WO1998006759A9 - Group iv zwitterion ansa metallocene (zam) catalysts for alpha-olefin polymerization - Google Patents
Group iv zwitterion ansa metallocene (zam) catalysts for alpha-olefin polymerizationInfo
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- WO1998006759A9 WO1998006759A9 PCT/US1997/013793 US9713793W WO9806759A9 WO 1998006759 A9 WO1998006759 A9 WO 1998006759A9 US 9713793 W US9713793 W US 9713793W WO 9806759 A9 WO9806759 A9 WO 9806759A9
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- Prior art keywords
- group
- substituted
- unsubstituted
- alkyl
- aryl
- Prior art date
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 12
- 239000004711 α-olefin Substances 0.000 title abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims description 41
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- 239000001257 hydrogen Substances 0.000 claims description 35
- 150000002431 hydrogen Chemical class 0.000 claims description 33
- 125000003545 alkoxy group Chemical group 0.000 claims description 24
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 20
- 150000001336 alkenes Chemical class 0.000 claims description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 14
- 229910052796 boron Inorganic materials 0.000 claims description 14
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Chemical group 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 9
- KLGZELKXQMTEMM-UHFFFAOYSA-N hydride Chemical compound [H-] KLGZELKXQMTEMM-UHFFFAOYSA-N 0.000 claims description 9
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910021480 group 4 element Inorganic materials 0.000 claims description 4
- 229910021478 group 5 element Inorganic materials 0.000 claims description 4
- 229910021476 group 6 element Inorganic materials 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 3
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 5
- 125000001153 fluoro group Chemical group F* 0.000 claims 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims 1
- 239000003426 co-catalyst Substances 0.000 abstract description 9
- 150000001450 anions Chemical class 0.000 abstract description 4
- 150000001768 cations Chemical class 0.000 abstract 1
- 230000027455 binding Effects 0.000 description 7
- 239000003446 ligand Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M Lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 230000001264 neutralization Effects 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000003775 Density Functional Theory Methods 0.000 description 3
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 3
- 230000003197 catalytic Effects 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 238000006713 insertion reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000004057 DFT-B3LYP calculation Methods 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 125000004432 carbon atoms Chemical group C* 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000379 polymerizing Effects 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N Trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J Zirconium(IV) chloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- 229910007928 ZrCl2 Inorganic materials 0.000 description 1
- 229910007932 ZrCl4 Inorganic materials 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 238000007068 beta-elimination reaction Methods 0.000 description 1
- 230000024881 catalytic activity Effects 0.000 description 1
- 239000011951 cationic catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
Definitions
- ZAM Group IV Zwitterion Ansa Metallocene (ZAM) Catalysts For Alpha-Olefin Polymerization
- the present invention generally relates to olefin polymerization catalysts, and more specifically to single component metallocene catalysts for ⁇ -olefin polymerization.
- catalysts require an anionic co-catalyst (or a catalyst activator) , typically perfluorophenylborates or methyl aluminoxane (MAO) , to generate the catalytically active cationic fourteen electron d° species .
- anionic co-catalyst typically perfluorophenylborates or methyl aluminoxane (MAO)
- MAO-based systems predominate in industrial applications.
- MAO must be present in large molar excess (200-2000 times that of the metallocene catalyst) , its presence accounts for over 50% of the cost of the catalytic system. In addition to the increased expense, little is known about MAO's structure or role in the polymerization reaction. Moreover, because MAO may also provide an additional route for chain termination (via chain transfer to the trimethyl aluminum) , this complicates the design of more selective catalysts.
- Another approach is to incorporate a counter anion for a Group IV catalyst directly into the ligand.
- Jordan, et al . (Crowther, et al . , J. Am . Chem. Soc . 113:1455 (1991)) prepared catalyst in which one cyclopentadienyl (Cp) ligand is replaced by a dianionic dicarbolide ligand.
- Cp cyclopentadienyl
- the resulting complex was expected to be capable of ⁇ -olefin polymerization.
- these complexes readily undergo ⁇ - elimination, have low activity, and only oligomerize polypropylene.
- Figure 1 illustrates the result of energy calculations comparing a zwitterion ansa metallocene (ZAM) catalyst with a standard Ziegler-Natta catalyst for each step of olefin polymerization.
