WO2013077944A1 - Composés catalyseurs amidinate, leur procédé d'utilisation et polymères ainsi produits - Google Patents

Composés catalyseurs amidinate, leur procédé d'utilisation et polymères ainsi produits Download PDF

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WO2013077944A1
WO2013077944A1 PCT/US2012/059195 US2012059195W WO2013077944A1 WO 2013077944 A1 WO2013077944 A1 WO 2013077944A1 US 2012059195 W US2012059195 W US 2012059195W WO 2013077944 A1 WO2013077944 A1 WO 2013077944A1
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group
substituted
independently
borate
chain transfer
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PCT/US2012/059195
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John R. Hagadorn
Ian C. STEWART
Matthew S. Bedoya
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Exxonmobil Chemical Patents Inc.
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Publication of WO2013077944A1 publication Critical patent/WO2013077944A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
    • C08F2410/01—Additive used together with the catalyst, excluding compounds containing Al or B

Definitions

  • This invention relates to amidinate catalyst compositions and their use in olefin polymerization processes to produce ethylene polymers.
  • ethylene/propylene polymerizations using: 1) diethylzinc; 2) triethylaluminum, tri-isobutylaluminum, or tri-n-propuyl aluminum; and 3) [(C 5 Me 5 )Hf(Me)[N(Et)C(Me)N(Et)]] [B(C 6 F 5 ) 4 ] are disclosed in Angew. Chem. Int. Ed. 2010, 49, pp. 1768-1772.
  • Zhang, W. and Sita, L. R., J. Am. Chem. Soc. 2008, 130, pp. 442-443 discloses a catalyst system that uses "living coordinative chain-transfer polymerization" to produce very narrow molecular weight distribution atactic PP, e.g., a catalyst system featuring an anionic cyclopentadienyl (or substituted cyclopentadienyl) donor ligand.
  • WO 2009/061499 Al discloses a process for the preparation of polyolefins via living coordinative chain transfer polymerization using a catalyst system featuring an anionic cyclopentadienyl (or substituted cyclopentadienyl) donor ligands.
  • WO 2007/035485 Al discloses catalytic "olefin diblock copolymers" produced using chain transfer in series reactors not using catalyst systems.
  • U.S. Patent No. 6,262, 198 discloses amidinato metal complexes in combination with an activator, but absent chain transfer agent, for the polymerization of olefins.
  • Examples 1-3 disclose the combination of bis[N,N'-bis(trimethylsilyl)benzamidinato metal dichloride (where the metal is Zr or Ti) with methylalumoxane at ratios of from 1000: 1 to 5000: 1 to produce polyethylene having an Mw/Mn of from 27 to 98.
  • WO 2005/092935 discloses magnesium adducts in combination with amidinates, but absent activator and chain transfer agent.
  • Run Number 3 on Table 2 produced a polyethylene having an Mw of 602,000 and an Mw/Mn of 2.3.
  • Group 4 bisamido catalysts are disclosed in U.S. Patent No. 5,318,935. Bidentate bisarylamido catalysts are disclosed by D. H. McConville, et al, Macromolecules 1996, 29, pp. 5241-5243.
  • U.S. Patent No. 6,891,006 discloses yttrium based catalyst complexes used to polymerize ethylene that obtains low Mw/Mns.
  • U.S. Patent No. 5,502, 128 discloses polymerization of ethylene with methylalumoxane and (N,N'-dimethyl-p-toluamidinate)titanium (IV) trichloride dimer or N,N'-bis(trimethylsilyl)benzamidinate titanium (IV) triisopropoxide, but absent chain transfer agent.
  • group 4 transition metal (such as zirconium) amidinate catalysts undergo rapid and reversible chain transfer to aluminum (such as tri-n- octylaluminum).
  • aluminum such as tri-n- octylaluminum
  • the reversibility of these chain transfer processes can also be modulated by addition of a chain transfer agent, resulting in production of bi- or multi-modal molecular weight distribution polymers.
  • This invention relates to a method to polymerize olefins comprising: 1) contacting, at the transition temperature or higher, olefins with an amidinate catalyst compound, a chain transfer agent, and a non-coordinating anion activator, where the molar ratio of the chain transfer agent(s) to amidinate catalyst compound(s) is 5: 1 or more, and where the amidinate catalyst compound is represented by the formula:
  • This also invention relates to a method to polymerize olefins comprising contacting, at the transition temperature or higher, olefins (such as C2 to C40 olefins) with an amidinate catalyst compound, a chain transfer agent, and a non-coordinating anion activator, where the molar ratio of the chain transfer agent(s) to amidinate catalyst compound(s) is 5 : 1 or more, and where the amidinate catalyst com ound is preferably represented by the formula:
  • M is Group 4 metal
  • R 1 is hydrogen, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group having 1 to 40 carbon atoms;
  • R 2 and R 3 are each, independently, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group having 1 to 40 carbon atoms;
  • each L is, independently, a Lewis base, provided that each L is not a cyclopentadienyl group; each A is, independently, any anionic ligand, provided that each L is not a cyclopentadienyl group; x is 1, 2, or 3;
  • y is 0, 1, 2, or 3;
  • z 0, 1, 2, or 3;
  • x + y is equal to the coordination number of M, preferably 3 or 4;
  • This invention also relates to new amidinate catalyst compounds represented by the formula:
  • M is Group 4 metal
  • R 1 is a substituted or unsubstituted tolyl or benzyl group having 7 to 40 carbon atoms, preferably a substituted tolyl, benzyl (such as naphthyl);
  • R 2 and R 3 are each, independently, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group having 1 to 40 (preferably 3 to 40) carbon atoms;
  • each L is, independently, a Lewis base, provided that each L is not a cyclopentadienyl group; each A is, independently, any anionic ligand, provided that each A is not a cyclopentadienyl group;
  • x is 1, 2, or 3;
  • y is 0, 1, 2, or 3;
  • z 0, 1, 2, or 3;
  • x + y is equal to the coordination number of M, preferably 3 or 4.
  • This invention also relates to a method to obtain a polymer having a multimodal (preferably bimodal) molecular weight distribution comprising contacting olefins (such as C2 to C40 olefins), at a temperature below the transition temperature, with an amidinate catalyst compound, at least one chain transfer agent, and a non-coordinating anion activator, where the molar ratio of the chain transfer agent(s) to amidinate catalyst compound(s) is 5: 1 or more, and where the amidinate catal st compound is preferably represented by the formula:
  • M is Group 4 metal
  • R 1 is hydrogen, or a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group having 1 to 40 carbon atoms;
  • R 2 and R 3 are each, independently, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group having 1 to 40 (preferably 3 to 40) carbon atoms;
  • each L is, independently, a Lewis base, provided that each L is not a cyclopentadienyl group; each A is, independently, any anionic ligand, provided that each A is not a cyclopentadienyl group;
  • x is 1, 2, or 3;
  • y is 0, 1, 2, or 3;
  • z 0, 1, 2, or 3;
  • x + y is equal to the coordination number of M, preferably 3 or 4;
  • This invention also relates to metallated polymers, preferably represented by the formula ⁇ 20 3 or M 2 R 20 2 , where R 20 is a polyolefin having an Mn of 50,000 g/mol or more, M 1 is a group 13 atom, and M 2 is a group 12 atom.
  • Figure 1 is a plot of (nanograms of polymer / Mn of polymer) vs. nanomols of A10ct3 using data from Runs 2-7 of Table 3.
  • Figure 2 is an overlay of GPC traces showing the effect of increasing Od ⁇ Al on
  • Figure 3 is an overlay of GPC traces showing the effect of increasing Od ⁇ Al on
  • Figure 4 is an overlay of Overlay of GPC traces showing the effect of increasing Oct3Al on Catalyst 2/NCAl in the presence of Et2Zn.
  • the tallest trace (on the right) is Experiment 3
  • the far left trace is Experiment 11
  • the remaining trace is Experiment 8 from Table 5.
  • Figure 5 is an overlay of GPC traces showing the effect of increasing Od ⁇ Al on Catalyst 1/NCAl.
  • the tallest trace on the left is Experiment 10
  • the shortest trace on the left is Experiment 7
  • the trace in the middle is Experiment 2 from Table 5.
  • Figure 6 is an overlay of GPC traces showing the effect of increasing Od ⁇ Al on
  • Figure 7 is an overlay of GPC traces showing the effect of increasing Od ⁇ Al on catalyst 2/NCA2.
  • the tallest peak (on the right) is Experiment 15, the next tallest peak (on the left) is Experiment 20, and the shorter peak in the middle is Experiment 18 from Table 5.
  • Figure 8 is an overlay of GPC traces showing the effect of increasing Od ⁇ Al on Catalyst 2/NCA2 in the presence of Et2Zn.
  • the tallest peak is Experiment 15 and the shorter peak is Experiment 14 from Table 5.
  • Figure 9 is an overlay of GPC traces showing the effect of increasing Od ⁇ Al on Catalyst 1/NCA2.
  • the tallest peak (on the left) is Experiment 21
  • the second tallest peak (on the right) is Experiment 13
  • the third tallest peak (on the left) is Experiment 19
  • the shortest peak on the left is Experiment 16 from Table 5.
