeric or oligomeric aluminoxanes (also referred to as alumoxanes); neutral Lewis acids; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). Combinations of one or more of the foregoing additives and techniques are also contemplated. The term "aluminum alkyl" means a monoalkylaluminum dihydride or dihalide, a dialkylaluminum hydride or halide, or a trialkylaluminum. Examples of polymeric or oligomeric aluminoxanes include methylaluminoxane, methylaluminoxane modified with triisobutylaluminum, and isobutylaluminoxane.

[0109] The Lewis acid activated cocatalyst comprises a (C1-C 20 )hydrocarbyl substituent. In some embodiments, the Group 13 metal compound is tri((C1-C 20 ) alkyl) substituted aluminum or tri((C1-C 20 In other embodiments, the Group 13 metal compound is a tri(hydrocarbyl)substituted aluminum, a tri((C1-C 20 )alkyl)-boron compounds, tri((C1-C 10 )alkyl)aluminum, tri((C6-C 18 ) aryl) boron compounds and their halogenated (including perhalogenated) derivatives. In other embodiments, the Group 13 metal compound is tri(fluoro-substituted phenyl) borane, tri(pentafluorophenyl) borane. In some embodiments, the activating cocatalyst is tri((C1-C 20 ) alkyl borate (e.g., trityl tetrafluoroborate) or tris((C1-C 20 )alkyl)ammonium tetra((C1-C 20)alkyl)borane (e.g., bis(octadecyl)methylammoniumtetra(pentafluorophenyl)borane). As used herein, the term "ammonium" refers to a nitrogen cation, which is ((C1-C 20 )alkyl)4N + 、((C1-C 20 )alkyl)3N(H) + 、((C1-C 20 )alkyl)2N(H)2 + 、(C1-C 20 )Hydrocarbon N(H)3 + or N(H)4 + , where there are two or more (C1-C 20 ) hydrocarbon groups, they may be the same or different.

[0110] The combination of a neutral Lewis acid activated cocatalyst comprises a tri((C1-C4)alkyl)aluminum and a tri((C6-C 18 In some embodiments, the present invention provides a mixture of a combination of a (pentafluorophenyl)borane and a (pentafluorophenyl)borane. Other embodiments are combinations of such neutral Lewis acid mixtures with polymeric or oligomeric aluminoxanes and combinations of a single neutral Lewis acid (especially tris(pentafluorophenyl)borane) with polymeric or oligomeric aluminoxanes. The molar ratio of (metal-ligand complex): (tris(pentafluorophenyl)borane): (aluminoxane) [e.g., (Group 4 metal-ligand complex): (tris(pentafluorophenyl)borane): (aluminoxane)] is 1:1:1 to 1:10:30, and in other embodiments is 1:1:1.5 to 1:5:10.

[0111] The catalyst system comprising the metal-ligand complex of formula (I) can be activated to form an active catalyst composition by combining with one or more cocatalysts (e.g., a cation-forming cocatalyst, a strong Lewis acid, or a combination thereof). Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes (especially methylaluminoxane) and inert, compatible, non-coordinating, ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl) methyl, tetrakis(pentafluorophenyl)borate (1-)amine, and combinations thereof.

[0112] In some embodiments, one or more of the aforementioned activating co-catalysts may be used in combination with one another. A specific example of a co-catalyst combination is a mixture of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane or ammonium borate with an oligomeric or polymeric aluminoxane compound. The ratio of the total number of moles of the metal-ligand complex of one or more formula (I) to the total number of moles of the one or more activating co-catalysts in the activating co-catalyst is 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, at least 1:1000 in some other embodiments; and 10:1 or less, and 1:1 or less in some other embodiments. When aluminoxane is used alone as an activating co-catalyst, preferably, the number of moles of aluminoxane employed is at least 100 times the number of moles of the metal-ligand complex of formula (I). In some other embodiments, when tri(pentafluorophenyl)borane is used alone as an activating co-catalyst, the ratio of the number of moles of tri(pentafluorophenyl)borane employed to the total number of moles of the one or more metal-ligand complexes of formula (I) is 0.5: 1 to 10: 1, 1: 1 to 6: 1, or 1: 1 to 5: 1. The remaining activating co-catalyst is typically employed in a molar amount approximately equal to the total molar amount of the one or more metal-ligand complexes of formula (I).

[0113] Aggregation methods

[0114] Any conventional polymerization process may be employed to produce the polyolefin compositions according to the present disclosure. Such conventional polymerization processes include, but are not limited to, solution polymerization processes, particle forming polymerization processes, and combinations thereof using one or more conventional reactors such as loop reactors in parallel or in series, isothermal reactors, fluidized bed reactors, stirred tank reactors, batch reactors, and / or any combination thereof.

[0115] In one embodiment, the polyolefin composition according to the present disclosure may be produced, for example, via a solution phase polymerization process using one or more loop reactors, isothermal reactors, and combinations thereof.

[0116] Generally speaking, the solution phase polymerization process is carried out in one or more well-stirred reactors such as one or more loop reactors or one or more spherical isothermal reactors at a temperature in the range of 120°C to 300°C, 120°C to 250°C, 150°C to 300°C, 150°C to 250°C, or 160°C to 215°C and at a pressure in the range of 300 psi to 1500 psi; for example, at a pressure in the range of 400 psi to 750 psi. The residence time in the solution phase polymerization process is generally in the range of 2 minutes to 30 minutes; for example, in the range of 5 minutes to 15 minutes. Ethylene, one or more solvents, one or more high temperature olefin polymerization catalyst systems, one or more cocatalysts and / or scavengers, and optionally one or more comonomers are continuously fed to one or more reactors. Exemplary solvents include, but are not limited to, isoparaffins. For example, such solvents can be purchased from ExxonMobil Chemical Co., Houston, Texas, under the name ISOPAR E. The resulting mixture of ethylene-based polymer and solvent is then removed from the reactor and the ethylene-based polymer is separated.The solvent is typically recovered via a solvent recovery unit (ie, heat exchanger and vapor liquid separator drum) and subsequently recycled back into the polymerization system.

[0117] In one embodiment, ethylene-based polymers can be produced via solution polymerization in a single reactor system (e.g., a single loop reactor system), wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of one or more high temperature olefin polymerization catalyst systems, optionally one or more other catalysts, and optionally one or more co-catalysts. In one embodiment, ethylene-based polymers can be produced via solution polymerization in a dual reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of one or more olefin polymerization catalyst systems, optionally one or more other catalysts, and optionally one or more co-catalysts. In one embodiment, ethylene-based polymers can be produced via solution polymerization in a dual reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more alpha-olefins are polymerized in both reactors in the presence of one or more high temperature olefin polymerization catalyst systems as described herein.

[0118] Polyolefins

[0119] The catalytic system described in the preceding paragraph is utilized to polymerize olefins, mainly ethylene and propylene. In some embodiments, there is only a single type of olefin or alpha-olefin in the polymerization scheme, thereby forming a homopolymer. However, additional alpha-olefins can be incorporated into the polymerization procedure. Additional alpha-olefin comonomers generally have no more than 20 carbon atoms. For example, alpha-olefin comonomers may have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary alpha-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, and 4-methyl-1-pentene. For example, one or more alpha-olefin comonomers may be selected from the group consisting of: propylene, 1-butene, 1-hexene, and 1-octene; or in an alternative, selected from the group consisting of: 1-hexene and 1-octene.