- ZAM zwitterion ansa metallocene
- Figure 2 illustrates transition state enthalpies for two ZAM catalysts and a standard Ziegler-Natta catalyst .
- ZAM zwitterion ansa metallocene
- M is selected from a group consisting of Group III, Group IV, Group V, and Group VI elements
- E is boron or aluminum
- R x and R 2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C x to C 10 alkyl, substituted or unsubstituted to C 6 to C 15 aryl, and substituted and unsubstituted C x to C 10 alkoxy;
- R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , and R l ⁇ are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C x to C 10 alkyl, substituted or unsubstituted C to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 12 ) 3 where R 12 is selected from the group consisting of C- L to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl; and,
- R 7 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R 13 ) 3 where R 13 is selected from a group consisting of C ⁇ to C 10 alkyl, C 6 to C 15 aryl, and C 3 to C 10 cyclolalkyl .
- each pair of adjacent radicals on the cyclopentadienyl rings (e.g., R 4 and R 5 or R 10 and R 1X ) together may also form a cyclic group having 4 to 15 carbon atoms which in turn may be further substituted.
- M is a Group IV metal
- R and R 2 are each an electron withdrawing group
- R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , and R l are each selected from a group consisting of hydrogen, methyl, isopropyl, tert-butyl and trimethylsilyl .
- M is zirconium.
- the invention further includes a method for polymerizing olefins comprising the step of contacting an olefin with a catalyst of the type described above.
- the olefin may be a C 3 -C 10 ⁇ -olefin, and the olefin may be contacted with the catalyst in the presence of a solvent .
- the catalysts of the present invention are zwitterion ansa metallocenes that are referred to as ZAM catalysts.
- the inventive catalysts eliminates the need for a counterion like MAO while retaining or improving most of the various kinetic steps in olefin polymerization over prior art Ziegler-Natta catalysts .
- ZAM catalysts are of the general formula:
- M is selected from a group consisting of Group III, Group IV, Group V, and Group VI elements;
- E is boron or aluminum;
- R ⁇ and R 2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C ⁇ to C 10 alkyl, substituted or unsubstituted to C 6 to C 15 aryl, and substituted and unsubstituted C to C 10 alkoxy;
- R 3 , R 4 , R 5 , R 6 , R 8 , R 9 , R 10 , and R ⁇ are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C-_ to C 10 alkyl, substituted or unsubstituted C-_ to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 12 ) 3 where R 12 is selected from the group consisting of C to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl; and, R 7 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R 13 ) 3 where R 13 is selected from a group consisting of C to C 10 alkyl, C 6 to C 15 aryl, and C 3 to C 10
- each pair of adjacent radicals on the cyclopentadienyl rings may also form a cyclic group having 4 to 15 carbon atoms which in turn may be further substituted.
- Examples of compounds wherein one or more pairs of adjacent radicals form cyclic ring include but are not limited to:
- R-_ and R 2 are each a group which increases the electrophilicity of the metal center.
- suitable groups include but are not limited to F, C 6 F 5 , and CF 3 .
- M is a Group IV metal
- R 3 3,' R 4 ,' R5e,' R ⁇ 6 6,' R ⁇ a 8#' R ⁇ 9' R 10' and R ⁇ l are each selected from a group consisting of hydrogen, methyl, isopropyl, tert-butyl and trimethylsilyl .
- M is zirconium.
- E is boron or aluminum
- R r and R 2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C ⁇ to C 10 alkyl, substituted or unsubstituted to C 6 to C 15 aryl, and substituted and unsubstituted C to C 10 alkoxy;
- R 3 , R 4 , R 5 , and R 6 are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C to C 10 alkyl, substituted or unsubstituted C-, ⁇ to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 9 ) 3 where R 9 is selected from the group consisting of C to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl, wherein each pair of adjacent radicals together also may form a substituted or unsubstituted cyclic group having 4 to 15 carbons;
- R 7 is selected from a group consisting of hydrogen, substituted or unsubstituted C to C 10 alkyl, substituted or unsubstituted C x to C 10 alkoxy, substituted or unsubstituted C 6 to C 15 aryl, substituted or unsubstituted C 3 to C 10 cycloalkyl, and Si(R 10 ) 3 where R 10 is selected from the group consisting of C x to C 10 alkyl, C 6 to C 15 aryl, or C 3 to C 10 cycloalkyl; and,
- R 8 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R 11 ) 3 where R x is selected from a group consisting of C to C 10 alkyl, C 6 to C 15 aryl, and C 3 to C 10 cyclolalkyl .