  • Figure 10 is an overlay of GPC traces showing the effect of increasing Od ⁇ Al on Catalyst 1/NCA2 in the presence of Et2Zn.
  • the tallest peak (on the left) is Experiment 21
  • the next tallest peak (on the right) is Experiment 14, and the nearly flat trace is Experiment 17 from Table 5.
  • Figure 11 is an overlay of GPC traces showing the effect of increasing Od ⁇ Al on Catalyst 2/NCAl in the presence of Et2Zn.
  • the tallest peak (on the right) is Experiment 22
  • the next tallest peak (on the right) is Experiment 23
  • the shorter bimodal peak is Experiment 25 from Table 5.
  • Figure 12 is an overlay of GPC traces showing the effect of increasing Od ⁇ Al on Catalyst 2/NCAl in the presence of iP ⁇ Zn. In order from right to left, the traces are of Experiments 31, 30, and 29 from Table 5, respectively.
  • Figure 13 is an overlay of GPC traces showing the effect of increasing Od ⁇ Al on Catalyst 1/NCAl in the presence of Et2Zn.
  • the tallest peak (on the right) is Experiment 28, the next tallest peak (on the left) is Experiment 27, and the shorter peak underneath the tallest peak (on the right) is Experiment 26 from Table 5.
  • Figure 14 is an overlay of GPC traces the effect of increasing Od ⁇ Al on 1/NCAl in the presence of iP ⁇ Zn Experiments 32, 33, and 34 from Table 5.
  • the tallest peak (on the right) is Experiment 32
  • the next tallest peak (on the right) is Experiment 34
  • the shortest peak (on the right) is Experiment 33.
  • polyolefin as used herein means an oligomer or polymer of two or more olefin mer units and specifically includes oligomers and polymers as defined below.
  • An "olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • a “mono-olefin” has one double bond, either alpha or internal.
  • An ethylene polymer or oligomer contains at least 50 mol% of ethylene, a propylene polymer or oligomer contains at least 50 mol% of propylene, a butene polymer or oligomer contains at least 50 mol% of butene, and so on.
  • a polymer or copolymer when referred to as comprising an olefin (such as ethylene), the olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • a copolymer when a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
  • a "polymer” "polymer” has two or more of the same or different mer units.
  • a “homopolymer” is a polymer having mer units that are the same.
  • a “copolymer” is a polymer having two or more mer units that are different from each other.
  • a “terpolymer” is a polymer having three mer units that are different from each other.
  • the term “different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically.
  • An oligomer is typically a polymer having a low molecular weight (such as Mn of less than 25,000 g/mol, preferably less than 2,500 g/mol) or a low number of mer units (such as 75 mer units or less, typically 50 mer units or less, even 20 mer units or less, even 10 mer units or less).
  • polymer encompasses the terms “copolymer” and “terpolymer;” “terpolymer;” for example, the term “ethylene polymer” includes ethylene copolymers and ethylene terpolymers.
  • Mn is number average molecular weight
  • Mw is weight average molecular weight
  • Mz is z average molecular weight
  • wt% is weight percent
  • mol% is mole percent.
  • Molecular weight distribution (MWD) also referred to as polydispersity, is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol.
  • Me is methyl
  • Et is ethyl
  • Pr is propyl
  • nPr is n-propyl
  • iPr is isopropyl
  • Bu is butyl
  • nBu is normal butyl
  • iBu is isobutyl
  • Oct is octyl
  • Ph is phenyl
  • Bn is benzyl
  • THF or thf is tetrahydrofuran.
  • MAO is methylalumoxane and is defined to have an Mw of 58.06 g/mol.
  • substituted generally means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom or a heteroatom containing group.
  • methyl cyclopentadiene is a cyclopentadiene (Cp) group substituted with a methyl group
  • ethyl alcohol is an ethyl group substituted with an -OH group.
  • hydrocarbyl radical is defined to be to C 4 Q radicals, that may be linear, branched, or cyclic (aromatic or non-aromatic); and include substituted hydrocarbyl radicals as defined below.
  • Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom has been substituted with a heteroatom or heteroatom containing group, preferably with at least one functional group such as halogen (CI, Br, I, F), NR*2, OR*, SeR*, TeR*, PR*2, AsR*2,
  • R* is, independently, hydrogen or a hydrocarbyl.
  • a “substituted alkyl” or “substituted aryl” group is an alkyl or aryl radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom, a heteroatom containing group, or a linear, branched, or cyclic substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms.
  • a “substituted tolyl or benzyl” is a tolyl or benzyl, where at least one hydrogen has been replaced by a non hydrogen atom, for example, naphthyl is considered a substituted benzyl.
  • silylcarbyl radical silylcarbyl
  • silcarbyl group is defined to be a Q to C 4 Q hydrocarblyl group that may be linear, branched, or cyclic (aromatic or non-aromatic) substituted with at least one Si atom.
  • a "substituted silylcarbyl” group is a silylcarbyl group where at least one hydrogen has been substituted with a non- hydrogen, non-carbon atom.
  • a hydrocarbyl radical substituted with two or more Si atoms is considered a substituted silylcarbyl group.
  • a cyclopentadienyl group is defined to mean an unsubstituted cyclopentadienyl compound or a heteroatom or hydrocarbyl substituted cyclopentadienyl compound.
  • substituted indenes, unsubstituted indenes, substituted fluorenes, and unsubstituted fluorenes are considered to be substituted cyclopentadienyl compounds.
  • multimodal molecular weight distribution or “multimodal GPC trace” is meant that the gel permeation chromatography (GPC) trace has more than one peak or inflection point.
  • An inflection point is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versa).
  • bimodal molecular weight distribution is meant the GPC trace has two peaks or inflection points, e.g., two peaks, one peak and one inflection point, or two inflection points. Unless otherwise stated, the GPC trace (absorbance vs. retention time) is obtained according to the Rapid GPC method described in the examples below.
  • the transition temperature is that temperature where the catalyst system (e.g., the amidinate catalyst compound(s), the activator(s), and the chain transfer agent(s)), first produces polymer having: 1) an Mw (determined by GPC) from A" g/mol to Z' g/mol, where A" is (1/q x (yield of polyolefin in grams / mols of chain transfer agent + mols of transition metal catalyst compound)); and Z' is (1/m x (yield of polyolefin in grams / mols of chain transfer agent + mols of transition metal catalyst compound)), where q is 0.5, and m is 4; and 2) an Mw/Mn of 2.0 or less, where the catalyst system is tested in the polymerization conditions of interest at temperatures varying from 50°C to 140°C at 5°C intervals.
  • the catalyst system e.g., the amidinate catalyst compound(s), the activator(s), and the chain transfer agent(s)
  • a molar ratio of the chain transfer agent(s) to amidinate compound(s) of 25 : 1 is used.
  • q is 1 and m is 3.5, alternately q is 1.5 and m is 3.
  • This invention relates to a method to polymerize olefins comprising contacting olefins (preferably C 2 to C40 olefins, preferably C 2 to C20 alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof) with an amidinate catalyst compound, a chain transfer agent and a non- coordinating anion activator.
  • olefins preferably C 2 to C40 olefins, preferably C 2 to C20 alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof
  • a non coordinating anion activator when activated with a non coordinating anion activator, were found to polymerize ethylene in the presence of trialkyl aluminum (such as A10ct3) to yield polymers of narrow polydispersity.
  • trialkyl aluminum such as A10ct3
  • A10ct3 trialkylaluminum
  • this provides a route to end-aluminated polyethylene which can be used to prepare other end-functionalized derivatives.
  • the herein described catalyst system can enable the production of diblock or multiblock copolymers when employed in either multiple reactors or as components of a mixed catalyst system wherein chain transfer occurs between the catalysts.
  • a chain- transfer catalyst such as a dialkyl zinc, e.g., Et 2 Zn
  • temperatures below the transition temperature bimodal molecular weight distributions are obtained, and can be modulated with increasing chain transfer agent (such as A10ct3) concentration.