[0120] Ethylene-based polymers, such as homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as α-olefins, can contain at least 50 weight percent of monomer units derived from ethylene. All individual values ​​and subranges encompassed by "at least 50 weight percent" are disclosed herein as separate embodiments; for example, ethylene-based polymers, i.e. homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as α-olefins, can contain at least 60 weight percent of monomer units derived from ethylene; at least 70 weight percent of monomer units derived from ethylene; at least 80 weight percent of monomer units derived from ethylene; or 50 weight % to 100 weight percent of monomer units derived from ethylene; or 80 weight % to 100 weight percent of units derived from ethylene.

[0121] In some embodiments, the ethylene-based polymer may include at least 90 mole percent of units derived from ethylene. All individual values ​​and subranges from at least 90 mole percent are included herein and disclosed as separate embodiments herein. For example, the ethylene-based polymer may include at least 93 mole percent of units derived from ethylene; at least 96 mole percent of units; at least 97 mole percent of units derived from ethylene; or alternatively, 90 mole percent to 100 mole percent of units derived from ethylene; 90 mole percent to 99.5 mole percent of units derived from ethylene; or 97 mole percent to 99.5 mole percent of units derived from ethylene.

[0122] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50%; other embodiments include at least 0.5 mole percent (mol%) to 25 mol%; and in other embodiments, the amount of additional α-olefin includes at least 5 mol% to 10 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0123] Any conventional polymerization process may be employed to produce ethylene polymers. Such conventional polymerization processes include, but are not limited to, for example, solution polymerization, gas phase polymerization, slurry phase polymerization, and combinations thereof using one or more conventional reactors such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors in parallel or series, or any combination thereof.

[0124] In one embodiment, ethylene-based polymers can be produced via solution polymerization in a dual reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of a catalyst system as described herein and optionally one or more cocatalysts. In another embodiment, ethylene-based polymers can be produced via solution polymerization in a dual reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of a catalyst system in the present disclosure and as described herein and optionally one or more other catalysts. The catalyst system as described herein can be optionally used in the first reactor or the second reactor in combination with one or more other catalysts. In one embodiment, ethylene-based polymers can be produced via solution polymerization in a dual reactor system (e.g., a dual loop reactor system), wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of a catalyst system as described herein in these two reactors.

[0125] In another embodiment, the ethylene-based polymer can be produced via solution polymerization in a single reactor system (e.g., a single loop reactor system) wherein ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system as described within the present disclosure and optionally one or more cocatalysts as described in the preceding paragraphs.

[0126] Ethylene-based polymers can also include one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers and combinations thereof. Ethylene-based polymers can contain any amount of additives. According to the weight of ethylene-based polymers and one or more additives, ethylene-based polymers can include about 0 percent to about 10 percent of the gross weight of such additives. Ethylene-based polymers can further include fillers, which can include, but are not limited to, organic or inorganic fillers. By the combined weight of ethylene-based polymers and all additives or fillers, ethylene-based polymers can contain about 0 to about 20 weight percent fillers, such as calcium carbonate, talcum powder or Mg (OH) 2. Ethylene-based polymers can further be blended with one or more polymers to form a blend.

[0127] In some embodiments, a polymerization process for producing an ethylene-based polymer may comprise polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, wherein the catalyst system incorporates at least one metal-ligand complex of formula (I). The density of a polymer produced by such a catalyst system incorporating a metal-ligand complex of formula (I) may be, for example, 0.850 g / cm according to ASTM D792 (incorporated herein by reference in its entirety). 3 Up to 0.960g / cm 3 、0.880g / cm 3 Up to 0.920g / cm 3 、0.880g / cm 3 Up to 0.910g / cm 3 or 0.880g / cm 3 Up to 0.900g / cm 3 .

[0128] In another embodiment, the melt flow ratio (I) of the polymer produced by the catalyst system comprising the metal-ligand complex of formula (I) is 10 / I2) is 5 to 20, wherein the melt index I2 is measured according to ASTM D1238 (incorporated herein by reference in its entirety) at 190°C and a load of 2.16 kg, and the melt index I 10 Measured according to ASTM D1238 at 190°C and 10 kg load. In other embodiments, the melt flow ratio (I 10 / I2) is 5 to 10, and in other embodiments, the melt flow ratio is 5 to 9.

[0129] In some embodiments, the polymer produced by the catalyst system including the metal-ligand complex of formula (I) has a molecular weight distribution (MWD) of 1 to 25, wherein MWD is defined as M w / M n , where M w is the weight average molecular weight, and M n is the number average molecular weight. In other embodiments, the polymer produced by the catalyst system has an MWD of 1 to 6. Another embodiment includes an MWD of 1 to 3; and other embodiments include an MWD of 1.5 to 2.5.

[0130]

[0013] Embodiments of the catalyst systems described in this disclosure produce unique polymer properties due to the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

[0131] Unless otherwise noted, all solvents and reagents were obtained from commercial sources and used as received. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether were purified by passing through activated alumina and, in some cases, through Q-5 Reactants. Solvents used for experiments performed in a nitrogen-filled glove box were obtained by purifying the solvents in an activated The samples were further dried by storing over 1000 μl molecular sieves. Glassware for moisture sensitive reactions was dried in an oven overnight before use. NMR spectra were recorded on Varian 400-MR and VNMRS-500 spectrometers. LC-MS analysis was performed using a Waters e2695 Separations Module coupled to a Waters 2424ELS detector, a Waters 2998PDA detector, and a Waters 3100ESI mass detector. LC-MS separation was performed on an XBridge C18 3.5 μm 2.1×50 mm column using a gradient of 5:95 to 100:0 acetonitrile to water and 0.1% formic acid as the ionizer. HRMS analysis was performed using an Agilent 1290 Infinity LC with a Zorbax EclipsePlus C18 1.8 μm 2.1 x 50 mm column coupled to an Agilent 6230 TOF Mass Spectrometer with electrospray ionization. 1 H NMR data are reported as follows: chemical shift (multiplicity (br = broad, s = singlet, d = doublet, t = triplet, q = quartet, p = quintet, sex = sextet, sept = septet, and m = multiplet), integration and assignment). The values ​​are reported downfield from internal tetramethylsilane (TMS, scale δ) using residual protons in the deuterated solvent as reference. 1 Chemical shifts (in ppm) for H NMR data were obtained using 1 H decoupling method was used to determine 13 C NMR data and chemical shifts are reported in ppm downfield from tetramethylsilane (TMS, scale δ) compared to the reference using the residual protons in the deuterated solvent.

[0132] Composition Conventional GPC

[0133] Chromatographic system is composed of PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with internal IR5 infrared detector (IR5). The automatic sampler oven chamber is set to 160 degrees Celsius, and the column chamber is set to 150 degrees Celsius. The column used is 4 Agilent "Mixed A" 30cm 20 micron linear mixed bed columns. The chromatographic solvent used is 1,2,4 trichlorobenzene and contains 200ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters, and the flow rate is 1.0 ml / min.