- R 7 is tert-butyl or trimethyl-silyl .
- These compounds are variations of traditional metallocene catalysts and are generally referred to as mono-Cp "constrained- geometry catalysts" (or CGC) .
- CGC constrained- geometry catalysts
- the invention further includes a method for polymerizing olefins comprising the step of contacting an olefin with a catalyst of the types described above.
- the olefin may be a C 3 -C 10 ⁇ -olefin, and the olefin may be contacted with the catalyst in the presence of a solvent .
- the constrained-geometry embodiment of the present invention may be synthesized by known methods in the art, including but not limited to the protocol described by Organometallics, 9 : 866-869 (1990) which is incorporated herein by reference.
- the metallocene catalysts of the present invention may also be prepared by a variety of methods known in the art including the protocol described below. Although the protocol is for the preparation of (C 6 F 5 ) 2 B (C 5 H 4 ) 2 ZrCH 3 , persons skilled in the art would readily know how to adapt the protocol for the various inventive embodiments.
- DFT Density Functional Theory
- the Zr was described with the LACVP Hay Wadt effective core potential (ECP) to replace the core electrons [leaving the (4s) 2 (4p) 6 [ (4d) (5s) (5p)] 4 electrons to be described explicitly] and using the standard double zeta contraction.
- ECP effective core potential
- the results of the insertion reaction are summarized in Figure 1 which displays the energies along the reaction coordinates for ZAM I and control II.
- Figure 1 illustrates, the standard cationic metallocene binds ethylene exothermically by approximately 23 kcal/mol while the corresponding ZAM binds exothermically by about 16 kcal/mol.
- the insertion barrier for the cationic metallocene ranges from about 6-10 kcal/mol while ZAM has an insertion barrier of just less than 3 kcal/mol.
- the remaining energies of the ZAM catalyst were consistent with the energies of the cationic catalyst at the same level of theory.
- the energetics for the insertion reaction for ZAM I, ZAM III and control II are summarized in figure 2.
- the results for ZAM I and control II were calculated using DLDA-B3LYP and are consistent with the results using NLDA-GGAII.
Abstract
Single component metallocene catalysts for α-olefin polymerization are disclosed. Prior art cation metallocene catalysts have required a separate anion co-catalyst like methyl aluminoxane (MAO). However, because the inventive zwitterion ansa metallocene (ZAM) catalysts have a 'built-in' anion co-catalyst functionality, the need for a separate anion co-catalyst is eliminated.
Description
PATENT APPLICATION
Group IV Zwitterion Ansa Metallocene (ZAM) Catalysts For Alpha-Olefin Polymerization
FIELD OF THE INVENTION
The present invention generally relates to olefin polymerization catalysts, and more specifically to single component metallocene catalysts for α-olefin polymerization.
This application claims the benefit of U.S. Provisional Application No. 60/024,395 filed August 9, 1996 which is incorporated herein by reference. The U.S. Government has certain rights in this invention pursuant to Grant NO. CHE- 9522179 awarded by the National Science Foundation.
BACKGROUND OF THE INVENTION
Polymers made by metallocene catalysts are gaining an increasing share of the worldwide plastics market. Many of these industrial catalysts are Kaminsky type ansa-metallocenes derived from 1.
These catalysts require an anionic co-catalyst (or a catalyst activator) , typically perfluorophenylborates
or methyl aluminoxane (MAO) , to generate the catalytically active cationic fourteen electron d° species .
Of the two classes of co-catalysts, MAO-based systems predominate in industrial applications.
Because MAO must be present in large molar excess (200-2000 times that of the metallocene catalyst) , its presence accounts for over 50% of the cost of the catalytic system. In addition to the increased expense, little is known about MAO's structure or role in the polymerization reaction. Moreover, because MAO may also provide an additional route for chain termination (via chain transfer to the trimethyl aluminum) , this complicates the design of more selective catalysts.