  • This invention relates to a method to polymerize olefins comprising:
  • olefins preferably C2 to C40 olefins, preferably C 2 to C20 alpha olefins, preferably olefins selected from the group consisting of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene dodecene, and isomers thereof
  • an amidinate catalyst compound a chain transfer agent, and a non-coordinating anion activator, where the molar ratio of the chain transfer agent(s) to amidinate catalyst compound(s) is 5: 1 or more, (alternately 10: 1 or more, alternately 20: 1 or more, alternately 25:
  • M is Group 4 metal (preferably Hf or Zr); each L is, independently, a Lewis base, provided that each L is not a cyclopentadienyl group; each A is, independently, any anionic ligand, provided that each A is not a cyclopentadienyl group; x is 1, 2, or 3; y is 0, 1, 2, or 3; z is 0, 1, 2, or 3; where x + y is equal to the coordination number of M, preferably 3 or 4; and 2) obtaining polymer having an Mw (determined by GPC) of 500,000 g/mol or less (preferably 450,000 g/mol or less, preferably 400,000 g/mol or less), Mw/Mn of 1.5 or less (alternately 1.4 or less, alternately 1.3 or less), and an Mn (determined by GPC) of from A' g/mol to Z g/mol, where A' is (1/q x (yield of polyolefin in grams / mols of chain transfer agent + mols
  • This invention also relates to a method to polymerize olefins comprising:
  • olefins preferably C2 to C40 olefins, preferably C2 to C20 alpha olefins, preferably olefins selected from the group consisting of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof
  • an amidinate catalyst compound a chain transfer agent, and a non-coordinating anion activator, where the molar ratio of the chain transfer agent(s) to amidinate catalyst compound(s) is 5: 1 or more, (alternately 10: 1 or more, alternately 20: 1 or more, alternately 25:
  • M is Group 4 metal, preferably Ti, Hf, or Zr;
  • R 1 is hydrogen, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group (preferably a hydrocarbyl group or substituted hydrocarbyl group) having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms;
  • R 2 and R 3 are each, independently, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group (preferably a hydrocarbyl group or substituted hydrocarbyl group) having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms; each L is, independently, a Lewis base, provided that each L is not a cyclopentadienyl group; each A is, independently, any anionic ligand, provided that each L is not a cyclopentadienyl group;
  • x is 1, 2, or 3;
  • y is 0, 1, 2, or 3;
  • z 0, 1, 2, or 3;
  • x + y is equal to the coordination number of M, preferably 3 or 4;
  • This invention also relates to a method to obtain a polymer having a multimodal
  • olefins preferably C2 to C40 olefins, preferably C2 to C20 alpha olefins, preferably olefins selected from the group consisting of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof
  • an amidinate catalyst compound a chain transfer agent, and a non-coordinating anion activator, where the molar ratio of the chain transfer agent(s) to amidinate catalyst compound(s) is 5: 1 or more, (alternately 10: 1 or more, alternately 20: 1 or more, alternately 25
  • M is Group 4 metal, preferably Hf, Zr, or Ti;
  • R 1 is hydrogen, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group (preferably a hydrocarbyl group or substituted hydrocarbyl group) having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms;
  • R 2 and R 3 are each, independently, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group (preferably a hydrocarbyl group or substituted hydrocarbyl group) having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms; each L is, independently, a Lewis base, provided that each L is not a cyclopentadienyl group; each A is, independently, any anionic ligand, provided that each A is not a cyclopentadienyl group;
  • x is 1, 2, or 3;
  • y is 0, 1, 2, or 3;
  • z 0, 1, 2, or 3;
  • x + y is equal to the coordination number of M, preferably 3 or 4;
  • this invention relates to a process to polymerize olefins comprising contacting the olefins with one or more chain transfer agents, one or more activators and one or more amidinate catalyst compounds, preferably represented by the formula:
  • M is Group 4 metal, preferably Hf, Zr, and/or Ti, preferably Hf or Zr;
  • R 1 is a hydrogen, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group (preferably a hydrocarbyl group or substituted hydrocarbyl group) having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms), preferably an alkyl, substituted alkyl, aryl, or substituted aryl group having 1 to 40 (preferably 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms), preferably R 1 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl (including isobutyl, sec -butyl, tert-butyl, and n- butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl
  • R 2 and R 3 are each, independently, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group (preferably a hydrocarbyl group or substituted hydrocarbyl group) having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms), preferably an alkyl, substituted alkyl, aryl, or substituted aryl group having 1 to 40 (preferably 1 to 20 carbon atoms, preferably 2 to 12 carbon atoms), preferably selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl (including isobutyl, sec -butyl, tert-butyl, and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl
  • each A is, independently, any anionic ligand, preferably a hydrocarbyl radical, a halogen (preferably chlorine), a hydride, an amide, an alkoxide, a sulfide, an alkyl sulfonate, a phosphide, an amine, a phosphine, an ether, or a combination thereof or two A groups may be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms, preferably each A is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, amines, phosphines, ethers, and a combination thereof, (two A's may form a part of a fused ring or
  • x is 1, 2, or 3, preferably 1 or 2
  • y is 0, 1, 2, or 3, preferably 2 or 3;
  • z is 0, 1, 2, or 3, preferably 0, 1, or 2, preferably 0 or 1, preferably 0;
  • x + y is equal to the oxidation number of M, preferably 3 or 4, preferably 4.
  • R 1 , R 2 , and R 3 may be as described for the equivalent positions at column 3, lines 20-44 of U.S. Patent No. 6,262, 198.
  • the two aminate ligands may be linked to one another by the radicals R 1 , R 2 , and/or R 3 .
  • Suitable bridge members are C C ⁇ -alkylene bridges or diorganosilyl bridges, for example dimethylsilyl, diethylsilyl or diphenylsilyl, or mixed C C ⁇ -alkylene/diorganosilyl bridges, for example, — CH2 ⁇ Si(CH3)2 ⁇ CH 2 — or - Si(CH 3 ) 2 -CH 2 -Si(CH 3 ) 2 -.
  • M is Zr and each A is benzyl; Y is 4-x, and x is 1 or 2. In a preferred embodiment, M is Zr and each A is methyl; Y is 4-x, and x is 1 or 2.
  • M is Hf and each A is methyl; Y is 4-x, and x is 1 or 2.
  • M is Hf and each A is benzyl; Y is 4-x, and x is 1 or 2.
  • M is Ti and each A is benzyl; Y is 4-x, and x is 1 or 2.
  • M is Ti and each A is chloride; Y is 4-x, and x is 1 or 2. In a preferred embodiment, M is Ti and each A is methyl; Y is 4-x, and x is 1 or 2.
  • This invention also relates to new amidinate catalyst compounds represented by the formula:
  • R 1 is a substituted or unsubstituted tolyl or benzyl group having 7 to 40 carbon atoms (preferably 7 to 20 carbon atoms), preferably a substituted tolyl or benzyl, preferably R 1 is selected from the group consisting of mesityl, adamantyl, benzyl, tolyl, naphthyl, chlorophenyl, phenol, substituted phenol, CH 2 C(CH 3 )3, 2,6-diethylphenyl, 2,6- diisopropylphenyl, 2-isopropylphenyl, 2-ethyl-6-methylphenyl, 3,5-ditertbutylphenyl, 2- tertbutylphenyl, 2,3,4,5,6-pentamethylphenyl, and substituted analogs and isomers thereof; R 2 and R 3 are each, independently, a hydrocarbyl group, a silylcarbyl group, a substituted silylcar
  • each L is, independently, a neutral Lewis base, such as tetrahydrofuran, dialkyl ether (such as diethylether), dioxane, pyridine, pyrrole, tertiary amines, and the like; provided that each L is not a cyclopentadienyl group;
  • a neutral Lewis base such as tetrahydrofuran, dialkyl ether (such as diethylether), dioxane, pyridine, pyrrole, tertiary amines, and the like
  • each A is, independently, any anionic ligand, preferably a hydrocarbyl radical, a halogen (preferably chlorine), a hydride, an amide, an alkoxide, a sulfide, an alkyl sulfonate, a phosphide, an amine, a phosphine, an ether or a combination thereof, or two A groups may be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms, preferably each A is, independently, selected from the group consisting of hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides, amides, alkoxides, sulfides, phosphides, halides, amines, phosphines, ethers, and a combination thereof, (two A's may form a part of a fused ring or
  • y is 0, 1, 2, or 3, preferably 2 or 3;
  • z is 0, 1, 2, or 3, preferably 0, 1 or 2, preferably 0 or 1, preferably 0;
  • x + y is equal to the coordination number of M, preferably 3 or 4.
  • the amidinate catalyst compound is one or more of:
  • Amidinate catalysts compounds can typically be prepared by reaction of 1 to 3 molar equivalents of carbodiimide with a transition metal reagent containing reactive metal carbon bonds.
  • a transition metal reagent containing reactive metal carbon bonds For example, the reaction of two equivalents of 1,3-diisopropylcarbodiimide with tetrabenzylzirconium affords bis [N,N'-diisopropylphenylacetamidinate]zirconium(IV) dibenzyl, which has the formula [PhCH 2 ( 'Pr)2]2Zr(CH 2 Ph)2.
  • chain transfer agent is defined to mean a compound that receives a polymeryl fragment from a catalyst compound, except that hydrogen is defined to not be a chain transfer agent for purposes of this invention.
  • Chain transfer agents (CTA's) useful herein include triakyl aluminum compounds and dialkyl zinc compounds (where the alkyl is preferably a Q to C40 alkyl group, preferably a C2 to C20 alkyl group, preferably a C2 to C ⁇ alkyl group, preferably a C2 to Cg group, such as methyl, ethyl, propyl (including isopropyl and n-propyl), butyl (including n-butyl, sec -butyl, and iso-butyl) pentyl, hexyl, heptyl, octyl, and isomers an analogs thereof).
  • trialkyl aluminum compounds and dialkyl zinc compounds having from 1 to 8 carbons in each alkyl group such as triethylaluminum (TEAL), tri(i-propyl) aluminum, tri(i-butyl) aluminum (TIBAL), tri(n-hexyl) aluminum, tri(n-octyl) aluminum (TNOAL), diethyl zinc, diisobutyl zinc, and dioctyl zinc.
