WO2013081726A1 - Fonctionnalisation de polymères à terminaison vinyle par métathèse croisée par ouverture de cycle - Google Patents

Fonctionnalisation de polymères à terminaison vinyle par métathèse croisée par ouverture de cycle Download PDF

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WO2013081726A1
WO2013081726A1 PCT/US2012/059191 US2012059191W WO2013081726A1 WO 2013081726 A1 WO2013081726 A1 WO 2013081726A1 US 2012059191 W US2012059191 W US 2012059191W WO 2013081726 A1 WO2013081726 A1 WO 2013081726A1
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mol
propylene
group
oligomer
polymer
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PCT/US2012/059191
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English (en)
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Matthew W. Holtcamp
Donna J. Crowther
Caol P. Huff
Patrick Brant
Jacqueline A. LOVELL
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Exxonmobil Chemical Patents Inc.
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Priority claimed from US13/306,263 external-priority patent/US8604148B2/en
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to CN201280056901.1A priority Critical patent/CN103987755B/zh
Priority to EP12854390.7A priority patent/EP2785763A4/fr
Publication of WO2013081726A1 publication Critical patent/WO2013081726A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/334—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms
    • C08G2261/3342—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing heteroatoms derived from cycloolefins containing heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

  • This invention is directed toward functionalization of polymers, particularly vinyl- terminated polymers.
  • polymers may be functionalized to improve toughness, enhance the acceptance of flame retardants, mineral stiffeners, glass or wood fibers, or other desired ingredients.
  • Polymers may also be modified to help them combine more usefully or deliver higher value when recycled. Modifications can improve wetting, aid mix dispersion, filler adhesion, melt processing, surface-to-surface attraction, and other performance features.
  • Such polymers are of interest for use in a broad range of applications as lubricants, compatibilizers, tie-layer modifiers, surfactants, and surface modifiers, among other things.
  • Metathesis is generally thought of as the interchange of radicals between two compounds during a chemical reaction.
  • metathesis reactions such as ring opening metathesis, acyclic diene metathesis, ring closing metathesis, and cross metathesis.
  • R. T. Mathers and G. W. Coates, Chem. Commun., 2004, pp. 422- 423 disclose examples of using cross-metathesis to functionalize polyolefins containing pendant vinyl groups to form polar- functionalized products with a graft-type structure.
  • ROCM ring-open cross metathesis
  • U.S. 2008/0064891 discloses ROCM reaction of cyclic olefins with seed oils and the like comprising contacting: (a) at least one olefinic substrate selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol; with (b) at least one cyclic olefin as a cross-metathesis partner; in the presence of (c) a ruthenium alkylidene olefin metathesis catalyst; and (d) under conditions effective to allow ring insertion cross-metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate.
  • olefinic substrate selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an
  • WO 98/40373 discloses ROCM on solid supports to isolate the olefin immobilized on the resin, preventing unwanted olefin polymerization. Additional references of interest include: U.S. Patent Nos. 4,988,764; 6,225,432; EP 1 693 357; USSN 12/487,739; and USSN 12/143,663.
  • This invention relates to a polymer represented by the formula (A)
  • R2 and R3 are the same or different and each is hydrogen or a hydrocarbyl group having from 1 to 40 carbon atoms, or R2 and R3 are joined to form a five-membered or six-membered ring, or substituted analogs thereof;
  • X is C, N, or O
  • n is an integer from 1 to 10,000;
  • polymer comprises one or more vinyl terminated macromonomer derived units.
  • This invention also relates to a polymer represented by the formula (A):
  • R2 and R3 are the same or different and each is hydrogen or a hydrocarbyl group having from 1 to 40 carbon atoms, or R2 and R3 are joined to form a five-membered or six-membered ring, or substituted analogs thereof;
  • X is C, N, or O
  • n is an integer from 1 to 10,000;
  • the dotted line indicates an optional double bond
  • a copolymer comprising (a) from about 20 mol% to about 99.9 mol% of at least one C 5 to C 4 o higher olefin and (b) from about 0.1 mol% to about 80 mol% of propylene; and or (iii) a copolymer comprising (a) from about 80 mol% to about 99.9 mol% of at least one C 4 olefin and (b) from about 0.1 mol% to about 20 mol% of propylene.
  • This invention also relates to a process to produce the polymers described above.
  • This invention also relates to a composition comprising the polymers described above.
  • Figure 1 is a representation of some of the possible outcomes of ring opening cross- metathesis.
  • Polyolefin means an oligomer or polymer of two or more olefin mer units and specifically includes oligomers and polymers as defined below.
  • An “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • a “mono-olefin” has one double bond, for example, an alpha, omega, pendant, or internal double bond.
  • a “polymer” has two or more of the same or different mer units.
  • a “homopolymer” is a polymer having mer units that are the same.
  • a “copolymer” is a polymer having two or more mer units that are different from each other.
  • a “terpolymer” is a polymer having three mer units that are different from each other.
  • the term “different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers and the like.
  • An oligomer is typically a polymer having a low molecular weight (such as an Mn of less than 25,000 g/mol, preferably less than 2,500 g/mol) or a low number of mer units (such as 75 mer units or less, typically 50 mer units or less, even 20 mer units or less, even 10 mer units or less).
  • a low molecular weight such as an Mn of less than 25,000 g/mol, preferably less than 2,500 g/mol
  • a low number of mer units such as 75 mer units or less, typically 50 mer units or less, even 20 mer units or less, even 10 mer units or less.
  • a polymer or copolymer is referred to as comprising an olefin, including, but not limited to ethylene, propylene, and butene
  • the olefin present in such polymer or copolymer is the polymerized form of the olefin.
  • a copolymer is said to have an "ethylene" content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.
  • an ethylene polymer or oligomer contains at least 50 mol% of ethylene
  • a propylene polymer or oligomer contains at least 50 mol% of propylene
  • a butene polymer or oligomer contains at least 50 mol% of butene, and so on.
  • Mn is number average molecular weight
  • Mw is weight average molecular weight
  • Mz is z average molecular weight.
  • Molecular weight distribution is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol.
  • substituted means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom or a heteroatom containing group.
  • methyl cyclopentadiene is a cyclopentadiene (Cp) group substituted with a methyl group
  • ethyl alcohol is an ethyl group substituted with an -OH group.
  • hydrocarbyl radical is defined to be Cj to C20 radicals, that may be linear, branched, or cyclic (aromatic or non-aromatic); and include substituted hydrocarbyl radicals as defined below.
  • Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom has been substituted with a heteroatom or heteroatom containing group, preferably with at least one functional group such as halogen (CI, Br, I, F), R*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR* 2 , SR*, BR*2, SiR* 3 , GeR* 3 , SnR* 3 , PbR* 3 , and the like or where at least one heteroatom has been inserted within the hydrocarbyl radical, such as halogen (CI, Br, I, F), O, S, Se, Te, NR*, PR*, AsR*, SbR*, BR*, SiR* 2 , GeR* 2 , SnR* 2 , PbR* 2 , and the like, where R* is, independently, hydrogen or a hydrocarbyl.
  • halogen CI, Br, I, F
  • R*2 OR*, Se
  • a “substituted alkyl” is an alkyl radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom, a heteroatom containing group, or a cyclic substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms.
  • a "substituted aryl” group is an aryl radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom, a heteroatom containing group, or a linear, branched, or cyclic substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms.
  • a "heteroatom containing ring” is a cyclic ring where one or more ring vertices are occupied by a heteroatom (N, O, P, S).
  • tetrahydrofuran is a heteroatom containing ring, having an oxygen atom as part of the ring backbone.
  • anionic ligand is a negatively charged ligand which donates one or more pairs of electrons to a metal ion.
  • neutral donor ligand is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.
  • catalysts are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers.
  • the transition metal compound used for catalysis may be described as a catalyst precursor, a pre- catalyst compound, a catalyst, or a catalyst compound, and these terms are used interchangeably.
  • a "reactor” is any container(s) in which a chemical reaction occurs.
  • Mol% means mole percent
  • wt% means weight percent
  • vol% means volume percent
  • This invention relates to a new class of functionalized polymers and processes to produce them. These polymers are end-functionalized with a cyclic functional group and possess the ability to be further functionalized through a terminal vinyl group. This ability to add further functionality post-polymerization affords appreciable synthetic flexibility that may be of tremendous commercial utility. For instance, bulk polymer properties such as viscosity may be tailored by utilizing this synthetic handle to increase the size and viscosity of the polymer.
  • functionalized vinyl-terminated polymers also referred to as functionalized vinyl terminated macromonomers
  • processes to produce them are discussed further below. FUNCTIONALIZED VINYL TERMINATED POLYMERS
  • This invention relates to a polymer represented by the formula (A):
  • R is a hydrocarbyl group having greater than 25 carbon atoms, preferably greater than 30 carbon atoms, greater than 40 carbon atoms, or greater than 50 carbon atoms; preferably from 31 to 100,000 carbons, from 40 to 75,000 carbons, from 50 to 60,000 carbons; preferably Ri is represented by the formula (B):
  • Cm is a C 4 to C 4 Q olefin derived unit (preferably Cm is one or more derived units of butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof); m is an integer from 3 to 39 (preferably from 3 to 29, preferably from 4 to 19, preferably from 4 to 1 1); and p is an integer greater than 1 (preferably from 1 to 10,000, from 1 to 5,000, from 1 to 2,500, from 1 to 1,000, from 1 to 500, or from 1 to 50);
  • Ri is represented by the formula (C):
  • Cm is a C3 to C 4 Q olefin derived unit (preferably Cm is one or more derived units of propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof); m is an integer from 2 to 39 (preferably from 2 to
  • R ) and R3 are the same or different and each is hydrogen or a hydrocarbyl group having from 1 to 40 carbon atoms (preferably from 1 to 30, from 2 to 15, and from 2 to 12), or R2 and R3 are joined to form a five-membered or six-membered ring, or substituted analogs thereof (preferably R 2 and R3 are joined to form a heteroatom containing ring; preferably R2 and R3 are joined to form a dicarboxylic anhydride);
  • X is C, N, or O (preferably X is C or O, preferably X is C);
  • n is an integer from 1 to 10,000 (preferably from 1 to 5,000, from 1 to 2,500, from 1 to 1,000, from 1 to 500, or from 1 to 50);
  • polymer preferably Ri
  • the polymer comprises one or more vinyl terminated macromonomer derived units (preferably the vinyl terminated macromonomer is one or more of:
  • a copolymer having an Mn of 300 g/mol or more comprising (a) from about 20 mol% to about 99.9 mol% of at least one C5 to C 4 Q higher olefin, and (b) from about 0.1 mol% to about 80 mol% of propylene, wherein the higher olefin copolymer has at least 40% allyl chain ends;
  • a propylene oligomer comprising more than 90 mol% propylene and less than 10 mol% ethylene wherein the oligomer has: at least 93% allyl chain ends, a number average molecular weight (Mn) of about 500 g/mol to about 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0, and less than 100 ppm aluminum;
  • a propylene oligomer comprising: at least 50 mol% propylene and from 10 mol% to 50 mol% ethylene, wherein the oligomer has: at least 90% allyl chain ends, an Mn of about 150 g/mol to about 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.2: 1.0, wherein monomers having four or more carbon atoms are present at from 0 mol% to 3 mol%;
  • a propylene oligomer comprising: at least 50 mol% propylene, from 0.1 mol% to 45 mol% ethylene, and from 0.1 mol% to 5 mol% C 4 to olefin, wherein the oligomer has: at least 90% allyl chain ends, an Mn of about 150 g/mol to about 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0;
  • a propylene oligomer comprising: at least 50 mol% propylene, from 0.1 mol% to 45 mol% ethylene, and from 0.1 mol% to 5 mol% diene, wherein the oligomer has: at least 90% allyl chain ends, an Mn of about 150 g/mol to about 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.7: 1 to 1.35: 1.0; and
  • Ri is preferably not an ethylene polymer. In any embodiment described herein, Ri is preferably not a propylene polymer. In any embodiment described herein, Ri is preferably not a butene polymer.