[0134] Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards ranging from 580 g / mol to 8,400,000 g / mol and arranged in 6 "cocktail" mixtures with at least ten times intervals between individual molecular weights. Standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 g of polystyrene standards were prepared in 50 ml of solvent, and for molecular weights less than 1,000,000, 0.05 g of polystyrene standards were prepared in 50 ml of solvent. The polystyrene standards were pre-dissolved at 80°C with gentle stirring for 30 minutes, then cooled and the room temperature solution transferred to a 160°C autosampler dissolution oven to cool for 30 minutes. The polystyrene standard peak molecular weights were converted to polyethylene molecular weights using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

[0135] M 聚乙烯 =A×(M 聚苯乙烯 ) b (Equation 1)

[0136] Where M is the molecular weight, A has a value of 0.4315, and B equals 1.0.

[0137] A fifth order polynomial was used to fit the calibration points to the corresponding polyethylene equivalents.A small adjustment (approximately 0.375 to 0.445) was made to A to correct for column resolution and band broadening effects such that a linear homopolymer polyethylene standard was obtained at 120,000 Mw.

[0138] Total plate counts for the GPC column set were performed with decane, which was introduced into the blank sample via a micro pump controlled by the PolymerChar GPC-IR system. The plate count of the chromatography system should be greater than 18,000 for 4 Agilent "Mixed A" 30 cm 20 micron linear mixed bed columns.

[0139] The samples were prepared semi-automatically using the PolymerChar "Instrument Control" software, where the target weight of the sample was set to 2 mg / ml, and the solvent (containing 200 ppm BHT) was added to a septum-capped vial previously sparged with nitrogen via the PolymerChar high temperature autosampler. The samples were dissolved at 160 degrees Celsius for 2 hours under "slow" shaking.

[0140] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR spectrometer, according to equations 2-4, the PolymerChar GPCOne TM The software was used to calculate the Mn value of the baseline-subtracted IR chromatogram at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) 、Mw (GPC) and Mz (GPC) Calculation.

[0141]

[0142] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate for each sample (Flow Rate (Nominal)) by comparing the RV of the corresponding decane peak in the sample (RV (FM Sample)) with the retention volume of the decane peak in the narrow standard calibration (RV (FM Calibration)). It was then assumed that any changes in the decane marker peak time were related to a linear change in the flow rate (Flow Rate (Effective)) throughout the run. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated as Equation 5. By PolymerCharGPCOne TM The software completes the processing of the flow marker peaks. An acceptable flow rate correction is such that the effective flow rate should be within + / - 0.5% of the nominal flow rate.

[0143] Flow rate (effective) = flow rate (nominal) * (RV (FM calibration) / RV (FM sample)) (Equation 5)

[0144] Composition Conventional UHMW GPC

[0145] Chromatographic system is composed of PolymerChar GPC-IR (Valencia, Spain) high temperature GPC chromatograph equipped with internal IR5 infrared detector (IR5). The automatic sampler oven chamber is set to 165 degrees Celsius, and the column chamber and detector are set to 155 degrees Celsius. The column used is a mixed pore size column of 4TOSOH TSKgel GMHHR-H (30) HT 30-micron particle size. The chromatographic solvent used is 1,2,4 trichlorobenzene and contains 200ppm of butylated hydroxytoluene (BHT). The solvent source is nitrogen sparged. The injection volume used is 200 microliters, and the flow rate is 1.0 ml / min.

[0146] The calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards, with molecular weights ranging from 580 g / mol to 8,400,000 g / mol, and arranged in 6 "mixed liquid" mixtures, with at least ten times of spacing between individual molecular weights. Standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 g of polystyrene standards were prepared in 50 ml of solvent, and for molecular weights less than 1,000,000, 0.05 g of polystyrene standards were prepared in 50 ml of solvent. Separately prepared polystyrene standards of 10,000,000 g / mol and 15,000,000 g / mol (both from Agilent Technologies) were also prepared, at 0.5 mg / mL and 0.3 mg / mL, respectively. The polystyrene standards were pre-dissolved at 80°C with gentle stirring for 30 minutes, then cooled and the room temperature solution transferred to a 160°C autosampler dissolution oven to cool for 30 minutes. The polystyrene standard peak molecular weight was converted to polyethylene molecular weight using Equation 1 (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)).

[0147] A third order polynomial was used to fit the corresponding polyethylene equivalent calibration points. A small adjustment (approximately 0.375 to 0.445) was made to A to correct for column resolution and band broadening effects, resulting in a linear homopolymer polyethylene standard at 120,000 Mw.

[0148] Total plate counts for the GPC column set were performed with decane, which was introduced into the blank sample via a micropump controlled by the PolymerChar GPC-IR system. For a 4TOSOH TSKgel GMHHR-H(30)HT 30 micron particle size mixed pore size column, the plate count of the chromatography system should be greater than 12,000.

[0149] The samples were prepared semi-automatically using the PolymerChar "Instrument Control" software, where the target weight of the sample was set to 2 mg / ml, and the solvent (containing 200 ppm BHT) was added to a septum-capped vial previously sparged with nitrogen via the PolymerChar high temperature autosampler. The samples were dissolved at 160 degrees Celsius for 2 hours under "slow" shaking.

[0150] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR spectrometer, according to equations 2-4, the PolymerChar GPCOne TM The software was used to calculate the Mn value of the baseline-subtracted IR chromatogram at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) 、Mw (GPC) and Mz (GPC) Calculation.

[0151] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by the PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate for each sample (Flow Rate (Nominal)) by comparing the RV of the corresponding decane peak in the sample (RV (FM Sample)) with the retention volume of the decane peak in the narrow standard calibration (RV (FM Calibration)). It was then assumed that any changes in the decane marker peak time were related to a linear change in the flow rate (Flow Rate (Effective)) throughout the run. After calibrating the system based on the flow marker peak, the effective flow rate (relative to the narrow standard calibration) was calculated as Equation 5. By PolymerCharGPCOne TM The software completes the processing of the flow marker peaks. An acceptable flow rate correction is such that the effective flow rate should be within + / - 0.5% of the nominal flow rate.

[0152] IR5GPC Octene Composition Calibration

[0153] Calibration for IR5 detector dosing was performed using at least ten ethylene-based polymer standards (octene as comonomer) produced in a solution process (polyethylene homopolymer and ethylene / octene copolymer) from a single reactor over a single site metallocene catalyst, with narrow SCB distribution and known comonomer content (e.g., by 13C NMR method, Qiu et al., Anal. Chem.) 2009, 81, 8585-8589) in a solution process (polyethylene homopolymer and ethylene / octene copolymer) from a single reactor by a single-site metallocene catalyst, the known monomer content is in the range of from homopolymer (0 SCB / 1000 total C) to about 40 SCB / 1000 total C, where total C = carbon in the main chain + carbon in the branch chain. Each standard has a weight average molecular weight of 36,000 g / mole to 126,000 g / mole, as measured by GPC. The molecular weight distribution (Mw / Mn) of each standard is 2.0 to 2.5. The SCB standard polymer properties are shown in Table A.

