# US 5,705,572 A · Continuous process for making melt-processable optical grade ring-opened polycyclic olefin (co)polymers in a single-stage multi-zoned reactor > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,705,572 A - Document ID: US5705572A - Status: Granted - Kind: A - Application number: 08/512,588 - Filed: 1995-08-08 - Granted: 1998-01-06 - Earliest claimed: 1989-03-31 - Assignees: The B.F. Goodrich Company - Inventors: Kong Sung Yi; Linwood Powers Tenney; Parley Clive Lane, Jr.; John Victor Wessel; Nancy Susan Marchant - Web page: https://patentgrep.com/patent/US5705572A ## CPC - C08G 61/08: of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring - G11B 7/2538: polycycloolefins [PCO] - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - G11B: INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER (recording measured values in a way that does not require playback through a transducer G01D9/00; recording or playback apparatus using mechanically marked tape, e.g. punched paper tape, or using unit records, e.g. punched or magnetically marked cards G06K; transferring data from one type of record carrier to another G06K1/18; circuits for coupling output of reproducer to radio receiver H04B1/20; gramophone pick-ups or like acoustic electromechanical transducers or circuits therefor H04R) ## Abstract 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. ## Claims ### Claim 1 A two-step process for hydrogenating a feedstream essentially free of an unreacted monomer(s) from a polymerization zone, said feedstream consisting essentially of (i) an unsaturated polymer formed by ring-opening metathesis polymerization (ROMP) of at least one multi-ringed monoolefinically unsaturated cycloolefin monomer, selected from the group consisting of bicyclo› 2.2.1.!hept-2-ene ("norbornene" "NB") and substituted embodiments thereof, (ii) a diluent amount of C.sub.6 -C.sub.8 -cycloalkane, (iii) a lower C.sub.3 -C.sub.7 .alpha.-olefin, and (iv) spent polymerization catalyst for forming said unsaturated polymer, said two-step process comprising, (a) continuously introducing said feedstream directly from a polymerization zone into a first hydrogenation zone at a pressure in the range from 1380 kPa (200 psig)-5000 kPa (700 psig), and a temperature at which less than 10% of said polymer is isomerized in the presence of said spent polymerization catalyst present in an amount in the range from 0.5 part to 6.5 parts by wt/100 parts of polymer, a filter aid, and an effective amount of a nickel-containing hydrogenation catalyst in an amount sufficient to produce a partially hydrogenated feedstream; and, in a second step, (b) introducing said partially hydrogenated feedstream into a second hydrogenation zone at a pressure in the range from 1380 kPa (200 psig)-5000 kPa (700 psig), and a temperature at which less than 10% of said polymer is isomerized, without removing said polymerization catalyst introduced into said first hydrogenation zone, and mixing said partially hydrogenated feedstream with additional nickel-containing hydrogenation catalyst in an amount sufficient to produce a slurry of an essentially fully hydrogenated feedstream; whereby more than 97% of double bonds in the unsaturated feedstream are converted to single bonds without deleteriously affecting the hydrogenation catalyst which is recovered for reuse. ### Claim 2 (depends on 1) The process of claim 1 wherein said spent catalyst consists essentially of a residue of a catalyst system consisting essentially of a catalyst selected from the group consisting of an organoammonium molybdate, a molybdenum halide, a tungsten oxyhalide and a tungsten halide, in combination with an organoaluminumhalide co-catalyst, present in a ratio of catalyst:co-catalyst:monomer in the molar range from 1:1:1000 to 1:10:10,000, and said lower C.sub.3 -C.sub.7 .alpha.-olefin chain transfer agent is selected from the group consisting of butene, 1-pentene and 1-hexene present in an amount in the range from about 10-80 mol per cent based on the mols of said monomer present. ### Claim 3 (depends on 2) The process of claim 2 wherein, said polymer is a homopolymer, and, said monomer is selected from the group consisting of tetracyclododecene, 5-ethylidenyl-2-tetracyclododecene and 9-(C.sub.1 -C.sub.3)alkyltetracyclododecene. ### Claim 4 (depends on 2) The process of claim 2 wherein at least one said monomer is selected from the group consisting of tetracyclododecene and a 9-(C.sub.1 -C.sub.3)alkyltetracyclododecene, and said polymer is a copolymer. ### Claim 5 (depends on 2) The process of claim 2 wherein said hydrogenation catalyst is a supported nickel catalyst, said polymer has a weight average molecular weight M.sub.w lower than 100,000, said first hydrogenation zone is at a temperature in the range from about 25.degree. C.-60.degree. C. and said second hydrogenation zone is at a temperature in the range from about 60.degree. C.-130.degree. C. ### Claim 6 (depends on 2) The process of claim 2 wherein said hydrogenation catalyst is a homogeneous nickel catalyst, said polymer has a weight average molecular weight M.sub.w lower than 300,000, said first hydrogenation zone is at a temperature in the range from about 20.degree. C.-40.degree. C. and said second hydrogenation zone is at a temperature in the range from about 40.degree. C.-80.degree. C. ### Claim 7 (depends on 2) The process of claim 2 wherein said 9-(C.sub.1 -C.sub.3)alkyltetracyclododecene is selected from the group consisting of methyltetracyclododecene and ethyltetracyclododecene. ### Claim 8 (depends on 4) The process of claim 4 wherein at least one said monomer is cyclopentadiene trimer and the amount thereof is limited to an amount which contributes 1% by weight of symmetrical trimer relative to the weight of other cycloolefin monomers present. ### Claim 9 (depends on 8) The process of claim 8 wherein at least one said monomer is dicyclopentadiene present in an amount in excess of 35% by weight, and said cyclopentadiene trimer is present in an amount in the range from 1-5% by weight, based on the weight of all cycloolefin monomers. ### Claim 10 (depends on 4) The process of claim 4 wherein at least one said monomer is tetracyclododecene present in an amount in the range from 40-60% having an exo-component in the range of 10-20% of the TD present, the remainder being another monomer selected from the group consisting of dicyclopentadiene and 9-(C.sub.1 -C.sub.3)alkyltetracyclododecene. ### Claim 11 (depends on 2) The process of claim 2 including after step (b) subjecting said hydrogenated feedstream to a multiple, sequential filtration process for separating essentially all solids therefrom, said process comprising, (c) filtering said solids at a pressure in the range from 3500 kPa-4900 kPa (500-700 psig), and a temperature in the range from 75.degree. C.-120.degree. C., in a primary filtration zone containing primary plate-and-frame filter means, said primary openings in the range from 20-30 .mu.m; (d) recovering solid particles larger than said primary openings and producing a primary filtrate containing solids smaller than said primary openings and essentially free of solid particles larger than said primary openings; (e) filtering said solids smaller than said primary openings, at a pressure in the range from 1380 kPa-4900 kPa (200-700 psig), in a secondary filtration zone containing secondary plate-and-frame filter means, said secondary plate-and-frame filter means having secondary screening means with secondary openings having a nominal diameter of 1 .mu.m; (f) recovering solid particles larger than 1 .mu.m and producing an essentially gel-free semi-polished secondary filtrate containing solids smaller than 1 .mu.m and essentially free of solid particles larger than 1 .mu.m; (g) filtering said semi-polished filtrate through a cartridge filter means having a porous filter medium with pores no larger than in the range from 0.4-0.5 .mu.m; (h) recovering solid particles larger than said pores and producing a polished filtrate; whereby more than 99% by weight of spent polymerization catalyst, and used hydrogenation catalyst present in said essentially saturated polymer is removed to produce a solution of saturated polymer which meets particle count specifications for optical grade polymer.