  • Ri is derived from vinyl terminated polymer (i) described above. In a preferred embodiment of the invention Ri is derived from vinyl terminated polymer (ii) described above. In a preferred embodiment of the invention Ri is derived from vinyl terminated polymer (iii) described above.
  • Vm is a C x to C y olefin derived unit
  • x and y are the integers described above
  • Cm as depicted in the formulae has one less carbon than the olefin it was derived from, i.e., one carbon of the originating olefin is incorporated into the polymer backbone.
  • the polymer is represented by the formula
  • X is C, N, or O (preferably C or O, preferably C); n is an integer from 1 to 10,000 (preferably from 1 to 5,000, from 1 to 2,500, from 1 to 1,000, from 1 to 500, or from 1 to 50); Cm is a C3 to C40 olefin derived unit (preferably Cm is one or more derived units of propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof); m is an integer from 2 to 39 (preferably from 2 to 29, preferably from 3 to 19,
  • the vinyl terminated macromonomer derived units are derived from (i), (ii) or (iii) above.
  • this invention relates to a polymer represented by the formula
  • R 2 and R3; X, n, and the dotted line are as defined above and Ri is
  • a polymer preferably having an Mn of at least 200 g/mol (measured by l H NMR), comprising of one or more C 4 to C 4 Q higher olefin derived units (preferably C5 to C40 higher olefin derived units), where the higher olefin polymer comprises substantially no propylene derived units; and or
  • a copolymer preferably having an Mn of at least 300 g/mol (measured by l H NMR), comprising (a) from about 20 mol% to about 99.9 mol% of at least one C5 to C40 higher olefin and (b) from about 0.1 mol% to about 80 mol% of propylene; and or
  • a copolymer preferably having an Mn of at least 300 g/mol (measured by l H NMR), comprising (a) from about 80 mol% to about 99.9 mol% of at least one C4 olefin and (b) from about 0.1 mol% to about 20 mol% of propylene.
  • the polymer is hydrogenated.
  • the polymers produced herein may be hydrogenated by contacting the polymer with hydrogen and a hydrogenation catalyst. This hydrogenation step is often used to reduce the bromine number (preferably below 2.0, preferably below 1.8). Bromine number is determined by ASTM D 1159. In a preferred embodiment, the bromine number of the hydrogenated polymer decreases by at least 50% (preferably at least 75%) as compared to the starting polymer.
  • the hydrogenation catalyst is selected from the group consisting of supported Group 7, 8, 9, and 10 metals, preferably the hydrogenation catalyst selected from the group consisting of one or more of Ni, Pd, Pt, Co, Rh, Fe, Ru, Os, Cr, Mo, and W, supported on silica, alumina, clay, titania, zirconia, or mixed metal oxide supports.
  • a preferred hydrogenation catalyst is nickel supported on kieselguhr, or platinum or palladium supported on alumina, or cobalt-molybdenum supported on alumina.
  • a high nickel content catalyst such as 60% Ni on Kieselguhr catalyst, is used, or a supported catalyst with high amount of Co-Mo loading.
  • the hydrogenation catalyst is nickel supported on Kieselguhr, silica, alumina, clay, or silica-alumina.
  • the polymer is contacted with hydrogen (preferably at a hydrogen pressure of from 25 psi to 2500 psi (0.17 MPa to 17.24 MPa), preferably from 100 psi to 2000 psi (0.69 MPa to 13.79 MPa)), and a hydrogenation catalyst at a temperature from 25°C to 350°C, preferably 100°C to 300°C, and/or a time period from 5 minutes to 100 hours, preferably from 5 minutes to 24 hours.
  • hydrogen preferably at a hydrogen pressure of from 25 psi to 2500 psi (0.17 MPa to 17.24 MPa), preferably from 100 psi to 2000 psi (0.69 MPa to 13.79 MPa
  • a hydrogenation catalyst at a temperature from 25°C to 350°C, preferably 100°C to 300°C, and/or a time period from 5 minutes to 100 hours, preferably from 5 minutes to 24 hours.
  • the hydrogenation process can be accomplished in a slurry reactor in a batch operation or in a continuous stirred tank reactor (CSTR), where the catalyst, hydrogen, and the polymer are continuously added to the reactor to allow for certain residence time, usually 5 minutes to 10 hours to allow complete hydrogenation of the unsaturated olefins.
  • the amount of catalyst added is usually very small, for example, 0.001 wt% to 20 wt% of the polymer feed or preferably 0.01 wt% to 10 wt%, to compensate for the catalyst deactivation.
  • the catalyst and hydrogenated polymer are continuously withdrawn from the reactor.
  • the product mixture may then be filtered, centrifuged, or settled to remove the solid hydrogenation catalyst.
  • the catalyst can be regenerated and reused.
  • the hydrogenation process can also be accomplished by a fixed bed process, in which the solid catalyst is packed inside a tubular reactor and heated to reactor temperature.
  • compositions comprising the polymers produced herein are also disclosed.
  • the composition is a lubricant or lubricant base stock, an adhesive, a viscosity modifier, or a fuel additive.
  • a novel lubricant comprises the polymers produced in this invention, alone or together with one or more other base stocks, including Group I to Group V base stocks with kinematic viscosity (ASTM D445) range from 1.5 cSt to 100 cSt at 100°C to formulate suitable viscosity grades.
  • additives of one or more of: thickeners, viscosity index improvers, antioxidants, anti-wear additives, detergent/dispersant/inhibitor packages, and/or anti-rust additives may be added.
  • the polymers produced herein are combined with one or more of dispersants, detergents, friction modifiers, traction improving additives, demulsifiers, defoamants, chromophores (dyes), and/or haze inhibitors.
  • dispersants detergents, friction modifiers, traction improving additives, demulsifiers, defoamants, chromophores (dyes), and/or haze inhibitors.
  • These fully formulated lubricants can be used in automotive crank case oil (engine oil), industrial oil, grease, or gas turbine engine oil.
  • additives used in finished lubricant formulations are examples of additives used in finished lubricant formulations. Additional information on additives used in product formulation can be found in "Lubricants and Lubrications", Ed. By T. Mang and W. Dresel, by Wiley-VCH GmbH, Weinheim 2001.
  • the polymers prepared herein may be further functionalized by reacting a heteroatom containing group (preferably amines, aldehydes, alcohols, acids, succinic acid, maleic acid, and/or maleic anhydride) with the polymer, with or without a catalyst.
  • a heteroatom containing group preferably amines, aldehydes, alcohols, acids, succinic acid, maleic acid, and/or maleic anhydride
  • a heteroatom containing group preferably amines, aldehydes, alcohols, acids, succinic acid, maleic acid, and/or maleic anhydride
  • a heteroatom containing group preferably amines, aldehydes, alcohols, acids, succinic acid, maleic acid, and/or maleic anhydride
  • Examples include catalytic hydrosilylation, hydroformylation, hydroboration, epoxidation, hydration, dihydroxylation, hydroamination, or maleation with or without activators such as free radical generators (e.g
  • the functionalized polymers can be used in lubricant, oil additivation, and many other applications.
  • the vinyl end group of the polymers of the present invention is synthetically facile thereby allowing for functionalization of the resultant polymer.
  • Some examples of functionalized polymers include those that are functionalized with maleic acid or maleic anhydride groups.
  • the functionalized polymers can in turn be derivatized with a derivatizing compound, such as described in U.S. Patent No. 6,022,929; A. Toyota, T. Tsutsui, and N. Kashiwa, Polymer Bulletin 48, 213-219, 2002; and J. Am. Chem. Soc, 1990, 112, 7433- 7434.
  • the derivatizing compound can react with the functional groups of the functionalized capped polymer by any means known in the art, such as nucleophilic substitution, Mannich Base condensation, and the like.
  • the derivatizing compound can be polar and/or contain reactive derivative groups.
  • Preferred derivatizing compounds are selected from hydroxy containing compounds, amines, metal salts, anhydride containing compounds, and acetyl halide containing compounds.
  • the derivatizing compounds can comprise at least one nucleophilic group and preferably at least two nucleophilic groups.
  • An exemplary derivatized polymer may be made by contacting a functionalized polymer, for example, one substituted with a carboxylic acid/anhydride or ester, with a nucleophilic reagent, for example, amines, alcohols (including polyols), amino alcohols, reactive metal compounds and the like.
  • a nucleophilic reagent for example, amines, alcohols (including polyols), amino alcohols, reactive metal compounds and the like.
  • the functionalized polymers of the present invention may be produced in any manner known to one of skill in the art. These functionalized polymers are advantageously produced from vinyl terminated macromonomers, such as those described in USSN 13/072,288; USSN 13/072,249; and USSN 12/143,663. More particularly, in embodiments of the present invention, processes for producing a polymer comprise contacting at least (A) one cyclic olefin with (B) at least one vinyl terminated macromonomer in the presence of (C) a metathesis catalyst, under suitable polymerization conditions.
  • the product comprises a ROCM product of a cyclic olefin and a vinyl terminated macromonomer.
