Polymerization process using an improved bulky ligand...

Details Polymerization process using an improved bulky ligand... Polymerization process using an improved bulky ligand...

1998-11-13

2003-10-14

Lu, Caixia (Department: 1713)

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

Synthetic resins

Polymers from only ethylenic monomers or processes of...

C526S068000, C526S129000, C526S160000, C526S165000, C526S170000, C526S943000

Reexamination Certificate

active

06632901

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to a polymerization process using an improved bulky ligand metallocene-type catalyst system. The catalyst system comprises a bulky ligand metallocene-type compound having at least one fluoride leaving group or fluorine containing leaving group. At least one leaving group is abstractable from the bulky ligand metallocene type compound to render it catalytically active in the polymerization of olefins.
BACKGROUND OF THE INVENTION
Advances in polymerization and catalysis have resulted in the ability to produce many new polymers having improved physical and chemical properties useful in a wide variety of superior products and applications. With the development of new catalysts the choice of polymerization process (solution, slurry, high pressure or gas phase) for producing a particular polymer have been greatly expanded. Also, advances in polymerization technology has provided more efficient, highly productive and economically enhanced processes. Especially illustrative of these advances is the development of the technology field utilizing bulky ligand metallocene-type catalyst systems.
As with a new technology field, particularly in the polyolefins industry, a small savings in cost often determines whether a commercial endeavor is even feasible. This aspect in the metallocene technology field is evident by the number of participants in the industry looking for new ways to reduce cost. In particular, there has been tremendous focus in the industry on developing new and improved bulky ligand metallocene-type catalyst systems. Some have focused on designing the catalyst systems to produce new polymers, others on improved operability, and many more on improving catalyst productivity. The productivity of a catalyst, that is the amount of polymer produced per gram of the catalyst, usually is the key economic factor that can make or break a new commercial development in the polyolefin industry.
From the early stages in the metallocene technology field, beginning with the discovery of the utility of alumoxane as a cocatalyst in the early 1980's, to the discovery of substitutions on the bulky ligands of the metallocene-type compounds, through the development of non-coordinating anions, and today with the ever increasing number of new metallocene-type bulky ligand compounds, catalyst productivity has been a primary focus.
Evidence of this can be seen in this subset of the art discussing various bulky ligand metallocene-type catalyst compounds and catalyst systems described in U.S. Pat. Nos. 4,530,914, 4,542,199, 4,769,510, 4,871,705, 4,937,299, 5,017,714, 5,055,438, 5,096,867, 5,130,030, 5,120,867, 5,124,418, 5,198,401, 5,210,352, 5,229,478, 5,264,405, 5,278,264, 5,278,119, 5,304,614, 5,324,800, 5,347,025, 5,350,723, 5,384,299, 5,391,790, 5,391,789, 5,399,636, 5,408,017, 5,491,207, 5,455,366, 5,534,473, 5,539,124, 5,554,775, 5,621,126, 5,684,098, 5,693,730, 5,698,634, 5,710,297, 5,712,354, 5,714,427, 5,714,555, 5,728,641, 5,728,839, 5,753,577, 5,767,209, 5,770,753, 5,770,664 and 5,814,574, European Patent Nos. EP-A-0 591 756, EP-A-0 520 732, EP-A-0 420 436, EP-B1 0 485 822, EP-B1 0 485 823, EP-A2-0 743 324 and EP-B1 0 518 092 and PCT Publication Nos. WO 91/04257, WO 92/00333, WO 93/08221, WO 93/08199, WO 94/01471, WO 96/20233, WO 97/15582, WO 97/19959, WO 97/46567, WO 98/01455, WO 98/06759 and WO 98/011144.
There are many more examples in the metallocene-type art. However, there is a small subset that discuss the importance of the leaving group, the ligand capable of being abstracted and rendering the metallocene-type catalyst system capable of polymerizing olefins. Some in art discuss using chloride or methyl leaving groups, for example U.S. Pat. Nos. 4,542,199 and 4,404,344 respectively.
