Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2006-04-04
2006-04-04
Harlan, Robert D. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S269000, C526S270000, C526S276000, C526S333000, C526S336000, C526S339000, C526S308000, C526S319000, C526S329000, C526S171000
Reexamination Certificate
active
07022789
ABSTRACT:
The present invention relates to telechelic polymers having crosslinkable end groups of the formulaand methods for preparing the same wherein n is an integer;is an alkadienyl group; Y is an alkyl group; and Z is crosslinkable end group. In general, the inventive synthesis involves reacting a functionalized chain transfer agent having crosslinkable ends with a cycloalkene in the presence of a ruthenium or osmium catalyst of the formulawherein:M is ruthenium or osmium;X and X1are independently any anionic ligand;L and L1are any neutral electron donor ligand;R and R1are each hydrogen or a substituted or unsubstituted substituent wherein the substituent is selected from the group consisting of C1–C20alkyl, C2–C20alkenyl, C2–C20alkynyl, aryl, C1–C20carboxylate, C1–C20alkoxy, C1–C20alkenyloxy, C2–C20alkynyloxy, aryloxy, C2–C20alkoxycarbonyl, C1–C20alkylthio, C1–C20alkylsulfonyl and C1–C20alkylsulfinyl. In another aspect of the invention, methods for controlling the molecular weight of the resulting telechelic polymer are also presented.
REFERENCES:
patent: 5312940 (1994-05-01), Grubbs et al.
patent: 5710298 (1998-01-01), Grubbs et al.
patent: 5728917 (1998-03-01), Grubbs et al.
patent: 5831108 (1998-11-01), Grubbs et al.
patent: 6465590 (2002-10-01), Maughon et al.
patent: 6867274 (2005-03-01), Maughon et al.
Nubel, et al., “Preparation of an ester-terminated telechelic polybutadiene by a two-step olefin metathesis process,” J. Mol. Catalysis A Chem. (1997) 115:43-50.
Kennedy, et al., “New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers) 28. Glycidyl ethers of bisphenol- and trisphenol-PIB and their curing to epoxy resins,” Polymer Bull. (1982) 8:571-578.
Kennedy, et al., “New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers) 36. New networks from α, ω-di(methacryloyloxy)-polyisobutylene,” Polymer Bull. (1983) 10:146-151.
Marmo, et al., “ADMET depolymerization. Synthesis of perfectly difunctional (f=2.0) telechelic polybutadiene oligomers,” Macromolecules (1995) 28:2602-2605.
Chung, “Synthesis of functional polymers via borane monomers and metathesis catalysis,” J. Mol. Catal. (1992) 76:15-31.
Otton, et al., “Metathesis of functionalized olefins: homogeneous cross-metathesis of cycloolefin and ethylenic esters,” J. Mol. Catal. (1992) 76:15-31.
Pinazzi, et al., “Application of metathesis reactions to the synthesis of α, ω functional prepolymers,” J. Mol. Catal. (1980) 8:313-324.
Gu, et al., “Synthesis of glycol diglycidyl ethers using phase-transfer catalysis,” Synthesis (1985) 6:649-651.
Reyx, et al., “Application de la reaction de metathese a la synthese de prepolymeres α, ω-bifonctionnels. Partie 3: Mise au point des conditions d'obtention de composes dieniques et trieniques par cometathese du cyclopentense avec l'octene-4 et l'hexene-3 dioate de dimethyle,” J. Mol. Catal. (1987) 42:289-299.
Cramail, et al., “Functional oligomers of norbornene. Part 1. Oligomerization by ring-opening metathesis polymerization in the presence of unsaturated diesters,” J. Mol. Catal. (1991) 65:193-203.
Hummel, “Polymer degradation by cross-metathesis,” Pure Appl. Chem. (1982) 54:351-364.
Aoshima, “Synthesis of functionalized linear poly(divinylbenzene) with hydroxyl pendants and/or endgroups,” J. Polymer Sci. (1984) 22:2443-2453.