[0154] Table A: Copolymer Standards

[0155]

[0156]

[0157] The “IR5 Area Ratio” (or “IR5 Area Response”) of the “Baseline-Subtracted Area Response of the IR5 Methyl Channel Sensor” to the “Baseline-Subtracted Area Response of the IR5 Measurement Channel Sensor” was calculated for each of the “Copolymer” standards. 甲基通道面积 / IR5 测量通道面积 ”)” (including standard filters and filter wheels supplied by PolymerChar: Part No. IR5_FWM01 as part of the GPC-IR instrument). A linear fit of comonomer wt% frequency versus “IR5 Area Ratio” was constructed in the form of Equation 6 below:

[0158] Comonomer weight % = A0 + [A1 × (IR5 甲基通道面积 / IR5 测量通道面积 )] (Equation 6)

[0159] Where A0 is the "Comonomer wt%" intercept at "IR5 Area Ratio" of zero, and A1 is the slope of "Comonomer wt%" relative to "IR5 Area Ratio" and represents the increase in comonomer wt% as a function of "IR5 Area Ratio". For narrow PDI and narrow SCBD standard materials, the IR5 Area Ratio is equal to the IR5 Height Ratio.

[0160] Improved comonomer content analysis method (iCCD)

[0161] (Cong and Parrott et al., WO2017040127A1). iCCD testing was performed using a Crystallization Elution Fractionator (CEF) (PolymerChar, Spain) equipped with an IR-5 detector (PolymerChar, Spain) and a two-angle light scattering detector model 2040 (Precision Detectors, now Agilent Technologies). Just before the IR-5 detector in the detector oven, a 5 cm or 10 cm (length) X 1 / 4" (ID) stainless steel guard column filled with 20 to 27 micron glass (MoSCi Corporation, USA) was installed. Ortho-dichlorobenzene (US ODCB, 99% anhydrous or industrial grade) was used. From EMD Chemicals obtained silica gel 40 (particle size 0.2mm-0.5mm, catalog number 10181-3) (previously used for drying ODCB solvent). The CEF instrument was equipped with an automatic sampler with N2 sweep function. ODCB was bubbled with dry nitrogen (N2) for one hour before use. Sample preparation was performed with an automatic sampler at a concentration of 4mg / ml (unless otherwise specified) at 160°C, under shaking, for 1 hour. The injection volume was 300pl. The temperature profile of the iCCD was: crystallization from 105°C to 30°C at 3°C / min, thermal equilibrium at 30°C for 2 minutes (including the elution time of the soluble fraction set to 2 minutes), and elution from 30°C to 140°C at 3°C / min. The flow rate during crystallization was 0.0ml / min. The flow rate during elution was 0.50ml / min. Data were collected at a rate of one data point per second.

[0162] The iCCD column was filled with gold-plated nickel particles (Bright7GNM8-NiS, Nippon Chemical Industrial Co.) in a stainless steel tube of 15 cm (length) X 1 / 4" (ID). The column was filled and conditioned according to references (Cong, R.; Parrott, A.; Hollis, C.; Cheatham, M. W02017040127A1). The final pressure of the TCB slurry filling was 150 bar.

[0163] The column temperature calibration was performed by using a reference material linear homopolymer polyethylene (with zero comonomer content, melt index (I2) of 1.0, polydispersity Mw / Mn of approximately 2.6 by conventional gel permeation chromatography, 1.0 mg / ml) and a mixture of ODCB containing eicosane (2 mg / ml). The iCCD temperature calibration consisted of four steps: (1) calculation of the delay volume, which was defined as the temperature offset between the measured peak elution temperature of eicosane minus 30.00°C; (2) subtraction of the temperature offset of the elution temperature from the iCCD raw temperature data. It should be noted that this temperature bias is a function of experimental conditions, such as elution temperature, elution flow rate, etc.; (3) Create a linear calibration line that converts elution temperature in the range of 30.00°C to 140.00°C so that the linear homopolymer polyethylene reference has a peak temperature at 101.0°C and eicosane has a peak temperature at 30.0°C; (4) For the soluble fraction measured isothermally at 30°C, according to reference (Cerk and Cong et al., US9,688,795), the elution temperature below 30.0°C is linearly extrapolated by using an elution heating rate of 3°C / min.

[0164] The relationship between comonomer content and elution temperature of iCCD was constructed by using 12 reference materials (ethylene homopolymers and ethylene-octene random copolymers made with single-site metallocene catalysts with ethylene equivalent weight average molecular weights ranging from 35,000 to 128,000). All of these reference materials were analyzed in the same manner as previously specified at 4 mg / mL. The reported elution peak temperatures were linearly fitted to the linear equation y = -6.3515x + 101.00, where y represents the elution temperature of iCCD, and x represents the octene mole %, and R 2 It is 0.978.

[0165] The molecular weight of the polymer and the molecular weight of the polymer fractions were determined directly from the LS detector (90 degree angle) and the concentration detector (IR-5) by assuming a shape factor of 1 and all virial coefficients equal to zero according to the Rayleigh-Gans-Debys approximation (Striegel and Yau, Modern Size Exclusion Liquid Chromatogram, pp. 242 and 263). The integration window was set to integrate the entire chromatogram over the elution temperature range (temperature calibration specified above) from 23.0°C to 120°C.

[0166] Calculation of molecular weight (Mw) from iCCD involves the following four steps:

[0167] (1) Measure the offset between detectors. The offset is defined as the geometric volume offset between the LS detector and the concentration detector. It is calculated as the difference in elution volume (mL) of the polymer peak between the concentration detector and the LS chromatogram. This is converted to a temperature offset using the elution heat rate and the elution flow rate. The polydispersity M of a linear high density polyethylene (0 comonomer content, melt index (I2) of 1.0, and a conventional gel permeation chromatography method) was used. w / M n The same experimental conditions as the normal iCCD method described above were used, except for the following parameters: crystallization from 140°C to 137°C at 10°C / min, thermal equilibrium at 137°C for 1 minute as soluble fraction elution time, soluble fraction (SF) time of 7 minutes, elution from 137°C to 142°C at 3°C / min. The flow rate during crystallization was 0.0 ml / min. The flow rate during elution was 0.80 ml / min. The sample concentration was 1.0 mg / ml.

[0168] (2) Prior to integration, each LS data point in the LS chromatogram was shifted to correct for inter-detector bias.

[0169] (3) The baseline subtracted LS and concentration chromatograms from step (1) were integrated over the entire elution temperature range. The MW detector constant was calculated by using known MW HDPE samples in the range of 100,000 to 140,000 Mw and the area ratio of the LS and concentration integrated signals.

[00218] (4) The Mw of the polymer was calculated by using the ratio of the integrated light scattering detector (90 degree angle) to the concentration detector and using the MW detector constant.

[0170] The calculation of the half width is defined as the temperature difference between the front temperature at half the maximum peak height and the back temperature, the front temperature at half the maximum peak searching forward from 35.0°C and the back temperature at half the maximum peak searching backward from 119.0°C.