  • TEAL triethylaluminum
  • TIBAL tri(i-propyl) aluminum
  • TIBAL tri(i-butyl) aluminum
  • TNOAL tri(n-hexyl) aluminum
  • diethyl zinc diisobutyl zinc
  • diisobutyl zinc dioctyl zinc
  • the dialkyl zinc chain transfer agent is typically present in the reaction at a molar ratio of zinc to transition metal (from the amidinate catalyst compound) of 0.5: 1 or more, preferably from 0.5: 1 to 2000: 1, preferably from 1 : 1 to 1000: 1, preferably from 2: 1 to 800: 1, preferably from 3 : 1 to 700: 1, preferably from 4: 1 to 600: 1.
  • one or more triakyl aluminum compounds and one or more dialkyl zinc compounds are used as the alkyl.
  • the alkyl is preferably a C j to C 4 o alkyl group, preferably a C2 to C20 alkyl group, preferably a C2 to ( 3 ⁇ 4 alkyl group, preferably a C2 to Cg group, such as methyl, ethyl, propyl (including isopropyl and n-propyl), butyl (including n- butyl, sec -butyl and iso-butyl) pentyl, hexyl, heptyl, octyl, and isomers or analogs thereof) are used as the CTA.
  • Preferred combinations include TEAL, TIBAL, and/or TNOAL with Et2Zn, preferably TEAL and Et2Zn, or TIBAL and Et2Zn, or TNOAL and Et2Zn.
  • the trialkyl aluminum and dialkyl zinc compounds are present in the reaction at a molar ratio of Al to Zn of 1 : 1 or more, preferably 2: 1 or more, preferably 5: 1 or more, preferably 10: 1 or more, preferably 15: 1 or more preferably from 1 : 1 to 10,000: 1.
  • dialkyl zinc and trialkyl aluminum chain transfer agents is typically present in the reaction at a molar ratio of aluminum and zinc to transition metal (from the amidinate catalyst compound) of 5: 1 or more, preferably from 10: 1 to 2000: 1, preferably from 20: 1 to 1000: 1, preferably from 25: 1 to 800: 1, preferably from 50: 1 to 700: 1, preferably from 100: 1 to 600: 1.
  • suitable chain transfer agents for use herein include Group 1,
  • Preferred hydrocarbyl groups are alkyl groups, preferably linear or branched, C2 to Cg alkyl groups.
  • the chain transfer agent is typically present in the reaction at a molar ratio of metal of the chain transfer agent to transition metal (from the amidinate catalyst compound) of 5: 1 or more, preferably from 10: 1 to 2000: 1, preferably from 20: 1 to 1000: 1, preferably from 25: 1 to 800: 1, preferably from 50: 1 to 700: 1, preferably from 100: 1 to 600: 1.
  • Additional suitable chain transfer agents include the reaction product or mixture formed by combining the trialkyl aluminum or dialkyl zinc compound, preferably a tr ⁇ C Cg)alkyl aluminum or di(C 1 to Cg)alkyl zinc compound, with less than a stoichiometric quantity (relative to the number of hydrocarbyl groups) of a secondary amine or a hydroxyl compound, especially bis(trimethylsilyl)amine, t-butyl(dimethyl)siloxane, 2- hydroxymethylpyridine, di(n-pentyl) amine, 2,6-di(t-butyl)phenol, ethyl(l-naphthyl)amine, bis(2,3,6,7-dibenzo-l-azacycloheptaneamine), or 2,6-diphenylphenol.
  • the trialkyl aluminum or dialkyl zinc compound preferably a tr ⁇ C Cg)alkyl aluminum or di(C 1 to Cg)alkyl zinc compound
  • the primary reaction products of the foregoing combinations useful in the present invention as chain transfer agents include n-octylaluminum di(bis(trimethylsilyl)amide), i- propylaluminumbis(dimethyl(t-butyl)siloxide), and n-octylaluminum di(pyridinyl-2- methoxide), i-butylaluminum bis(dimethyl(t-butyl)siloxane), i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminum di(pyridine-2-methoxide), i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminum bis(2,6-di-t-butylphenoxide), n-octyla
  • chain transfer agents are typically present in the reaction at a molar ratio of metal of the chain transfer agent to transition metal (from the amidinate catalyst compound) of 5: 1 or more, preferably from 10: 1 to 2000: 1, preferably from 20: 1 to 1000: 1, preferably from 25: 1 to 800: 1, preferably from 50: 1 to 700: 1, preferably from 100: 1 to 600: 1.
  • activator and “activator” are used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation.
  • Non-limiting activators include aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts.
  • Preferred activators typically include ionizing anion precursor compounds that abstract a reactive, ⁇ - bound, metal ligand making the metal complex cationic and providing a charge-balancing noncoordinating or weakly coordinating anion.
  • alumoxane is present at zero mol%, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than 500: 1, preferably less than 300: 1, preferably less than 100: 1, preferably less than 1 : 1.
  • non-coordinating anion or "NCA” (also referred to a as a “non- coordinating anion activator,” or “NCAA”) means an anion which either does not coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base.
  • “Compatible” non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion.
  • Non-coordinating anions useful in accordance with this invention are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization.
  • an ionizing or stoichiometric activator such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, a tris perfluorophenyl boron metalloid precursor, or a tris perfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,459), or combination thereof.
  • neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.
  • neutral stoichiometric activators include tri-substituted boron, tellurium, aluminum, gallium, indium, or mixtures thereof.
  • the three substituent groups are each independently selected from alkyls, alkenyls, halogens, substituted alkyls, aryls, arylhalides, alkoxy, and halides.
  • the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds, and mixtures thereof; preferred are alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and aryl groups having 3 to 20 carbon atoms (including substituted aryls). More preferably, the three groups are alkyls having 1 to 4 carbon groups, phenyl, naphthyl, or mixtures thereof. Even more preferably, the three groups are halogenated, preferably fluorinated, aryl groups.
  • a preferred neutral stoichiometric activator is tris perfluorophenyl boron or tris perfluoronaphthyl boron.
  • Ionic stoichiometric activator compounds may contain an active proton, or some other cation associated with, but not coordinated to, or only loosely coordinated to, the remaining ion of the ionizing compound.
  • Such compounds and the like are described in European Publications EP 0 570 982 A; EP 0 520 732 A; EP 0 495 375 A; EP 0 500 944 Bl; EP 0 277 003 A; EP 0 277 004 A; U.S. Patent Nos. 5, 153, 157; 5, 198,401 ; 5,066,741; 5,206, 197; 5,241,025; 5,384,299; 5,502, 124; and U.S. Patent Application Serial No. 08/285,380, filed August 3, 1994; all of which are herein fully incorporated by reference.
  • Preferred compounds useful as an activator in the process of this invention comprise a cation, which is preferably a Bronsted acid capable of donating a proton, and a compatible non-coordinating anion which anion is relatively large (bulky), capable of stabilizing the active catalyst species (the Group 4 cation) which is formed when the two compounds are combined and said anion will be sufficiently labile to be displaced by olefinic, diolefinic, and acetylenically unsaturated substrates or other neutral Lewis bases, such as ethers, amines, and the like.
  • a cation which is preferably a Bronsted acid capable of donating a proton
  • a compatible non-coordinating anion which anion is relatively large (bulky)
  • the active catalyst species the Group 4 cation
  • EP 0 277,003 Al Two classes of useful compatible non-coordinating anions have been disclosed in EP 0 277,003 Al, and EP 0 277,004 Al : 1) anionic coordination complexes comprising a plurality of lipophilic radicals covalently coordinated to and shielding a central charge- bearing metal or metalloid core; and 2) anions comprising a plurality of boron atoms such as carboranes, metallacarboranes, and boranes.
  • the stoichiometric activators include a cation and an anion component, and are preferably represented by the following formula (II):
  • Z is (L-H) or a reducible Lewis Acid
  • L is an neutral Lewis base
  • H is hydrogen
  • (L- H) + is a Bronsted acid
  • a d" is a non-coordinating anion having the charge d-
  • d is an integer from 1 to 3.
  • the cation component may include Bronsted acids such as protonated Lewis bases capable of protonating a moiety, such as an alkyl or aryl, from the bulky ligand metallocene containing transition metal catalyst precursor, resulting in a cationic transition metal species.
  • Bronsted acids such as protonated Lewis bases capable of protonating a moiety, such as an alkyl or aryl, from the bulky ligand metallocene containing transition metal catalyst precursor, resulting in a cationic transition metal species.
  • the activating cation (L-H) ⁇ "1" is a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, ⁇ , ⁇ -dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N- dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers, such as dimethyl ether diethyl ether, tetrahydrofuran, and dio
  • Z is a reducible Lewis acid
  • Ar is aryl or aryl substituted with a heteroatom, a to C 4 Q hydrocarbyl, or a substituted to C 4 Q hydrocarbyl
  • the reducible Lewis acid is represented by the formula: (Ph 3 C + ), where Ph is phenyl or phenyl substituted with a heteroatom, a Q to C 4 Q hydrocarbyl, or a substituted to C 4 Q hydrocarbyl.