Webster, “Living polymerization methods,” Science (1991) 251:887-893.
Kennedy, “New telechelic polymers and sequential copolymers by polyfunctional initiator-transfer agents (inifers) XVII. Epoxy and aldehyde telechilic polyisobutylenes,” J. Polymer Sci. (1982) 20:2809-2817.
Chung, et al., “A new synthetic route to telechelic polymers,” Macromolecules (1991) 25:3718-3720.
Chung, et al., “Synthesis of telechelic 1,4-polybutadiene by metathesis reactions and borane monomers,” Macromolecules (1992) 25:5137-5144.
Marmo, et al., “Acyclic diene metathesis (ADMET) depolymerization synthesis of mass extract telechelic polybutadiene oligomers,” Macromolecule (1993) 28:1333-1339.
Chasmawala, et al., “Telechelic polyisobutylene: a facile synthesis via the cross metathesis reaction and trialkylborane-containing olefins,” Macromolecules (1995) 28:1333-1339.
Maughon, “Ruthenium alkylidene initiated living ring-opening metathesis polymerization (ROMP) of 3-substituted cyclobutenes,” Macromolecules (1997) 30:3459-3469.
Hillmyer, et al., “Ring-opening metathesis polymerization of functionalized cyclooctenes by a ruthenium-based metathesis catalyst,” Macromolecules (1995) 28:6311-6316.
Grubbs, et al., “Ring-opening metathesis and related processes in organic synthesis,” Acc. Chem. Res. (1995) 28:446-452.
Fu, et al., “Catalytic ring-opening metathesis of functionalized dienes by a ruthenium carbene complex,” J. Am. Chem. Soc. (1993) 115:9856-9857.
Maughon, “Synthesis and controlled cross-linking of polymers derived from ring-opening metathesis polymerization (ROMP),” Macromolecules (1996) 29:5766-5769.
Schwab, et al., “Synthesis and applications of RuCl2(=CHR')(PR3)2: the influence of the alkylidene moiety on metathesis activity,” J. Am. Chem. Soc. (1996) 118:100-110.
Schwab, et al., “Eine Reihe definierter Metathesekatalysatoren—Synthese von und Reaktionen mit RuCl2(=CHR')(PR3)2,” Angew. Chem. (1995) 107:2179-2181.
Nguyen, et al., “Synthesis and activities of a new single-component ruthenium-based olefin metathesis catalyst,” J. Am. Chem. Soc. (1993) 115:9858-9859.
Hillmyer, et al., “Utility of a ruthenium metathesis catalyst for the preparation of end-functionalized polybutadiene,” Macromolecules (1997)30:718-721.
Fraser, et al., “Degradable cyclooctadiene/acetal copolymers: versatile precursors to 1,4-hydroxytelechelic polyethylene,” Macromolecules (1995) 28:7256-7261.
Hillmyer, et al., “Chain transfer in the ring-opening metathesis polymerization of cyclooctadiene using discrete metal alkylidenes,” Macromolecules (1995) 28:8662-8667.
Hillmyer, et al., “Preparation of hydroxytelechelic poly(butadiene) via ring-opening metathesis polymerization employing a well-defined metathesis catalyst,” Macromolecules (1993) 26:872-874.
Fukui, et al., “Application of photo-crosslinkable resin to immobilization on an enzyme,” FEBS Lett. (1976)66:591-596.
Van Caeter, et al., “Telechelic polymers: new developments,” TRIP (1995)3:227-233.
Schwab, et al., “A series of well-defined metathesis catalysts—synthesis of [RuCl2(=CHR')(PR3)2] and its reactions,” Angew. Chem. Intl. Ed. Engl. (1995) 34:2039-2411.
Grubbs Robert H.
Maughon Bob R.
Morita Takeharu
California Institute of Technology
Harlan Robert D.
Reed Intellectual Property Law Group
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