Other

Advanced Polymer Technologies Corp.

Pti/end/corr

California Institute of Technology

The B. F. Goodrich Company

Cymetech, L.l.c.

A.p.t. Aerospace, L.l.c.

Charles S Woodson

Robert H Grubbs

Marc Andrew Hillmyer

Paul T Stricharczuk

Dennis J Janda

Timothy P Lodge

Mark W Warner

Steven D Drake

Norman A Deumite

Michael J Darnall

Larry L Cagle

Yu Ren

Ronald W Humble

The present invention relates to the post-polymerization fluorination methods of polymers produced via ring-opening metathesis polymerization. Unlike prior art methods that result in low product yields and generally involve chemically aggressive reagents, the inventive methods produce fluorinated polymers in quantitative yields and under mild conditions. In preferred embodiments, a source of difluorocarbene is reacted with the desired polydiene to form a fluorinated polymer product. In preferred embodiments, the source of difluorocarbene is hexafluoropropylene oxide and the polydiene is poly-dicyclopentadiene (&ldquo;poly-DCPD&rdquo;). Fluorination and the concomitant removal of unsaturated bonds result in polymers having improved physical properties such as improved strength characteristics, enhanced oxidative and chemical stability, and low surface energies.

Fluorinated polymers and methods for their preparation

Thermosetting resin pipes and pipe fittings are provided which are prepared by polymerizing a cyclic olefin monomer in the presence of a ruthenium or osmium metathesis polymerization catalyst. These articles may be prepared by various methods, such as centrifugal casting. Reinforced articles may also be prepared by filament winding.

Pipe made from metathesis polymerized olefins

Preferred embodiments of the present invention relate to rocket fuels comprising metal hydrides and poly-dicyclopentadiene (&ldquo;poly-DCPD&rdquo;). Although poly-DCPD also has physical and chemical properties that are compatible with being used as a rocket fuel in its own right, its primary function is as a binder for the metal hydride. Illustrative examples of metal hydrides include but are not limited to as aluminum hydrides, lithium hydrides, and lithium aluminum hydrides.

Rocket fuels based on metal hydrides and poly-DCPD

Compositions including fibers, fillers, reinforcing agents or other property-enhancing agents added to a polymeric matrix formed from DCPD monomer or related compounds such as norbornene and norbornadiene are disclosed. The composition has a mechanically forgiving matrix due to the polymer with the inherent strength and other physical properties of the enhancement agent according to the invention. Enhancement agents according to the invention generally include inorganic, organic and metallic substances in a variety of forms.

Polymeric composites including dicyclopentadiene and related monomers

Methods for synthesizing polyDCPD via ROMP of low grade DCPD starting materials using Ruthenium or Osmium carbene complex catalyst. Transparent or translucent polyDCPD materials. The Ruthenium or Osmium carbene complex catalysts having the formula ##STR1## where M may be Os or Ru; R and R.sup.1 may be the same or different and may be hydrogen or a substituent group including C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.1 -C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.1 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy, aryloxy, C.sub.2 -C.sub.20 alkoxycarbonyl, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 alkylsulfonyl and C.sub.1 -C.sub.20 alkylsulfinyl; X and X.sup.1 may be the same or different and may be any anionic ligand; and L and L.sup.1 may be the same or different and may be neutral electron donor. The low grade DCPD starting materials containing less than about 97% by weight of DCPD monomers.

Polymerization of low grade DCPD monomers using an olefin metathesis

Compositions and methods for catalyzing and controlling the rate of olefin metathesis reactions including Ring Opening Metathesis Polymerization (ROMP) reactions. The molding of polymer articles using ROMP polymers. The composition includes a Ruthenium or Osmium carbene complex catalyst and a gel modification additive. The Ruthenium or Osmium carbene complex catalyst having the formula ##STR1## where M may be Os or Ru; R and R.sup.1 may be the same or different and may be hydrogen or a substituent group including C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.1 -C.sub.20 alkyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.1 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy, aryloxy, C.sub.2 -C.sub.20 alkoxycarbonyl, C.sub.1 -C.sub.20 alkylthio, C.sub.1 -C.sub.20 alkylsulfonyl and C.sub.1 -C.sub.20 alkylsulfinyl; X and X.sup.1 may be the same or different and may be any anionic ligand; and L and L.sup.1 may be the same or different and may be neutral electron donor. The gel modification additive may be a neutral electron donor or a neutral Lewis base including phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine, or thioether. The gel modification additive may be a trialkylphosphine or triarylphosphine. Examples of gel modification additives include P(cyclohexyl).sub.3, P(cyclopentyl).sub.3, P(isopropyl).sub.3, P(phenyl).sub.3, and pyridine.

Method for extending the pot life of an olefin metathesis polymerization

Methods of forming polycycloolefins having high crosslink density are disclosed. Olefins are polymerized via a metathesis mechanism in the presence of a crosslinking agent and a catalyst. The crosslinking agent generally comprises a peroxide that decomposes into reactive species forming crosslinks during post-cure. The catalyst is a ruthenium or osmium carbene complex of the formula: ##STR1## wherein M is Os or Ru; R and R.sup.1 are independently selected from hydrogen or a hydrocarbon selected from the group consisting of C.sub.1 -C.sub.20 alkyl, C.sub.2 -C.sub.20 alkenyl, C.sub.2 -C.sub.20 alkynyl, C.sub.2 -C.sub.20 alkoxycarbonyl, aryl, C.sub.1 -C.sub.20 carboxylate, C.sub.1 -C.sub.20 alkoxy, C.sub.2 -C.sub.20 alkenyloxy, C.sub.2 -C.sub.20 alkynyloxy and aryloxy; X and X.sup.1 are independently selected from any anionic ligand; and L and L.sup.1 are independently selected from any neutral electron donor. Preferably, L and L.sup.1 are trialkylphosphine ligands and at least one of the alkyl groups on the phosphine ligand may be a secondary alkyl or cycloalkyl group, especially P(isopropyl).sub.3, P(cyclopentyl).sub.3 and P(cyclohexyl).sub.3. Preferred crosslinking agents are peroxides, such as t-butyl peroxide, 2,5-dimethyl-2,5-di-(tert-butylperoxy) hexyne-3, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di-(tert-butylperoxy) hexane or mixtures thereof. Olefins may be cyclic (e.g., monocyclic, bicyclic or tricyclic) or acyclic. Norbornene or norbornene derivatives are especially preferred.

Romp polymerization in the presence of peroxide crosslinking agents to

A centrifugally cast plastic pipe comprised of a polymer derived from monomers polymerized in bulk is provided. A pressurized cylindrical mold provides smooth inner and outer surfaces. Pipes with a wall thickness of from 1/8 inch to 3 inches and an outer diameter of 1 inch to 12 feet are provided.

Centrifugally cast pipe

A molded, one piece electrolytic cell head is provided which is obtained from a closed mold. The structure weighs more than 100 pounds and is comprised of bulk polymerized monomers having norbornene functionality. The structure provides improved performance over cell heads comprised of fiber glass reinforced polyester since fiber reinforcement is not required.

Growing community of inventors

Conroe, TX, United States of America

Charles S Woodson