As a result, there have been many attempts to modify the Group IV metallocene based catalytic system to eliminate the need for MAO. Although perfluorophenylborates (i.e., perfluorinated tetra- alkyl borates) may be substituted as the co-catalyst, their thermal instability and extreme sensitivity to oxygen make them impractical for large scale industrial applications.
An attractive alternative is to design a single component Ziegler Natta catalyst that does not require any co-catalyst. One such attempt is Bercaw' s series of iso-electronic Group III neutral metallocenes such as 2 (Burger, et al . , Am. Chem . Soc . 112:1566 (1990)). Although Bercaw' s catalysts have been enormously useful in elucidating the basic processes involved in olefin polymerization, they are
of limited use in industrial applications because of their low polymerization activity.
Another approach is to incorporate a counter anion for a Group IV catalyst directly into the ligand. In one attempt, Jordan, et al . (Crowther, et al . , J. Am . Chem. Soc . 113:1455 (1991)) prepared catalyst in which one cyclopentadienyl (Cp) ligand is replaced by a dianionic dicarbolide ligand. As a neutral d° species, the resulting complex was expected to be capable of α-olefin polymerization. Unfortunately, these complexes readily undergo β- elimination, have low activity, and only oligomerize polypropylene. The polarization of the dicarbolide- zirconium bond is believed to result in a more neutral metal center which makes the initial binding of the propylene less exothermic and the insertion into the Zr-R bond more disfavored since the Zr orbital would be less d-like. An attempt using a trimethylene methane ligand instead of the dicarbolide ligand also produced similar results (Rodriquez G. & Bazan G. C, J. Am . Chem. Soc . 113:1455 (1991) ) .
Consequently, a need exists for a single component Ziegler-Natta catalysts that is comparable to Kaminsky type ansa-metallocenes but without the need for a co-catalyst like MAO.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 illustrates the result of energy calculations comparing a zwitterion ansa metallocene (ZAM) catalyst with a standard Ziegler-Natta catalyst for each step of olefin polymerization.
Figure 2 illustrates transition state enthalpies for two ZAM catalysts and a standard Ziegler-Natta catalyst .
SUMMARY OF THE INVENTION
A single component neutral zwitterion ansa metallocene (ZAM) catalysts are disclosed. In embodiment of the inventive catalysts, compounds are of the general formula :
wherein
M is selected from a group consisting of Group III, Group IV, Group V, and Group VI elements;
E is boron or aluminum;
Rx and R2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted Cx to C10 alkyl, substituted or unsubstituted to C6 to C15 aryl, and substituted and unsubstituted Cx to C10 alkoxy;
R3, R4, R5, R6, R8, R9, R10, and Rlχ are each independently selected from a group consisting of hydrogen, substituted or unsubstituted Cx to C10 alkyl, substituted or unsubstituted C to C10 alkoxy, substituted or unsubstituted C6 to C15 aryl, substituted or unsubstituted C3 to C10 cycloalkyl, and Si(R12)3 where R12 is selected from the group consisting of C-L to C10 alkyl, C6 to C15 aryl, or C3 to C10 cycloalkyl; and,
R7 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R13)3 where R13 is selected from a group consisting of Cλ to C10 alkyl, C6 to C15 aryl, and C3 to C10 cyclolalkyl .
Moreover, each pair of adjacent radicals on the cyclopentadienyl rings (e.g., R4 and R5 or R10 and R1X) together may also form a cyclic group having 4 to 15 carbon atoms which in turn may be further substituted.
Preferably, M is a Group IV metal; R and R2 are each an electron withdrawing group; and R3, R4, R5, R6, R8, R9, R10, and R l are each selected from a group consisting of hydrogen, methyl, isopropyl, tert-butyl and trimethylsilyl . In especially preferred embodiments, M is zirconium.
The invention further includes a method for polymerizing olefins comprising the step of contacting an olefin with a catalyst of the type described above. The olefin may be a C3-C10 α-olefin, and the olefin may be contacted with the catalyst in the presence of a solvent .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The catalysts of the present invention are zwitterion ansa metallocenes that are referred to as ZAM catalysts. The inventive catalysts eliminates the need for a counterion like MAO while retaining or improving most of the various kinetic steps in olefin polymerization over prior art Ziegler-Natta catalysts .
