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WO1995001388A1 - Nouveau catalyseur de polymerisation metathetique a rupture de noyaux - Google Patents

Nouveau catalyseur de polymerisation metathetique a rupture de noyaux Download PDF

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Publication number
WO1995001388A1
WO1995001388A1 PCT/US1994/007433 US9407433W WO9501388A1 WO 1995001388 A1 WO1995001388 A1 WO 1995001388A1 US 9407433 W US9407433 W US 9407433W WO 9501388 A1 WO9501388 A1 WO 9501388A1
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Prior art keywords
substituted
hydrocarbyl
halocarbyl
group
radical
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PCT/US1994/007433
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English (en)
Inventor
Bruce Allan Harrington
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Exxon Chemical Patents Inc.
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Priority to JP7503660A priority Critical patent/JPH09501191A/ja
Priority to EP94921445A priority patent/EP0719294A1/fr
Publication of WO1995001388A1 publication Critical patent/WO1995001388A1/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
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes

Definitions

  • This invention relates to ring-opening metathesis polymerizations of cyclic olefins utilizing a transition metal catalyst system comprising a cyclopentadienyl transition metal complex and a noncoordinating anion.
  • This invention relates in part to the discovery that cyclopentadienyl transition metal complexes activated by ion exchange non-coordinating anions are capable of performing ring opening metathesis polymerizations.
  • This invention relates to methods utilizing these catalyst systems for ring opening metathesis polymerizations alone, sequentially or in conjunction with using these catalyst systems in olefin and alpha olefin coordination (•'Ziegler-Natta") type polymerizations.
  • this invention utilizes a catalyst system to ring-open metathesis polymerize (ROMP) cyclic olefins and utilizes the same catalyst system to polymerize any olefin without ring-opening.
  • ROMP ring-open metathesis polymerize
  • a unique aspect of this invention is that under certain conditions when the catalyst system is present with non-cyclic olefins and cyclic olefins, the cyclic olefins generally incorporate into the growing polymer chain without ring-opening. However, when only cyclic monomers are present or when the monomer feed contains predominantly cyclic olefins, the cyclic monomers do ring-open and form ROMP polymers.
  • the potential for cationically polymerizing the cyclic olefins is significantly limited. This simplifies the overall polymerization mechanism and limits the cyclic olefins to either Ziegler-Natta or metathesis polymerization.
  • a single catalyst/cocatalyst system there exists the ability to form Zeigler/Natta polyolefins and/or ROM polymers in a single reaction by adjusting reaction conditions.
  • (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*;
  • Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted- hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl- substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C2 0 ring to give a saturated or unsaturated polycyclic
  • A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;
  • M is a transition metal, preferably a group 4, 5, 6, 7 or 8 transition metal, even more preferably group 4 or 6 transition metal, even more preferably titanium, zirconium or hafnium;
  • X ⁇ is a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl- substituted organometalloid radical or halocarbyl- substituted organometalloid radical which radical may optionally be covalently bonded to both or either M and L or all or any M, S or S';
  • L is an olefin, diolefin or aryne ligand;
  • B is a chemically stable, non-nucleophilic anionic complex having a molecular diameter of 4 angstroms or greater or an anionic Lewis-acid activator resulting from the reaction of a Lewis-acid activator with the precursor to the cationic portion of the catalyst system described in formulae 1 or 2.
  • B' is a Lewis-acid activator
  • X- ⁇ can also be an alkyl group donated by the Lewis-acid activator; and d is an integer representing the charge of B.
  • Another class of preferred catalysts includes systems represented by the formulae (all references to groups being the new group notation of the Periodic Table of the Elements as described by Chemical and
