US20110282019A1 - Zwitterionic group viii transition metal initiators supported by olefin ligands - Google Patents
Zwitterionic group viii transition metal initiators supported by olefin ligands Download PDFInfo
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- US20110282019A1 US20110282019A1 US11/519,618 US51961806A US2011282019A1 US 20110282019 A1 US20110282019 A1 US 20110282019A1 US 51961806 A US51961806 A US 51961806A US 2011282019 A1 US2011282019 A1 US 2011282019A1
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- olefin
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- transition metal
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- 150000001336 alkenes Chemical class 0.000 title claims abstract description 35
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000003446 ligand Substances 0.000 title claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 10
- 239000003999 initiator Substances 0.000 title description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 125000003118 aryl group Chemical group 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 7
- 239000005977 Ethylene Substances 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 5
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentenylidene Natural products C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001638 boron Chemical class 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 4
- 125000003011 styrenyl group Chemical class [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 150000001941 cyclopentenes Chemical class 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims 3
- 150000002431 hydrogen Chemical class 0.000 claims 3
- 125000000879 imine group Chemical group 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 abstract description 13
- -1 polypropylene Polymers 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 229920001155 polypropylene Polymers 0.000 abstract description 8
- 239000000178 monomer Substances 0.000 abstract description 7
- 239000004705 High-molecular-weight polyethylene Substances 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 229940125904 compound 1 Drugs 0.000 description 7
- 229940125782 compound 2 Drugs 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910000071 diazene Inorganic materials 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- 0 */C(=C(\C)CC(CC)=C(C)C)C(C)C Chemical compound */C(=C(\C)CC(CC)=C(C)C)C(C)C 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- DSURITIZPFFNMX-GWWHUCCBSA-N C=C(O[B-](C#CC#CC#C(F)(F)(F)(F)F)(C#CC#CC#C(F)(F)(F)(F)F)C#CC#CC#C(F)(F)(F)(F)F)/C(C)=N(\[Ni+]C)C1=C(C(C)C)C=CC=C1C(C)C.CC1=CC=CC=C1 Chemical compound C=C(O[B-](C#CC#CC#C(F)(F)(F)(F)F)(C#CC#CC#C(F)(F)(F)(F)F)C#CC#CC#C(F)(F)(F)(F)F)/C(C)=N(\[Ni+]C)C1=C(C(C)C)C=CC=C1C(C)C.CC1=CC=CC=C1 DSURITIZPFFNMX-GWWHUCCBSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical compound CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000302 molecular modelling Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 1
- QTFAMGSTVLPCMS-UHFFFAOYSA-N 3-[2,6-di(propan-2-yl)phenyl]iminobutan-2-one Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N=C(C)C(C)=O QTFAMGSTVLPCMS-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- BGLQSGGWPMKSHK-GMPBIKSCSA-N C=C1O[Ni](CC2=CC=CC=C2)([PH](C)(C)C)N(C2=C(C(C)C)C=CC=C2C(C)C)=C1C.CC(=O)/C(C)=N/C1=C(C(C)C)C=CC=C1C(C)C.CC1=CC=CC=C1.CC1=CC=CC=C1.CC1=N(C2=C(C(C)C)C=CC=C2C(C)C)[Ni](C)[C+]=C1O[B-](C#CC#CC#C(F)(F)(F)(F)F)(C#CC#CC#C(F)(F)(F)(F)F)C#CC#CC#C(F)(F)(F)(F)F.CC1=N(C2=C(C(C)C)C=CC=C2C(C)C)[Ni](C)[C+]=C1O[B-](C#CC#CC#C(F)(F)(F)(F)F)(C#CC#CC#C(F)(F)(F)(F)F)C#CC#CC#C(F)(F)(F)(F)F.CCB(C#CC#CC#C(F)(F)(F)(F)F)C(C#CC#CC#C(F)(F)(F)(F)F)#CC#CC#C(F)(F)(F)(F)F Chemical compound C=C1O[Ni](CC2=CC=CC=C2)([PH](C)(C)C)N(C2=C(C(C)C)C=CC=C2C(C)C)=C1C.CC(=O)/C(C)=N/C1=C(C(C)C)C=CC=C1C(C)C.CC1=CC=CC=C1.CC1=CC=CC=C1.CC1=N(C2=C(C(C)C)C=CC=C2C(C)C)[Ni](C)[C+]=C1O[B-](C#CC#CC#C(F)(F)(F)(F)F)(C#CC#CC#C(F)(F)(F)(F)F)C#CC#CC#C(F)(F)(F)(F)F.CC1=N(C2=C(C(C)C)C=CC=C2C(C)C)[Ni](C)[C+]=C1O[B-](C#CC#CC#C(F)(F)(F)(F)F)(C#CC#CC#C(F)(F)(F)(F)F)C#CC#CC#C(F)(F)(F)(F)F.CCB(C#CC#CC#C(F)(F)(F)(F)F)C(C#CC#CC#C(F)(F)(F)(F)F)#CC#CC#C(F)(F)(F)(F)F BGLQSGGWPMKSHK-GMPBIKSCSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229910018553 Ni—O Inorganic materials 0.000 description 1
