The B. F. Goodrich Company

Parley C Lane, Jr

Linwood P Tenney

George M Benedikt

Paul T Stricharczuk

Gerald V Wootton

Nancy Susan Marchant

John Victor Wessel

Kong Sung Yi

Robert J Minchak

Kong S Yi

A continuous process for the solution polymerization of appropriate polycycloolefins in a ROMP zone to obtain a processable ROMP homo- or copolymer in solution, and subsequent hydrogenation of the ROMP (co)polymer without removing the residual ROMP catalyst and co-catalyst, provides an optical product having a mol wt M.sub.w in the range from 50,000-300,000 and polydispersity M.sub.w /M.sub.n in the range from 1.3-5.0, more preferably from 1.3-3, the lower the polydispersity the more desirable the physical properties of the (co)polymer. The process comprises, (A) continuously polymerizing a substantially anhydrous solution of said monomer by ring opening metathesis polymerization in at least a first and a last reaction zone of a multi-zoned, single-stage, reaction vessel to form an unsaturated polymer cement essentially free of unreacted monomer; (B) hydrogenating said unsaturated polymer cement in the presence of an effective amount of a nickel-containing hydrogenation catalyst in an amount sufficient to produce a hydrogenated cement wherein more than 97% of double bonds in said unsaturated polymer are converted to single bonds; (C) removing more than 99% by weight of spent polymerization catalyst, used hydrogenation catalyst and filter aid present in said hydrogenated cement to produce an essentially solids-free hydrogenated cement; (D) devolatilizing said solids-free hydrogenated cement to produce a thickened hydrogenated polymer cement, and, (E) recovering a solid polymer which meets particle count specifications for optical grade polymer.

Continuous process for making melt-processable optical grade ring-opened

A continuous process for the solution polymerization of appropriate polycycloolefins in a ROMP zone to obtain a processable ROMP homo- or copolymer in solution, and subsequent hydrogenation of the ROMP (co)polymer without removing the residual ROMP catalyst and co-catalyst, provides an optical product having a mol wt M.sub.w in the range from 50,000-300,000 and polydispersity M.sub.w /M.sub.n in the range from 1.3-5.0, more preferably from 1.3-3, the lower the polydispersity the more desirable the physical properties of the (co)polymer. The process comprises, (A) continuously polymerizing a substantially anhydrous solution of said monomer by ring opening metathesis polymerization in at least a first and a last reaction zone of a multi-zoned, single-stage, reaction vessel to form an unsaturated polymer cement essentially free of unreacted monomer; (B) hydrogenating said unsaturated polymer cement in the presence of an effective amount of a nickel-containing hydrogenation catalyst in an amount sufficient to produce a hydrogenareal cement wherein more than 97% of double bonds in said unsaturated polymer are converted to single bonds; (C) removing more than 99% by weight of spent polymerization catalyst, used hydrogenation catalyst and filter aid present in said hydrogenated cement to produce an essentially solids-free hydrogenated cement; (D) devolatilizing said solids-free hydrogenated cement to produce a thickened hydrogeneated polymer cement, and, (E) recovering a solid polymer which meets particle count specifications for optical grade polymer.

A process for increasing the molecular weight of cycloolefin monomers is provided by this invention which can be incorporated into ring-opening polymerization methods. This method is particularly suited for bulk polymerization processes but can also be used for solution polymerization processes. By increasing the molecular weight of the cycloolefin monomers, polymers having higher glass transition temperatures are obtained.

Method for preparing cycloolefin copolymers with improved heat stability

Liquid dicyclopentadiene feedstocks are provided for bulk polymerization by the addition of reactive norbornene function containing cycloolefin monomers to solid, high purity dicyclopentadiene compositions. These liquid dicyclopentadiene feedstocks provide a high degree of conversion to polymer under bulk polymerization conditions.

Liquid dicyclopentadiene feedstock for bulk polymerization

Thermoset polycycloolefins are obtained by polymerzing at an elevated temperature a cycloolefin containing at least one norbornene group in the presence of a metathesis catalyst system and also in the presence of an effective amount of a polyfunctional cycloolefin crosslinker containing at least one norbornene group, but preferably two or more, with two or more unsaturated sites, preferably two or more double bonds.

Polycycloolefins resistant to solvents

A polymer is precipitated from a cement containing the polymer dissolved in a nonpolar solvent by mixing the cement with a nonsolvent alcohol and water wherein the relative amount of water to the alcohol is different from the alcohol/water azeotropic composition and being such as to produce a polymer product in the form of discrete particles, the product having bulk density in excess of 0.08 g/cc or 5 lb/ft.sup.3, is capable of being easily filtered and dried, and is a polymer of a monomer that contains at least one norbornene group.