  • the reducible Lewis acid is triphenyl carbenium.
  • each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group.
  • suitable Ad- components also include diboron compounds as disclosed in U.S. Patent No. 5,447,895, which is fully incorporated herein by reference.
  • Suitable anion components also include so called expanded anions, preferably represented by the formula: (Z*J*j) "c d , wherein: Z* is an anion group of from 1 to 50 atoms, not counting hydrogen atoms, further containing two or more Lewis base sites, preferably selected from the group consisting of amide and substituted amide, amidinide and substituted amidinide, dicyanamide, imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, tricycanomethide, tetracycanoborate, puride, 1,2,3-triazolide, substituted 1,2,3-triazolide, 1,2,4-triazolide, substituted 1,2,4-triazolide, pyrimidinide, substituted pyrimidinide, tetraimidazoylborate, and substituted tetraimidazoylborate anions, wherein each substituent, if present, is a C ⁇ o hydrocarbyl,
  • this invention relates to a method to polymerize olefins comprising contacting olefins (preferably ethylene) with an amidinate catalyst compound, a chain transfer agent and a boron containing NCA activator represented by the formula (14):
  • Z is (L-H) or a reducible Lewis acid
  • L is an neutral Lewis base (as further described above)
  • H is hydrogen
  • (L-H) is a Bronsted acid (as further described above)
  • a d_ is a boron containing non-coordinating anion having the charge d " (as further described above); d is 1, 2, or 3.
  • the reducible Lewis acid is represented by the formula: (Ar 3 C + ), where Ar is aryl or aryl substituted with a heteroatom, a Ci to C40 hydrocarbyl, or a substituted Ci to C40 hydrocarbyl, preferably the reducible Lewis acid is represented by the formula: (Ph 3 C + ), where Ph is phenyl or phenyl substituted with a heteroatom, a to C40 hydrocarbyl, or a substituted Ci to C40 hydrocarbyl.
  • Z d + is represented by the formula: (L-H) d + , wherein L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, preferably (L-H) d + is a Bronsted acid selected from ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof.
  • This invention also relates to a method to polymerize olefins comprising contacting olefins (such as ethylene) with an amidinate catalyst compound, a chain transfer agent and an NCA activator represented by the formula (I):
  • R is a monoanionic ligand
  • M** is a Group 13 metal or metalloid
  • ArNHal is a halogenated, nitrogen-containing aromatic ring, polycyclic aromatic ring, or aromatic ring assembly in which two or more rings (or fused ring systems) are joined directly to one another or together
  • n is 0, 1, 2, or 3.
  • the NCA comprising an anion of Formula I also comprises a suitable cation that is essentially non-interfering with the ionic catalyst complexes formed with the transition metal compounds, preferably the cation is as described above.
  • R is selected from the group consisting of substituted or unsubstituted Q to C30 hydrocarbyl aliphatic or aromatic groups, where substituted means that at least one hydrogen on a carbon atom is replaced with a hydrocarbyl, halide, halocarbyl, hydrocarbyl or halocarbyl substituted organometalloid, dialkylamido, alkoxy, aryloxy, alkysulfido, arylsulfido, alkylphosphido, arylphosphide, or other anionic substituent; fluoride; bulky alkoxides, where bulky means C 4 to C20 hydrocarbyl groups; -SR l , -NR 2 2, and—PR 3 2, where each R 1 , R 2 , or R 3 is independently a substituted or unsubstituted hydrocarbyl as defined above; or a Q to C30 hydrocarbyl substituted organometalloid.
  • the NCA also comprises cation comprising a reducible Lewis acid represented by the formula: (Ar 3 C + ), where Ar is aryl or aryl substituted with a heteroatom, a Q to C 4 Q hydrocarbyl, or a substituted Ci to C 4 Q hydrocarbyl, preferably the reducible Lewis acid represented by the formula: (Ph 3 C + ), where Ph is phenyl or phenyl substituted with a heteroatom, a C j to C 4 Q hydrocarbyl, or a substituted C ⁇ to C 4 Q hydrocarbyl.
  • a reducible Lewis acid represented by the formula: (Ar 3 C + ) where Ar is aryl or aryl substituted with a heteroatom, a Q to C 4 Q hydrocarbyl, or a substituted Ci to C 4 Q hydrocarbyl
  • the reducible Lewis acid represented by the formula: (Ph 3 C + ) where Ph is phenyl or phenyl substituted with a heteroatom, a C j
  • the NCA also comprises a cation represented by the formula, (L- H)d wherein L is an neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; and d is 1, 2, or 3, preferably (L-H) d + is a Bronsted acid selected from ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof.
  • Another activator useful herein comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula (16):
  • OX e+ is a cationic oxidizing agent having a charge of e+; e is 1, 2, or 3; d is 1, 2 or 3 ; and A d" is a non-coordinating anion having the charge of d- (as further described above).
  • cationic oxidizing agents include: ferrocenium, hydrocarbyl-substituted ferrocenium, Ag + , or Pb +2 .
  • Preferred embodiments of A d" include tetrakis(pentafluorophenyl)borate.
  • amidinate catalyst compounds and CTA's described herein can be used with Bulky activators.
  • a "Bulky activator” as used herein refers to anionic activators represented by the formula:
  • each R 1 is, independently, a halide, preferably a fluoride
  • each R 2 is, independently, a halide, a to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R a , where R a is a Q to C20 hydrocarbyl or hydrocarbylsilyl group (preferably R2 is a fluoride or a perfluorinated phenyl group);
  • each R 3 is a halide, to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R a , where R a is a Ci to C20 hydrocarbyl or hydrocarbylsilyl group (preferably
  • R3 is a fluoride or a perfluorinated aromatic hydrocarbyl group); wherein R2 and R3 can form one or more saturated or unsaturated, substituted or unsubstituted rings (preferably R2 and R3 form a perfluorinated phenyl ring);
  • L is an neutral Lewis base
  • d is 1, 2, or 3;
  • the anion has a molecular weight of greater than 1020 g/mol
  • Molecular volume is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered “less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered “more bulky” than a substituent with a smaller molecular volume. Molecular volume may be calculated as reported in "A Simple 'Back of the Envelope' Method for Estimating the Densities and Molecular Volumes of Liquids and Solids," Journal of Chemical Education, Vol. 71, No. 11, November 1994, pp. 962-964.
  • MV Molecular volume
  • V s the scaled volume.
  • V s the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the following table of relative volumes. For fused rings, the V s is decreased by 7.5% per fused ring.
  • Exemplary bulky activators useful in catalyst systems herein include: trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammonium tetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate, tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -diethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethyl-(2,4,6- trimethylanilinium) tetrakis(perflu
  • boron compounds which may be used as an activator in the processes of this invention are:
  • tripropylammonium tetraphenylborate tri(n-butyl)ammonium tetraphenylborate, tri(t- butyl)ammonium tetraphenylborate, ⁇ , ⁇ -dimethylanilinium tetraphenylborate, N,N- diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium)
  • tetraphenylborate tropillium tetraphenylborate, triphenylcarbenium tetraphenylborate, triphenylphosphonium tetraphenylborate, triethylsilylium tetraphenylborate,
  • Preferred activators include N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(perfluorobiphenyl)borate, ⁇ , ⁇ -dimethylanilinium tetrakis(3 ,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Ph 3 C + ][B(C 6 F 5 ) 4 -], [Me 3 NH + ][B(C 6 F 5 )4-
  • the activator comprises a triaryl carbonium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3 ,4,6-tetrafluorophenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate).
  • a triaryl carbonium such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2,3 ,4,6
  • the activator comprises one or more of trialkylammonium tetrakis(pentafluorophenyl)borate, N,N-dialkylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, N,N-dialkylanilinium tetrakis- (2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N- dialkylanilinium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate,
  • any of the activators described herein may be mixed together before or after combination with the catalyst compound and/or CTA, preferably before being mixed with the catalyst compound and/or CTA.
  • two NCA activators may be used in the polymerization and the molar ratio of the first NCA activator to the second NCA activator can be any ratio.
  • the molar ratio of the first NCA activator to the second NCA activator is 0.01 : 1 to 10,000: 1, preferably 0.1 : 1 to 1000: 1, preferably 1 : 1 to 100: 1.
  • the typical activator-to-catalyst ratio e.g., all NCA activators-to-catalyst ratio is a 1 : 1 molar ratio. Alternate preferred ranges include from 0.1 : 1 to 100: 1, alternately from
  • a particularly useful range is from 0.5: 1 to 10: 1, preferably 1 : 1 to 5: 1.
  • catalyst compounds can be combined with combinations of alumoxanes and NCA's (see, for example, U.S. Patent Nos.
  • scavengers may be used. Suitable compounds which may be utilized as scavengers include, for example, isobutylalumoxanes, such as IBAO-65, modified alumoxanes, such as MMAO 3A, and the like.
  • alpha olefin refers to an olefin where the carbon-carbon double bond occurs between the alpha and beta carbons of the chain.