- XGCTUKUCGUNZDN-UHFFFAOYSA-N [B].O=O Chemical compound [B].O=O XGCTUKUCGUNZDN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 238000001897 boron-11 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010516 chain-walking reaction Methods 0.000 description 1
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- 238000009833 condensation Methods 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000005595 deprotonation Effects 0.000 description 1
- 238000010537 deprotonation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- POHPFVPVRKJHCR-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl)alumane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1[Al](C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F POHPFVPVRKJHCR-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
Definitions
- the invention relates generally to the polymerization of olefin monomers and in particular to polymerization by zwitterionic metal catalysts.
- Nickel-based olefin oligomerization and polymerization initiators are of interest in industrial and academic laboratories [1, 2]. Cationic versions are the most commonly encountered [3]. Neutral species, although less active, are under investigation because of their higher tolerance toward functionalities [4, 5, 6, 7]. Zwitterionic counterparts are the least common and provide an intermediate range of reactivities [8].
- the present invention provides a zwitterionic Group VIII transition metal complex containing the simple and relatively small 3-(arylimino)-but-1-en-2-olato ligand that initiates the polymerization or co-polymerization of olefins.
- a novel feature of this catalyst is that the active species is stabilized by a chelated olefin adduct.
- the present invention also provides a process of polymerizing olefin monomers using zwitterionic catalysts.
- the olefin preferably a monomer, is selected from the group consisting essentially of: (1) olefins having formula R v CH ⁇ CH 2 , wherein R v is hydrogen, a substituted or unsubstituted hydrocarbyl group, or a substituted or unsubstituted hydrocarbyl bearing functional group; (2) a substituted or unsubstituted cyclopentene, (3) a substituted or unsubstituted styrene, (4) a substituted or unsubstituted norbornene derivative bearing functional group, and (5) a polar olefin.
- Preferred olefins are polypropylene and ethylene for the formation of polypropylene and high density polyethylene.
- the zwitterionic Group VIII transition metal complex acts as an initiator in the formation of polymers and co-polymers, but in this specification will be referred to either as an initiator or catalyst.
- FIG. 1 is an Oak Ridge Thermal Ellipsoid Program (ORTEP) molecular modeling drawing of an intermediate compound in the production of an initiator of this invention, at the 50% probability level, with hydrogen atoms omitted for clarity; and
- ORTEP Oak Ridge Thermal Ellipsoid Program
- FIG. 2 is an ORTEP molecular modeling drawing of the initiator of this invention, at the 50% probability level, with hydrogen atoms omitted for clarity.
- the initiator/catalyst of the present invention is a zwitterionic Ni complex containing a 3-(arylimino)-but-1-en-2-olato ligand stabilized by a chelated olefin adduct.