  • A' is a bridging group
  • (C5H5_y_ x S x ) is a cyclopentadienyl ring substituted with from zero to five S radicals each S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C4 to C2 0 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; x is from 0 to 5 denoting the degree of substitution;
  • M is titanium, zirconium or hafnium
  • Xl and X 2 are independently a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl-substituted organometalloid radical or halocarbyl-substituted organometalloid radical which radical may optionally be covalently bonded to both or either M, S or S' ;
  • J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2;
  • S' is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl- substituted organometalloid; and
  • z is the coordination number of the element J; y is 0 or 1;
  • L is an olefin, diolefin or aryne ligand, or a neutral Lewis base; L can also be a second transition metal compound of the same type such that the two metal center M and M* are bridged by X and *i wherein M* has the same meaning as M, X'l has the same meaning as X- and X'2 has the same meaning as X2 where such dimeric compounds which are precursors to the cationic portion of the catalyst are represented by the formula:
  • B 1 is a chemically stable, non-nucleophilic anionic complex having a molecular diameter of 4 angstroms or greater or an anionic Lewis-acid activator resulting from the reaction of a Lewis-acid activator with the precursor to the cationic portion of the catalyst system described in the formulae.
  • B* is a Lewis-acid activator
  • X ⁇ can also be an alkyl group donated by the Lewis-acid activator
  • d is an integer representing the charge of B' .
  • the catalysts are preferably prepared by combining at least two components.
  • the first component is a cyclopentadienyl derivative of a transition metal compound containing at least one ligand which will combine with the second component or at least a portion thereof such as a cation portion thereof.
  • the second component is an ion-exchange compound comprising a cation which will irreversibly react with at least one ligand contained in said transition metal compound (first component) and a non- coordinating anion which is either a single coordination complex comprising a plurality of lipophilic radicals covalently coordinated to and shielding a central formally charge-bearing metal or metalloid atom or an anion comprising a plurality of boron atoms such as polyhedral boranes, carboranes and metallacarboranes.
  • the cation portion of the second component may comprise Bronsted acids such as protons or protonated Lewis bases or may comprise reducible Lewis acids such as ferricinum, tropyliu , triphenylcarbenium or silver cations.
  • the second component is a Lewis-acid complex which will react with at least one ligand of the first component, thereby forming an ionic species described in the formulae above with the ligand abstracted from the first component now bound to the second component.
  • suitable anions for the second component may be any stable and bulky anionic complex having the following molecular attributes: 1) the anion should have a molecular diameter greater than 4 A; 2) the anion should form stable ammonium salts; 3) the negative charge on the anion should be delocalized over the framework of the anion or be localized within the core of the anion; 4) the anion should be a relatively poor nucleophile; and 5) the anion should not be a powerful reducing to oxidizing agent.
  • Anions meeting these criteria such as polynuclear boranes.
  • the second component reacts with one of the ligands of the first component, thereby generating an anion pair consisting of a Group 4 metal cation and the aforementioned anion, which anion is compatible with and noncoordinating towards the Group 4 metal cation formed from the first component.
  • the anion of the second compound must be capable of stabilizing the Group 4 metal cation's ability to function as a catalyst and must be sufficiently labile to permit displacement by an olefin, diolefin or an acetylenically unsaturated monomer during polymerization.
  • the catalysts of this invention may be supported.
  • U.S. Patents 4,808,561, issued 2-28-89; 4,897,455 issued 1-3-90; and 5,057,475 issued 10-15-91 disclose such supported catalysts and the methods to produce such and are herein incorporated by reference.
