Catalyst and methods for polymerizing cycloolefins

Details Catalyst and methods for polymerizing cycloolefins Catalyst and methods for polymerizing cycloolefins

1999-10-05

2002-09-24

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...

C526S281000, C526S282000, C526S284000, C526S285000, C526S301000, C526S308000, C526S309000, C526S310000, C526S319000, C526S332000, C526S347100

Reexamination Certificate

active

06455650

ABSTRACT:

TECHNICAL FIELD OF THE INVENTION
The present invention relates to methods for the addition polymerization of cycloolefins using a cationic Group 10 metal complex and a weakly coordinating counteranion.
BACKGROUND OF THE INVENTION
Polycyclic addition polymers having directly linked polycyclic repeating units without any internal backbone unsaturation are desirous from the standpoint of their inherent thermal oxidative stability and high glass transition temperature (Tg) profiles. Recent objectives in synthesis have focused on incorporating pendant functional substituents onto the polycyclic backbone, enabling this class of polymer to be utilized for a wide variety of uses. These objectives have been successfully met in part because of the advent of late transition metal catalysts and their tolerance to functional groups. An increasingly important use for such polymers has been in the manufacture of microelectronic and optical devices. An important consideration in the manufacturing of polymers for microelectronic and optical applications is polymer purity. While specific classes of transition metal catalysts are tolerant to functional groups, there is a trade off in that monomer to catalyst ratios must be high in order to overcome the poisoning effects of the functional group on the catalyst. Consequently, many polymers contain metallic residues as a result of the high catalyst loading in the reaction medium. Traces of transition metals have been shown to catalyze the thermal oxidative degradation of polymers. In addition, metal residues in the polymer also deleteriously affect the polymer properties by raising the dielectric constant of the polymer and interfere with light transmittance through the polymer matrix. In order to be useful the residual metals must be removed from the polymer to below an acceptable level.
One method of catalyzing the polymerization of cycloolefins is through the use of cationic transition metal complexes. Goodall et al. (U.S. Pat. No. 5,569,730) describe a method for polymerizing cycloolefins monomers such as norbornene and hydrocarbyl substituted norbornene-type monomers in the presence of a chain transfer agent and a single or multicomponent catalyst system capable of providing a Group VIII transition metal cation source. The preferred single component catalyst consists of a transition metal cation complex containing an allyl ligand and a weakly coordinating counteranion. The multicomponent catalyst system employs a Group VIII transition metal ion source, an organoaluminum compound and an optional component selected from Lewis acids, strong BrØnsted acids, electron donor compounds, and halogenated organic compounds. The monomer to Group VIII transition metal molar ratios are broadly disclosed to range from 1000:1 to 100,000:1, with a preferred range of 3000:1 to 10,000:1.
Goodall et al.(U.S. Pat. No. 5,705,503) and McIntosh et al. (WO 97/20871) disclose that norbornene-type monomers containing functional substituents can be successfully polymerized with single and multicomponent transition metal catalysts of the classes disclosed in the '730 patent supra. However, the molar ratio of monomer to Group VIII transition metal ranges from 20:1 to 100,000:1. In fact the highest monomer to Group VIII metal ratio actually employed is only about 5000:1 which is exemplified in Example 15 of the '503 specification.
In addition to the Group VIII single and multicomponent catalyst systems disclosed supra, Goodall et al. (WO 97/33198) disclose a single component catalyst system suitable for polymerizing functionally substituted norbornene-type monomers. The single component catalyst comprises nickel, a two electron donor ligand (preferably a &pgr;-arene ligand) and a pentafluorophenyl ligand. The disclosed molar ratio of monomer to nickel ranges from 2000:1 to 100:1.
In view of the foregoing it is apparent that a relatively high catalyst loading (based on the Group VIII metal content) is necessary for the polymerization reaction to proceed efficiently. A higher catalyst loading in the monomer at the onset of the polymerization reaction, however, means that a higher residual metal content will be present in the polymer product. Residual metals are difficult and expensive to remove. Therefore there is a need for a high activity transition metal catalyst system capable of polymerizing substituted and unsubstituted cycloolefin monomers.
SUMMARY OF THE INVENTION
Accordingly, it is a general object of the invention to provide a polymerizable polycycloolefin composition comprising a high activity catalyst system.
It is another object of the invention to provide polymers with low levels of residual Group 10 metals.
It is a further object of the invention to provide a process for polymerizing polycycloolefin monomers in contact with a high activity Group 10 catalyst.
It is another object of the invention to provide a process for polymerizing polycycloolefin monomers in solution in contact with a high activity Group 10 catalyst system.
It is still another object of the invention to provide a process for polymerizing polycycloolefin monomers in mass in contact with a high activity Group 10 catalyst system.
It is another object of the invention to provide a high activity single or multicomponent Group 10 catalyst system for the polymerization of polycycloolefin monomers.
It still is a further object of the invention to provide a two component catalyst Group 10 system comprising a procatalyst and an activator.
These and other objects of the invention are accomplished by contacting a polymerizable polycycloolefin monomer charge with a high activity catalyst system comprising a Group 10 metal cation complex and a weakly coordinating counteranion complex of the formula:
[(R)
z
′M(L′)
x
(L″)
y
]
b
[WCA]
d
wherein M represents a Group 10 transition metal; R′ represents an anionic hydrocarbyl containing ligand; L′ represents a Group 15 neutral electron donor ligand; L″ represents a labile neutral electron donor ligand; z is 0 or 1; x is 1 or 2; y is 0, 1, 2, or 3, and the sum of x, y, and z equals 4; and b and d are numbers representing the number of times the cation complex and weakly coordinating counteranion complex (WCA), respectively, are taken to balance the electronic charge on the overall catalyst complex. The monomer charge can be neat or in solution, and is contacted with a preformed catalyst of the foregoing formula. Alternatively, the catalyst can be formed in situ by admixing the catalyst forming components in the monomer charge.