[0171] Chain transfer constant calculation

[0172] The chain transfer constant was calculated using the Mayo equation shown in Equation 7, where Mn0 is the Mn without any hydrogen added to the reactor, H2 and ethylene concentrations are liquid phase concentrations, and c CTHis the ratio of the hydrogenolysis rate constant to the growth rate constant. The reactor volume was 3.414 L, the liquid phase ethylene concentration was estimated to be 0.539 M, and the estimated hydrogen concentrations were 1.17 mM, 2.31 mM, 4.53 mM, 8.74 mM, and 16.3 mM for 10 mmol, 20 mmol, 40 mmol, 80 mmol, and 160 mmol H2, respectively. For each hydrogen loading, the Mn value was calculated using Equation 7. The Solver feature of MS Excel was used to vary c CTH The value of is chosen to simultaneously minimize the sum of the squared deviations of the calculated Mn values ​​from the experimental Mn values ​​for all hydrogen loadings.

[0173]

[0174] Batch Reactor Polymerization Procedure

[0175] The raw materials (ethylene, 1-octene) and process solvent (narrow boiling range high purity isoparaffin solvent, commercially available from ExxonMobil Corporation under the trademark ISOPAR E) were purified with molecular sieves and then introduced into the reaction environment. ISOPAR E and 1-octene were charged to a one gallon (3.79 L) stirred autoclave reactor. The reactor was then heated to the desired temperature and charged with ethylene to reach the desired pressure. If necessary, hydrogen was also added at this time. In a dry box under an inert atmosphere, the catalyst composition was prepared by mixing the desired precatalyst and one or more optional additives as required with additional solvent to obtain a total volume of about 15 mL-20 mL. The activated catalyst mixture was then rapidly injected into the reactor. The reactor pressure and temperature were kept constant by feeding ethylene during the polymerization reaction and cooling the reactor as required. After 10 minutes, the ethylene feed was turned off and the solution was transferred to a resin pot purged with nitrogen. The polymer was thoroughly dried in a vacuum oven and the reactor was thoroughly rinsed with hot ISOPAR E between each polymerization run.

[0176] Procedure for polymerization in continuous reactor A

[0177] Raw materials (ethylene, 1-octene) and process solvents (narrow boiling range high purity isoparaffin solvents, commercially available from ExxonMobil Corporation under the trademark Isopar E) are purified with molecular sieves and subsequently introduced into the reaction environment. Hydrogen is supplied in a pressurized cylinder at a high purity level and is not further purified. The reactor monomer feed (ethylene) stream is pressurized to a reaction pressure higher than 525psig via a mechanical compressor. Solvent and comonomer (1-octene) feeds are pressurized to a reaction pressure exceeding 525psig via a mechanical positive displacement pump. MMAO-3A commercially available from Nouryon is used as an impurity scavenger. Each catalyst component (primary catalyst or cocatalyst) is manually diluted in batches to a specified component concentration with a purified solvent (Isopar E) and pressurized to a reaction pressure exceeding 525psig. The cocatalyst is [HNMe (C 18 H 37 )2][B(C6F5)4], and is used in a 1.2 molar ratio relative to the metal-ligand complex of formula (I), formula (V) or relative to the sum of the complexes of formula (I) and formula (V). All reaction feed flows are measured with mass flow meters and independently controlled with computer automated valve control systems.

[0178] Continuous solution polymerization is carried out in one or more of a 5 liter (L) continuously stirred tank reactor (CSTR), a 5.7L CSTR and / or a plug flow reactor. The CSTR reactor independently controls all fresh solvent, monomer, comonomer, hydrogen and catalyst component feeds. The plug flow reactor has independent control of the catalyst component feed. The temperature of the combined solvent, monomer, comonomer and hydrogen fed to the reactor is controlled at any temperature between 5°C and 50°C, and is typically 25°C. The fresh comonomer feed of the polymerization reactor is fed together with the solvent feed. The fresh solvent feed is usually controlled with each injector receiving half of the total fresh feed mass flow rate. The cocatalyst is fed based on a calculated value of a specified molar ratio (1.2 molar equivalents) with the primary catalyst. Close to each fresh injection position, a static mixing element is used to mix the feed stream with the circulating polymerization reactor contents. The effluent from the polymerization reactor system (containing solvent, monomer, comonomer, hydrogen, catalyst components and molten polymer) leaves and passes through a control valve (responsible for maintaining the pressure of the reactor system at a specified target). As the stream leaves the reactor, it comes into contact with water to stop the reaction. Additionally, various additives, such as antioxidants, can be added at this time. The stream then passes through another set of static mixing elements to evenly disperse the catalyst deactivator and additives.

[0179] After the addition of additives, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components and molten polymer) passes through a heat exchanger to increase the temperature of the stream in preparation for separation of the polymer from other lower boiling reaction components. The stream then enters a secondary separation and de-volatilization system where the polymer is removed from the solvent, hydrogen and unreacted monomer and comonomer. The separated and de-volatilized polymer melt is pumped through a die specially designed for underwater granulation, cut into uniform solid beads, dried and transferred to boxes for storage.

[0180] Procedure for polymerization in continuous reactor B

[0181] Raw materials (ethylene, 1-octene, 1-hexene) and process solvents (narrow boiling range high purity isoparaffin solvent Isopar-E TM , commercially available from ExxonMobil Corporation) with molecular sieve purification, then introduced into the reaction environment. Hydrogen is supplied in a high purity grade in a pressurized cylinder and is not further purified. The reactor monomer feed (ethylene) stream is pressurized to a reaction pressure higher than 725psig via a mechanical compressor. The solvent and comonomer (1-hexene or 1-octene) feed are pressurized to a reaction pressure exceeding 725psig via a mechanical positive displacement pump. MMAO-3A commercially available from Akzo Nobel is used as an impurity scavenger. Each catalyst component (main catalyst cocatalyst) is manually diluted in batches to a specified component concentration with a purified solvent (Isopar E) and is pressurized to a reaction pressure exceeding 725psig. The cocatalyst is [HNMe (C 18 H 37 )2][B(C6F5)4] and was used at a 1.2 molar ratio relative to the primary catalyst. All reaction feed streams were measured with mass flow meters and independently controlled with a computer automated valve control system.

[0182] Continuous solution polymerization is carried out in a 5 liter (L) continuous stirred tank reactor (CSTR). The reactor can independently control all fresh solvent, monomer, comonomer, hydrogen and catalyst component feeds. The temperature of the combined solvent, monomer, comonomer and hydrogen fed to the reactor is controlled at any temperature between 5°C and 50°C, and is usually 25°C. The fresh comonomer feed of the polymerization reactor is fed together with the solvent feed. The fresh solvent feed is usually controlled with each injector receiving half of the total fresh feed mass flow rate. The cocatalyst is fed based on the calculated value of the specified molar ratio (1.2 molar equivalents) with the main catalyst component. Close to each fresh injection position, the feed stream is mixed with the circulating polymerization reactor contents using a static mixing element. The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst component and molten polymer) leaves the first reactor loop and passes through a control valve (responsible for maintaining the pressure of the reactor at a specified target). When the stream leaves the reactor, it contacts water to stop the reaction. In addition, various additives such as antioxidants can be added at this time. The stream then passes through another set of static mixing elements to evenly disperse the catalyst deactivator and additives.