  • this invention also relates to a process to produce a polymer represented by the formula (A):
  • R ) and R3 are the same or different and each is hydrogen or a hydrocarbyl group having from 1 to 40 carbon atoms, or R2 and R3 are joined to form a five-membered or six-membered ring, or substituted analogs thereof;
  • X is C, N, or O
  • n is an integer from 1 to 10,000;
  • polymer comprises one or more vinyl terminated macromonomer derived units; the process comprising contacting:
  • cyclic olefin preferably norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, and substituted derivatives therefrom; more preferably cyclooctene, 1,5- cyclooctadiene, 1 -hydroxy -4-cyclooctene, 1 -acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, cis-5-norbornene-endo-2,3- dicarboxylic anhydride, dimethyl norbornene carboxylate, norbornene-exo-2,3-carboxylic anhydride, and their respective homologs and derivatives) with at least
  • M is a Group 8 metal, preferably Ru or Os, preferably Ru;
  • X and X 1 are, independently, any anionic ligand, preferably a halogen (preferably chlorine), an alkoxide or a triflate, or X and X 1 may be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non- hydrogen atoms;
  • L and L 1 are, independently, a neutral two electron donor, preferably a phosphine or a N- heterocyclic carbene, L and L 1 may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L and X may be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L 1 and X 1 may be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • R 4 and R 5 are, independently, hydrogen or Ci to C30 substituted or unsubstituted hydrocarbyl (preferably a Q to C30 substituted or unsubstituted alkyl or a substituted or unsubstituted C 4 to C30 aryl);
  • R 5 and L 1 or X 1 may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • R 4 and L or X may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • M is Os or Ru, preferably Ru
  • X, X l , L, and L 1 are as described above for Formula E;
  • R 9 and R 10 may be different or the same and may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl; and/or
  • M* is a Group 8 metal, preferably Ru or Os, preferably Ru;
  • X* and X 1 * are, independently, any anionic ligand, preferably a halogen (preferably chlorine), an alkoxide or an alkyl sulfonate, or X* and X 1 * may be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L* is N-R**, O, P-R**, or S, preferably N-R** or O (R** is a to C30 hydrocarbyl or substituted hydrocarbyl, preferably methyl, ethyl, propyl or butyl);
  • R* is hydrogen or a to C30 hydrocarbyl or substituted hydrocarbyl, preferably methyl
  • R 1 *, R 2 *, R 3 *, R 4 *, R 5 *, R 6 *, R 7 *, and R 8 * are, independently, hydrogen or a C ⁇ to C 30 hydrocarbyl or substituted hydrocarbyl, preferably methyl, ethyl, propyl or butyl, preferably R 1 *, R 2 *, R 3 *, and R 4 * are methyl;
  • each R 9 * and R 13 * are, independently, hydrogen or a Q to C30 hydrocarbyl or substituted hydrocarbyl, preferably a C 2 to hydrocarbyl, preferably ethyl;
  • R 10 *, R 1 1 *, R 12 * are, independently hydrogen or a Ci to C30 hydrocarbyl or substituted hydrocarbyl, preferably hydrogen or methyl;
  • each G is, independently, hydrogen, halogen or Q to C30 substituted or unsubstituted hydrocarbyl (preferably a Ci to C30 substituted or unsubstituted alkyl or a substituted or unsubstituted C 4 to C30 aryl); and
  • any two adjacent R groups may form a single ring of up to 8 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • M" is a Group 8 metal (preferably M is ruthenium or osmium, preferably ruthenium);
  • each X is independently an anionic ligand (preferably selected from the group consisting of halides, alkoxides, aryloxides, and alkyl sulfonates, preferably a halide, preferably chloride);
  • R" 1 and R" 2 are independently selected from the group consisting of hydrogen, a to C30 hydrocarbyl, and a Q to C30 substituted hydrocarbyl (preferably R" 1 and R" 2 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert- butyl, sec -butyl, cyclohexyl, and cycloo
  • R" 3 and R" 4 are independently selected from the group consisting of hydrogen, to hydrocarbyl groups, substituted Q to hydrocarbyl groups, and halides (preferably R" 3 and R" 4 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert-butyl, sec -butyl, cyclohexyl, and cyclooctyl); and
  • L" is a neutral donor ligand, preferably L" is selected from the group consisting of a phosphine, a sulfonated phosphine, a phosphite, a phosphinite, a phosphonite, an arsine, a stibine, an ether, an amine, an imine, a sulfoxide, a carboxyl, a nitrosyl, a pyridine, a thioester, a cyclic carbene, and substituted analogs thereof; preferably a phosphine, a sulfonated phosphine, an N-heterocyclic carbene, a cyclic alkyl amino carbene, and substituted analogs thereof (preferably L" is selected from a phosphine, an N-heterocyclic carbene, a cyclic alkyl amino carbene, and substituted analogs thereof); and/or
  • M" is a Group 8 metal (preferably M is ruthenium or osmium, preferably ruthenium);
  • each X is independently an anionic ligand (preferably selected from the group consisting of halides, alkoxides, aryloxides, and alkyl sulfonates, preferably a halide, preferably chloride);
  • R" 1 and R" 2 are independently selected from the group consisting of hydrogen, a Ci to C30 hydrocarbyl, and a Q to C30 substituted hydrocarbyl (preferably R" 1 and R" 2 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert- butyl, sec -butyl, cyclohexyl, and cyclo
  • R" 3 , R" 4 , R" 5 , and R" 6 are independently selected from the group consisting of hydrogen, Ci to C12 hydrocarbyl groups, substituted to hydrocarbyl groups, and halides (preferably R" 3 , R" 4 , R" 5 , and R" 6 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert-butyl, sec -butyl, cyclohexyl, and cyclooctyl); and
  • a temperature of 20°C to 200°C preferably 50°C to 160°C, preferably 60°C to 140°C
  • a pressure of 0 MPa to 1000 MPa preferably 0.5 MPa to 500 MPa, preferably 1 MPa to 250 MPa
  • a residence time of 0.5 seconds to 10 hours preferably 1 second to 5 hours, preferably 1 minute to 1 hour.
  • the catalyst is represented by formula F. In a preferred embodiment, the catalyst is represented by formula G. In a preferred embodiment, the catalyst is represented by formula H. In a preferred embodiment, the catalyst is represented by formula I.
  • the ROCM involves a tandem sequence in which a cyclic olefin is opened and a vinyl terminated macromonomer is crossed onto the newly formed termini. After the initial ring opening of the cyclic olefin, the metal-bound intermediate has two options: reaction with another cyclic olefin or reaction with the vinyl terminated macromonomer.
  • a cyclic olefin will undergo a ring opening reaction in the presence of the catalyst at a rate constant k RQ
  • the vinyl terminated macromonomer will undergo a cross-metathesis reaction with the ring opened cyclic olefin at a rate constant k ⁇ .
  • k CM is greater than or equal to k R0
  • the ROCM product is predominantly a monomer, dimer, and/or oligomer. More specifically, when k CM is approximately equal to k R0 , the ROCM product is predominantly a dimer, while when k RQ is greater than ⁇ M , the ROCM product is predominantly higher Mw.
  • Oligomers are of particular interest because their internal olefin moieties may be further functionalized by metathesis or other transformations. It should be appreciated that k RQ will be higher for moderately and highly strained cyclic olefins such as norbornadiene, but lower for low-strain olefins such as cyclopentene and cyclohexene.
  • the reactants are typically combined in a reaction vessel at a temperature of 20°C to 200°C (preferably 50°C to 160°C, preferably 60°C to 140°C) and a pressure of 0 MPa to 1000 MPa (preferably 0.5 MPa to 500 MPa, preferably 1 MPa to 250 MPa) for a residence time of 0.5 seconds to 10 hours (preferably 1 second to 5 hours, preferably 1 minute to 1 hour).
  • the molecular weight of the polymer products may be controlled by, inter alia, choice of catalyst, ratio of vinyl terminated macromonomer to cyclic olefin, and/or possibly temperature.
  • the olefin pressure is typically greater than 5 psig (34.5 kPa); preferably, greater than 10 psig (68.9 kPa); and more preferably, greater than 45 psig (310 kPa).
  • the aforementioned pressure ranges may also be suitably employed as the total pressure of olefin and diluent.
  • the aforementioned pressure ranges may be suitably employed for the inert gas pressure.
  • the quantity of metathesis catalyst that is employed in the process of this invention is any quantity that provides for an operable metathesis reaction.
  • the ratio of moles of monomers (e.g., cyclic olefins and vinyl terminated macromonomer) to moles of metathesis catalyst is typically greater than 10: 1, preferably greater than 100: 1, preferably greater than 1,000: 1, preferably greater than 10,000: 1, preferably greater than 25,000: 1, preferably greater than 50,000: 1, preferably greater than 100,000: 1).
  • 0.00001 moles to 1.0 moles, preferably 0.0001 moles to 0.05 moles, preferably 0.0005 moles to 0.01 moles of catalyst are charged to the reactor per mole of vinyl terminated macromonomer charged.
  • 0.00001 moles to 1.0 moles, preferably 0.0001 moles to 0.05 moles, preferably 0.0005 moles to 0.01 moles of catalyst are charged to the reactor per mole of cyclic olefin charged.
  • the ratio of vinyl terminated macromonomer to cyclic olefin monomer is preferably
  • the process is typically a solution process, although it may be a bulk or high pressure process. Homogeneous processes are preferred. (A homogeneous process is defined to be a process where at least 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process is particularly preferred. (A bulk process is defined to be a process where reactant concentration in all feeds to the reactor is 70 vol% or more.) Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst or other additives, or amounts typically found with the reactants, e.g., propane in propylene).
  • Suitable diluents/solvents for the process include non-coordinating, inert liquids.
  • Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof such as can be found commercially (IsoparTM); perhalogenated hydrocarbons, such as perfluorinated C4 0 alkanes, chlorobenzene, and aromatic and alkyl substituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene.
  • straight and branched-chain hydrocarbons such as isobutane, butane
  • aliphatic hydrocarbon solvents are preferred, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof.
  • the solvent is not aromatic.
  • aromatics are present in the solvent at less than 1 wt%, preferably at 0.5 wt%, preferably at 0 wt% based upon the weight of the solvents.
  • suitable diluents/solvents also include aromatic hydrocarbons, such as toluene or xylenes, and chlorinated solvents, such as dichloromethane.
  • the feed for the process comprises 60 vol% solvent or less, based on the total volume of the feed, preferably 40 vol% or less, preferably 20 vol% or less.
  • the process is a slurry process.
  • slurry process or "slurry polymerization process” means a polymerization process where a supported catalyst is employed and monomers are polymerized on the supported catalyst particles. At least 95 wt% of polymer products derived from the supported catalyst is in granular form as solid particles (not dissolved in the diluent).
  • the process may be batch, semi-batch, or continuous.
  • continuous means a system that operates without interruption or cessation.
  • a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn.
  • Useful reaction vessels include reactors (including continuous stirred tank reactors, batch reactors, reactive extruders, pipes, or pumps).
  • the productivity of the process is at least 200 g of polymer (preferably polymer represented by formula (A)) per mmol of catalyst per hour, preferably at least 5000 g/mmol/hour, preferably at least 10,000 g/mmol/hr, preferably at least 300,000 g/mmol/hr.
  • This invention further relates to a process, preferably an in-line process, preferably a continuous process, to produce polymer represented by formula (A), comprising introducing cyclic olefin, vinyl terminated macromonomer, and alkene metathesis catalyst into a reactor, obtaining a reactor effluent containing polymer, optionally removing (such as flashing off) solvent, unused monomer and/or other volatiles, obtaining polymer then hydrogenating or functionalizing the polymer.