  • transition metal compounds useful as first compounds in the preparation of the improved catalyst of this invention are cyclopentadienyl derivatives of group 4, 5, 6, 7 or 8 transition metals, preferably titanium, zirconium and hafnium.
  • useful cyclopentadienyl compounds may be represented by the following general formulae:
  • (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*;
  • Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted- hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl- substituted organometalloid, disubstituted boron, disubstituted pnicftogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C 4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;
  • R is a substituent on one of the cyclopentadienyl radicals which is also bonded to the metal atom;
  • A' is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings;
  • L is an olefin, diolefin or aryne ligand; and Xl and X 2 are, independently, hydride radicals, hydrocarbyl radicals, substituted hydrocarbyl radicals, halocarbyl radicals, substituted halocarbyl radicals, and hydrocarbyl- and halocarbyl-substituted organometalloid radicals, substituted pnictogen radicals, or substituted chalcogen radicals; or X- ⁇ and X2 are joined and bound to the metal atom to form a metallacycle ring containing from 3 to 20 carbon atoms; or X j and X2 together can be an olefin, diolefin or aryne ligand; (C5H5_y_ x S x ) is a cyclopentadienyl ring substituted with from zero to five S radicals, each substituent group S being, independently, a radical group which is a hydrocar
  • M is titanium, zirconium or hafnium;
  • X ! and X 2 are independently a hydride radical, hydrocarbyl radical, substituted-hydrocarbyl radical, hydrocarbyl-substituted organometalloid radical or halocarbyl-substituted organometalloid radical which radical may optionally be covalently bonded to both or either M and L or all or any M, S or S' ;
  • (JS z _ ⁇ _y) is a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; and z is the coordination number of the element J; y is 0 or 1; L is an olefin, diolefin or aryne ligand, or a neutral Lewis base.
  • Illustrative compounds include: bis(cyclopentadienyl)hafnium dimethyl, ethylenebis(tetrahydroindenyl)zirconium dihidryde, bis(pentamethyl)zirconium ethylidene, dimethylsilyl(l- fluorenyl) (cyclopentadienyl)zirconium dimethyl and the like; bis(cyclopentadienyl) (1,3-butadiene(zirconium) , bis(cyclopentadienyl) (2,3-dimethyl-1,3-butadiene) zirconium, bis(pentamethylcyclopentadienyl) (benzene) zirconium, bis(pentamethylcyclopentadienyl) titanium ethylene and the like; (pentamethylcyclopentadienyl) (tetramethylcyclopenta
  • Preferred ionic catalysts can be prepared by reacting the transition metal compound with some neutral Lewis acids, such as B(C5Fs) 3 , which upon reaction with the hydrolyzable ligand (x) of the transition metal compound forms an anion, such as ([B(C 6 F5)3(X) ] ⁇ ) , which stabilizes the cationic transition metal species generated by the reaction.
  • Ionic catalysts can be, and preferably are, prepared with activator components which are ionic compounds or compositions.
  • the above ionic compounds may comprise non-coordinating counter cations such as Bronsted acids(, for example R3NH+) , carbonium ions (for example ph3C + ) , reducible cations (for example Cp Fe + ) and the like.
  • H is a hydrogen atom
  • [L"-H] is a Bronsted acid
  • M* is a metal or metalloid
  • Qi to Q n are, independently, bridged or unbridged hydride radicals, dialkylamido radicals, alkoxide and aryloxide radicals, hydrocarbyl and substituted- hydrocarbyl radicals, halocarbyl and substituted- halocarbyl radicals and hydrocarbyl and halocarbyl- substituted organometalloid radicals and any one, but not more than one, of Q- ⁇ to Q n may be a halide radical; m is an integer representing the formal valence charge of M; and n is the total number of ligands g.
  • any metal or metalloid capable of forming an anionic complex which is stable in water may be used or contained in the anion of the second compound.
  • Suitable metals include, but are not limited to , aluminum, gold, platinum and the like.
  • Suitable metalloids include, but are not limited to, boron, phosphorus, silicon and the like.
  • Compounds containing anions which comprise coordination complexes containing a single metal or metalloid atom are, of course, well known and many, particularly such compounds containing a single boron atom in the anion portion, are available commercially. In light of this, salts containing anions comprising a coordination complex containing a single boron atom are preferred.