In one embodiment, ZAM catalysts are of the general formula:
wherein
M is selected from a group consisting of Group III, Group IV, Group V, and Group VI elements; E is boron or aluminum;
R± and R2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted Cλ to C10 alkyl, substituted or unsubstituted to C6 to C15 aryl, and substituted and unsubstituted C to C10 alkoxy;
R3, R4, R5, R6, R8, R9, R10, and R ι are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C-_ to C10 alkyl, substituted or unsubstituted C-_ to C10 alkoxy, substituted or unsubstituted C6 to C15 aryl, substituted or unsubstituted C3 to C10 cycloalkyl, and Si(R12)3 where R12 is selected from the group consisting of C to C10 alkyl, C6 to C15 aryl, or C3 to C10 cycloalkyl; and, R7 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R13)3 where R13 is selected from a group consisting of C to C10 alkyl, C6 to C15 aryl, and C3 to C10 cyclolalkyl .
Moreover, each pair of adjacent radicals on the cyclopentadienyl rings (e.g., R4 and R5 or R10 and Rl ) together may also form a cyclic group having 4 to 15 carbon atoms which in turn may be further substituted. Examples of compounds wherein one or more pairs of adjacent radicals form cyclic ring include but are not limited to:
and
In preferred embodiments, R-_ and R2 are each a group which increases the electrophilicity of the metal center. Illustrative examples of suitable groups include but are not limited to F, C6F5, and CF3. It is also preferred that M is a Group IV metal, and R3 3,' R4,' R5e,' R ^66,' R ^a8#' R ^9' R 10' and Rχl are each selected from a group consisting of hydrogen,
methyl, isopropyl, tert-butyl and trimethylsilyl . In especially preferred embodiments, M is zirconium.
Another embodiment of the present invention are compounds of the general formula:
wherein
E is boron or aluminum;
Rr and R2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted Cλ to C10 alkyl, substituted or unsubstituted to C6 to C15 aryl, and substituted and unsubstituted C to C10 alkoxy;
R3, R4, R5, and R6 are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C to C10 alkyl, substituted or unsubstituted C-,^ to C10 alkoxy, substituted or unsubstituted C6 to C15 aryl, substituted or unsubstituted C3 to C10 cycloalkyl, and Si(R9)3 where R9 is selected from the group consisting of C to C10 alkyl, C6 to C15 aryl, or C3 to C10 cycloalkyl, wherein each pair of adjacent radicals
together also may form a substituted or unsubstituted cyclic group having 4 to 15 carbons;
R7 is selected from a group consisting of hydrogen, substituted or unsubstituted C to C10 alkyl, substituted or unsubstituted Cx to C10 alkoxy, substituted or unsubstituted C6 to C15 aryl, substituted or unsubstituted C3 to C10 cycloalkyl, and Si(R10)3 where R10 is selected from the group consisting of Cx to C10 alkyl, C6 to C15 aryl, or C3 to C10 cycloalkyl; and,
R8 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R11)3 where R x is selected from a group consisting of C to C10 alkyl, C6 to C15 aryl, and C3 to C10 cyclolalkyl .
In preferred compounds of this embodiment, R7 is tert-butyl or trimethyl-silyl . These compounds are variations of traditional metallocene catalysts and are generally referred to as mono-Cp "constrained- geometry catalysts" (or CGC) . Compounds where E = Si were one of the first single-site catalysts to be developed and are used to produce polymers which posesess desirable strength properties while still allowing for easy processibility . Based upon energy calculations for single component metallocene catalysts, it is believed that these compounds would similarly display catalytic activity without the need for a co-catalyst.
The invention further includes a method for polymerizing olefins comprising the step of contacting an olefin with a catalyst of the types described above. The olefin may be a C3-C10 α-olefin,
and the olefin may be contacted with the catalyst in the presence of a solvent .
The constrained-geometry embodiment of the present invention may be synthesized by known methods in the art, including but not limited to the protocol described by Organometallics, 9 : 866-869 (1990) which is incorporated herein by reference.