[0183] After the addition of additives, the effluent (containing solvent, monomer, comonomer, hydrogen, catalyst components and molten polymer) passes through a heat exchanger to increase the temperature of the stream, thereby preparing the polymer for separation from other lower boiling reaction components. Subsequently, the stream enters a secondary separation and de-volatilization system, in which the polymer is removed from the solvent, hydrogen and unreacted monomers and comonomers. The separated and devolatilized polymer melt is pumped to a devolatilization extruder. The polymer strands leave the extruder and enter a cooling water bath where the polymer crystallizes and then enters a strand pelletizer for pelletizing.

[0184] Example

[0185] The results of the polymerization reactions of the procatalysts PN-1, PN-2 or PN-3 in combination with BPP-1, BPP-2, BPP-3, BPP-4, BPP-5, BPP-6, BPP-7, BPP-8, BPP-9 or BPP-10 are tabulated and discussed. One or more features of the present disclosure are illustrated according to the following examples:

[0186]

[0187]

[0188] Polymerization conditions: 3.79L (1Gal) batch reactor, 1250g Isopar-E; main catalyst: activator = 1:1.2; activator: ([HNMe(C 18 H 37)2][B(C6F5)4]); 50 equivalents of MMAO-3A; reaction time 10 minutes. 160°C: 60 g 1-octene; ethylene, pressure reached 320 psi. 190°C: 65 g 1-octene; ethylene, pressure reached 410 psi.

[0189] Table 1: Changes in weight average molecular weight when hydrogen is introduced at 160°C

[0190]

[0191]

[0192] Table 2: Changes in weight average molecular weight when hydrogen is introduced at 190°C

[0193]

[0194] Table 3: Polymer compositions produced from PN-1 and BPP-1 at four different hydrogen loadings at 190 °C

[0195] catalyst Hydrogen loading Mn(g / mol) Mw(g / mol) Mz(g / mol) Mw / Mn Mz / Mn C1 PN-1 5mmol 28,100 56,800 111,900 2.0 4.0 C2 BPP-1 5mmol 209,400 509,900 915,700 2.4 4.4 I1 PN-1 / BPP-1 0mmol 142,800 302,400 558,100 2.1 3.9 I2 PN-1 / BPP-1 5mmol 60,300 300,500 788,800 5.0 13.1 I3 PN-1 / BPP-1 20mmol 11,000 85,000 468,700 7.7 42.6 I4 PN-1 / BPP-1 40mmol 5,700 83,400 453,900 14.5 79.0

[0196] Table 4: Polymer compositions produced from PN-1 and BPP-4 at four different hydrogen loadings at 160 °C

[0197] catalyst Hydrogen loading Mn(g / mol) Mw(g / mol) Mz(g / mol) Mw / Mn Mz / Mn C3 PN-1 5mmol 38,600 66,900 107,200 1.7 2.8 C4 BPP-4 5mmol 261,200 496,000 839,600 1.9 3.2 I5 PN-1 / BPP-4 0mmol 268,500 485,800 801,700 1.8 3.0 I6 PN-1 / BPP-4 5mmol 46,500 122,300 350,200 2.6 7.5 I7 PN-1 / BPP-4 20mmol 13,200 63,500 375,500 4.8 28.5 I8 PN-1 / BPP-4 40mmol 6,640 94,900 499,300 14.3 75.2

[0198] Table 5: Polymer compositions produced from PN-1 and BPP-5 at four different hydrogen loadings at 160 °C

[0199] catalyst Hydrogen loading Mn(g / mol) Mw(g / mol) Mz(g / mol) Mw / Mn Mz / Mn C3 PN-1 5mmol 38,600 66,900 107,200 1.7 2.8 C5 BPP-5 5mmol 4,670 692,900 1,346,000 148.5 288.5 I9 PN-1 / BPP-5 0mmol 9,250 816,200 1,990,000 88.2 215.1 I10 PN-1 / BPP-5 5mmol 93,100 512,200 1,229,000 5.5 13.2 I11 PN-1 / BPP-5 20mmol 14,740 225,500 594,300 15.3 40.3 I12 PN-1 / BPP-5 40mmol 8,540 124,700 322,400 14.6 37.8

[0200] Table 6: Polymer compositions produced from PN-1 and BPP-6 at four different hydrogen loadings at 160 °C

[0201] catalyst Hydrogen loading Mn(g / mol) Mw(g / mol) Mz(g / mol) Mw / Mn Mz / Mn C3 PN-1 5mmol 38,600 66,900 107,200 1.7 2.8 C6 BPP-6 5mmol 195,500 722,200 1,411,000 3.7 7.2 I13 PN-1 / BPP-6 0mmol 305,900 647,800 1,203,000 2.1 1.9 I14 PN-1 / BPP-6 5mmol 49,200 206,500 883,000 4.2 18.0 I15 PN-1 / BPP-6 20mmol 15,200 82,100 431,000 5.4 28.4 I16 PN-1 / BPP-6 40mmol 11,700 108,600 334,000 9.3 28.5

[0202] Table 7: Polymer compositions produced from PN-1 and BPP-7 at four different hydrogen loadings at 160 °C

[0203] catalyst Hydrogen loading Mn(g / mol) Mw(g / mol) Mz(g / mol) Mw / Mn Mz / Mn C3 PN-1 5mmol 38,600 66,900 107,200 1.7 2.8 C7 BPP-7 5mmol 193,300 661,100 1,378,000 3.4 7.1 I17 PN-1 / BPP-7 0mmol 361,100 1,016,000 2,205,000 2.2 6.1 I18 PN-1 / BPP-7 5mmol 40,500 210,500 977,000 5.2 24.1 I19 PN-1 / BPP-7 20mmol 27,000 254,400 687,500 9.4 25.5 I20 PN-1 / BPP-7 40mmol 16,900 165,800 386,400 9.8 22.9

[0204] Table 8: Polymer compositions produced from PN-1 and BPP-8 at 160 °C at three different hydrogen loadings

[0205] catalyst Hydrogen loading Mn(g / mol) Mw(g / mol) Mz(g / mol) Mw / Mn Mz / Mn C8 PN-1 10mmol 24,200 47,210 91,340 2.2 3.8 C9 BPP-8 10mmol 101,200 589,700 1,267,000 5.8 12.5 I21 PN-1 / BPP-8 10mmol 23,070 243,900 1,090,000 7.1 19.1 I22 PN-1 / BPP-8 20mmol 34,380 418,600 931,800 12.2 27.1 I23 PN-1 / BPP-8 40mmol 19,800 241,700 556,800 12.2 28.1

[0206] Table 9: Polymer compositions produced from PN-1 and BPP-8 at 190 °C at four different hydrogen loadings

[0207] catalyst Hydrogen loading Mn(g / mol) Mw(g / mol) Mz(g / mol) Mw / Mn Mz / Mn C1 PN-1 5mmol 28,100 56,800 111,900 2.0 4.0 C10 BPP-8 5mmol 111,800 517,400 1,001,000 4.6 9.0 I24 PN-1 / BPP-8 0mmol 58,410 280,300 684,800 4.8 11.7 I25 PN-1 / BPP-8 5mmol 46,450 193,600 660,600 4.2 14.2 I26 PN-1 / BPP-8 20mmol 15,900 158,200 507,600 9.9 31.9 I27 PN-1 / BPP-8 40mmol 11,630 163,200 456,600 14.0 39.3

[0208] Some BPP catalysts have larger Mz / Mn values, such as in C9 and C10. For example, BPP-8 produces polymers with a low molecular weight tail that results in a larger Mz / Mn, as listed in C10. However, when this catalyst is combined with the PN catalysts shown in the results for I21-I23 and I24-I27, an increase in Mz / Mn relative to the starting value is still observed.