  • a process preferably an in-line process, preferably a continuous process, to produce polymer represented by formula (A), comprising introducing cyclic olefin, vinyl terminated macromonomer, and alkene metathesis catalyst into a reactor, obtaining a reactor effluent containing polymer, optionally removing (such as flashing off) solvent, unused monomer and/or other volatiles, obtaining polymer then hydrogenating or functionalizing the polymer.
  • reaction zone also referred to as a "polymerization zone” is defined as an area where activated catalysts and monomers are contacted and a polymerization reaction takes place.
  • each reactor is considered as a separate polymerization zone.
  • each polymerization stage is considered as a separate polymerization zone.
  • the process produces the metathesis product (polymers having the formula A disclosed herein) in good yield (greater than 50%).
  • the process produces little or no dimerization.
  • the extent of dimerization is determined by the comparison of the degree of polymerization (ROCM) as obtained from methods A and B, described in the Examples.
  • the degree of ROCM obtained from Method A differs from that obtained from Method B by less than 25%, preferably less than 20%, preferably less than 15%, and most preferably less than 10%.
  • the cyclic olefin may be a single cyclic olefin, or a combination of cyclic olefins, that is a mixture of two or more different cyclic olefins.
  • the cyclic olefins may be strained or unstrained, monocyclic, or polycyclic; and may optionally include heteroatoms and/or one or more functional groups.
  • dicyclopentadiene, norbornene, norbomadiene, ethylidene norbornene, and vinyl norbornene are polycyclic.
  • Suitable cyclic olefins include, but are not limited to norbornene, norbomadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, and substituted derivatives therefrom.
  • substituents include, but are not limited to, hydroxyl, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen.
  • Preferred cyclic olefins include cyclooctene, 1,5 -cyclooctadiene, 1 -hydroxy-4-cyclooctene, 1 -acetoxy-4-cyclooctene, 5- methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbomadiene, and their respective homologs and derivatives, preferably norbornene, norbomadiene, cis-5- norbornene-endo-2,3-dicarboxylic anhydride, dimethyl norbornene carboxylate, norbornene- exo-2,3 -carboxylic anhydride, and dicyclopentadiene.
  • the cyclic olefin is derived from substituted or unsubstituted cyclopentadiene, such as dicyclopentadiene, norbornene, norbomadiene, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, dimethyl norbornene carboxylate, norbornene-exo-2,3 -carboxylic anhydride, ethylidene norbornene, vinyl norbornene, and the like.
  • substituted or unsubstituted cyclopentadiene such as dicyclopentadiene, norbornene, norbomadiene, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, dimethyl norbornene carboxylate, norbornene-exo-2,3 -carboxylic anhydride, ethylidene norbornene, vinyl norbornene, and the like.
  • a "vinyl terminated macromonomer,” as used herein, refers to one or more of:
  • a copolymer having an Mn of 300 g/mol or more comprising (a) from about 20 mol% to about 99.9 mol% of at least one C5 to C 4 Q higher olefin, and (b) from about 0.1 mol% to about 80 mol% of propylene, wherein the higher olefin copolymer has at least 40% allyl chain ends;
  • a copolymer having an Mn of 300 g/mol or more (measured by !fi NMR), and comprises (a) from about 80 mol% to about 99.9 mol% of at least one C 4 olefin, (b) from about 0.1 mol% to about 20 mol% of propylene; and wherein the vinyl terminated macromonomer has at least 40% allyl chain ends relative to total unsaturation;
  • a propylene oligomer comprising more than 90 mol% propylene and less than 10 mol% ethylene wherein the oligomer has: at least 93% allyl chain ends, a number average molecular weight (Mn) of about 500 g/mol to about 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0, and less than 100 ppm aluminum;
  • a propylene oligomer comprising: at least 50 mol% propylene and from 10 mol% to 50 mol% ethylene, wherein the oligomer has: at least 90% allyl chain ends, an Mn of about 150 g/mol to about 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.2: 1.0, wherein monomers having four or more carbon atoms are present at from 0 mol% to 3 mol%;
  • a propylene oligomer comprising: at least 50 mol% propylene, from 0.1 mol% to 45 mol% ethylene, and from 0.1 mol% to 5 mol% C 4 to olefin, wherein the oligomer has: at least 90% allyl chain ends, an Mn of about 150 g/mol to about 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0;
  • a propylene oligomer comprising: at least 50 mol% propylene, from 0.1 mol% to 45 mol% ethylene, and from 0.1 mol% to 5 mol% diene, wherein the oligomer has: at least 90% allyl chain ends, an Mn of about 150 g/mol to about 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.7: 1 to 1.35: 1.0; and
  • the vinyl terminated macromonomer has an Mn of at least 200 g/mol, (preferably 200 g/mol to 100,000 g/mol, preferably 200 g/mol to 75,000 g/mol, preferably 200 g/mol to 60,000 g/mol, preferably 300 g/mol to 60,000 g/mol, or preferably 750 g/mol to 30,000 g/mol) (measured by l R NMR), and comprise one or more (preferably two or more, three or more, four or more, and the like) C 4 to C 4 Q (preferably C 4 to C30, C 4 to C20, or C 4 to ( 3 ⁇ 4, preferably butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene
  • the vinyl terminated macromonomers may also comprise ethylene derived units, preferably at least 5 mol% ethylene (preferably at least 15 mol% ethylene, preferably at least 25 mol% ethylene, preferably at least 35 mol% ethylene, preferably at least 45 mol% ethylene, preferably at least 60 mol% ethylene, preferably at least 75 mol% ethylene, or preferably at least 90 mol% ethylene).
  • ethylene derived units preferably at least 5 mol% ethylene (preferably at least 15 mol% ethylene, preferably at least 25 mol% ethylene, preferably at least 35 mol% ethylene, preferably at least 45 mol% ethylene, preferably at least 60 mol% ethylene, preferably at least 75 mol% ethylene, or preferably at least 90 mol% ethylene).
  • the vinyl terminated macromonomers described herein have an Mn (measured by NMR) of greater than 200 g/mol (preferably 300 g/mol to 60,000 g/mol, 400 g/mol to 50,000 g/mol, 500 g/mol to 35,000 g/mol, 300 g/mol to 15,000 g/mol, 400 g/mol to 12,000 g/mol, or 750 g/mol to 10,000 g/mol), and comprise:
  • the vinyl terminated macromonomer has at least 40% allyl chain ends (preferably at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, or at least 80% allyl chain ends, at least 90% allyl chain ends, at least 95% allyl chain ends) relative to total unsaturation; and, optionally, an isobutyl chain end to allyl chain end ratio of less than 0.70: 1, less than 0.65: 1, less than 0.60: 1, less than 0.50: 1, or less than 0.25: 1 ; and further optionally, an allyl chain end to vinylidene chain end ratio of greater than 2: 1 (preferably greater than 2.5: 1, greater than 3 : 1, greater than 5: 1, or greater than 10: 1); and even further optionally, an allyl chain end to vinylene ratio is greater than 1 : 1 (preferably greater than 2: 1 or greater than 5: 1).
  • allyl chain ends preferably at least 50% allyl chain ends, at least 60% allyl chain ends, at least
  • the vinyl terminated macromonomer has an Mn of 300 g/mol or more (measured by NMR, preferably 300 g/mol to 60,000 g/mol, 400 g/mol to 50,000 g/mol, 500 g/mol to 35,000 g/mol, 300 g/mol to 15,000 g/mol, 400 g/mol to 12,000 g/mol, or 750 g/mol to 10,000 g/mol), and comprises:
  • the vinyl terminated macromonomer has at least 40% allyl chain ends (preferably at least 50% allyl chain ends, at least 60% allyl chain ends, at least 70% allyl chain ends, or at least 80% allyl chain ends, at least 90% allyl chain ends, at least 95% allyl chain ends) relative to total unsaturation, and in some embodiments, an isobutyl chain end to allyl chain end ratio of less than 0.70: 1, less than 0.65: 1, less than 0.60: 1, less than 0.50: 1, or less than 0.25: 1, and in further embodiments, an allyl chain end to vinylidene group ratio of more than 2: 1, more than 2.5: 1, more than 3 : 1 , more than 5 : 1 , or more than 10: 1.
  • allyl chain end to vinylidene group ratio of more than 2: 1, more than 2.5: 1, more than 3 : 1 , more than 5 : 1 , or more than 10: 1.
  • Such macromonomers are also further described in USSN 13/072,2
  • the vinyl terminated macromonomer is a propylene co-oligomer having an Mn of 300 g/mol to 30,000 g/mol as measured by NMR (preferably 400 g/mol to 20,000 g/mol, preferably 500 g/mol to 15,000 g/mol, preferably 600 g/mol to 12,000 g/mol, preferably 800 g/mol to 10,000 g/mol, preferably 900 g/mol to 8,000 g/mol, preferably 900 g/mol to 7,000 g/mol), comprising 10 mol% to 90 mol% propylene (preferably 15 mol% to 85 mol%, preferably 20 mol% to 80 mol%, preferably 30 mol% to 75 mol%, preferably 50 mol% to 90 mol%) and 10 mol% to 90 mol% (preferably 85 mol% to 15 mol%, preferably 20 mol% to 80 mol%, preferably 25 mol% to 70 mol%, preferably 10 mol% to
  • the vinyl terminated macromonomer is a propylene oligomer, comprising more than 90 mol% propylene (preferably 95 mol% to 99 mol%, preferably 98 mol% to 9 mol%) and less than 10 mol% ethylene (preferably 1 mol% to 4 mol%, preferably 1 mol% to 2 mol%), wherein the oligomer has: at least 93% allyl chain ends (preferably at least 95%, preferably at least 97%, preferably at least 98%); a number average molecular weight (Mn) of about 400 g/mol to about 30,000 g/mol, as measured by l K NMR (preferably 500 g/mol to 20,000 g/mol, preferably 600 g/mol to 15,000 g/mol, preferably 700 g/mol to 10,000 g/mol, preferably 800 g/mol to 9,000 g/mol, preferably 900 g/mol to 8,000 g/mol, preferably 1,000 g/mol to
  • the vinyl terminated macromonomer is a propylene oligomer, comprising: at least 50 mol% (preferably 60 mol% to 90 mol%, preferably 70 mol% to 90 mol%) propylene and from 10 mol% to 50 mol% (preferably 10 mol% to 40 mol%, preferably 10 mol% to 30 mol%) ethylene, wherein the oligomer has: at least 90% allyl chain ends (preferably at least 91%, preferably at least 93%, preferably at least 95%o, preferably at least 98%>); an Mn of about 150 g/mol to about 20,000 g/mol, as measured by l K NMR (preferably 200 g/mol to 15,000 g/mol, preferably 250 g/mol to 15,000 g/mol, preferably 300 g/mol to 10,000 g/mol, preferably 400 g/mol to 9,500 g/mol, preferably 500 g/mol to 9,000 g/mol, preferably 750 g/
  • the vinyl terminated macromonomer is a propylene oligomer, comprising: at least 50 mol% (preferably at least 60 mol%, preferably 70 mol% to 99.5 mol%, preferably 80 mol% to 99 mol%, preferably 90 mol% to 98.5 mol%) propylene, from 0.1 mol% to 45 mol% (preferably at least 35 mol%, preferably 0.5 mol% to 30 mol%, preferably 1 mol% to 20 mol%, preferably 1.5 mol% to 10 mol%) ethylene, and from 0.1 mol% to 5 mol% (preferably 0.5 mol% to 3 mol%, preferably 0.5 mol% to 1 mol%) C 4 to Ci2 olefin (such as butene, hexene or octene, preferably butene), wherein the oligomer has: at least 90% allyl chain ends (preferably at least 91%, preferably at least 93%, preferably at least 95%
  • the vinyl terminated macromonomer is a propylene oligomer, comprising: at least 50 mol% (preferably at least 60 mol%, preferably 70 mol% to 99.5 mol%, preferably 80 mol% to 99 mol%, preferably 90 mol% to 98.5 mol%) propylene, from 0.1 mol% to 45 mol% (preferably at least 35 mol%, preferably 0.5 mol% to 30 mol%, preferably 1 mol% to 20 mol%, preferably 1.5 mol% to 10 mol%) ethylene, and from 0.1 mol% to 5 mol% (preferably 0.5 mol% to 3 mol%, preferably 0.5 mol% to 1 mol%) diene (such as C 4 to alpha-omega dienes (such as butadiene, hexadiene, octadiene), norbornene, ethylidene norbornene, vinylnorbornene, norbornadiene, and di
  • the vinyl terminated macromonomer is a propylene homo-oligomer, comprising propylene and less than 0.5 wt% comonomer, preferably 0 wt% comonomer, wherein the oligomer has:
  • At least 93% allyl chain ends (preferably at least 95%, preferably at least 96%, preferably at least 97%, preferably at least 98%, preferably at least 99%);
  • Mn a number average molecular weight of about 500 g/mol to about 20,000 g/mol, as measured by l R NMR (preferably 500 g/mol to 15,000 g/mol, preferably 700 g/mol to
  • the vinyl terminated macromonomers may be homopolymers, copolymers, terpolymers, and so on.