The metallocene catalysts of the present invention may also be prepared by a variety of methods known in the art including the protocol described below. Although the protocol is for the preparation of (C6F5) 2B (C5H4) 2ZrCH3 , persons skilled in the art would readily know how to adapt the protocol for the various inventive embodiments.
(C6F5)2BC1 is mixed with two equivalents of
Li (C5H4) S (CH3) 3 and condensed with diethyl ether at -78°C. The mixture is slowly warmed to room temperature and allowed to stir overnight. ZrCl4 in toluene is slowly added and allowed to stir overnight at 80°C. The product is extracted from LiCl by rinsing with toluene or crashing out LiCl from the tetrahydrofuran (THF) solution with toluene, thus leaving the ligand in solution.
As illustrated by the synthetic scheme, (C6F5) 2B (C5H4)2ZrCH3 is prepared by treating
ZrC14
IBtCeFsJJIQCeHsJJ
To demonstrate the performance of the inventive catalysts with prior art catalysts, the insertion reaction of methyl metallocene complexes with a molecule of ethylene was computationally followed for three illustrative ZAM catalysts and two standard
Ziegler-Natt catalysts. The ZAM catalysts studied were of the formula :
wherein R = H and E = B in embodiment I (ZAM I) ; R = F and E = B for embodiment II (ZAM II) ; and R = H and E = Al in embodiment III (ZAM III) .
The two standard Group IV metallocenes were of the formula :
wherein E = C in control I and E = Si for control II.
Density Functional Theory (DFT) calculations were carried out using the PS-GVB-DFT program.
Ringnalda, et al . , PS-GVB, 2.3 Schrδdinger, Inc. 1996; Slater, J. C, Quantum Theory of Molecules and Solids, vol , 4 . The Self -Consistent Field for Molecules and Solids (McGraw-Hill, New York, 1974) ; and Perdew, J. P. Electronic Structure Theory of Solids, Ziesche, P. & Eschrig, H. eds. (Akademie Verlag, Berlin, 1991) . The Zr was described with the
LACVP Hay Wadt effective core potential (ECP) to replace the core electrons [leaving the (4s) 2 (4p) 6 [ (4d) (5s) (5p)]4 electrons to be described explicitly] and using the standard double zeta contraction. Hay, et al . , J. Phys . Chem. 82:270 (1985) . All other atoms, B, C, H, were described using the 6-31G** basis. Frisch, et al . , J. Chem . Phys . 80:3265 (1984). Collectively this ECP Basis is referred to as LACVP**. The NLDA implementation of DFT with GGAII functional (NLDA-GGAII) as well as the Becke 3 Yang, Lee, Parr functionals (NLDA-B3LYP) were used. All geometries for stable intermediates and for transition states were fully optimized with the above basis and method. Unless otherwise noted, the geometry was optimized without geometry constraints . Interesting, despite using different ah ini tio methods, the energies calculated for control II are virtually identical to those previously obtained by Morokuma's group (Yoshida, et al . , Organometallics 14:746 (1995) ) .
The results of the insertion reaction are summarized in Figure 1 which displays the energies along the reaction coordinates for ZAM I and control II. As Figure 1 illustrates, the standard cationic metallocene binds ethylene exothermically by approximately 23 kcal/mol while the corresponding ZAM binds exothermically by about 16 kcal/mol. The insertion barrier for the cationic metallocene ranges from about 6-10 kcal/mol while ZAM has an insertion barrier of just less than 3 kcal/mol. The remaining energies of the ZAM catalyst were consistent with the energies of the cationic catalyst at the same level of theory.
The energetics for the insertion reaction for ZAM I, ZAM III and control II are summarized in figure 2. The results for ZAM I and control II were calculated using DLDA-B3LYP and are consistent with the results using NLDA-GGAII.
It is to be understood that while the invention has been described above in conjunction with preferred specific embodiments, the description and examples are intended to illustrate and not limit the scope of the invention.