- the present invention provides a catalyst of the following formula 1:
- M is a Group VIII transition metal such as Ni, Pd, Pt
- R′ is a one electron hydrocarbyl, such as methyl, ethyl, substituted or unsubstituted R′ is ⁇ benzyl (which is a combination of a sigma bond and a pi-bond from the bound aromatic unit), and the like
- L′ is a two electron ligand, such as a phosphine, amine, olefin, ether, and the like, or is a link to R′ when R′ is R′ is ⁇ benzyl
- X′ is a two electron donor, such as imine, phosphine, carbonyl, and the like
- each R, R′′, R′′′, R iv is independently hydrogen, an alkyl or a substituted or unsubstituted aryl group
- (L) n is a tether group, such as a series of methylene carbons, oxygen, amine, and the like, wherein n
- M is nickel
- R′ is ⁇ benzyl
- L′ is linked to R′
- X′ is an imine
- R is an aryl group
- R′′ is an alkyl group
- R iv is an alkyl group
- R′′′ is hydrogen
- n 0;
- X′′ is oxygen
- LA is a trisubstituted boron.
- a particularly preferred catalyst is compound 2 shown in the scheme 1 below, having the structure:
- Structural characterization of compound 1 reveals a distorted square-planar geometry with a cis relationship between the benzyl ligand and the imine nitrogen.
- the 3-(2,6-diisopropylphenylimino)-but-1-en-2-olato ligand coordinates to the nickel via the nitrogen and oxygen atoms with Ni—O and Ni—N bond lengths of 1.9031(16) and 1.9555(18) ⁇ , respectively.
- the C2-O distance (1.319(6) ⁇ ) is characteristic of a single bond, while the C1-C2 (1.371(7) ⁇ ) distance is more indicative of a double bond. These observations are consistent with the charge distribution as shown for structures of compound 2(A) and 2(B) in Scheme 1.
- the C3-N distance (1.300(6) ⁇ ) is close to that observed in compound 1 (1.294(3) ⁇ ).
- the N—Ni bond length (1.900(4) ⁇ ) is 0.055 ⁇ is shorter than that of compound 1 (1.9555(18) ⁇ ), revealing a more electron deficient metal center in the zwitterionic compound.
- the olefin preferably a monomer
- the olefin is selected from the group consisting essentially of: (1) olefins having formula R v CH ⁇ CH 2 , wherein R v is hydrogen, a substituted or unsubstituted hydrocarbyl group, or a substituted or unsubstituted hydrocarbyl bearing functional group; (2) a substituted or unsubstituted cyclopentene, (3) a substituted or unsubstituted styrene, (4) a substituted or unsubstituted norbornene derivative bearing functional group, and (5) a polar olefin.
- Preferred olefins are polypropylene and ethylene for the formation of polypropylene and high density polyethylene.
- the zwitterionic catalysts of this invention catalyze the formation of polypropylene and high molecular weight polyethylene, e.g., having a molecular weight from 50 K to over a million Daltons
- PDI polydispersity index
- the PDI is a measure of the distribution of molecular weights in a given polymer sample and is the weight average molecular weight divided by the number average molecular weight. It indicates the distribution of individual molecular weight number average molecular weights in a batch of polymers.
- the PDI has a value always greater than 1, but as the polymer chains approach uniform chain length, the PDI approaches unity.
- Compound 2 also initiates propylene polymerization to produce high molecular weight PP (Table 1, entries 6-8).
- the product is purified by precipitation from toluene using acetone.
- 13 C NMR spectroscopy indicates the PP is isotactic rich with an mmmm pentad fraction of 0.6.
- diimine nickel initiators provide atactic or syndiotactic structures [3, 26]. Chain-end control by using compound 2 is suggested by the observation of mmrm sequence and absence of mmrr and mrrm sequences [27].
- Example 4 can be repeated with a catalyst of formula 1 in which M is Pd, L′ is phosphine, R′ is methyl, X′ is carbonyl, R is methyl, R′′ is ethyl, R′′′ is phenyl, R iv is hydrogen, n is 1 and L is oxygen, X′′ is amine, and LA is Al(C 6 F 5 ) 3 .