  • Vinyl terminated macromonomers generally have a saturated chain end (or terminus) and/or an unsaturated chain end, or terminus.
  • the unsaturated chain end of the vinyl terminated macromonomer comprises an "allyl chain end” or a "3-alkly” chain end.
  • An allyl chain end is represented by CH ⁇ CH- in the formula:
  • a 3-alkyl chain end (where the alkyl is a to C38 alkyl), also referred to as a "3- alkyl vinyl end group” or a “3-alkyl vinyl termination”, is represented by the formula:
  • R b is a to C38 alkyl group, preferably a Ci to C20 alkyl group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, docecyl, and the like.
  • the amount of 3-alkyl chain ends is determined using 13 C NMR as set out below.
  • 13 C NMR data is collected at 120°C at a frequency of at least 100 MHz, using a Bruker 400 MHz NMR spectrometer.
  • a 90 degree pulse, an acquisition time adjusted to give a digital resolution between 0.1 and 0.12 Hz, at least a 10 second pulse acquisition delay time with continuous broadband proton decoupling using swept square wave modulation without gating is employed during the entire acquisition period.
  • the spectra is acquired with time averaging to provide a signal to noise level adequate to measure the signals of interest.
  • Samples are dissolved in tetrachloroethane-d2 at concentrations between 10 wt% to 15 wt% prior to being inserted into the spectrometer magnet.
  • the "allyl chain end to vinylidene chain end ratio” is defined to be the ratio of the percentage of allyl chain ends to the percentage of vinylidene chain ends.
  • the “allyl chain end to vinylene chain end ratio” is defined to be the ratio of the percentage of allyl chain ends to the percentage of vinylene chain ends.
  • Vinyl terminated macromonomers typically also have a saturated chain end.
  • the saturated chain end may be a C 4 or greater (or “higher olefin”) chain end, as shown in the formula below:
  • n is an integer selected from 4 to 40. This is especially true when there is substantially no ethylene or propylene in the polymerization.
  • the polymer chain may initiate growth in an ethylene monomer, thereby generating a saturated chain end which is an ethyl chain end.
  • the polymer chain may initiate growth in a propylene monomer, thereby generating an isobutyl chain end.
  • An "isobutyl chain end" is defined to be an end or terminus of a polymer, represented as shown in the formula below:
  • Mn ( l R NMR) is determined according to the following NMR method.
  • l R NMR data is collected at either room temperature or 120°C (for purposes of the claims, 120°C shall be used) in a 5 mm probe using a Varian spectrometer with a !H frequency of 250 MHz, 400 MHz, or 500 MHz (for the purpose of the claims, a proton frequency of 400 mHz is used).
  • Data is recorded using a maximum pulse width of 45°C, 8 seconds between pulses and signal averaging 120 transients.
  • Spectral signals are integrated and the number of unsaturation types per 1000 carbons are calculated by multiplying the different groups by 1000 and dividing the result by the total number of carbons.
  • Mn is calculated by dividing the total number of unsaturated species into 14,000, and has units of g/mol.
  • the chemical shift regions for the olefin types are defined to be between the following spectral regions.
  • Unsaturation Tvpe Region (ppm) Number of hydrogens per structure
  • Mn may also be determined using a GPC-DRI method, as described below.
  • Mn is determined by NMR.
  • Mn, Mw, and Mz may be measured by using a Gel Permeation Chromatography (GPC) method using a High Temperature Size Exclusion Chromatograph (SEC, either from Waters Corporation or Polymer Laboratories), equipped with a differential refractive index detector (DRI).
  • GPC Gel Permeation Chromatography
  • SEC High Temperature Size Exclusion Chromatograph
  • DRI differential refractive index detector
  • the nominal flow rate is 0.5 cm 3 /min and the nominal injection volume is 300 ⁇ ⁇ .
  • the various transfer lines, columns and differential refractometer (the DRI detector) are contained in an oven maintained at 135°C.
  • Solvent for the SEC experiment is prepared by dissolving 6 grams of butylated hydroxy toluene as an antioxidant in 4 liters of Aldrich reagent grade 1,2,4 trichlorobenzene (TCB). The TCB mixture is then filtered through a 0.7 ⁇ glass pre-filter and subsequently through a 0.1 ⁇ Teflon filter. The TCB is then degassed with an online degasser before entering the SEC.
  • Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 160°C with continuous agitation for about 2 hours. All quantities are measured gravimetrically.
  • the TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/mL at room temperature and 1.324 g/mL at 135°C.
  • the injection concentration is from 1.0 to 2.0 mg/mL, with lower concentrations being used for higher molecular weight samples.
  • Prior to running each sample the DRI detector and the injector are purged. Flow rate in the apparatus is then increased to 0.5 mL/minute, and the DRI is allowed to stabilize for 8 to 9 hours before injecting the first sample.
  • the concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, 3 ⁇ 4RJ, using the following equation:
  • K D RJ is a constant determined by calibrating the DRI
  • (dn/dc) is the refractive index increment for the system.
  • (dn/dc) 0.104 for propylene polymers and ethylene polymers, and 0.1 otherwise.
  • concentration is expressed in g/cm 3
  • molecular weight is expressed in g/mol
  • intrinsic viscosity is expressed in dL/g.
  • a suitable metathesis catalyst is a compound that catalyzes the reaction between a cyclic olefin and a vinyl terminated macromonomer to produce a polymer represented by the formula (A).
  • the alkene metathesis catalyst is represented by the Formula (E):
  • M is a Group 8 metal, preferably Ru or Os, preferably Ru;
  • X and X 1 are, independently, any anionic ligand, preferably a halogen (preferably chlorine), an alkoxide or a triflate, or X and X 1 may be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non- hydrogen atoms;
  • L and L 1 are, independently, a neutral two electron donor, preferably a phosphine or a N- heterocyclic carbene, L and L 1 may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L and X may be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L 1 and X 1 may be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • R 4 and R 5 are, independently, hydrogen or Q to C30 substituted or unsubstituted hydrocarbyl (preferably a Q to C30 substituted or unsubstituted alkyl or a substituted or unsubstituted C4 to C 3() aryl);
  • R 5 and L 1 or X 1 may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • R 4 and L or X may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms.
  • Preferred alkoxides include those where the alkyl group is a phenol, substituted phenol (where the phenol may be substituted with up to 1, 2, 3, 4, or 5 C to (3 ⁇ 4 hydrocarbyl groups) or a Q to hydrocarbyl, preferably a to C ⁇ Q alkyl group, preferably methyl, ethyl, propyl, butyl, or phenyl.
  • Preferred phosphines are represented by the formula: PR 3 ' R 4 ' R 5 ', where R 3 ' is a secondary alkyl or cycloalkyl (preferably a C3 to (3 ⁇ 4 secondary alkyl or cycloalkyl), and R 4 ' and R 5 ' are aryl, Q to CIQ primary alkyl, secondary alkyl, or cycloalkyl. R 4 ' and R 5 ' may be the same or different.
  • Preferred phosphines include P(cyclohexyl)3, P(cyclopentyl)3, and/or P(isopropyl)3.
  • Preferred triflates are represented by the Formula (J):
  • R A is hydrogen or a Q to C30 hydrocarbyl group, preferably a Q to (3 ⁇ 4 alkyl group, preferably methyl, ethyl, propyl, butyl, or phenyl.
  • N-heterocyclic carbenes are represented by the Formula (II) or the Formula (II).
  • each R B is independently a hydrocarbyl group or substituted hydrocarbyl group having 1 to 40 carbon atoms, preferably methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, nonyl, decyl, cyclodecyl, dodecyl, cyclododecyl, mesityl, adamantyl, phenyl, benzyl, tolulyl, chlorophenyl, phenol, substituted phenol, or CH 2 C(CH 3 ) 3 ; and
  • each R c is hydrogen, a halogen, or a Q to (3 ⁇ 4 hydrocarbyl group, preferably hydrogen, bromine, chlorine, methyl, ethyl, propyl, butyl, or phenyl.
  • one of the N groups bound to the carbene in formula (II) or (III) is replaced with an S, O, or P atom, preferably an S atom.
  • N-heterocyclic carbenes include the compounds described in Hermann, W. A. Chem. Eur. J., 1996, 2, pp. 772 and 1627; Enders, D. et al. Angew. Chem. Int. Ed., 1995, 34, pg. 1021; Alder R. W., Angew. Chem. Int. Ed., 1996, 35, pg. 1121; and Bertrand, G. et al., Chem. Rev., 2000, 100, pg. 39.