Claims
1. A metallocene catalyst of the formula:
wherein
M is selected from a group consisting of Group III, Group IV, Group V, and Group VI elements;
E is boron or aluminum;
R and R2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted Cx to C10 alkyl, substituted or unsubstituted to C6 to C15 aryl, and substituted and unsubstituted C to C10 alkoxy;
R3, R4, R5, R6, R8, R9, R10, and R are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C to C10 alkyl, substituted or unsubstituted Cx to C10 alkoxy, substituted or unsubstituted C6 to C15 aryl, substituted or unsubstituted C3 to C10 cycloalkyl, and Si(R12)3, where R12 is selected from the group consisting of C to C10 alkyl, C6 to C15 aryl, or C3 to C10 cycloalkyl, wherein each pair of adjacent radicals together also may form a substituted or unsubstituted cyclic group having 4 to 15 carbons; and,
R7 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R13)3 where R13 is selected from a group consisting of Cx to C10 alkyl, C6 to C15 aryl, and C3 to C10 cyclolalkyl.
2. The catalyst as in claim 1 wherein M is a Group IV metal .
3. The catalyst as in claim 2 wherein M is zirconium.
4. The catalyst as in claim 1 wherein E is boron.
5. The catalyst as in claim 3 wherein R1# R2, R3 , R4, R5, R6, R8, R9, R10, and R x are each hydrogen.
6. The catalyst in claim 3 wherein E is boron;
Rχ and R2 are each independently selected from a group consisting of hydrogen, fluorine, CF3 , and C6F5; R3, R4, R5, R6, R8, R9, R10, and R11 are each independently selected from a group consisting of hydrogen, methyl, isopropyl, tert-butyl, and trimethylsilyl; and,
R7 is selected from a group consisting of methyl, tert-butyl, benzyl, phenyl, trimethylsilyl, and a hydride.
7. A metallocene of the formula comprising:
wherein
E is boron or aluminum and R is selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted Cx to C10 alkyl, substituted or unsubstituted to C6 to
C15 aryl, and substituted and unsubstituted C to C10 alkoxy.
8. The metallocene as in claim 7 wherein the alkyl, aryl, or alkoxy is substituted with at least one electron withdrawing group.
9. The metallocene as in claim 7 wherein the alkyl, aryl, or alkoxy is substituted with at least one fluorine atom.
10. The metallocene as in claim 9 wherein the alkyl, aryl, or alkoxy is a perfluorinated alkyl, perfluorinated aryl, or a perfluorinated alkoxy.
11. The metallocene as in claim 7 wherein E is boron .
12. The metallocene as in claim 11 wherein R is hydrogen .
13. The metallocene as in claim 11 wherein R is fluorine .
14. The metallocene as in claim 11 wherein R is C6F5 or CF3
15. A compound according to the formula:
wherein
E is boron or aluminum;
R and R2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted Cx to C10 alkyl, substituted or unsubstituted to C6 to C15 aryl, and substituted and unsubstituted C to C10 alkoxy;
R3 , R4, R5, and R6 are each independently selected from a group consisting of hydrogen, substituted or unsubstituted C to C10 alkyl, substituted or unsubstituted Cx to C10 alkoxy, substituted or unsubstituted C6 to C15 aryl, substituted or unsubstituted C3 to C10 cycloalkyl, and Si(R9)3 where R9 is selected from the group consisting of Cx to C10 alkyl, C6 to C15 aryl, or C3 to C10 cycloalkyl, wherein each pair of adjacent radicals together also may form a substituted or unsubstituted cyclic group having 4 to 15 carbons;
R7 is selected from a group consisting of hydrogen, substituted or unsubstituted C to C10 alkyl, substituted or unsubstituted Cx to C10 alkoxy, substituted or unsubstituted C6 to C15 aryl, substituted or unsubstituted C3 to C10 cycloalkyl, and Si(R10)3 where R10 is selected from the group consisting of C to C10 alkyl, C6 to C15 aryl, or C3 to C10 cycloalkyl; and,
R8 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(Rι:L)3 where Rx is selected from a group consisting of Cx to C10 alkyl, C6 to C15 aryl, and C3 to C10 cyclolalkyl .