- Example 4 can be repeated with a catalyst of formula 1 in which M is Pt, L′ is amine, R′ is ethyl, X′ is imine, R is ethyl, R′′ is propyl, R′′′ is hydrogen, R iv is hydrogen, n is 0, X′′ is phosphine, and LA is a proton.
- Example 4 can be repeated with a catalyst of formula 1 in which M is Pd, L′ is ether, R′ is propyl, X′ is phosphine, R is ethyl, R′′ is propyl, R′′′ is n-methyl phenyl, R iv is methyl, n is 1 and L is amine, X′′ is oxygen, and LA is BF 3 .
- Example 4 can be repeated using an olefin having formula R v CH ⁇ CH 2 , wherein R v is a hydrocarbyl group.
- Example 4 can be repeated using an olefin having formula R v CH ⁇ CH 2 , wherein R v is styrene as the olefin.
- Example 4 can be repeated using cyclopentene as the olefin.
- Example 4 can be repeated using a norbornene bearing functional group as the olefin.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
- This invention was made with Government support under Grant No. DE-FG03098ER14910 from the United States Department of Energy. The Government has certain rights in this invention.
- The invention relates generally to the polymerization of olefin monomers and in particular to polymerization by zwitterionic metal catalysts.
- Nickel-based olefin oligomerization and polymerization initiators are of interest in industrial and academic laboratories [1, 2]. Cationic versions are the most commonly encountered [3]. Neutral species, although less active, are under investigation because of their higher tolerance toward functionalities [4, 5, 6, 7]. Zwitterionic counterparts are the least common and provide an intermediate range of reactivities [8].
- While developing tandem catalytic processes [9, 10, 11, 12], one of the inventors discovered that the reactivity of SHOP-type catalysts such as [(C6H5)2PC6H4C(O)O-κ2P,O]Ni(η3—CH2CMeCH2) [13] increases upon addition of B(C6F5)3 [14, 15]. Carbonyl coordination to the borane gives zwitterionic [(C6H5)2PC6H4C(O—B(C6F5)3)O-κ2P, O]Ni(η3—CH2CMeCH2) and removes electron density from nickel. Examination of ligand/reactivity relationships for cationic Ni(diimine) initiators [3, 16] led to the design and synthesis of {(H3C)C[═NAr]C[O—B(C6F5)3][═NAr]-κ2N,N′}Ni(η3—CH2C6H5), with which high molecular weight polyethylene (PE) can be produced for bulky aromatic (Ar) substituents [17]. Several other ligand types have been reported that are amenable to the concept of Lewis acid attachment on a ligand site to redistribute electron density, including 3-(1-arylimino-ethyl)-acetylacetonato [18], 2-diphenylphosphinylbenzamido [19], N-(2-benzoylphenyl)benzamido [20], α-iminoenamido [21], 2-(alkyldeneamino)benzoato [22] and iminoamido pyridine [23]. However, none of these systems has been able to produce high molecular weight PE, in the absence of bulky Ar substituents, or polypropylene.
- The present invention provides a zwitterionic Group VIII transition metal complex containing the simple and relatively small 3-(arylimino)-but-1-en-2-olato ligand that initiates the polymerization or co-polymerization of olefins. A novel feature of this catalyst is that the active species is stabilized by a chelated olefin adduct.
- The present invention also provides a process of polymerizing olefin monomers using zwitterionic catalysts. In particular, the olefin, preferably a monomer, is selected from the group consisting essentially of: (1) olefins having formula RvCH═CH2, wherein Rv is hydrogen, a substituted or unsubstituted hydrocarbyl group, or a substituted or unsubstituted hydrocarbyl bearing functional group; (2) a substituted or unsubstituted cyclopentene, (3) a substituted or unsubstituted styrene, (4) a substituted or unsubstituted norbornene derivative bearing functional group, and (5) a polar olefin. Preferred olefins are polypropylene and ethylene for the formation of polypropylene and high density polyethylene.