  • the metathesis catalyst is one or more of tricyclohexylphosphine[l,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][3-phenyl-lH- inden-l-ylidene]ruthenium(II) dichloride,
  • the catalyst is l,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazol-2-ylidene[2- (i-propoxy)-5 -( ,N-dimethylaminosulfonyl)phenyl]methyleneruthenium(II) dichloride and/ or tricyclohexylphosphine[3 -phenyl- lH-inden- 1 -ylidene] [ 1 ,3 -bis(2,4,6-trimethylphenyl)-4,5- dihydroimidazol-2-ylidene]ruthenium(II) dichloride.
  • the metathesis catalyst is represented by Formula (E) above, where: M is Os or Ru; R 5 is hydrogen; X and X 1 may be different or the same and are any anionic ligand; L and L 1 may be different or the same and are any neutral electron donor; and R 4 may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl.
  • R 4 is preferably hydrogen, C ⁇ to C20 alkyl, or aryl.
  • the Q to C20 alkyl may optionally be substituted with one or more aryl, halide, hydroxy, to C20 alkoxy, or C2 to C20 alkoxycarbonyl groups.
  • the aryl may optionally be substituted with one or more Q to C20 alkyl, aryl, hydroxyl, Q to C 5 alkoxy, amino, nitro, or halide groups.
  • L and L 1 are preferably phosphines of the formula PR 3 ' R 4 ' R 5 ', where R 3 ' is a secondary alkyl or cycloalkyl, and R 4 ' and R 5 ' are aryl, to C ⁇ Q primary alkyl, secondary alkyl, or cycloalkyl.
  • R 4 ' and R 5 ' may be the same or different.
  • L and L 1 are preferably the same and are - P(cyclohexyl)3, -P(cyclopentyl)3, or -P(isopropyl)3.
  • X and X 1 are most preferably the same and are chlorine.
  • the metathesis catalyst is a ruthenium and/or osmium carbene compound represented by the Formula (F):
  • R 9 and R 10 may be different or the same and may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl.
  • the R 9 and R 10 groups may optionally include one or more of the following functional groups: alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen groups.
  • Such compounds and their synthesis are described in, inter alia, U.S. Patent No. 6,111,121.
  • the metathesis catalyst useful herein may be any of the catalysts described in U.S. Patent Nos. 6,111,121; 5,312,940; 5,342,909; 7,329,758; 5,831,108; 5,969,170; 6,759,537; 6,921,735; and U.S. Patent Publication No. 2005-0261451 Al, including, but not limited to,
  • the metathesis catalyst is represented by the formula (G):
  • M* is a Group 8 metal, preferably Ru or Os, preferably Ru;
  • X* and X 1 * are, independently, any anionic ligand, preferably a halogen (preferably chlorine), an alkoxide or an alkyl sulfonate, or X* and X 1 * may be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L* is N-R**, O, P-R**, or S, preferably N-R** or O (R** is a to C30 hydrocarbyl or substituted hydrocarbyl, preferably methyl, ethyl, propyl or butyl);
  • R* is hydrogen or a Q to C30 hydrocarbyl or substituted hydrocarbyl, preferably methyl;
  • R 1 *, R 2 *, R 3 *, R 4 *, R 5 *, R 6 *, R 7 *, and R 8 * are, independently, hydrogen or a C ⁇ to C 30 hydrocarbyl or substituted hydrocarbyl, preferably methyl, ethyl, propyl or butyl, preferably R 1 *, R 2 *, R 3 *, and R 4 * are methyl;
  • each R 9 * and R 13 * are, independently, hydrogen or a Q to C30 hydrocarbyl or substituted hydrocarbyl, preferably a C2 to hydrocarbyl, preferably ethyl;
  • R 10 *, R 11 *, R 12 * are, independently hydrogen or a to C30 hydrocarbyl or substituted hydrocarbyl, preferably hydrogen or methyl;
  • each G is, independently, hydrogen, halogen or Q to C30 substituted or unsubstituted hydrocarbyl (preferably a Q to C30 substituted or unsubstituted alkyl or a substituted or unsubstituted C4 to C30 aryl); and
  • any two adjacent R groups may form a single ring of up to 8 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms.
  • any two adjacent R groups may form a fused ring having from 5 to 8 non- hydrogen atoms.
  • the non-hydrogen atoms are C and/or O.
  • the adjacent R groups form fused rings of 5 to 6 ring atoms, preferably 5 to 6 carbon atoms.
  • adjacent is meant any two R groups located next to each other, for example R 3 * and R 4 * can form a ring and/or R 1 !* and R 12 * can form a ring.
  • the metathesis catalyst compound comprises one or more of:
  • the invention relates to a metathesis catalyst comprising: a Group 8 metal complex represented by the formula (H):
  • M" is a Group 8 metal (preferably M is ruthenium or osmium, preferably ruthenium);
  • each X" is independently an anionic ligand (preferably selected from the group consisting of halides, alkoxides, aryloxides, and alkyl sulfonates, preferably a halide, preferably chloride);
  • R" 1 and R" 2 are independently selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a Q to C30 substituted hydrocarbyl (preferably R" 1 and R" 2 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert- butyl, sec -butyl, cyclohexyl, and cycl
  • R" 3 and R" 4 are independently selected from the group consisting of hydrogen, to hydrocarbyl groups, substituted Q to hydrocarbyl groups, and halides (preferably R" 3 and R" 4 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert-butyl, sec -butyl, cyclohexyl, and cyclooctyl); and
  • L" is a neutral donor ligand, preferably L" is selected from the group consisting of a phosphine, a sulfonated phosphine, a phosphite, a phosphinite, a phosphonite, an arsine, a stibine, an ether, an amine, an imine, a sulfoxide, a carboxyl, a nitrosyl, a pyridine, a thioester, a cyclic carbene, and substituted analogs thereof; preferably a phosphine, a sulfonated phosphine, an N-heterocyclic carbene, a cyclic alkyl amino carbene, and substituted analogs thereof (preferably L" is selected from a phosphine, an N-heterocyclic carbene, a cyclic alkyl amino carbene, and substituted analogs thereof).
  • a "cyclic carbene” may be defined as a cyclic compound with a neutral dicoordinate carbon center featuring a lone pair of electrons.
  • Such cyclic carbenes may be represented by the formula (IV) below:
  • n is a linking group comprising from one to four ring vertices selected from the group consisting of C, Si, N, P, O, and S, with available valences optionally occupied by H, oxo, hydrocarbyl, or substituted hydrocarbyl groups; preferably, n comprises two ring vertices of carbon with available valences occupied by H, oxo, hydrocarbyl or substituted hydrocarbyl groups; preferably n is C2H2, C2H4, or substituted versions thereof;
  • each E is independently selected from the group comprising C, N, S, O, and P, with available valences optionally occupied by Lx, Ly, Lz, and Lz'; preferably, at least one E is a C; preferably, one E is a C and the other E is a N; preferably, both E's are C; and
  • Lx, Ly, Lz, and Lz' are independently selected from the group comprising hydrogen, hydrocarbyl groups, and substituted hydrocarbyl groups; preferably, Lx, Ly, Lz, and Lz' are independently selected from the group comprising a hydrocarbyl group and substituted hydrocarbyl group having 1 to 40 carbon atoms; preferably, Lx, Ly, Lz, and Lz' are independently selected from the group comprising C ⁇ Q alkyl, substituted C ⁇ Q alkyl, C2 0 alkenyl, substituted C2 0 alkenyl, C2.10 alkynyl, substituted C2.10 alkynyl, aryl, and substituted aryl; preferably, Lx, Ly, Lz, and Lz' are independently selected from the group comprising methyl, ethyl, propyl, butyl (including isobutyl and n-butyl), pentyl, cyclopentyl, hexyl, cyclohexy
  • Useful substituents include C ⁇ Q alkyl, C2-10 alkenyl, C2-10 alkynyl, aryl, C _io alkoxy, C2 0 alkenyloxy, C2 0 alkynyloxy, aryloxy, C2 0 alkoxycarbonyl, C ⁇ Q alkylthio, C ⁇ Q alkylsulfonyl, fluoro, chloro, bromo, iodo, oxo, amino, imine, nitrogen heterocycle, hydroxy, thiol, thiono, phosphorous, and carbene groups.
  • Lx, Ly, and Lz are as defined above.
  • at least two of Lx, Ly, Lz, and Lz' may be joined to form a 3- to 12-membered spirocyclic ring, with available valences optionally occupied by H, oxo, halogens, hydrocarbyl or substituted hydrocarbyl groups.
  • Useful substituents include C ⁇ Q alkyl, C2 0 alkenyl, C2 0 alkynyl, aryl, C ⁇ Q alkoxy, C2.
  • NHCs N-heterocyclic carbenes
  • NHCs are cyclic carbenes of the types described in Formula
  • NHCs may be represented by the formula:
  • n, Lx, and Ly are as described above in Formula (IV).
  • NHCs include: where Lx and Ly are as described above.
  • Other useful NHCs include the compounds described in Hermann, W. A. Chem. Eur. J. 1996, 2, 772 and 1627; Enders, D. et al., Angew. Chem. Int. Ed. 1995, 34, 1021; Alder R. W., Angew. Chem. Int. Ed. 1996, 35, 1121; USSN 61/314,388; and Bertrand, G. et al., Chem. Rev. 2000, 100, 39.
  • CAACs cyclic alkyl amino carbines
  • CAACs are cyclic carbenes of the types described in Formula II above, where one E is N and the other E is C, and the available valences on the N and C are occupied by Lx, Ly, and Lz.
  • CAACs may be represented by the formula:
  • n, Lx, Ly, and Lz are as described above in Formula (IV).
  • Some partic include
  • CAACs include the compounds described in U.S. Patent No. 7,312,331 ; USSN
  • carbenes useful in embodiments of the present invention include thiazolyidenes,
  • P -heterocyclic carbenes PLCs
  • cyclopropenylidenes P -heterocyclic carbenes (PHCs)
  • L is neutral donor ligands.
  • L" may also be a phosphine having a formula PHR" 5 R" 6 .
  • the Group 8 metal complex may be represented by the formula (I):
  • M" is a Group 8 metal (preferably M is ruthenium or osmium, preferably ruthenium);
  • each X" is independently an anionic ligand (preferably selected from the group consisting of halides, alkoxides, aryloxides, and alkyl sulfonates, preferably a halide, preferably chloride);
  • R" 1 and R" 2 are independently selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a Q to C30 substituted hydrocarbyl (preferably R" 1 and R" 2 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert- butyl, sec -butyl, cyclohexyl, and cycl
  • At least one phosphine ligand is a secondary phosphine ligand.
  • R" 3 and R" 4 or R" 5 and R" 6 are selected from the group consisting of to C 12 hydrocarbyl groups, substituted to C 12 hydrocarbyl groups, and halides.
  • both donor ligands are secondary phosphine ligands and R" 3 , R" 4 , R" 5 , and R" 6 are selected from the group consisting of Q to C 12 hydrocarbyl groups, substituted to C 12 hydrocarbyl groups, and halides.