16. A method for olefin polymerization, comprising: contacting the olefin with a catalyst of the formula :
wherein M is selected from a group consisting of Group
III, Group IV, Group V, and Group VI elements; E is boron or aluminum; Rx and R2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C to C10 alkyl, substituted or unsubstituted to C6 to C15 aryl, and substituted and unsubstituted Cx to C10 alkoxy;
R3 , R4, R5, R6, R8, R9, R10, and R are each independently selected from a group consisting of hydrogen, substituted or unsubstituted Cx to C10 alkyl, substituted or unsubstituted Cx to C10 alkoxy, substituted or unsubstituted C6 to C15 aryl, substituted or unsubstituted C3 to C10 cycloalkyl, and Si(R12)3 where R12 is selected from the group consisting of Cx to C10 alkyl, C6 to C15 aryl, or C3 to C10 cycloalkyl, wherein each pair of adjacent radicals together also may form a substituted or unsubstituted cyclic group having 4 to 15 carbons; and,
R7 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R13)3 where R13 is selected from a group consisting of Cx to C10 alkyl, C6 to C15 aryl, and C3 to C10 cyclolalkyl .
17. The method as in claim 16 wherein
M is zirconium;
E is boron; Rx and R2 are each independently selected from a group consisting of hydrogen, fluorine, CF3 , and C6F5;
R3, R4, R5, R6, R8, R9, R10, and RX1 are each independently selected from a group consisting of hydrogen, methyl, isopropyl, tert-butyl, and trimethylsilyl; and,
R7 is selected from a group consisting of methyl, tert-butyl, benzyl, phenyl, trimethylsilyl, and a hydride .
18. A method for olefin polymerization, comprising: contacting the olefin with a catalyst of the formula :
wherein
E is boron or aluminum and
R is selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted Cx to C10 alkyl, substituted or unsubstituted to C6 to C15 aryl, and substituted and unsubstituted C to C10 alkoxy.
19. The method as in claim 18 wherein E is boron
20. The method as in claim 19 wherein the alkyl, aryl, or alkoxy is substituted with one or more fluorine atoms.
21. The method as in claim 19 wherein R is hydrogen, fluorine, CF3, or C6F5.
22. A method for olefin polymerization, comprising: contacting the olefin with a catalyst of the formula:
E is boron or aluminum;
Rx and R2 are each independently selected from a group consisting of hydrogen, fluorine, substituted or unsubstituted C to C10 alkyl, substituted or unsubstituted to C6 to C15 aryl, and substituted and unsubstituted Cχ to C10 alkoxy;
R3, R4, R5, and R6 are each independently selected from a group consisting of hydrogen, substituted or unsubstituted Cx to C10 alkyl, substituted or unsubstituted C to C10 alkoxy, substituted or unsubstituted C6 to C15 aryl, substituted or unsubstituted C3 to C10 cycloalkyl, and Si(R9)3 where R9 is selected from the group consisting of Cx to C10 alkyl, C6 to C15 aryl, or C3 to C10 cycloalkyl, wherein each pair of adjacent radicals together also may form a substituted or unsubstituted cyclic group having 4 to 15 carbons;
R7 is selected from a group consisting of hydrogen, substituted or unsubstituted Cx to C10 alkyl, substituted or unsubstituted C to C10 alkoxy, substituted or unsubstituted C6 to C15 aryl, substituted or unsubstituted C3 to C10 cycloalkyl, and Si(R10)3 where R10 is selected from the group consisting of C to C10 alkyl, C6 to C15 aryl, or C3 to C10 cycloalkyl; and,
R8 is selected from a group consisting of hydrogen, methyl, tert-butyl, benzyl, phenyl, hydride, and Si(R1:L)3 where R is selected from a group consisting of Cx to C10 alkyl, C6 to C15 aryl, and C3 to C10 cyclolalkyl .
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EP97938137A EP0920455B1 (en) | 1996-08-09 | 1997-08-08 | Group iv zwitterion ansa metallocene (zam) catalysts for alpha-olefin polymerization |
DE69723084T DE69723084T2 (en) | 1996-08-09 | 1997-08-08 | CATALYST BASED ON A ZWITTERIONIC ANSA METALLOCENS OF GROUP IV FOR THE POLYMERIZATION OF ALPHA OLEFINS |
AU40532/97A AU4053297A (en) | 1996-08-09 | 1997-08-08 | Group iv zwitterion ansa metallocene (zam) catalysts for alpha-olefin polymerization |
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