  • ethylene, propylene, butene, hexene, and octene are alpha olefins that are particularly useful in embodiments herein.
  • the olefin may also be substituted at any position along the carbon chain with one or more substituents.
  • Suitable substituents include, without limitation, alkyl, preferably, alkyl; cycloalkyl, preferably, C3.6 cycloalkyl; as well as hydroxy, ether, keto, aldehyde, and halogen functionalities.
  • Preferred olefins include ethylene, propylene, butene, pentene, hexene, octene, nonene, decene, undecene, dodecene, and the isomers thereof.
  • the olefin monomers comprise ethylene, preferably ethylene and a C3 to comonomer (such as propylene, butene, pentene, heptene, octene, nonene, decene, undecene, dodecene, and mixtures thereof).
  • a C3 to comonomer such as propylene, butene, pentene, heptene, octene, nonene, decene, undecene, dodecene, and mixtures thereof.
  • the olefin monomer is ethylene without comonomer, e.g., comonomer is present at 0 wt%.
  • the reactants are typically combined in a reaction vessel at a temperature of 20°C to 200°C (preferably 50°C to 160°C, preferably 60°C to 140°C) and a pressure of 0 MPa to 1000 MPa (preferably 0.5 MPa to 500 MPa, preferably 1 MPa to 250 MPa) for a residence time of 0.5 seconds to 10 hours (preferably 1 second to 5 hours, preferably 1 minute to 1 hour).
  • the molecular weight of the polymer products may be controlled by, inter alia, choice of catalyst, ratio of CTA to amidinate catalyst compound, and/or possibly temperature.
  • the polymerization temperature is 50°C or more, preferably 60°C or more, preferably 70°C or more, preferably 80°C or more, and 250°C or less, preferably 200°C or less, preferably 175°C or less, preferably 150°C or less, preferably 130°C or less, preferably 120°C or less.
  • the olefin pressure is typically greater than 5 psig (34.5 kPa); preferably, greater than 10 psig (68.9 kPa); and more preferably, greater than 45 psig (310 kPa).
  • the aforementioned pressure ranges may also be suitably employed as the total pressure of olefin and diluent.
  • the aforementioned pressure ranges may be suitably employed for the inert gas pressure.
  • the quantity of catalyst that is employed in the process of this invention is any quantity that provides for an operable polymerization reaction.
  • the ratio of moles of olefin monomers to moles of amidinate catalyst compound is typically greater than 10: 1 ; preferably, greater than 100: 1; preferably, greater than 1000: 1; preferably, greater than 10,000: 1 ; preferably, greater than 25,000: 1; preferably, greater than 50,000: 1; preferably, greater than 100,000: 1.
  • 0.00001 to 1.0 moles, preferably 0.0001 to 0.05 moles, preferably 0.0005 to 0.01 moles of catalyst are charged to the reactor per mole of olefin charged.
  • 0.00001 to 1.0 moles, preferably 0.0001 to 0.05 moles, preferably 0.0005 to 0.05 moles of amidinate catalyst compound are charged to the reactor per mole of CTA charged.
  • alumoxanes are not present in the reaction.
  • less than 0.5 mol%, preferably 0 mol% alumoxane is present in the reaction zone; alternately, the alumoxane is present at a molar ratio of aluminum to transition metal less than 500: 1; preferably, less than 300: 1; preferably, less than 100: 1; preferably, less than 1 : 1.
  • the polymerization process is typically a solution process, although it may be a bulk or high pressure process. Homogeneous processes are preferred. (A homogeneous process is defined to be a process where at least 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process is particularly preferred. (A bulk process is defined to be a process where reactant concentration in all feeds to the reactor is 70 volume % or more.) Alternately, no solvent or diluent is present or added in the reaction medium (except for the small amounts used as the carrier for the catalyst or other additives, or amounts typically found with the reactants, e.g., propane in propylene).
  • Suitable diluents/solvents for the process include non-coordinating, inert liquids.
  • Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (IsoparTM); perhalogenated hydrocarbons, such as perfluorinated C4 0 alkanes, chlorobenzene, and aromatic; and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene.
  • straight and branched-chain hydrocarbons such as isobutan
  • aliphatic hydrocarbon solvents are preferred, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof.
  • the solvent is not aromatic.
  • aromatics are present in the solvent at less than 1 wt%, preferably at 0.5 wt%, preferably at 0 wt% based upon the weight of the solvents.
  • suitable diluents/solvents also include aromatic hydrocarbons, such as toluene or xylenes, and chlorinated solvents, such as dichloromethane.
  • the feed for the process comprises 60 vol% solvent or less, based on the total volume of the feed, preferably 40 vol% or less, preferably 20 vol% or less.
  • the process is a slurry process.
  • slurry process or “slurry polymerization process” means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt% of polymer products derived from the supported catalyst are in granular form as solid particles (not dissolved in the diluent).
  • the process may be batch, semi-batch, or continuous.
  • continuous means a system that operates without interruption or cessation.
  • a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.
  • Useful reaction vessels include reactors (including continuous stirred tank reactors, batch reactors, reactive extruders, pipes, or pumps).
  • the productivity of the process is at least 200 g of polymer
  • This invention further relates to a process, preferably an in-line process, preferably a continuous process, to produce polymer, comprising introducing olefin, CTA, activator, and amidinate catalyst compound into a reaction zone, obtaining a reactor effluent containing polymer, optionally removing (such as flashing off) solvent, unused monomer and/or other volatiles, obtaining polymer then functionalizing the polymer.
  • a process preferably an in-line process, preferably a continuous process, to produce polymer, comprising introducing olefin, CTA, activator, and amidinate catalyst compound into a reaction zone, obtaining a reactor effluent containing polymer, optionally removing (such as flashing off) solvent, unused monomer and/or other volatiles, obtaining polymer then functionalizing the polymer.
  • reaction zone is defined as an area where activated catalysts and monomers are contacted and a polymerization reaction takes place.
  • each reactor is considered as a separate reaction zone.
  • each polymerization stage is considered as a separate reaction zone.
  • olefin homopolymers and copolymers typically of one or more of ethylene (such as propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene), preferably having an Mw of from 500 to 500,000 g/mol (alternately from 1000 to 450,000 g/mol, alternately from 1500 to 400,000 g/mol), and an Mw/Mn of from 1 to 1.5, preferably 1.1 to 1.4, preferably 1.1 to 1.3.
  • ethylene such as propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene
  • the processes described herein produce olefin homopolymers and copolymers having an Mn (determined by GPC) of from A' g/mol to Z g/mol, where A' is (1/q x (yield of polyolefin in grams / mols of chain transfer agent + mols of transition metal catalyst compound)); and Z is (1/m x (yield of polyolefin in grams / mols of chain transfer agent + mols of transition metal catalyst compound)), where q is 0.5 and m is 4, alternately, q is 1 and m is 3.5, alternately q is 1.5 and m is 3, alternately q is 2 and m is 3.
  • olefin homopolymers and copolymers typically of one or more of ethylene (such as propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene), preferably having an Mw of from 500 to 4,500,000 g/mol (alternately from 1000 to 2,000,000 g/mol, alternately from 1500 to 1,500,000 g/mol), and a multimodal molecular weight distribution, preferably a bimodal molecular weight distribution (as indicated by a multimodal or bimodal GPC trace, respectively).
  • ethylene such as propylene, butene, pentene, hexene, octene, nonene, decene, undecene, and dodecene
  • the polymer produced (preferably an ethylene polymer) has a Tm of 100°C or more, preferably 1 10°C or more, preferably 115°C or more, preferably 120°C or more, preferably 125°C or more, preferably 130°C or more.
  • the polymer produced comprises at least 30 wt% (preferably at least 40 wt%, preferably at least 50 wt%, preferably at least 60 wt%, preferably at least 70 wt%, preferably at least 80 wt%, preferably at least 90 wt%, preferably at least 95 wt%, preferably at least 99 wt%, based upon the weight of the polymer) of ethylene.
  • the polymer produced herein comprises 90 to 100 wt% or more ethylene and 0 to 10 wt% comonomer (such as propylene, butene, pentene, hexene, octene, nonene, decene, undecene, dodecene, or a mixture thereof), preferably from 95 wt% to 99.9 wt% ethylene to 0.1 wt% to 5 wt% comonomer, preferably from 98 wt% to 99.0 wt% ethylene and 1 wt% to 2 wt% comonomer, based upon the weight of the polymer.
  • comonomer such as propylene, butene, pentene, hexene, octene, nonene, decene, undecene, dodecene, or a mixture thereof
  • the polymers produced by the invention described herein also preferably have a metal group attached thereto such as aluminum or zinc and are referred to as end-metallated polyolefins.
  • the polymeric product Prior to exposure to air or any other reactive molecules, the polymeric product will preferably comprise end-metallated polyolefin of the formula M(polyolefin) n (R) y .
  • M the metal of the chain transfer agent(s), typically Al or Zn; n is 1, 2, or 3; y is 3 or 2, depending on the coordination number of the metal in the chain transfer agent; and R is hydrocarbyl radical, substituted hydrocarbyl (such as an alkyl, substituted alkyl, aryl or substituted aryl), preferably having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms.