  • At least one donor ligand is a primary phosphine ligand.
  • one of R" 3 and R" 4 or one of R" 5 and R" 6 is selected from the group consisting of to C 12 hydrocarbyl groups, substituted to C 12 hydrocarbyl groups, and halides.
  • both donor ligands are primary phosphine ligands and one of R" 3 and R" 4 and one of R" 5 and R" 6 is selected from the group consisting of to C 12 hydrocarbyl groups, substituted to C 12 hydrocarbyl groups, and halides.
  • R" 3 and R" 4 form a ring.
  • L" is a phosphine having a formula PHR" 5 R" 6
  • R" 5 and R" 6 form a ring.
  • R" 3 and R" 4 form a ring and R" 5 and R" 6 form a ring.
  • R" 3 and at least one of R" 5 and R" 6 may form a ring, thereby forming a chelating phosphine ligand.
  • R" 4 and at least one of R" 5 and R" 6 may form a ring, thereby forming a chelating phosphine ligand.
  • the Group 8 metal complex is selected from:
  • the catalyst employed in the process of this invention may be bound to or deposited onto a solid support.
  • the Group 8 metal complex may be bound to or deposited onto a solid support, which may simplify catalyst recovery.
  • the support may increase catalyst strength and attrition resistance.
  • Suitable catalyst supports include, without limitation, silicas; aluminas; silica-aluminas; aluminosilicates, including zeolites and other crystalline porous aluminosilicates; as well as titanias; zirconia; magnesium oxide; carbon; and cross-linked polymeric resins, such as functionalized cross- linked polystyrenes, e.g., chloromethyl-functionalized cross-linked polystyrenes; preferably silica or alumina.
  • the Group 8 metal complex may be deposited onto the support by any method known to those skilled in the art, including, for example, impregnation, ion- exchange, deposition-precipitation, and vapor deposition.
  • a component of the catalyst such as the Group 8 metal complex
  • the catalyst may be immobilized by one or more covalent bonds with one or more of substituents of a ligand of the Group 8 metal complex.
  • the Group 8 metal complex may be deposited onto a silica support. Further, the Group 8 metal complex may be preloaded onto the solid support before forming the catalyst of the present invention. Alternatively, the supported catalyst may be generated in situ.
  • the catalyst compound may be loaded onto the catalyst support in any amount, provided that the metathesis process of this invention proceeds to the metathesis products.
  • the catalyst compound is loaded onto the support in an amount based on the weight of the transition metal, preferably the Group 8 metal, preferably ruthenium or osmium, relative to the total weight of the catalysts plus support.
  • the catalyst compound may be loaded onto the support in an amount greater than about 0.01 wt% of the Group 8 metal, based upon the weight of the catalysts plus support and preferably, greater than about 0.05 wt% of the Group 8 metal.
  • the catalyst compound is loaded onto the support in an amount that is less than about 20 wt% of the Group 8 metal, and preferably less than about 10 wt% of the Group 8 metal.
  • this invention relates to:
  • R is a hydrocarbyl group having greater than 25 carbon atoms (preferably greater than 30 carbon atoms, greater than 40 carbon atoms, or greater than 50 carbon atoms; preferably from 31 carbon atoms to 100,000 carbon atoms, from 40 carbon atoms to 75,000 carbon atoms, from 50 carbon atoms to 60,000 carbon atoms; preferably R is represented by the formula (B):
  • Cm is a C 4 to C 4 Q olefin derived unit (preferably Cm is one or more units derived from butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof); m is an integer from 3 to 39 (preferably from 3 to 29, preferably from 4 to 19, preferably from 5 to 1 1); and p is an integer greater than 1 (preferably from 1 to 10,000, from 1 to 5,000, from 1 to 2,500, from 1 to 1,000, from 1 to 500, or from 1 to 50); preferably R is represented by the formula (
  • Cm is a C3 to C 4 Q olefin derived unit (preferably Cm is one or more derived units of propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof); m is an integer from 2 to 39 (preferably from 2 to 29, preferably from 3 to 19, preferably from 4 to 1 1); and p is an integer greater than 1 (preferably from 1 to 10,000, from 1 to 5,000, from 1 to 2,500, from 1 to 1,000, from 1 to 500, or from 1 to 50);
  • R ) and R3 are the same or different and each is hydrogen or a hydrocarbyl group having from 1 to 40 carbon atoms (preferably from 1 to 30, from 2 to 15, and from 2 to 12), or R > and R3 are joined to form a five-membered or six-membered ring, or substituted analogs thereof (preferably R2 and R3 are joined to form a heteroatom containing ring; preferably R2 and R3 are joined to form a dicarboxylic anhydride);
  • X is C, N, or O (preferably X is C or O, preferably X is C);
  • n is an integer from 1 to 10,000 (preferably from 1 to 5,000, from 1 to 2,500, from 1 to 1,000, from 1 to 500, or from 1 to 50);
  • the dotted line indicates an optional double bond
  • the polymer comprises one or more vinyl terminated macromonomer derived units (preferably the vinyl terminated macromonomer is one or more of:
  • a vinyl terminated polymer having an Mn of at least 200 g/mol (measured by NMR) comprising of one or more C 4 to C 4 Q higher olefin derived units, where the higher olefin polymer comprises substantially no propylene derived units; and wherein the higher olefin polymer has at least 5% allyl chain ends;
  • a copolymer having an Mn of 300 g/mol or more comprising (a) from about 20 mol% to about 99.9 mol% of at least one C 5 to C 4 Q higher olefin, and (b) from about 0.1 mol% to about 80 mol% of propylene, wherein the higher olefin copolymer has at least 40% allyl chain ends;
  • a copolymer having an Mn of 300 g/mol or more (measured by NMR) and comprises (a) from about 80 mol% to about 99.9 mol% of at least one C 4 olefin and (b) from about 0.1 mol% to about 20 mol% of propylene, wherein the vinyl terminated macromonomer has at least 40% allyl chain ends relative to total unsaturation;
  • a propylene oligomer comprising more than 90 mol% propylene and less than 10 mol% ethylene wherein the oligomer has: at least 93% allyl chain ends, a number average molecular weight (Mn) of about 500 g/mol to about 20,000 g/mol, an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0, and less than 100 ppm aluminum;
  • a propylene oligomer comprising: at least 50 mol% propylene and from 10 mol% to 50 mol% ethylene, wherein the oligomer has: at least 90% allyl chain ends, an Mn of about 150 g/mol to about 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.2: 1.0, wherein monomers having four or more carbon atoms are present at from 0 mol% to 3 mol%;
  • a propylene oligomer comprising: at least 50 mol% propylene, from 0.1 mol% to 45 mol% ethylene, and from 0.1 to 5 mol% C 4 to C 12 olefin, wherein the oligomer has: at least 90% allyl chain ends, an Mn of about 150 to about 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.8: 1 to 1.35: 1.0;
  • a propylene oligomer comprising: at least 50 mol% propylene, from 0.1 to 45 mol% ethylene, and from 0.1 mol% to 5 mol% diene, wherein the oligomer has: at least 90% allyl chain ends, an Mn of about 150 g/mol to about 10,000 g/mol, and an isobutyl chain end to allylic vinyl group ratio of 0.7: 1 to 1.35: 1.0; and
  • n is an integer from 1 to 10,000 (preferably from 1 to 5,000, from 1 to 2,500, from 1 to 1,000, from 1 to 500, or from 1 to 50);
  • Cm is a C3 to C40 olefin derived unit (preferably Cm is one or more derived units of propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof); m is an integer from 2 to 39 (preferably from 2 to 29, preferably from 3 to 19, preferably from 4 to 11); and p is an integer greater than 1 (preferably
  • M is a Group 8 metal, preferably Ru or Os, preferably Ru;
  • X and X 1 are, independently, any anionic ligand, preferably a halogen (preferably chlorine), an alkoxide or a triflate, or X and X 1 may be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non- hydrogen atoms;
  • L and L 1 are, independently, a neutral two electron donor, preferably a phosphine or a N- heterocyclic carbene, L and L 1 may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L and X may be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L 1 and X 1 may be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • R 4 and R 5 are, independently, hydrogen or Q to C30 substituted or unsubstituted hydrocarbyl (preferably a Q to C30 substituted or unsubstituted alkyl or a substituted or unsubstituted C 4 to C 3() aryl);
  • R 5 and L 1 or X 1 may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • R 4 and L or X may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • M is Os or Ru, preferably Ru
  • X, X l , L, and L 1 are as described above for Formula E;
  • R 9 and R 10 may be different or the same and may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl; and/or
  • M* is a Group 8 metal, preferably Ru or Os, preferably Ru;
  • X* and X 1 * are, independently, any anionic ligand, preferably a halogen (preferably chlorine), an alkoxide or an alkyl sulfonate, or X* and X 1 * may be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • L* is N-R**, O, P-R**, or S, preferably N-R** or O (R** is a to C30 hydrocarbyl or substituted hydrocarbyl, preferably methyl, ethyl, propyl or butyl);
  • R* is hydrogen or a to C30 hydrocarbyl or substituted hydrocarbyl, preferably methyl
  • R 1 *, R 2 *, R 3 *, R 4 *, R 5 *, R 6 *, R 7 *, and R 8 * are, independently, hydrogen or a C ⁇ to C 30 hydrocarbyl or substituted hydrocarbyl, preferably methyl, ethyl, propyl or butyl, preferably R 1 *, R 2 *, R 3 *, and R 4 * are methyl;
  • each R 9 * and R 13 * are, independently, hydrogen or a Q to C30 hydrocarbyl or substituted hydrocarbyl, preferably a C2 to hydrocarbyl, preferably ethyl;
  • R 10 *, R 1 1 *, R 12 * are, independently hydrogen or a to C30 hydrocarbyl or substituted hydrocarbyl, preferably hydrogen or methyl;
  • each G is, independently, hydrogen, halogen or Q to C30 substituted or unsubstituted hydrocarbyl (preferably a Q to C30 substituted or unsubstituted alkyl or a substituted or unsubstituted C4 to C30 aryl); and
  • any two adjacent R groups may form a single ring of up to 8 non-hydrogen atoms or a multinuclear ring system of up to 30 non-hydrogen atoms;
  • M" is a Group 8 metal (preferably M is ruthenium or osmium, preferably ruthenium);
  • each X" is independently an anionic ligand (preferably selected from the group consisting of halides, alkoxides, aryloxides, and alkyl sulfonates, preferably a halide, preferably chloride);
  • R" 1 and R" 2 are independently selected from the group consisting of hydrogen, a Q to C30 hydrocarbyl, and a Q to C30 substituted hydrocarbyl (preferably R" 1 and R" 2 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert- butyl, sec -butyl, cyclohexyl, and cycl
  • R" 3 and R" 4 are independently selected from the group consisting of hydrogen, to hydrocarbyl groups, substituted Q to hydrocarbyl groups, and halides (preferably R" 3 and R" 4 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert-butyl, sec -butyl, cyclohexyl, and cyclooctyl); and
  • L" is a neutral donor ligand, preferably L" is selected from the group consisting of a phosphine, a sulfonated phosphine, a phosphite, a phosphinite, a phosphonite, an arsine, a stibine, an ether, an amine, an imine, a sulfoxide, a carboxyl, a nitrosyl, a pyridine, a thioester, a cyclic carbene, and substituted analogs thereof; preferably a phosphine, a sulfonated phosphine, an N-heterocyclic carbene, a cyclic alkyl amino carbene, and substituted analogs thereof (preferably L" is selected from a phosphine, an N-heterocyclic carbene, a cyclic alkyl amino carbene, and substituted analogs thereof); and/or
  • M" is a Group 8 metal (preferably M is ruthenium or osmium, preferably ruthenium);
  • each X" is independently an anionic ligand (preferably selected from the group consisting of halides, alkoxides, aryloxides, and alkyl sulfonates, preferably a halide, preferably chloride);
  • R" 1 and R" 2 are independently selected from the group consisting of hydrogen, a C to C30 hydrocarbyl, and a Q to C30 substituted hydrocarbyl (preferably R" 1 and R" 2 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert- butyl, sec -butyl, cyclohexyl, and cycl
  • R" 3 , R" 4 , R" 5 , and R" 6 are independently selected from the group consisting of hydrogen, C to C 2 hydrocarbyl groups, substituted to hydrocarbyl groups, and halides (preferably R" 3 , R" 4 , R" 5 , and R" 6 are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert-butyl, sec -butyl, cyclohexyl, and cyclooctyl);
  • a temperature of 20°C to 200°C preferably 50°C to 160°C, preferably 60°C to 140°C
  • a pressure of 0 MPa to 1000 MPa preferably 0.5 MPa to 500 MPa, preferably 1 MPa to 250 MPa
  • a residence time of 0.5 seconds to 10 hours preferably 1 second to 5 hours, preferably 1 minute to 1 hour.