  • the preferred activator compounds comprising boron may be represented by the following general formula:
  • Ar x and Ar 2 are the same or different aromatic or substituted-aromatic hydrocarbon radicals containing from 6 to 20 carbon atoms and may be linked to each other through a stable bridging group; and X 3 and 4 are, independently, hydride radicals, hydrocarbyl and substituted-hydrocarbyl radicals, halocarbyl and substituted-halocarbyl radicals, hydrocarbyl- and halocarbyl-substituted organometalloid radicals, disubstituted pnictogen radicals, substituted chalcogen radicals and halide radicals, with the provision that X 3 and X4 will not be halide at the same time.
  • Ar ⁇ and Ar may, independently, be any aromatic of substituted-aromatic hydrocarbon radical.
  • Suitable aromatic radicals include, but are not limited to, phenyl, naphthyl and anthracenyl radicals.
  • Suitable substituents on the substituted-aromatic hydrocarbon radicals include, but are not necessarily limited to, hydrocarbyl radicals, organometalloid radicals, alkoxy and aryloxy radicals, alkylamido radicals, fluorocarbyl and fluorohydrocarbyl radicals and the like such as those useful as X 3 and X4.
  • the substituent may be ortho, meta or para, relative to the carbon atoms bonded to the boron atom.
  • each may be the same or a different aromatic or substituted- aromatic radical as are Ar ⁇ and Ar2, or the same may be a straight or branched alkyl, alkenyl or alkenyl radical, a cyclic hydrocarbon radical or an alkyl- substituted cyclic hydrocarbon radical.
  • X 3 and X 4 may also, independently be alkoxy or dialkylamido radicals wherein the alkyl portion of said alkoxy and dialkylamido radicals, hydrocarbyl radicals and organometalloid radicals and the like.
  • Ar x and Ar2 could be linked to either X 3 or X4.
  • X 3 and X 4 may also be linked to each other through a suitable bridging group.
  • the most preferred activator compounds comprising boron may be represented by the following general formula:
  • activator compounds comprising boron
  • L- N,N-dialkylanilinium salts
  • Q is a simple hydrocarbyl such as methyl, butyl, cyclohexyl, or phenyl
  • Q is a polymeric hydrocarbyl of indefinite chain length such as polystyrene, polyisoprene, or poly-paramethylstyrene.
  • Polymeric Q substituents on the most preferred anion offer the advantage of providing a highly soluble ion- exchange activator component and final ionic catalyst.
  • Soluble catalysts and/or precursors are often preferred over insoluble waxes, oils, phases, or solids because they can be diluted to a desired concentration and can be transferred easily using simple equipment in commercial processes.
  • Activator components based on anions which contain a plurality of boron atoms may be represented by the following general formulae: [L»-H] c [(CX)a(BX) m X b ]c- or
  • [L"-H] is either H+ or a Bronsted acid derived from the protonation of a neutral Lewis base
  • X, X', X", X6, X7 and Xs are, independently, hydride radicals, halide radicals, hydrocarbyl radicals, substituted-hydrocarbyl radicals, halocarbyl radicals, substituted-halocarbyl radicals, or hydrocarbyl- or halocarbyl-substituted organometalloid radicals;
  • Illustrative, but not limiting, examples of second components which can be used in preparing catalyst systems utilized in the process of this invention wherein the anion of the second component contains a plurality of boron atoms are mono-, di-, trialkylammonium and phosphonium and dialkylarylammonium and -phosphonium salts such as bis[tri(n-butyl)ammonium] dodecaborate, bis[tri(n- butyl)ammonium]decachlorodecaborate, tri(n- butyl)ammonium dodecachlorododecaborate, tri(n- butyl)ammonium 1-carbadecaborate, tri(n-butyl)ammonium 1-carbaudecaborate, tri(n-butyl)ammonium 1- carbadodecaborate, tri(n-butyl)ammonium 1- trimethylsilyl-1-carbadecaborate, tri(n-butyl)ammonium dibromo
  • the monomers that may be ring-opening metathesis polymerized (ROMPed) with the above catalyst system include any cyclic or multicyclic olefin, cyclic diolefin or cyclic polyene.
  • Preferred cyclics include strained olefins and diolefins, preferably norbornene, dicyclopentadiene, ethylidene norbornene, vinyl norbnene, cyclopentene, cyclobutene, tetracyclododecene and their substituted isomers.
  • Especially preferred cyclics include norbornene and cyclopentene.
