Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
1999-12-08
2002-02-26
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, C526S283000, C526S171000, C526S172000, C526S134000
Reexamination Certificate
active
06350832
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to nickel and palladium catalysts that are capable of polymerizing polycyclic olefins via addition polymerization to yield saturated, high glass transition temperature polymers. The saturated polymers can be prepared as thermoplastic or thermoset materials and have improved oxidative resistance, high temperature behavior, and better mechanical properties after aging than cyclic polymers prepared by ring-opening metathesis polymerization.
BACKGROUND OF THE INVENTION
Preparation of thermoset cycloolefin polymers by the ring opening metathesis polymerization (ROMP) is a relatively recent development in the polymer art. Reaction injection molding (RIM) of polyolefins by the ring-opening of metathesis polymerizable polycyclic olefinic monomers in the presence of alkylidene complexes is a particularly important aspect of polycyclic olefin chemistry. For example, Klosiewicz (U.S. Pat. Nos. 4,400,340 and 4,520,181) discusses a method whereby polydicyclopentadiene can be prepared by combining a plurality of reactant monomer streams. Klosiewicz discloses the preparation of ROMP polymers from dicyclopentadiene via a two-stream reaction injection molding technique wherein one stream, includes a “procatalyst”, and the second stream, includes a “procatalyst activator” or “activator”. The monomer reactant streams are combined in a mix head where the procatalyst and activator generate an active metathesis catalyst.
The reactive catalyst/monomer mixture is immediately injected into a old where, within a matter of seconds, polymerization takes place forming a solid article in the shape of the mold. Although such metathesis catalysts are very effective in the polymerization of polycyclic olefins, the unsaturated nature of the starting monomers is retained in the polymer backbone. In addition, the resultant polymer contains a repeat unit with one less cyclic unit than did the starting monomer as shown in the reaction scheme below.
In sharp contrast, despite being formed from the same monomer, an addition-polymerized polycyclic olefin is clearly distinguishable over a ROMP polymer. Because of the different (addition) mechanism, the addition polymer has no backbone C═C unsaturation as shown in the reaction scheme below.
The difference in structures of ROMP and addition polymers of polycyclic monomers is evidenced in their properties, e.g., thermal properties, mechanical properties after aging, and polymer surface quality. The addition-type polymer of polycyclic olefins such as norbornene has a high Tg of about 350° C. The unsaturated ROMP polymer of norbornene exhibits a Tg of about 35° C., and exhibits poor thermal stability at high temperature above 200° C. because of its high degree of backbone unsaturation.
Ring-opened metathesis polymers and copolymers of dicyclopentadiene are known to have excellent glass transition temperatures (Tg) and high impact resistance. Because of their high Tg values, however, these polymers are difficult to melt process once formed. Crosslinking in the melt also occurs when the ring-opened polymer or copolymer contains a pendant five member unsaturated ring such as results when dicyclopentadiene is used to form the polymer or copolymer. Crosslinked polymers are extremely difficult to melt process. This poses a significant disadvantage to solution polymerized polymers which must be melt processed to provide finished articles. In contrast, for polymers and copolymers prepared in bulk, processing, in terms of melt flow, is less of a problem since the polymerization takes place in a mold and in the shape desired. Melt processing for such bulk polymerized polymers and copolymers is normally not required. Therefore, bulk polymerization provides significant advantages where high temperature resistance is desired in the finished article.
Suld, Schneider, and Myers (U.S. Pat. No. 4,100,338) disclose a method to polymerize norbornadiene to a solid polymer in the presence of a catalytic system of nickel acetylacetonate or a nickel-phosphine complex and an alkyl aluminum chloride. They note that if the temperature increases too much then cooling is required to successfully polymerize the monomer. Typically, polynorbornadiene is processed at temperatures of less than 100° C. Generally, however, the polymerization of the norbornadiene with an optimal amount of the catalyst system is not characterized by a rapid exotherm.
In similar fashion, Brownscombe and Willis (U.S. Pat. No. 4,451,633) polymerized an olefinic monomer feed in the presence of a Ziegler-Natta type coordination catalyst system comprising a Group IV metal containing component and activator hydrides and halides, an organometal activator selected from Groups I to III. This method permits the production of polyolefinic articles that are difficult or impossible to produce from polyolefinic powder or pellets by convention methods. The monomer feed in U.S. Pat. No. 4,451,633 comprises aliphatic and cycloaliphatic alpha olefins as well as other diolefins (producing polymeric articles containing some unsaturation).
Polymers having improved heat resistance can be obtained through the use of comonomers. For example, the heat resistance of dicyclopentadiene can be increased by copolymerizing DCPD with a crosslinking or bulky comonomer. However, the improved heat resistance obtained at the cost of decreased impact resistance.
Sjardijn and Snel (U.S. Pat. No. 5,093,441) employed ring-opening metathesis polymerization on specifically bulky norbornenes (generated from the 1:1 Diels-Alder adducts of cyclopentadiene and norbornene, norbornadiene and cyclooctadiene) to provide copolymers showing tailored properties, such as increased glass transition temperature. Likewise, Hara, Endo, and Mera (European Patent Application No. 287762 A2) prepared highly crosslinked copolymers by metathesis from heat treated cyclooctadiene and dicyclooctadiene.
Tsukamoto and Endo (Japanese Patent Application, 9-188714, 1997) polymerized ethylidene norbornene via Ziegler type polymerization in a RIM process to yield addition polymerized solid objects. The disclosed catalyst comprise a Group IV metal containing procatalyst and Group III metal containing activator.
Nagaoka el, al. (Japanese Published Application No. 8-325329, 1996) describe a process for the polymerization of a polycycloolefin polymer via reaction injection molding (RIM) in the presence of a Group 10 transition metal compound and a cocatalyst. A molded article containing no unsaturated bonds is polymerized from norbornene-type monomers containing only one polymerizable norbornene functionality. There is no disclosure or suggestion of a crosslinked polymer product or a procatalyst species containing both a Group 15 electron donating ligand (e.g., triphenylphosphine) and a hydrocarbyl ligand that are coordinated to the Group 10 metal. The co-catalyst species are selected from a myriad of compounds including organoaluminums, Lewis acids, and various borate salts. The use of simple Group 1, Group 2 and transition metal salts are not discussed or exemplified. Accordingly, a Group 10 metal catalytic species that requires the presence of both a Group 15 electron donating ligand and a hydrocarbyl ligand are not contemplated. In addition, there is no suggestion, implication, or teaching of the important combination of a Group 10 metal procatalyst containing a Group 15 electron donor ligand and a hydrocarbyl ligand in combination with a weakly coordinating anion salt activator.
Goodall et al. (U.S. Pat. Nos. 5,705,503; 5,571,881; 5,569,730, and 5,46,819) have shown that Group 10 catalyst systems are useful in generating thermoplastic addition polymers from a variety of norbornene derivatives in polar and non-polar solvents. The catalyst system employs a Group 10 metal ion source, a Lewis acid, an organoaluminum compound, and a weakly coordinating anion. The glass transition temperature of the polymers are in the range of 150° C. to 350° C. In the absence of a “chain transfer agents” polynorbornene polymers are generated whose molecular w
Bell Andrew
Fondran John C.
Goodall Brian L.
Rhodes Larry F.
Dunlap Thoburn T.
Hudak & Shunk Co. LPA
Rabago R.
The B. F. Goodrich Company
Wu David W.
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