Catalyst activator

Details Catalyst activator Catalyst activator

1999-11-19

2001-07-31

Wu, David W. (Department: 1713)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S160000, C526S943000, C502S103000, C502S152000, C568S943000

Reexamination Certificate

active

06268445

ABSTRACT:

The present invention relates to compounds that are useful as catalyst components. More particularly the present invention relates to such compounds that are particularly adapted for use in the coordination polymerization of unsaturated compounds comprising two Group 13 metal or metalloid atoms and a ligand structure including at least one bridging group connecting ligands on two Group 13 metal or metalloid atoms thereof. Such compounds are particularly advantageous for use in a polymerization process wherein catalyst, catalyst activator, and at least one polymerizable monomer are combined under polymerization conditions to form a polymeric product.
It is previously known in the art to activate Ziegler-Natta polymerization catalysts, particularly such catalysts comprising Group 3-10 metal complexes containing delocalized &pgr;-bonded ligand groups, by the use of Bronsted acid salts capable of transferring a proton to form a cationic derivative or other catalytically active derivative of such Group 3-10 metal complex. Preferred Bronsted acid salts are such compounds containing a cation/anion pair that are capable of rendering the Group 3-10 metal complex catalytically active. Suitable activators comprise fluorinated arylborate anions, most preferably, the tetrakis(pentafluorophenyl)borate anion. Additional suitable anions include sterically shielded diboron anions of the formula:
wherein:
S is hydrogen, alkyl, fluoroalkyl, aryl, or fluoroaryl, Ar
F
is fluoroaryl, and X
1
is either hydrogen or halide, disclosed in U.S. Pat. No. 5,447,895. Additional examples include carborane compounds such as are disclosed and claimed in U.S. Pat. No. 5,407,884.
Additional bisborane compounds lacking in aromatic bridging groups have been previously disclosed in U.S. Pat. No. 5,496,960
, Angew. Chem. Int. Ed. Engl
., (1995) 34(7), 809-11
, Polyhedron
, (1997), 17(1), 119-124
, Organometallics
, (1994), 13(10) 3755-7
, Aust. J. Chem
. (1979), 32(11), 2381-93 and
Spectrochim, ACTA, PART A
, (1968), 24(8), 1125-33.
Examples of preferred charge separated (cation/anion pair) activators are protonated ammonium, sulfonium, or phosphonium salts capable of transferring a hydrogen ion, disclosed in U.S. Pat. No. 5,198,401, U.S. Pat. No. 5,132,380, U.S. Pat. No. 5,470,927, and U.S. Pat. No. 5,153,157, as well as oxidizing salts such as carbonium, ferrocenium and silyilium salts, disclosed in U.S. Pat. No. 5,350,723, U.S. Pat. No. 5,189,192 and U.S. Pat. No. 5,626,087.
Further suitable activators for the above metal complexes include strong Lewis acids including (trisperfluorophenyl)borane and tris(perfluorobiphenyl)borane. The former composition has been previously disclosed for the above stated end use in EP-A-520,732, whereas the latter composition is similarly disclosed by Marks, et al., in
J. Am. Chem. Soc
., 118, 12451-12452 (1996).
Despite the satisfactory performance of the foregoing catalyst activators under a variety of polymerization conditions, there is still a need for improved cocatalysts for use in the activation of various metal complexes under a variety of reaction conditions. Accordingly, it would be desirable if there were provided compounds that could be employed in solution, slurry, gas phase or high pressure polymerizations and under homogeneous or heterogeneous process conditions having improved activation properties.
According to the present invention there is now provided Group 13 containing compounds useful as catalyst activators in neutral (Lewis acid) or charge separated (cation/anion pair) form, corresponding to the formula:
wherein:
B
1
and B
2
independently each occurrence are Group 13 metal or metalloid atoms, preferably boron;
Z* is an optional divalent bridging group containing from 1 to 20 atoms, not counting hydrogen atoms;
R
1
and R
2
independently each occurrence are monovalent, anionic ligand groups containing from 1 to 40 atoms not counting hydrogen atoms, and, for cationic compounds, additionally comprising a dissociated cation moiety;
Ar
f1
and Ar
f2
independently each occurrence are monovalent, fluorinated organic groups containing from 6 to 100 carbon atoms, optionally, an Ar
f1
and an R
2
group, or an Ar
f2
and an R
1
group together form a divalent bridging group, and further optionally an Ar
f1
group and an Ar
f2
group together form a C
6-100
divalent bridging group,
z is 0 or 1,
r and s independently are 0, 1 or 2, and
m and n are 1, 2 or 3;
with the proviso that when z is 0, at least one of Ar
f1
and Ar
f2
are joined together, and the sum of r, z and m is 3 or 4, in the former event B
1
is neutral and in the latter event B
1
is negatively charged, said charge being balanced by a cation component of one R
1
; and the sum of s, z and n is 3 or 4, in the former event B
2
is neutral and in the latter event B
2
is negatively charged, said charge being balanced by a cation component of one R
2
.
Additionally according to the present invention there is provided a catalyst composition for polymerization of an ethylenically unsaturated, polymerizable monomer comprising, in combination, the above described compound and a Group 3-10 metal complex, or the reaction product of such combination.
Additionally according to the present invention there is provided a process for polymerization of one or more ethylenically unsaturated, polymerizable monomers comprising contacting the same, optionally in the presence of an inert aliphatic, alicyclic or aromatic hydrocarbon, with the above catalyst composition.
The foregoing compounds are uniquely adapted for use in activation of a variety of metal complexes, especially Group 4 metal complexes, under standard and atypical olefin polymerization conditions. They are uniquely capable of forming monomeric and dimeric cationic metal complexes when combined with neutral metallocene complexes under such polymerization conditions. Because of this fact, the foregoing compounds are capable of forming highly desirable olefin polymers having enhanced levels of long chain branching, stereospecificity and comonomer distribution. In particular, bis-anions, due to the pairing of active catalyst sites in close proximity to one another, are capable of providing a higher local concentration of active catalyst site at the point of polymer formation. Moreover, such paired catalyst sites may be comprised of two disparate metals or metal ligand arrangements, or otherwise tailored to provide desirable polymer properties. For example, the use of symmetrical or unsymmetrical bis-anions results in two catalytically active sites that are held in close proximity during a polymerization reaction, thereby providing a large increase in local concentration of active catalyst sites. This increased local concentration of active catalyst sites leads to enhanced polymer stereostructure, molecular weight and microstructure. Certain catalyst sites in close proximity result in random comonomer incorporation, others affect the stereospecificity of their close neighbor. By controlling the random versus clustered distribution of comonomer, blocky or non-blocky copolymers can be prepared. Additionally, the two catalysts associated with each bis-anion may themselves be nonspecific or stereospecific, such that the resulting combination catalyst is adapted to produce block copolymers via polymer interchange between such nonspecific and stereospecific catalysts. The degree of long-chain branching in polyolefins produced using multiple catalyst sites on bis-anions is enhanced due to the rate of reincorporation of in situ generated vinyl terminated macromonomer into the growing polymer chain due to the higher local concentration of catalyst.
DETAILED DESCRIPTION OF THE INVENTION
All references herein to elements belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1995. Also any reference to the Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. When, in reference to a cation portion of any compound

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