  • Olefin and alpha olefin monomers that may be polymerized by the above catalyst system include monoenes, dienes, and polyenes in linear branched or cyclic structures.
  • Preferred monomers include alpha olefins, particularly alpha olefins having 2 to 40 - 20 -
  • Especially preferred monomers include the alpha-olefins, ethylene and propylene.
  • any cycloolefin can be copolymerized with an olefin in the present process.
  • the cycloolefin includes cyclized ethylenic or acetylenic unsaturation which polymerizes in the presence of the metallocene catalyst substantially by insertion polymerization, generally without ring opening, so that the ring structure in which the unsaturation is present is incorporated into the polymer backbone.
  • alpha olefin is not present or is present in very limited concentrations the cyclo-olefin including cyclized ethylenic or acetylenic unsaturation ROMP's in the presence of the activated transition metal catalyst substantially without insertion so that the ring structure containing the double bond is opened and becomes a part of the linear polymer backbone.
  • Suitable cycloolefins generally correspond to one of the formulae:
  • each Ra through Rs is independently hydrogen, halogen, hydrocarbyl, or halohydrocarbyl; ac and dc are integers of 2 or more, and be and cc are integers of 0 or more.
  • cycloolefins according to formula A are cyclobutene, cyclopentene, 3-methylcyclopentene, 4-methylcyclopentene,
  • Preferred monocycloolefins according to formula A have from 4 to 12 carbon atoms, more preferably 4 to 5 or 7 to 8 carbon atoms.
  • Cycloolefins according to formulae B and C can be prepared by condensing cyclopentadienes with the corresponding olefins and/or cycloolefins in a Diels-
  • cycloolefins according to formula C are as follows: tricyclo(4.3.0.12,5)-3-decene; tricyclo(4.3.0.12,5)-3.7-decediene; 2-methyltricyclo(4.3.0.l2,5)-3-decene;
  • one olefin of a polyene is substantially more reactive for polyermization than another.
  • This enables one to use dienes and polyenes as a major component of the polymer without obtaining substantial crosslinking.
  • dicyclopentadiene or ethylidene norbornene can be polymerized exclusively through the norbornene- li e olefin in an addition polymerization.
  • polyenes having two or more double bonds can optionally be used in a relatively minor proportion to impart higher molecular weight to the copolymer and/or provide residual pendant side chain unsaturation for functionalization or crosslinking.
  • the polyenes can participate in polymerization at two (or more) sites, these monomers tend to promote chain extension which can double or quadruple the molecular weight at low incorporation.
  • the polyene is not present in such high amounts which might result in excessive crosslinking and produce insoluble gel formation.
  • the molecular weight is suitably increased by including the optional polyene in the copolymer at from 0.5 to 3 mole percent
  • Suitable chain-extending, molecular-weight- increasing polyenes include, for example, alpha-omega dienes having from 5 to 18 carbon atoms, such as 1,4- pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7- octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10- - 27 -
  • suitable polyenes generally also include other linear or branched aliphatic dienes and trienes, monocyclic dienes and trienes, bicyclic dienes and trienes, polycyclic dienes and trienes, aromatic dienes, and the like.
  • non-conjugated branched aliphatic dienes and polyenes include 1,4- hexadiene, 6-methyl-l,4-heptadiene, 4-isopropyl-l,4- hexadiene, 4-methyl-l,4-hexadiene, 5-methyl- 1,4hexadiene, 4-ethyl-l,4-hexadiene, l-phenyl-4propyl- 1,4-hexadiene, 4,5-dimethyl-l,4-hexadiene, 6-phenyl- 1,4-hexadiene, 5-methyl-l,5-octadiene, 6-methyl-l,5- octadiene, 6-methyl-l,5-heptadiene, 5,7-dimethyl-l,5- octadiene, 4,5-dipropyl-l,4-octadiene, 5-propyl-6- methyl-1,5-heptadiene
  • non-conjugated monocyclic dienes and polyenes include 4- vinylcyclohexene, 4-propenylcyclohexene, 1,4- cyclohexadiene, l-vinyl-4-l(l-propenyl)-cyclohexane, 4- methyl-l,4-cyclooctadiene, 4-methyl l-5-propyl-l,4- cyclooctadiene, 5-methylcyclopentadiene, 1,5,9- cyclododecatriene, trans-l,2-divinylcyclobutane, and 1,4-divinylcyclohexane.
  • non-conjugated bicyclic dienes including: norbornadiene,
  • non-conjugated polycyclic dienes include: dicyclopentadiene, methyl substituted dicyclopentadienes, dimethyl substituted dicyclopentadienes,