[0209] Table 10: Polymer compositions produced from PN-1 and BPP-9 at four different hydrogen loadings at 160 °C

[0210] catalyst Hydrogen loading Mn(g / mol) Mw(g / mol) Mz(g / mol) Mw / Mn Mz / Mn C11 PN-1 5mmol 32,940 73,180 119,100 2.2 3.6 C12 BPP-9 5mmol 234,400 574,000 1,178,000 2.5 5.0 I28 PN-1 / BPP-9 0mmol 207,600 531,900 1,142,000 2.6 5.5 I29 PN-1 / BPP-9 5mmol 25,800 97,500 380,700 3.9 14.7 I30 PN-1 / BPP-9 20mmol 10,180 82,600 477,200 5.8 46.9 I31 PN-1 / BPP-9 40mmol 5,960 87,700 475,900 5.4 79.8

[0211] Table 11: Polymer combinations produced from PN-1 and BPP-10 at two different hydrogen loadings at 160 °C thing

[0212] catalyst Hydrogen loading Mn(g / mol) Mw(g / mol) Mz(g / mol) Mw / Mn Mz / Mn C17 PN-1 5mmol 32,940 73,180 119,100 2.2 3.6 C20 BPP-10 5mmol 106,500 215,700 376,800 2.0 3.5 C21 PN-1 / BPP-10 0mmol 146,000 339,700 687,700 2.3 4.7 I25 PN-1 / BPP-10 20mmol 13,400 51,100 199,900 3.8 15.0

[0213] Table 12: Polymer compositions produced from PN-3 and BPP-1 at four different hydrogen loadings at 160 °C

[0214] catalyst Hydrogen loading Mn(g / mol) Mw(g / mol) Mz(g / mol) Mw / Mn Mz / Mn C11 PN-3 5mmol 22,550 55,400 118,900 2.5 5.2 C12 BPP-1 5mmol 226,600 719,400 1,435,000 3.2 6.3 I32 PN-3 / BPP-1 0mmol 93,230 320,400 763,000 3.4 8.2 I33 PN-3 / BPP-1 5mmol 23,860 141,300 734,800 5.9 30.8 C11 PN-3 / BPP-1 20mmol 11,170 337,500 1,078,000 30.2 96.5 C12 PN-3 / BPP-1 40mmol 7,570 295,200 847,700 38.9 112.0

[0215] Table 13: Polymer compositions produced from PN-3 and BPP-1 at four different hydrogen loadings at 190 °C

[0216] catalyst Hydrogen loading Mn(g / mol) Mw(g / mol) Mz(g / mol) Mw / Mn Mz / Mn C15 PN-3 5mmol 20,140 54,900 135,100 2.7 6.7 C2 BPP-1 5mmol 209,400 509,900 915,700 2.4 4.4 I38 PN-3 / BPP-1 0mmol 74,900 220,200 479,000 2.9 6.4 I39 PN-3 / BPP-1 5mmol 24,340 129,400 514,700 5.3 21.1 I41 PN-3 / BPP-1 20mmol 8,460 183,600 656,300 21.7 77.6 I41 PN-3 / BPP-1 40mmol 7,920 236,300 609,500 29.9 77.0

[0217] Table 14: Polymer compositions produced from PN-3 and BPP-7 at four different hydrogen loadings at 160 °C

[0218]

[0219]

[0220] Table 15 Polymer compositions produced from PN-3 and BPP-7 at four different hydrogen loadings at 190 °C

[0221] catalyst Hydrogen loading Mn(g / mol) Mw(g / mol) Mz(g / mol) Mw / Mn Mz / Mn C15 PN-3 5mmol 20,140 54,900 135,100 2.7 6.7 C15 BPP-7 5mmol 126,700 385,400 724,800 3.0 5.7 I46 PN-3 / BPP-7 0mmol 89,720 262,100 581,000 2.9 6.5 I47 PN-3 / BPP-7 5mmol 25,550 120,900 437,100 4.7 17.1 I48 PN-3 / BPP-7 20mmol 11,000 130,200 366,200 11.8 33.3 I49 PN-3 / BPP-7 40mmol 7,520 91,200 226,900 12.1 30.2

[0222] Table 16 Reactor and feed conditions for producing Comparative Examples C16-C21 and Inventive Examples I50-I57

[0223]

[0224]

[0225] Table 17: PN-1 and BPP-7, PN-1 and BPP-1, PN-1 and BPP-6 in dual reactor and single reactor units and polymer compositions produced by PN-1 and BPP-11 .

[0226]

[0227] Table 18: Chain transfer constants to hydrogen (cH2) for selected catalysts at 160°C

[0228]

[0229]

[0230] *Calculated at 190°C

[0231] Figure 3GPC traces of polyethylene produced by dual catalysts with PN-1 and BPP-1 are shown. As the amount of hydrogen increases, the molecular weight of the polyethylene produced separates into two distinct peaks. Changes in hydrogen levels significantly affect the molecular weight of PE produced by PN, but the MW of PE produced by BPP-1 remains largely unchanged. Under 0H2, the molecular weight of PE produced by PN-1 is very similar and overlapping with that of PE produced by BPP-1. However, when the H2 level is increased from 5mmol to 20mmol and then to 40mmol, the MW of PE produced by PN-1 decreases significantly, while the MW of PE produced by BPP-1 remains essentially unchanged, resulting in Figure 3 Double peaks in the GPC trace.

[0232] The inherent difference in comonomer incorporation between the PN-1 catalyst and the BPP-1 catalyst results in resins produced by the dual catalysts having a distinct density distribution between low molecular weight segment polyethylene and higher molecular weight segment polyethylene, such as Figure 4 shown. Figure 4 The lower molecular weight segmented polyethylene shown in has a lower level of comonomer incorporation (about 3 wt %) than the high molecular weight segmented polyethylene (about 18 wt %) due to the different catalysts that produce the various portions of the material.