Precipitation of polycycloolefins having high bulk density

Precipitation of a polymer from polymer cement containing about 15 to 80% solids is accomplished by mixing the cement with water and a nonsolvent near or above the boiling point of a ternary azeotrope whereby the polymer precipitates forming a slurry and the ternary azeotrope is withdrawn as a vapor, separating the polymer from the liquid phase and recycling the liquid phase to the mixing step, the polymer cement being a honey-like solution in a nonpolar solvent of a polymer prepared by ring opening polymerization in the nonpolar solvent of at least one cyclic olefin containing at least one norbornene group, the nonsolvent is selected from lower alcohols that form binary azeotropes with water, and the ternary azeotrope comprising the nonpolar solvent, the nonsolvent, and water. The process can be operated either in batchwise segments or continuously throughout.

Precipitation of polycycloolefins

Precipitation of polymer from a polymer cement comprising the polymer dissolved in cyclohexane is accomplished by mixing the cement with methanol whereby the polymer precipitates forming a polymer slurry comprising polymer solids dispersed in cyclohexane and methanol, heating the polymer slurry to vaporize methanol and cyclohexane in azeotropic proportion, condensing the vaporized methanol and cyclohexane whereby it separates into an upper phase that is nearly all cyclohexane and a lower phase that is rich in methanol, separating the phases, and separating the polymer from the residual slurry comprising polymer solids dispersed in methanol, the polymer being a reaction product formed by ring opening polymerization of at least one monomer containing at least one norbornene group. The process can be conducted in batchwise segments or continuously throughout.

Anhydrous precipitation of polycycloolefins

Process for preconcentrating polymer cement normally containing about 15% solids comprising mixing therewith an amount of a hydrocarbon nonsolvent liquid sufficient to form a two-phase system but insufficient to precipitate the polymer, and separating the two phases; the polymer cement is a honey-like solution of a polymer prepared by ring opening polymerization of at least one monomer containing the norbornene group in a nonpolar hydrocarbon solvent; the upper phase being a thin hydrocarbon liquid comprising nonsolvent, a substantial portion of the nonpolar solvent in the polymer cement, and impurities, and the lower phase being a preconcentrated polymer cement containing at least 20% solids.

Nonsolvent preconcentration of polymeric cycloolefins

Thermoplastic copolymers comprise (1) tetracyclododecene, at least one alkyltetracyclododecene, or a mixture thereof copolymerized by ring opening with (2) norbornene, at least one alkylnorbornene or a mixture thereof, (3) dicyclopentadiene, and (4) at least one acyclic monoolefin or nonconjugated acyclic olefin. The copolymers can be calendered and thermoformed, for example, to make rigid automotive goods such as glovebox covers, hubcaps, and the like.

Cycloolefin copolymers

Improved process for vapor phase cracking of dicyclopentadiene and synthesis of 2,3-dihydrodicyclopentadiene therefrom. Initially, a feedstock consisting essentially of dicyclopentadiene and cyclopentene is subjected to thermocracking in the vapor phase, resulting in the conversion of dicyclopentadiene to monomeric cyclopentadiene. The presence of cyclopentene in the feed stock is believed to minimize coke formation on the interior walls of the cracking chamber. Subsequent selective catalytic hydrogenation of the resulting mixture converts substantially all of the monomeric cyclopentadiene to cyclopentene. The cyclopentene, prepared in the above manner, can be combined with additional quantitie;s of dicyclopentadiene and the resultant mixture subjected to dimerization in the liquid phase at elevated temperatures, thereby forming the monomer, 2,3-dihydrodicyclopentadiene.

Vapor phase cracking of dicyclopentadiene and synthesis of

1,2-Dihydrodicyclopentadiene is copolymerized by ring opening with (1) norbornene, at least one alkylnorbornene or a mixture thereof and (2) at least one acyclic monoolefin or nonconjugated acyclic olefin. The copolymers can be calendered and thermoformed, for example, to make rigid automotive goods such as glovebox covers, hubcaps, and the like.

Ring-opened copolymers of dihydrodiclopentadiene, norbornene or

Dimethylnorbornene, isopropylnorbornene or a mixture thereof is copolymerized by ring opening with (1) at least one acyclic monoolefin or nonconjugated acyclic olefin and (2) optionally, dicyclopentadiene. The copolymers are thermoplastics which can be calendered and thermoformed, for example, to make rigid automotive goods such as glovebox covers, hubcaps and the like.

Growing community of inventors

Cuyahoga Falls, OH, United States of America

Parley C Lane, Jr