- The zwitterionic Group VIII transition metal complex acts as an initiator in the formation of polymers and co-polymers, but in this specification will be referred to either as an initiator or catalyst.
-
FIG. 1 is an Oak Ridge Thermal Ellipsoid Program (ORTEP) molecular modeling drawing of an intermediate compound in the production of an initiator of this invention, at the 50% probability level, with hydrogen atoms omitted for clarity; and -
FIG. 2 is an ORTEP molecular modeling drawing of the initiator of this invention, at the 50% probability level, with hydrogen atoms omitted for clarity. - The initiator/catalyst of the present invention is a zwitterionic Ni complex containing a 3-(arylimino)-but-1-en-2-olato ligand stabilized by a chelated olefin adduct. In particular, the present invention provides a catalyst of the following formula 1:
- wherein M is a Group VIII transition metal such as Ni, Pd, Pt;
R′ is a one electron hydrocarbyl, such as methyl, ethyl, substituted or unsubstituted R′ is→benzyl (which is a combination of a sigma bond and a pi-bond from the bound aromatic unit), and the like;
L′ is a two electron ligand, such as a phosphine, amine, olefin, ether, and the like, or is a link to R′ when R′ is R′ is→benzyl;
X′ is a two electron donor, such as imine, phosphine, carbonyl, and the like;
each R, R″, R″′, Riv is independently hydrogen, an alkyl or a substituted or unsubstituted aryl group;
(L)n is a tether group, such as a series of methylene carbons, oxygen, amine, and the like, wherein n is 0 or 1;
X″ is a component having two electron donor functionality, such as oxygen, amine, phosphine, and the like;
LA is a Lewis Acid, such as a trisubstituted boron, trisubstituted aluminum or a proton; and
the olefin bearing X″ is bound to the metal center. - In preferred embodiments:
- M is nickel;
- R′ is→benzyl;
- L′ is linked to R′
- X′ is an imine;
- R is an aryl group;
- R″ is an alkyl group;
- Riv is an alkyl group;
- R″′ is hydrogen;
- n is 0;
- X″ is oxygen; and
- LA is a trisubstituted boron.
- A particularly preferred catalyst is compound 2 shown in the scheme 1 below, having the structure:
- Preparation of the zwitterionic Ni complex catalysts of this invention is exemplified by the specific reactions shown in Scheme 1:
- As shown in Scheme 1, synthetic access begins with 3-(2,6-diisopropylphenylimino)-butan-2-one [24], which is obtained by condensation of 2,6-diisopropylaniline with 2,3-butanedione. Deprotonation with NaH in THF provides the sodium salt in 80% yield. Subsequent reaction of the salt with Ni(PMe3)2(η1—CH2C6H6)Cl [25] provides a new compound, which contains the ligand fragment (1H NMR in C6D6: 4.91, 4.63 ppm), an η1-benzyl group (1H NMR: 7.56 ppm) and PMe3. Single crystals of the product were obtained from a solution of pentane and the results are shown in
FIG. 1 . The product is thus (3-(2,6-diisopropylphenylimino)-but-1-en-2-olato)(η1-benzyl)-(trimethylphosphine)-nickel (compound 1 as shown in Scheme 1). - Structural characterization of compound 1 reveals a distorted square-planar geometry with a cis relationship between the benzyl ligand and the imine nitrogen. The 3-(2,6-diisopropylphenylimino)-but-1-en-2-olato ligand coordinates to the nickel via the nitrogen and oxygen atoms with Ni—O and Ni—N bond lengths of 1.9031(16) and 1.9555(18) Å, respectively. The C1-C2 (1.344(3) Å) and C3-N (1.294(3) Å) distances are consistent with double bond character, whereas the C2-C3 (1.486(3) Å), C3-C4 (1.497(3) Å) and C2-O (1.315(3) Å) distances reveal single bond character. These data indicate localized bonding in the chelating ring.