  • non-conjugated aromatic dienes include alkyl styrenes and the like.
  • dicyclopentadiene or a similar cyclopolyene
  • it may be used in either the endo or exo form or both.
  • the exo form is used.
  • the polymerization may be conducted at any suitable temperature known to those of ordinary skill in the art.
  • the temperature may range from -100 degrees C to 250 degrees C, preferably from -50 to 200 degrees C.
  • the catalyst is preferably used in an amount to provide a starting monomer to catalyst ratio of from 1 to 10 9 , preferably 100 to 10 7 .
  • the polymerization time may usually range from less than one minute to 10 hours or more.
  • the reaction pressure may range from sub- atmospheric to atmospheric to 1000 MPa, preferably from atmospheric to 500 MPa.
  • Polymerization methods are not particularly limited and include bulk polymerization, gas phase polymerization, solution polymerization and suspension polymerization.
  • suitable solvents include aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; alicyclic hydrocarbons such as cyclopentane; cyclohexane and methylcyclohexane; aliphatic hydrocarbons such as pentane, hexane, heptane, and octane; and halogenated hydrocarbons such as chloroform and di-chloromethane. These solvents can be used alone or in combination. Monomers such as alpha olefins and cyclic olefins can also be used as solvents.
  • the polymerization may be conducted in any vessel suitable for the chosen reaction conditions. Furthermore, two or more vessels may be run in series or parallel to produce intimate blends of different polymers or blends of varieties of the "same" polymer, i.e. a 1000 Mw homopolyethylene blended with a 100,000 Mw homopolyethylene.
  • the polymers produced by this invention can range from plastics, thermoplastics, thermoplastic olefins (TPO's) , thermoplastic elastomers(TPE's) , thermosets and elastomers.
  • TPO's thermoplastic olefins
  • TPE's thermoplastic elastomers
  • thermosets and elastomers thermosets and elastomers.
  • intimate blend is defined to be a mixed combination of at least two polymers neither of which are necessarily in network form provided that at least one of which is synthesized in the immediate presence of the other(s) such that the mixture does not significantly phase separate.
  • interpenetrating network is defined to be an intimate combination of at least two polymers, at least one of which is in network form and at least one of which is synthesized in the immediate presence of the other(s) .
  • Network is herein defined to include polymers having intra-chain associations, aggregations, or other interactions between segments of the same polymer chain or chain type as well as covalently crosslinked polymers
  • ROMP polymerization of the monomer would occur and produce ring-opened polymer chains.
  • an alpha olefin could be introduced into the reactor and allowed to polymerize. This sequence would produce an intimate blend of ring-opened polymer and alpha-olefin polymer.
  • the ring-opened cyclic polymer could be a polymer of one or more cyclic monomers and the olefin polymer could be a polymer of one or more olefins.
  • the ROMP of cyclic dienes and alpha olefins could produce a network of ROM thermoset interdispersed with Ziegler-Natta thermoplastic olefin in an interpenetrating network or intimate blend.
  • an intimate blend or interpenetrating network of two or more ROMP polymers can also be produced, preferably by sequential addition of different cyclic monomers.
  • ROMP results in unsaturated chains, it is occasionally desirable to hydrogenate the resulting copolymers and/or polymer mixtures to make a predominantly saturated polymer mixture. Hydrogenation can improve oxidative and thermal stability.
  • block copolymers and tapered block copolymers could be made by varying monomer addition, concentrations and other reaction conditions such as temperature and pressure.
  • the catalyst described above can be used to create vinyl terminated polymers or macromonomers.
  • Such a vinyl terminated polymer could then be combined with cyclic monomers to produce block copolymers and/or long chain branches, depending on the reaction conditions and monomers chosen.
  • ROMP'ed monomers and the olefin polymerized monomers that will occur to those of ordinary skill in the art. These combinations are within the scope of this invention and intended to be covered hereby.