  • the polymer produced herein contains an aluminum group at the terminus of the polymer.
  • the process described herein produces a metallated polymer represented by the formula: M 1 R 20 3 or M 2 R 20 2, preferably represented by the formula: A1R 20 3 or ZnR 20 2, where each R 20 is, independently, a polyolefin having an Mn of 50,000 g/mol or more (preferably 100,000 or more, preferably 150,000 or more, preferably 200,000 or more), M 1 is a group 13 atom (Al, B, or Ga), and M 2 is a group 12 atom (preferably Zn).
  • each R 20 is, independently, a homopolymer or a copolymer comprising one of more of C2 to C20 olefins, preferably C2 to C20 alpha olefins, preferably C2 to alpha olefins, preferably one or more of ethylene, propylene, butene, pentene, octene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof.
  • each R 20 is, independently, is an ethylene polymer, such as homopolyethylene or an ethylene copolymer comprising ethylene and from 0.1 mol% to 50 mol% comonomer (preferably from 0.1 mol% to 20 mol%, preferably from 0.5 mol% to 10 mol%, preferably from 1 mol% to 5 mol% comonomer), where the comonomer is preferably one of more of C3 to C20 olefins, preferably C3 to C20 alpha olefins, preferably C3 to alpha olefins, preferably one or more of propylene, butene, pentene, octene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof.
  • comonomer is preferably one of more of C3 to C20 olefins, preferably C3 to C20 alpha olefins
  • end-metallated polyolefins can be reacted with a broad range of molecules to produce new end-functionalized polyolefins.
  • trialkylaluminums are known to react with halides, such as iodine or bromine, to produce haloalkyls.
  • Analogous chemistry with end-metallated polyolefins will produce end-halogenated polyolefins.
  • Other electrophiles can also be reacted with end-metallated polyolefins to produce other derivatives.
  • Reaction with carbon dioxide will form a carboxylate species that upon quenching with water will form an organic acid capped polyolefin.
  • Reaction with isocyanates similarly would produce an amide-functionalized polyolefin.
  • Other useful functionalization reactions include reaction with oxygen, ozone, or peroxides to form end- hydroxy functionalized polyolefins.
  • the metal-containing polyolefins are reacted with additional reactants (e.g., iodine, electrophiles, oxygen, peroxides, carbon dioxide, isocyanates, thioisocyanates, sulfur) to form polyolefin products containing a new functional group (e.g., carboxylic acid, hydroxy, amide) located at or near the end of the polyolefin chain.
  • additional reactants e.g., iodine, electrophiles, oxygen, peroxides, carbon dioxide, isocyanates, thioisocyanates, sulfur
  • the end-metallated polyolefins can be used to prepare block polyolefin products by growth of a second block using either coordinative polymerization (after chain transfer of the polymer chain to a suitable catalyst) or by the electronics process.
  • the metallated polymer produced herein is reacted with CO2 to produce an acid, which may then be further functionalized.
  • the metallated polymer produced herein is reacted with a halogen, which may then be further functionalized.
  • Mw, Mn, Mz, and Mw/Mn are determined according to GPC-SEC-DRI-LS method described in paragraphs [0600]-[0611] of U.S. Patent Application Publication No. 2008/0045638 at pages 37-38 including all references cited therein, except that dn/dc is 0.10 for all polymers.
  • Tm is determined by the DSC method described in the example section below.
  • this invention relates to:
  • An amidinate catalyst com ound is represented by the formula:
  • M is Group 4 metal, preferably Hf, Zr, or Ti;
  • R 1 is hydrogen, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group having 1 to 40 carbon atoms;
  • R 2 and R 3 are each, independently, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group having 1 to 40 carbon atoms;
  • each L is, independently, a Lewis base, provided that each L is not a cyclopentadienyl group; each A is, independently, any anionic ligand, provided that each A is not a cyclopentadienyl group;
  • x is 1, 2, or 3;
  • y is 0, 1, 2, or 3;
  • z 0, 1, 2, or 3;
  • x + y is equal to the coordination number of M, preferably 3 or 4, preferably 4.
  • R 1 is a substituted or unsubstituted tolyl or benzyl group having 7 to 40 carbon atoms, preferably is a substituted tolyl, benzyl (such as naphthyl);
  • R 2 and R 3 are each, independently, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group having 1 to 40 carbon atoms (preferably 3 to 40 carbon atoms);
  • each L is, independently, a Lewis base, provided that each L is not a cyclopentadienyl group; each A is, independently, any anionic ligand, provided that each A is not a cyclopentadienyl group;
  • z 0, 1, 2, or 3;
  • x + y is equal to the coordination number of M, preferably 3 or 4, preferably 4.
  • R 2 and R 3 are, independently, selected from the group consisting of propyl, isopropyl, butyl (including isobutyl, sec -butyl, tert-butyl, and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, benzyl, tolulyl, chlorophenyl, phenol, substituted phenol, CH 2 C(CH 3 )3 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2-isopropylphenyl, 2-ethyl-6-methylphenyl, 3,5-ditertbutylphenyl, 2- tertbutylphenyl, 2,3,4,5
  • each A is, independently, a hydrocarbyl radical, a halogen, a hydride, an amide, an alkoxide, a sulfide, an alkyl sulfonate, a phosphide, an amine, a phosphine, an ether or a combination thereof, or two A groups may be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms.
  • R 1 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl (including isobutyl, sec -butyl, tert-butyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, benzyl, tolulyl, chlorophenyl, phenol, substituted phenol, CH 2 C(CH 3 )3, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2- isopropylphenyl, 2-ethyl-6-methylphenyl, 3,5-ditertbutylphenyl,
  • R 1 is a substituted or unsubstituted tolyl or benzyl group having 7 to 40 carbon atoms and R 2 and R 3 are each, independently, a hydrocarbyl group, a silylcarbyl group, a substituted silylcarbyl group, or a substituted hydrocarbyl group having 1 to 40 carbon atoms (preferably 3 to 40 carbon atoms).
  • R 1 is a substituted tolyl or benzyl, such as naphthyl.
  • a method to polymerize olefins comprising:
  • olefins preferably C 2 to C 40 olefins, preferably C 2 to C20 alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof
  • amidinate catalyst compound of paragraph 1, 2, 3, 4, or 5 above a chain transfer agent, and a non-coordinating anion activator, where the molar ratio of the chain transfer agent(s) to amidinate catalyst compound(s) is 5: 1 or more (alternately 10: 1 or more, alternately 20: 1 or more, alternately 50: 1 or more, alternately 100: 1 or more); and
  • a method to obtain a polymer having a multimodal molecular weight distribution comprising contacting, at a temperature below the transition temperature, olefins (preferably C2 to C 4 o olefins, preferably C 2 to C20 alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof) with the amidinate catalyst compound of paragraph 1, 2, 3, 4, or 5 above, a chain transfer agent, and a non-coordinating anion activator, where the molar ratio of the chain transfer agent(s) to amidinate catalyst compound(s) is 5: 1 or more (alternately 10: 1 or more, alternately 20: 1 or more, alternately 50: 1 or more, alternately 100: 1 or more); and 2) obtaining polymer having a multimodal GPC trace.
  • olefins preferably C2
  • olefins comprise one or more of ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof.
  • a metallated polymer represented by the formula M 1 R 20 3 , M 2 R 20 2 , A1R 20 3 , or ZnR 20 2, wherein each R 20 is, independently, a polyolefin having an Mn of 50,000 g/mol or more, M 1 is a group 13 atom, and M 2 is a group 12 atom.
  • each R 20 is, independently, a homopolymer or a copolymer comprising one of more of C2 to C20 olefins preferably an ethylene polymer comprising ethylene and from 0 to 50 mol% comonomer, preferably an ethylene copolymer comprising ethylene and from 0.1 to 20 mol% comonomer.
  • NCA1 is ⁇ , ⁇ -dimethylanilinium tetrakis(pentafluorophenylborate).
  • NCA2 is triphenylcarbenium tetrakis(pentafluorophenylborate).
  • Catalyst 1 and Catalyst 2 are shown in Table 1, where Bn is benzyl.
  • Catalyst 3 is rac-dimethylsilylbis(indenyl) hafnium dimethyl.
  • Catalyst 4 is dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)titanium dimethyl.
  • Step a Et20 (20 mL) and o-tolylmagnesium bromide (5 mL in Et20, 10 mmol) were combined and cooled to -25°C. 1,3-Diisopropylcarbodiimide (1.20 g, 9.50 mmol) was then added in one portion. The mixture was allowed to warm to ambient temperature and stirred for 1.5 hours. Water (40 mL) was added and the organics were separated, dried over MgS0 4 , filtered, and evaporated to afford the amidine o-TolC(NiPr)NHiPr as a yellow oil (0.557 g, 26.9%).
  • Step b A benzene (2 mL) solution of o-TolC(NiPr)NHiPr (0.188 g, 0.861 mmol) was added dropwise to a benzene (5 mL) solution of ZrBn 4 (0.392 g, 0.861 mmol). The mixture was stirred overnight in the dark. The volatiles were removed under reduced pressure and the residue was extracted with hexane (8 mL). Filtration of the mixture followed by evaporation of the volatiles afforded the product as an orange oil that crystallized upon standing (0.458 g, 91.4%).