- The addition of 2 equivalents B(C6F5)3 to compound 1 in toluene results in the formation of Me3P—B(C6F5)3, which precipitates out of solution, and a new organometallic product. 1H NMR spectra of the product show the formation of two isomers in a 9:1 ratio. The upfield shift of the aromatic signals from —CH2C6H5 from 6.9 to 7.6 to 5.9 to 6.6 ppm indicates □3-coordination. The vinyl protons are observed as a pair of doublets in the range of 3.25 to 5.02 ppm. The 11B NMR spectrum shows a signal at −2.6 ppm, consistent with boron-oxygen coordination. 1H-NOE spectroscopy between the vinyl group and the benzyl group indicates that the sets of isomers arise from pseudorotamers of the benzyl ligand [23] and that the major isomer contains a cis relationship between the vinyl group and the benzyl group, as shown in Scheme 1.
- Single crystals of compound 2 formed from a toluene solution and the structure is shown in
FIG. 2 . Isomer 2(A) was obtained preferentially. The oxygen binds to the Lewis acidic boron and by doing so, forces coordination of the olefin to the nickel center. The distances from Ni to C1 and C2, are 2.109 (6) Å and 2.455(6) Å, respectively. The rotation of the C2-C3 bond and the C1-C2-C3-N torsional angle) (41.6(8)° optimize overlap between the π-orbital of the —C═CH2 group and Ni. The C2-O distance (1.319(6) Å) is characteristic of a single bond, while the C1-C2 (1.371(7) Å) distance is more indicative of a double bond. These observations are consistent with the charge distribution as shown for structures of compound 2(A) and 2(B) in Scheme 1. The C3-N distance (1.300(6) Å) is close to that observed in compound 1 (1.294(3) Å). The N—Ni bond length (1.900(4) Å) is 0.055 Å is shorter than that of compound 1 (1.9555(18) Å), revealing a more electron deficient metal center in the zwitterionic compound. - The zwitterionic initiators/catalysts enable the polymerization of olefins. In particular, the olefin, preferably a monomer, is selected from the group consisting essentially of: (1) olefins having formula RvCH═CH2, wherein Rv is hydrogen, a substituted or unsubstituted hydrocarbyl group, or a substituted or unsubstituted hydrocarbyl bearing functional group; (2) a substituted or unsubstituted cyclopentene, (3) a substituted or unsubstituted styrene, (4) a substituted or unsubstituted norbornene derivative bearing functional group, and (5) a polar olefin. Preferred olefins are polypropylene and ethylene for the formation of polypropylene and high density polyethylene. The zwitterionic catalysts of this invention catalyze the formation of polypropylene and high molecular weight polyethylene, e.g., having a molecular weight from 50 K to over a million Daltons
- Ethylene polymerization reactions with compound for 2 were studied, and the results of these studies are listed in Table 1.
-
TABLE 1 Polymerization of ethylene a and propylene b with compound 1 or 2. Com- Addi- Ex- pound tive T Time Activ- Tm ample (μmol) (equiv.) (° C.) (min) ityc Mw PDI (° C.) 1 2(6)a 0 30 10 453 135 500 5.86 135 2 2(3)a BCF(6) 30 8 2190 134 800 2.59 134 3 2(3)a BCF(6) 75 8 4050 149 700 6.90 117 4 2(2)a BCF(6) 75 5 6900 132 300 6.86 118 5 1(6)a 0 30 10 0 6 2(20)b BCF(2) 17 90 18 207 400 2.05 7 2(20)b BCF(3) 17 90 34 205 800 2.07 70 8 2(20)b BCF(3) 17 240 17 242 700 2.23 aPolymerization conditions: 28 g toluene, 100 psi ethylene. bPolymerization conditions: 20 g toluene, 26 mL propylene. cActivity in kg polymer/(mol cat · h). - Addition of 100 psi ethylene to a solution of compound 2 in toluene at 30° C. results in the quick consumption of the monomer and polymer formation (Example 1). Use of an additional 6 equivalents of B(C6F5)3 increases the activity of the catalyst and decreases the polydispersity index (PDI) of the polymer (Example 2). The PDI is a measure of the distribution of molecular weights in a given polymer sample and is the weight average molecular weight divided by the number average molecular weight. It indicates the distribution of individual molecular weight number average molecular weights in a batch of polymers. The PDI has a value always greater than 1, but as the polymer chains approach uniform chain length, the PDI approaches unity.