REFERENCES:
patent: 5705503 (1998-01-01), Goodall et al.
patent: 5912313 (1999-06-01), McIntosh, III et al.
patent: 196 42 866 (1998-04-01), None
patent: 197 16 312 (1998-10-01), None
patent: 95/14048 (1995-05-01), None
patent: 96/37529 (1996-11-01), None
patent: 97/20871 (1997-06-01), None
patent: 97/33198 (1997-09-01), None
patent: 98/45342 (1998-10-01), None
patent: 98/56839 (1998-12-01), None
patent: 99/23243 (1999-05-01), None
patent: 99/50320 (1999-10-01), None
patent: 00/06615 (2000-02-01), None
Fereidun Hojabri et al., Palladium/II-complexes as catalysts for olefinpolymerization, Sep. 18, 1975, vol. 17, pp. 710-712.
Marcello Zocchi et al., X-Ray Diffraction Studies on Catalysis: The Crystal Structure of Di-&mgr;-chloro-bis[(2′-3′-&eegr;-exo-3-allylnorborn-2-yl)palladium] and Comparison with Related Complexes Relevant to the Polymerizatin of Norbornene, Rec'd May 16, 1978, pp. 944-947.
Charles Tanielian et al., Influence de différents catalyseurs à bse d'éléments de transition du groupe VIII sur la polymérisation du norbornéne, Oct. 27, 1978, pp. 2022-2027.
Aysuman Sen et al., Reactions of electrophilic transition metal cations with olefins and small ring compounds. Rearrangements and polymerizations, Feb. 16, 1988, Journal of Organometallic Chemistry, 358 (1988), pp. 567-588.
L. Puech et al., A new route to concentrated microlatex of homogenous particle size: oligomerization of norbornene in aqueous emulsion catalyzed by PdCl2, New J.

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