Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Processes of preparing a desired or intentional composition...
Reexamination Certificate
1998-08-07
2001-10-30
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Processes of preparing a desired or intentional composition...
C524S035000, C524S080000, C526S145000, C526S146000, C526S147000, C526S171000, C526S281000, C526S283000, C502S152000, C502S155000, C502S156000, C556S022000, C556S136000
Reexamination Certificate
active
06310121
ABSTRACT:
BACKGROUND
1. Field of the Invention
The present invention relates to compositions and methods for catalyzing and controlling the rate of olefin metathesis reactions. More particularly, the present invention relates to compositions and methods for catalyzing and controlling the rate of Ring Opening Metathesis Polymerization (ROMP) reactions and the molding of polymer articles using polymers formed by ROMP. The polymer articles can include enhancement agents such as fillers, fibers, and other substances that can improve physical or other properties of the article.
2. Description of the Related Art
The molding of thermoset polymers is a technologically important processing technique. In one version of this technique, a liquid monomer (e.g., an olefin) and a polymerization catalyst are mixed and poured, cast or injected into a mold. The polymerization proceeds (the article “cures”) and on completion the molded part is removed from the mold for any post cure processing that is required. The polymerization reaction mixture may optionally contain added modifiers, fillers, reinforcements, pigments, etc.
To mold successfully, the reaction mixture must not cure so quickly that the liquid monomer/catalyst mixture polymerizes before the mixture can be introduced in to the mold. In addition, the mixture must not cure so quickly that it polymerizes before the mold is completely filled or before the catalyst has had time to completely dissolve. For convenience and expedient cycle time, it is also important that the catalyst activate within a reasonable time after the mold is filled.
The time during which the liquid monomer/catalyst mixture can be worked after the monomer and catalyst is mixed is called the “pot life” of the polymerization reaction mixture. The ability to control the “pot life” becomes even more important in the molding of large parts. The monomer/catalyst mixture may also be applied to articles as a coating, and in this case it is also important to be able to control the “pot life” of the mixture. Generally, it would be useful to be able to control the rate of reaction of catalyzed metathesis reactions including ROMP reactions.
Reaction Injection Molding (“RIM”) has previously been used for the molding of polymer articles using a polymerization catalyst and olefin monomer (U.S. Pat. Nos. 4,400,340 and 4,943,621). In these previous processes, a metal (W or Mo) containing compound is dissolved in a first monomer stream and an alkyl aluminum compound is dissolved in a second monomer stream. The monomer streams are then mixed and the metal containing compound and the alkyl aluminum compound react to form an active catalyst which then catalyzes the polymerization reaction. In the previous processes, the alkyl aluminum compound stream may also include an inhibitor, usually a Lewis base, which inhibits the rate of formation of the catalyst; however, in these previous processes, once the catalyst is formed, the polymerization reaction is extremely fast and there is no method to control “limited methods” the rate of polymerization initiated by the active catalyst species.
Previously, there has been few methods for producing a mixture of active catalyst species and monomer and controlling the rate of polymerization of the mixture other than by controlling the temperature of the monomer or the mold. Such control would be useful, for example, to produce a catalyst/monomer mixture in which the catalyst is substantially deactivated at room temperature. This mixture may then be poured, cast, or injected into a mold and the polymerization may then be initiated by heating the mixture.
There therefore exists a need for an olefin metathesis catalyst system that can be used to catalyze olefin metathesis reactions and control the rate of the catalyzed metathesis reaction. There is also a need for an olefin metathesis catalyst system that can be used to control the pot life of a monomer/catalyst mixture in a ROMP reaction.
Many mechanical structures would advantageously be formed from a material exhibiting, for example, the mechanical toughness of thermoplastics, the high heat distortion temperature and high flex modulus of thermosetting plastics, in addition to having excellent chemical inertness or corrosion resistance. In particular, it would be desirable to have a material that is tough but mechanically forgiving, for example, a material that will “give” to some degree without cracking or other failure.
It is known to modify the properties of a conventional epoxy or polyester, which typically produce somewhat brittle materials, with plasticizers or elastomers to enhance toughness, but these additives typically also degrade corrosion resistance and other properties of the polymer material. Likewise, these or similar additives may be unsuitable or unavailable for DCPD or related monomers.
SUMMARY
The present invention addresses these needs by providing a composition which may be used for catalyzing and controlling the rate of olefin metathesis reactions. The invention also provides a method for controlling an olefin metathesis reaction using the composition, a process for Ring Opening Metathesis Polymerization using the composition, and a method for molding polymer articles using ROMP catalyzed and controlled by the composition.
In one embodiment of the invention, the composition includes a Ruthenium or Osmium carbene complex catalyst and a gel modification additive. The Ruthenium or Osmium carbene complex catalyst includes a Ruthenium or Osmium metal center that is in a +2 oxidation state, has an electron count of 16, and is pentacoordinated and the gel modification additive is an electron donor or Lewis base. More specifically, the Ruthenium or Osmium carbene complex catalyst may have the formula
where M may be Os or Ru; R and R
1
may be the same or different and may be hydrogen or a substituent group including C
2
-C
20
alkenyl, C
2
-C
20
alkynyl, C
1
-C
20
alkyl, aryl, C
1
-C
20
carboxylate, C
1
-C
20
alkoxy, C
2
-C
20
alkenyloxy, C
2
-C
20
alkynyloxy, aryloxy, C
2
-C
20
alkoxycarbonyl, C
1
-C
20
alkylthio, C
1
-C
20
alkylsulfonyl and C
1
-C
20
alkylsulfinyl; X and X
1
may be the same or different and may be any anionic ligand; and L and L
1
may be the same or different and may be neutral electron donor. The substituent groups may be substituted with one or more groups including C
1
-C
5
alkyl, halide, C
1
-C
5
alkoxy, and phenyl. The phenyl group may be substituted with one or more groups including halide, C
1
-C
5
alkyl and C
1
-C
5
alkoxy. In addition to the above groups, the substituent group may be substituted with one or more functional groups selected from the group consisting of hydroxyl, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen. In a preferred embodiment, the R and R
1
groups may be the same or different and may be hydrogen, substituted aryl, unsubstituted aryl, substituted vinyl, and unsubstituted vinyl; where the substituted aryl and substituted vinyl may be substituted with one or more groups selected from the group consisting of hydroxyl, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, halogen, C
1
-C
5
alkyl, C
1
-C
5
alkoxy, unsubstituted phenyl, and phenyl substituted with a halide, C
1
-C
5
alkyl or C
1
-C
5
alkoxy.
In a preferred embodiment, the gel modification additive is a neutral electron donor or a neutral Lewis base. The gel modification additive may be a phosphine, sulfonates phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine, or thioether. More specifically, the gel modification additive may be a trialkylphosphine or triarylphosphine. Preferred gel modification additives include P(cyclohexyl)
3
, P(cyclopentyl)
3
, P(isopropyl)
3
, P(phenyl)
3
, and pyridine.
In a preferred embodiment of the invention, the composition includes a catalyst of the formula
Grubbs Robert H.
Woodson, Jr Charles S.
Cymetech, LLC
Harlan R.
Wu David W.
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