  • intimate blends of 3 to 50 weight percent ROMP polymer with 97 to 50 weight percent Ziegler-Natta polymer are preferred.
  • this invention also provides for new species of carbenes based on Ti, Zr and Hf, particularly Zr and Hf.
  • (A-Cp)M CR(R') , wherein (A-Cp) is either (Cp) (Cp*) or Cp-A'-Cp*; Cp and Cp* are the same or different cyclopentadienyl rings substituted with from zero to five substituent groups S, each substituent group S being, independently, a radical group which is a hydrocarbyl, substituted- hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl- substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or Cp and Cp* are cyclopentadienyl rings in which any two adjacent S groups are joined forming a C4 to C2 0 ring to give a saturated or unsaturated polycyclic cyclopen
  • a 1 is a bridging group, which group may serve to restrict rotation of the Cp and Cp* rings ;
  • M is any group 4, 5, 6, 7 or 8 metal, preferably Ti, Zr of Hf;
  • R and R 1 are independently a hydrogen or a Cx to C4 0 linear, cyclic or branched alkyl, preferably a O ⁇ to C20 linear, cyclic or branched alkyl, even more preferably hydrogen, R and R 1 may be the same or different alkyl groups, although in a preferred embodiment R and R' are the same alkyl group
  • A' is a bridging group
  • (C5H 5 _y_ x S x ) is a cyclopentadienyl ring substituted with from zero to five S radicals each S being, independently, a radical group which is a hydrocarbyl, substituted-hydrocarbyl, halocarbyl, substituted-halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen or halogen radicals, or any two adjacent S groups are joined forming a C 4 to C20 ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand; x is from 0 to 5 denoting the degree of substitution;
  • M is any group 4, 5, 6, 7 or 8 metal, preferably titanium, zirconium or hafnium; JS'(z-l-y) * s a heteroatom ligand in which J is an element from Group 15 of the Periodic Table of Elements with a coordination number of 3 or an element from Group 16 with a coordination number of 2; S• is a radical group which is a hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, or halocarbyl- substituted organometalloid; and z is the coordination number of the element J; y is 0 or 1; R and R' are independently a hydrogen or a O ⁇ to C 4 o linear, cyclic or branched alkyl, preferably a O ⁇ to C2 0 linear, cyclic or branched alkyl, even more - 36 -
  • R and R' may be the same or different alkyl groups, although in a preferred embodiment R and R 1 are the same alkyl group.
  • Carbenes which are useful in the practice of this invention include those which can be represented by the formula above where M is any group 4, 5, 6, 7 or 8 metal. Metal carbenes complex with olefins to form metalocycles that are possibly intermediates in metathesis reactions. Metalocycle structures are discussed in detail in "Olefin Metathesis" K.J. Ivin, Academic Press, New York (1989) .
  • a Ziegler-Natta polymer is a polymer that has incorporated a substantial amount of the cyclic monomers into the growing polymer chain resulting in a saturated chain, while maintaining the cyclic aspect of the monomer's structure.
  • a ROMP polymer is a polymer that has incorporated the cyclic monomers into the growing polymer chain resulting in an unsaturated chain without maintaining the cyclic aspect on the monomer's structure.
  • Mw and Mn Molecular weight (Mw and Mn) were measured by Gel Permeation Chromotography using a Waters 150 gel permeation chromatograph equipped with a differential refractive index (DRI) detector. The numerical analyses were performed using the commercially available standard Gel Permeation software package.
  • Proton NMR was used to detect ROM polymer and Ziegler-Natta polymer in the same sample.
  • the polymerization was allowed to proceed for 10 to 120 minutes or until the viscosity was such that the mixture flowed slowly or not at all.
  • the polymerization was killed by adding isopropyl alcohol.
  • White precipitate was filtered and dried.
  • the proton NMR of the product matched that of commercially available ROMP polynorbornene and the integration of the olefinic region indicated that there was one olefin per monomer unit.
  • M Monomer
  • NB norbornene
  • P propylene
  • **Run was at room temperature using lOg of norbornene in 300 ml of toluene.
  • 1 mix/ROMP polymer 300g of a mixture of addition polymer and ROMP polymer and 570 g of ROMP polymer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