- Thermal analysis indicates the polymer has high melting point, consistent with the highly linear polymer structure (7 branches/1000 carbons) revealed by 1H NMR spectroscopy. The activity increases with temperature and at 75° C. (entries 3 and 4) it is comparable to those of cationic diimine nickel initiators [3]. The polymers formed at high temperature have broad PDI, more branching in the backbone (23 branches/1000 carbons) and lower melting points. No reaction occurs by using compound 1 (Example 5).
- Compound 2 also initiates propylene polymerization to produce high molecular weight PP (Table 1, entries 6-8). The product is purified by precipitation from toluene using acetone. 13C NMR spectroscopy indicates the PP is isotactic rich with an mmmm pentad fraction of 0.6. In contrast, diimine nickel initiators provide atactic or syndiotactic structures [3, 26]. Chain-end control by using compound 2 is suggested by the observation of mmrm sequence and absence of mmrr and mrrm sequences [27]. Signals at 36.7, and 30.2 ppm in the 13C NMR spectra reveal the presence of polyethylene segments, which were observed previously in the PP formed with cationic Ni(diimine) initiators. It has been previously proposed that 2,1 monomer insertion and subsequent chain walking to give 1,ω-enchainments results in these linear segments [1]. The PP obtained has a broad Tm at 70° C. and a Tg at −23° C.
- Example 4 can be repeated with a catalyst of formula 1 in which M is Pd, L′ is phosphine, R′ is methyl, X′ is carbonyl, R is methyl, R″ is ethyl, R″′ is phenyl, Riv is hydrogen, n is 1 and L is oxygen, X″ is amine, and LA is Al(C6F5)3.
- Example 4 can be repeated with a catalyst of formula 1 in which M is Pt, L′ is amine, R′ is ethyl, X′ is imine, R is ethyl, R″ is propyl, R″′ is hydrogen, Riv is hydrogen, n is 0, X″ is phosphine, and LA is a proton.
- Example 4 can be repeated with a catalyst of formula 1 in which M is Pd, L′ is ether, R′ is propyl, X′ is phosphine, R is ethyl, R″ is propyl, R″′ is n-methyl phenyl, Riv is methyl, n is 1 and L is amine, X″ is oxygen, and LA is BF3.
- Example 4 can be repeated using an olefin having formula RvCH═CH2, wherein Rv is a hydrocarbyl group.
- Example 4 can be repeated using an olefin having formula RvCH═CH2, wherein Rv is styrene as the olefin.
- Example 4 can be repeated using cyclopentene as the olefin.
- Example 4 can be repeated using a norbornene bearing functional group as the olefin.
- In summary, we have demonstrated that a zwitterionic nickel complex supported by the 3-(2,6-diisopropylphenylimino)-but-1-en-2-olato ligand can be used to prepare high molecular weight PE and PP. The most noteworthy feature of the active site is that it is supported by an olefinic fragment, which lacks substantial steric hindrance. Such a structure departs from previous structure/reactivity relationships and theoretical predictions for cationic Ni(diimine) complexes, which require sterically demanding substituents to produce high molecular weight PE. Bonding from an olefin is considerably different from that of a nitrogen donor in that on-back bonding is a possibility. Whether this electronic feature is responsible for the increasing the ratio of the rate of chain propagation, relative to chain transfer or termination rates is unknown at this stage and requires theoretical analysis for elucidation.
- Although the present invention has been described in connection with the preferred embodiments, it is to be understood that modifications and variations may be utilized without departing from the principles and scope of the invention, as those skilled in the art will readily understand. Accordingly, such modifications may be practiced within the scope of the following claims.
-
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