[0233] Figure 5 and Figure 6 Similar behavior between other BPP catalysts and phosphinimine catalysts is shown. For example, Figure 5 and Figure 6 GPC data for the PN-1 / BPP-2 catalyst pair are shown. These GPC curves are similar to those above Figure 3 and Figure 4 GPC data for the PN-1 / BPP-1 catalyst pair shown in Figure 2. Here we see the same trend, where the molecular weights of the polymers produced by PN-1 and BPP-2 are similar in the absence of hydrogen, but when hydrogen is introduced, the molecular weight of the polyethylene produced by PN-1 decreases significantly, while the molecular weight of the PE produced by BPP-2 does not change much. Figure 8 , Fig. 9 and Fig.10 showed a similar trend.

Claims

1. A method for producing polyolefins, the method comprising reacting ethylene and optionally one or more olefin monomers in one reactor or multiple reactors in the presence of a catalyst system and optionally hydrogen; the catalyst comprising two or more catalysts, wherein at least one catalyst is derived from a bisphenylphenoxy procatalyst according to formula (I), and wherein at least one catalyst is derived from a phosphinimine procatalyst according to formula (V): in, In formula (I): M1 is titanium, zirconium, hafnium, scandium or yttrium; Each X is independently selected from (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, -CH2Si(R C ) 3-Q (OR C ) Q 、-Si(R C ) 3-Q (OR C ) Q 、-OSi(R C ) 3-Q (OR C ) Q 、-CH2Ge(R C ) 3-Q (OR C ) Q , -Ge(R C ) 3-Q (OR C ) Q 、-P(R C ) 2-W (OR C ) W 、-P(O)(R C ) 2-W (OR C ) W 、-N(R C )2、-NH(R C )、-N(Si(R C )3)2、-NR C Si(R C )3, -NHSi(R C )3. -OR C 、-SR C , -NO2, -CN, -CF3, -OCF3, -S(O)R C 、-S(O)2R C 、-OS(O)2R C 、-N=C(R C )2, -N=CH(R C )、-N=CH2、-N=P(R C )3. -OC(O)R C 、-C(O)OR C 、-N(R C )C(O)R C 、-N(R C )C(O)H、-NHC(O)R C 、-C(O)N(R C )2. -C(O)NHR C 、-C(O)NH2、halogen、B(R Y )4、Al(R Y )4 or Ga(R Y )4 or a monodentate ligand of hydrogen, wherein each R C Independently (C1-C 30 )alkyl or (C1-C 30 ) heteroalkyl, and each Q is 0, 1, 2 or 3, and each W is 0, 1 or 2; each R Y =–H, (C1-C 30 ) a hydrocarbon group or a halogen atom, wherein two X ligands can be linked to form a metal cyclize ring Each Y is independently a Lewis base; optionally, X and Y can be linked to form a ring and a bidentate ligand. m is 0, 1 or 2; n is 0, 1, and 2; R 1 and R 16 Independently selected from the group consisting of: –H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-, -N=C(R C 2. R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)-, halogen, a group having the formula (II), a group having the formula (III) and a group having the formula (IV): Where R 31-35 , R 41-48 and R 51-59 Each of the following is independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2.-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R N )-、(R C )2NC(O)- or halogen; R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 and R 15 are independently selected from -H, (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, -Si(R C )3, -Ge(R C )3. -P(R P )2、-N(R N )2-OR C 、-SR C 、-NO2、-CN、-CF3、R C S(O)-、R C S(O)2-、(R C )2C=N-、R C C(O)O-、R C OC(O)-、R C C(O)N(R)-、(R C )2NC(O)- and halogen; L is (C1-C 40 )alkylene or (C2-C 40 )heteroalkylene; and Each R in formula (I) C , R P and R N Independently (C1-C 30 ) hydrocarbon group, (C1-C 30 )heteroalkyl or -H; and: M2 is titanium, zirconium or hafnium; R 61 , R 62 , R 63 , R 64 and R 65 are independently H, (C1-C 50 ) hydrocarbon group, (C1-C 50 ) heteroalkyl, wherein R 62 , R 63 , R 64 and R 65 Any of are optionally linked to form a ring or polycyclic structure; R 66 , R 67 and R 68 Independently (C1-C 20 ) hydrocarbon group, (C1-C 20 ) heteroalkyl, (C6-C 30 ) aryl, (C5-C 30 ) heteroaryl, wherein R 66 , R 67 and R 68 Two of are optionally linked to form a ring.

2. The polymerization process according to claim 1, wherein the ratio of the hydrogen chain transfer constants of the procatalyst of formula (V) to the procatalyst of formula (I) is greater than or equal to 3 at 160°C.

3. The polymerization process according to claim 1, wherein R 1 and R 16 At least one of them is a group having formula (II).

4. The polymerization process according to claim 1, wherein R 1 and R 16 At least one of them is a group having formula (III).

5. The polymerization process according to any one of the preceding claims, wherein R 8 and R 9 are independently (C1-C4)alkyl.

6. The polymerization process according to any one of the preceding claims, wherein R 3 and R 14 is (C1-C 20 )alkyl.

7. The polymerization process according to any one of the preceding claims, wherein R 3 and R 14 It is tert-octyl or n-octyl.

8. The polymerization process according to any one of the preceding claims, wherein L is selected from -CH2(CH2) m CH2-、-CH2Si(R C )(R D )CH2-、-CH2Ge(R C )(R D )CH2-, -CH2(CH3)CH2CH*(CH3), bis(methylene)cyclohexane-1,2-diyl; -CH2CH(R C )CH2-、-CH2C(R C )2CH2-, where each R in L C is (C1-C 20 ) hydrocarbon group, and R in L D is (C1-C 20 ) hydrocarbon group.

9. The polymerization process according to any one of the preceding claims, wherein R 66 , R 67 and R 68 Independently (C1-C 20 )alkyl.

10. The polymerization process according to any one of the preceding claims, wherein R 66 , R 67 , R 68 are independently selected from the group consisting of methyl, ethyl, 1-propyl, 2-propyl (also known as isopropyl), 1,1-dimethylethyl (also known as tert-butyl), cyclopentyl, cyclohexyl, 1-butyl, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl, heptyl, n-octyl, tert-octyl (also known as 2,4,4-trimethylpent-2-yl), nonyl and decyl.

11. The polymerization process according to any one of the preceding claims, wherein R 61 , R 62 , R 63 , R 64 and R 65 is H or (C1-C3) alkyl; or R 61 , R 62 and R 64 is (C1-C3) alkyl, and R 63 , R 65 H, or R 61 and R 63 is (C1-C3) alkyl, and R 62 , R 64 , R 65 For H.

12. The polymerization process according to any one of claims 1 to 11, wherein R 61 , R 62 , R 63 , R 64 and R 65 One of the compounds is selected from -OMe and -NMe2.

13. The polymerization process according to any one of claims 1 to 10, wherein: (A)R 61 and R 62 connected to form a ring and optionally one or more R S Substitution, where R S Selected from the group consisting of: (C1-C 30 ) a hydrocarbon group; or (B)R 63 and R 64 connected to form a ring and optionally one or more R S Substitution, where R S Selected from the group consisting of: (C1-C 30 ) a hydrocarbon group; or (C) both (A) and (B); wherein (A), (B) or (C) and the cyclopentadienyl group of formula (V) has a structure selected from the group consisting of:

14. The polymerization process according to any one of the preceding claims, wherein the polymerization process is a solution polymerization process.

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