On utilise un système catalyseur de métaux de transition comprenant un composé d'un métal de transition et de cyclopentadiényle et un anion de non-coordination pour effectuer des polymérisations métathétiques à rupture de noyaux d'oléfines cycliques.
PCT/US1994/007433 1993-06-30 1994-06-30 Nouveau catalyseur de polymerisation metathetique a rupture de noyaux WO1995001388A1 (fr)

Priority Applications (2)

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JP7503660A JPH09501191A (ja) 1993-06-30 1994-06-30 開環複分解重合用の新規な触媒
EP94921445A EP0719294A1 (fr) 1993-06-30 1994-06-30 Nouveau catalyseur de polymerisation metathetique a rupture de noyaux

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US08/085,211 1993-06-30

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
WO1996016104A1 (fr) * 1994-11-17 1996-05-30 Ciba Specialty Chemicals Holding Inc. Procede pour la polymerisation d'olefines cycliques et composition photopolymerisable
EP0628566B1 (fr) * 1993-06-11 2003-03-26 Phillips Petroleum Company Metallocènes, leur préparation et leur utilisation
WO2012052436A1 (fr) * 2010-10-20 2012-04-26 Deutsche Institute Für Textil- Und Faserforschung Denkendorf Précatalyseurs pour la production de polyoléfines et leur utilisation
WO2014022482A1 (fr) * 2012-08-01 2014-02-06 California Institute Of Technology Polymérisation par méthathèse d'ényne sans solvant
US9234985B2 (en) 2012-08-01 2016-01-12 California Institute Of Technology Birefringent polymer brush structures formed by surface initiated ring-opening metathesis polymerization
US11724250B2 (en) 2018-09-20 2023-08-15 Exxonmobil Chemical Patents Inc. Metathesis catalyst system for polymerizing cycloolefins

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2023276873A1 (fr) * 2021-06-28 2023-01-05

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WO1992000333A2 (fr) * 1990-06-22 1992-01-09 Exxon Chemical Patents Inc. Catalyseurs en alliage organometallique de monocyclopentadienyle depourvu d'aluminium destines a la polymerisation d'olefines
EP0504418A1 (fr) * 1990-10-05 1992-09-23 Idemitsu Kosan Company Limited Procede de production de polymere de cycloolefine et de copolymere de cycloolefine et composition et moulage prepares a partir de ces composes
US5198401A (en) * 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions

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US5198401A (en) * 1987-01-30 1993-03-30 Exxon Chemical Patents Inc. Ionic metallocene catalyst compositions
WO1992000333A2 (fr) * 1990-06-22 1992-01-09 Exxon Chemical Patents Inc. Catalyseurs en alliage organometallique de monocyclopentadienyle depourvu d'aluminium destines a la polymerisation d'olefines
EP0504418A1 (fr) * 1990-10-05 1992-09-23 Idemitsu Kosan Company Limited Procede de production de polymere de cycloolefine et de copolymere de cycloolefine et composition et moulage prepares a partir de ces composes

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0628566B1 (fr) * 1993-06-11 2003-03-26 Phillips Petroleum Company Metallocènes, leur préparation et leur utilisation
WO1996016104A1 (fr) * 1994-11-17 1996-05-30 Ciba Specialty Chemicals Holding Inc. Procede pour la polymerisation d'olefines cycliques et composition photopolymerisable
US5821278A (en) * 1994-11-17 1998-10-13 Ciba Specialty Chemicals Corporation Process for polymerizing of cyclic olefins and a photopolymerizable composition
WO2012052436A1 (fr) * 2010-10-20 2012-04-26 Deutsche Institute Für Textil- Und Faserforschung Denkendorf Précatalyseurs pour la production de polyoléfines et leur utilisation
WO2014022482A1 (fr) * 2012-08-01 2014-02-06 California Institute Of Technology Polymérisation par méthathèse d'ényne sans solvant
US9147844B2 (en) 2012-08-01 2015-09-29 California Institute Of Technology Solvent-free enyne metathesis polymerization
US9234985B2 (en) 2012-08-01 2016-01-12 California Institute Of Technology Birefringent polymer brush structures formed by surface initiated ring-opening metathesis polymerization
US11724250B2 (en) 2018-09-20 2023-08-15 Exxonmobil Chemical Patents Inc. Metathesis catalyst system for polymerizing cycloolefins

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JPH09501191A (ja) 1997-02-04
EP0719294A1 (fr) 1996-07-03
CA2166193A1 (fr) 1995-01-12

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