  • the degree of ROCM, or number of norbornene anhydride units on the end of the functionalized copolymer was calculated by the ratio of the ⁇ H-NMR integration of total internal olefin (5.3 ppm - 5.7 ppm) to the CI3 ⁇ 4 olefin in the functionalized polymer (5.1 ppm - 5.3 ppm):
  • the degree of ROCM can be calculated by the ratio of the ⁇ H-NMR integration of product ring methine protons (2.75 ppm - 3.5 ppm) to the CH2 olefin in the functionalized polymer (5.1 ppm - 5.3 ppm).
  • This measure of catalyst activity is determined from the molar ratio of VTM to catalyst multiplied by the VTM conversion and the degree of ROCM:
  • a 2 L autoclave was filled with 600 mis isohexanes, 0.5 ml 1.0 M triisobutyl aluminum (in hexanes), 200 mis propylene, 100 mis hexene and the contents heated to 70°C.
  • a catalyst solution was made by reacting 10.7 mg of Metallocene E (structure below; synthesis of Metallocene E is disclosed in USSN 13/072,288), with 24.1 mg of dimethylanilinium tetrakis(perfluoronaphthyl)borate in 10 ml toluene. This solution (3.3 mis) was injected into the autoclave under high 2 pressure. The reaction proceeded for 30 minutes.
  • the autoclave was then cooled to room temperature, depressurized and the contents transferred to a beaker. Volatiles were removed and the product dried in vacuo at 70°C for 4 hrs. Yield was 126 g.
  • the copolymer had 97% vinyls, 3% vinylidenes, and Mn of 1600 g/mol by !H
  • Metallocene E as the catalyst, and dimethylaniliniumtetrakis(perfluoronaphthyl)borate as the activator.
  • Metallocene E was premixed with dimethylaniliniumtetrakis(perfluoronaphthyl)borate in a 1 : 1 ratio and fed into the reactor at a rate of 3.3 x 10 ⁇ 7 moles/minute.
  • Propylene (C3) was fed into the reactor at a rate of 15 g/minute, isohexane at a feed rate of 59.4 g/minute, butene (C4) at a feed rated of 8.0 g/minute, and tri-n-octyl aluminum at a feed rate of 5.2 x 10 "6 moles/minute.
  • Catalyst activity 18,400 kgP/molcat.
  • the copolymer had 92.4% vinyls, 4.4% vinylidenes, and Mn of 1726 g/mol by l R NMR.
  • Example 1 Synthesis of the ROCM reaction product of norbornene dicarboxylic anhydride with vinyl terminated hexene propylene copolymer.
  • the vinyl terminated hexene propylene copolymer (l .Og, described above) was placed in a 20 ml scintillation vial with 5 mis of tetrachloroethane-d2.
  • Cis-5-norbornene-endo-2,3- dicarboxylic anhydride (0.10 g, Sigma Aldrich, St. Louis, MO) was added to the mixture.
  • the solubility of the carboxylic anhydride was noted visually as minimal.
  • the vinyl terminated hexene propylene copolymer (1.4 g, as described above) was placed in a 20 ml scintillation vial with 5 mis of tetrachloroethane-d2.
  • Dimethyl norbornene dicarboxylate (0.14 g, Sigma Aldrich) was added to the mixture.
  • Example 3 Synthesis of the ROCM reaction product of norbornene dicarboxylic anhydride with vinyl terminated hexene propylene copolymer.
  • the product oil was characterized using !H- MR: 400 MHz (C 2 D 2 C1 4 ): ⁇ 5.9 (m, 0.45H), 5.3-5.7 (m, 1.05H), 5.1-5.3 (m, 0.86H), 5.0 (m, 0.15), 3.35-3.55 (m, 0.98H), 3.2-3.35 (m, 0.21H), 2.9-3.1 (m, 0.77H), 0.5-2.5 (m, 160H).
  • ⁇ H-NMR analysis indicated that the product oil consisted of a molar ratio of 83% anhydride functionalized hexene propylene copolymer product, 14% hexene-propylene copolymer starting material, and 3% anhydride starting material.
  • the degree of ROCM, or number of norbornene anhydride units on the end of the functionalized copolymer was calculated to be 1.2 using both methods A and B.
  • Catalyst TON was calculated to be 722.
  • Example 4 Synthesis of the ROCM reaction product of norbornene-exo-2.3 dicarboxylic anhydride with vinyl terminated hexene propylene copolymer.
  • the polymer product was analyzed by !H-NMR: 400 MHz (C 2 D 2 C1 4 ): ⁇ 5.9 (m, 0.08H), 5.3-5.7 (m, 0.89H), 5.1-5.3 (m, 0.17H) 5.0 (m, 0.08), 3.1-3.4 (m, 0.91H), 2.75-3.0 (m, 0.53H), 0.5-2.5 (m, 97.2H).
  • ⁇ H-NMR analysis indicated a molar ratio of 68% functionalized hexene-propylene copolymer product and 32% hexene-propylene copolymer starting material.
  • the degree of ROCM calculated using method A was 5.23 and method B was 4.23, the difference most likely indicating a significant amount of dimerization.
  • Catalyst TON was calculated to be 2499.
  • Example 5 Synthesis of the ROCM reaction product of norbornene-exo-2,3 dicarboxylic anhydride with vinyl terminated hexene propylene copolymer.
  • the reaction was quenched using lg silica, and the CHCI3 was removed under vacuum at 45°C overnight.
  • the translucent brown polymer was treated with approximately 150 mL of pentane.
  • the mixture was heated to 40°C and stirred for several hours to homogenize the mixture.
  • the mixture was then cooled for 2 hours to -25°C.
  • This mixture was then filtered using a plug of silica, followed by further filtration through 1 micron syringe filters.
  • the solvent was removed under a stream of nitrogen gas.
  • the polymer was further dried by sparging nitrogen gas directly into the polymer while heating it to 80°C.
  • the dried polymer was analyzed by !H- MR: 400 MHz (C 2 D 2 C1 4 ): ⁇ 5.9 (m, 0.32H), 5.3-5.7 (m, 1.35H), 5.1-5.3 (m, 0.57H), 2.75-3.5 (m, 2.51H), 0.5-2.5 (m, 93.9H).
  • ⁇ H-NMR showed 100% conversion of the vinyl terminated butene-propylene copolymer starting material.
  • the degree of ROCM was calculated to be 2.4 using method A and 2.2 using method B. According, little or no dimerization occurred.
  • Catalyst TON was calculated to be 1,820.
  • compositions, an element or a group of elements are preceded with the transitional phrase "comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases “consisting essentially of,” “consisting of,” “selected from the group of consisting of,” or “is” preceding the recitation of the composition, element, or elements and vice versa.

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Abstract

L'invention concerne un polymère d'une oléfine cyclique et d'un macromonomère à terminaison vinyle, ainsi que des procédés pour sa préparation.
PCT/US2012/059191 2011-11-29 2012-10-08 Fonctionnalisation de polymères à terminaison vinyle par métathèse croisée par ouverture de cycle WO2013081726A1 (fr)

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EP12854390.7A EP2785763A4 (fr) 2011-11-29 2012-10-08 Fonctionnalisation de polymères à terminaison vinyle par métathèse croisée par ouverture de cycle

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EP2826802A4 (fr) * 2012-03-16 2015-09-09 Zeon Corp Procédé de production de polymère hydrogéné par métathèse avec ouverture de cycle, et composition de résine
CN112154168A (zh) * 2018-03-29 2020-12-29 赢创运营有限公司 用于制备温度稳定的开环聚环烯烃的方法
US20240198321A1 (en) * 2020-07-08 2024-06-20 Centre National De La Recherche Scientifique Optically pure enantiomers of ruthenium complexes and uses thereof

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EP2826802A4 (fr) * 2012-03-16 2015-09-09 Zeon Corp Procédé de production de polymère hydrogéné par métathèse avec ouverture de cycle, et composition de résine
US9850325B2 (en) 2012-03-16 2017-12-26 Zeon Corporation Method for producing ring-opening metathesis polymer hydride, and resin composition
CN104003926A (zh) * 2014-05-30 2014-08-27 天津大学 基于烷基铵盐的侧链型磁性单体、聚合物及其制备方法和应用
CN104003926B (zh) * 2014-05-30 2016-06-15 天津大学 基于烷基铵盐的侧链型磁性单体、聚合物及其制备方法和应用
CN112154168A (zh) * 2018-03-29 2020-12-29 赢创运营有限公司 用于制备温度稳定的开环聚环烯烃的方法
CN112154168B (zh) * 2018-03-29 2023-07-25 赢创运营有限公司 用于制备温度稳定的开环聚环烯烃的方法
US20240198321A1 (en) * 2020-07-08 2024-06-20 Centre National De La Recherche Scientifique Optically pure enantiomers of ruthenium complexes and uses thereof

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