  • Ethylene/ 1 -octene copolymerizations were carried out in a parallel, pressure reactor, as generally described in U.S. Patent Nos. 6,306,658; 6,455,316; 6,489,168; WO 00/09255; and Murphy et al., J. Am. Chem. Soc, 2003, 125, pages 4306-4317, each of which is fully incorporated herein by reference to the extent not inconsistent with this specification.
  • a pre- weighed glass vial insert and disposable stirring paddle were fitted to each reaction vessel of the reactor, which contains 48 individual reaction vessels.
  • each vessel was individually heated to a set temperature (usually between 50°C and 1 10°C, see Table 2) and pressurized to a predetermined pressure of 1.38 MPa (200 psi) ethylene.
  • 1- Octene 100 microliters, 637 micromol was injected into each reaction vessel through a valve, followed by enough toluene to bring the total reaction volume, including the subsequent additions, to 5 niL.
  • Tri-n-octylaluminum in toluene was then added, if used.
  • the contents of the vessel were then stirred at 800 rpm.
  • An activator solution typically either 1.0-1.1 equiv of 0.40 mM dimethyl anilinium tetrakis-pentafluorophenyl borate ( CA1) in toluene was then injected into the reaction vessel along with 500 microliters toluene, followed by a toluene solution of catalyst (0.40 mM in toluene, between 20-80 nanomols of catalyst and another aliquot of toluene (500 microliters). Equivalence is determined based on the mol equivalents relative to the moles of the transition metal in the catalyst complex.
  • the reaction was then allowed to proceed until 20 psi (0.138 MPa) ethylene had been taken up by the reaction (ethylene pressure was maintained in each reaction vessel at the pre- set level by computer control). At this point, the reaction was quenched by pressurizing the vessel with compressed air.
  • the glass vial insert containing the polymer product and solvent was removed from the pressure cell and the inert atmosphere glove box, and the volatile components were removed using a Genevac HT-12 centrifuge and Genevac VC3000D vacuum evaporator operating at elevated temperature and reduced pressure. The vial was then weighed to determine the yield of the polymer product.
  • the resultant polymer was analyzed by Rapid GPC (see below) to determine the molecular weight, by FT-IR (see below) to determine octene incorporation, and by DSC (see below) to determine melting point.
  • the system was operated at an eluent flow rate of 2.0 mL/min and an oven temperature of 165°C. 1,2,4-trichlorobenzene was used as the eluent.
  • the polymer samples were dissolved in 1,2,4- trichlorobenzene at a concentration of 0.1 - 0.9 mg/mL. 250 uL of a polymer solution was injected into the system. The concentration of the polymer in the eluent was monitored using an evaporative light scattering detector.
  • the molecular weights presented in the examples are relative to linear polystyrene standards.
  • DSC Differential Scanning Calorimetry
  • the amount of 1-octene to ethylene incorporated in the polymers was determined by rapid FT-IR spectroscopy on a Bruker Equinox 55+ IR in reflection mode. Samples were prepared in a thin film format by evaporative deposition techniques. Weight percent 1-octene was obtained from the ratio of peak heights at 1378 and 4322 cm -1 . This method was calibrated using a set of ethylene/ 1-octene copolymers with a range of known wt% 1-octene content.
  • Runs 1-6 are data for the copolymerization of ethylene and 1-octene by a mixture of Catalysts 1 to 4 with 1.0 equivalent of NCA1.
  • Runs 5 and 6 which were performed at 105°C, produced very narrow molecular weight polymer, whereas Runs 1-4 run at 50°C and 80°C produced much higher molecular weight polymer of broader or bimodal Mw/Mn.
  • Runs 7-10 and 11-14 show that catalysts 3 and 4, respectively do not undergo reversible chain transfer, as Mw does not decrease with increasing levels of A10ct 3 .
  • Example 2 The polymerization process of Example 2 was repeated except that the temperature was kept at 95°C, 1-octene was omitted, and the amount of Od ⁇ Al was varied in each run.
  • Runs 1-8 show data for polymerizations performed at 95°C.
  • Runs 9-15 show data for polymerizations performed at 105°C.
  • Runs 16-23 show data for polymerizations run at 1 15°C. Data from Runs 2-15 and 17-23 show that very narrow molecular weight polymer can be obtained at all of these temperatures (i.e., 95°C, 105°C, or 1 15°C) when there are 6 or more molar equivalents of A10ct3 (relative to Catalyst 1) present in the reaction mixture.
  • Runs 1 and 16 did not contain and A10ct3 and did not produce polymer having an Mw/Mn less than 1.5.
  • Example 2 The polymerization process of Example 2 was repeated except that the temperature was kept at 95 °C, and the amount of Od ⁇ Al was varied in each run.
  • Shown in Table 4 are data for the copolymerization of ethylene and 1-octene by a mixture of Catalyst 1 with 1.0 molar equivalent of NCA1 at 95°C.
  • Run 1 contained 1000 nmol of dried MAO for use as a scavenger.
  • Data from Runs 2-7 show that very narrow molecular weight distribution polymer can be obtained when there are 6 or more molar equivalents of A10ct3 (relative to Catalyst 1) present in the reaction mixture.
  • Run 1 did not contain A10ct3 and did not produce polymer of very narrow molecular weight distribution.
  • Shown in Figure 1 is a plot of (nanograms of polymer / Mn of polymer) vs. (nanomols of Catalyst 1 plus nanomols of AlOd ⁇ ) using data from Runs 2-7.
  • the linear correlation indicates chain transfer from Catalyst 1 to aluminum and the slope of about 3 indicates that each aluminum contains 3 polymer chains
  • Figures 11 and 12 compare the effect of Et2Zn and iP ⁇ Zn, respectively, on Catalyst 2/NCAl.
  • Et2Zn Figure 1 1
  • Figure 11 shows bimodal molecular weight distributions at low Od ⁇ Al concentrations (as shown in Figure 11), while iP ⁇ Zn does not modulate the effect of Od ⁇ Al on Catalyst 2/NCAl (similar to Figure 2, with no chain transfer agent).
  • Figures 13 and 3 compare the effect of Et2Zn and iP ⁇ Zn, respectively, on Catalyst 1/NCAl.
  • compositions, an element or a group of elements are preceded with the transitional phrase “comprising”, it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of, “selected from the group consisting of,” or “is” preceding the recitation of the composition, element, or elements and

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Abstract

L'invention concerne un procédé pour polymériser des oléfines comprenant les étapes qui consistent à mettre en contact des oléfines avec un composé catalyseur amidinate, un agent de transfert de chaîne et un activateur, ledit composé catalyseur amidinate étant représenté par la formule : (amindinate)xM(A)y(L)z, formule dans laquelle M est un métal de groupe 4, chaque L désigne indépendamment une base de Lewis, à condition que chaque L ne soit pas un groupe cyclopentadiényle, chaque A est indépendamment un ligand anionique indépendant, à condition que chaque A ne soit pas un groupe cyclopentadiényle ; x désigne 1, 2 ou 3 ; y représente 0, 1, 2 ou 3 ; z désigne 0, 1, 2 ou 3 ; et x + y est égal au nombre de coordination de M, de préférence 3 ou 4.
PCT/US2012/059195 2011-11-21 2012-10-08 Composés catalyseurs amidinate, leur procédé d'utilisation et polymères ainsi produits WO2013077944A1 (fr)

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Publication number Priority date Publication date Assignee Title
KR20190060809A (ko) * 2016-09-30 2019-06-03 다우 글로벌 테크놀로지스 엘엘씨 포스파구아니딘 4족 금속 올레핀 중합 촉매
KR20190064597A (ko) * 2016-09-30 2019-06-10 다우 글로벌 테크놀로지스 엘엘씨 이중 연결 포스포구아니딘 4족 금속 착체 및 이로부터 생성된 올레핀 중합 촉매
JP2019530684A (ja) * 2016-09-30 2019-10-24 ダウ グローバル テクノロジーズ エルエルシー ビス連結ホスファグアニジン第ｉｖ族金属錯体およびそれから製造されたオレフィン重合触媒
JP2019534866A (ja) * 2016-09-30 2019-12-05 ダウ グローバル テクノロジーズ エルエルシー ホスファグアニジン第ｉｖ族金属オレフィン重合触媒
JP7011652B2 (ja) 2016-09-30 2022-01-26 ダウ グローバル テクノロジーズ エルエルシー ホスファグアニジン第ｉｖ族金属オレフィン重合触媒
KR102459739B1 (ko) * 2016-09-30 2022-10-28 다우 글로벌 테크놀로지스 엘엘씨 이중 연결 포스포구아니딘 4족 금속 착체 및 이로부터 생성된 올레핀 중합 촉매
KR102606000B1 (ko) * 2016-09-30 2023-11-27 다우 글로벌 테크놀로지스 엘엘씨 포스파구아니딘 4족 금속 올레핀 중합 촉매

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