Much of the metallocene-type art discuss the use generally of halogens as leaving groups. For example, European publication EP-A2 0 200 351 published in Nov. 5, 1986 mentions in a laundry list of possibilities, a few compounds having fluoride leaving groups, as does EP-A 1 0 705 849 published Apr. 10, 1996. However, although halogens are typically discussed in much of the art, the predominant focus has been on chlorine as a leaving group.
There are some disclosures and exemplifications of these compounds having fluoride groups in the art, for example:
E. F. Murphy, et al., “Synthesis and spectroscopic characterization of a series of substituted cyclopentadienyl Group 4 fluorides; crystal structure of the acetlacetonato complex [(acac)
2
(&eegr;
5
-C
5
Me
5
)Zr(&mgr;-F)SnMe
3
Cl]”, Dalton, (1996), 1983 incorporated herein by reference, describes the synthesis of some mono- and di-substituted cyclopentadienyl Group 4 fluoride compounds.
Herzog, et al., “Reactions of (&eegr;
5
-C
5
Me
5
)ZrF
3
, (&eegr;
5
-C
5
Me
4
Et)ZrF
3
, (&eegr;
5
-C
5
M4
5
)
2
ZrF
2
, (&eegr;
5
-C
5
Me
5
)HfF
3
, and (&eegr;
5
-C
5
Me
5
)TaF
4
with AlMe
3
. Structure of the First Hafnium-Aluminum-Carbon Cluster”, Organometallics 1996, 15, 909-917, incorporated herein by reference, describes the reactions of various compounds having fluoride leaving groups with an aluminum compound.
F. Garbassi, et al., Journal of Molecular Catalysis A: Chemical 101 (1995) 199-209 illustrates the binding energy of various leaving groups on zirconium compounds. In particular this article shows that a catalyst system of bis(cyclopentadienyl)zirconium dichloride in the polymerization of ethylene is more active than the di-fluoride analog.
PCT publication WO 97/07141 published Feb. 27, 1997 describes a number of metallocene-type compounds with fluoride leaving groups. This publication exemplifies their use with methylalumoxane in the polymerization of styrene and shows a single bis(cyclopentadienyl) titanium mono-fluoride having a very low productivity. Also, Kaminsky, et al., “Fluorinated Half-Sandwich Complexes as Catalysts in Syndiospecific Styrene Polymerization”, Macromolecules, Vol. 30, No. 25, 1997 describes that unbridged mono-cyclopentadienyl titanium trifluoride catalysts have a higher activity than the chlorinated compounds in the polymerization of styrene in the temperature range of from 10° C. to 70° C.
German publication DE 43 32 009 A1 describes a process for making organometallic fluorides by reacting an organometallic halide with tin fluoride. This publication appears to show that an unsupported catalyst system of methylalumoxane and a bis(pentamethylcyclopentadienyl)zirconium dichloride has a lower homopolyethylene productivity compared with double the amount of the difluoride at 70° C.
Considering the discussion above there is still a need for higher productivity catalyst systems capable of providing the efficiencies necessary for implementing commercial polyolefin process. Thus, it would be highly advantageous to have a polymerization process capable of producing new and improved polymers with improved catalyst productivities.
SUMMARY OF THE INVENTION
This invention provides for a process for polymerizing olefins in the presence of a bulky ligand metallocene-type catalyst compound having at least one fluoride or fluorine containing leaving group.
In one embodiment, the invention relates to a process for polymerizing olefins at a temperature greater than 70° C. in the presence of a catalyst system comprising a bulky ligand metallocene-type catalyst compound having at least one fluoride or fluorine containing leaving group. Preferably the catalyst system is supported.
In another embodiment, the invention is directed towards a process for polymerizing two or more alpha-olefins having from 2 to 20 carbon atoms at least one of which is ethylene or propylene in the presence of a catalyst system comprising a bulky ligand metallocene-type catalyst compound having at least one fluoride or fluorine containing leaving group. Preferably the catalyst system is supported.
In yet another embodiment, the invention is directed to a process for polymerizing propylene alone or in combination with one or more other olefins in the presence of a catalyst system comprising a bulky ligand me

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