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WO1997032913A1 - Composition polymerisable - Google Patents

Composition polymerisable Download PDF

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Publication number
WO1997032913A1
WO1997032913A1 PCT/EP1997/000816 EP9700816W WO9732913A1 WO 1997032913 A1 WO1997032913 A1 WO 1997032913A1 EP 9700816 W EP9700816 W EP 9700816W WO 9732913 A1 WO9732913 A1 WO 9732913A1
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WIPO (PCT)
Prior art keywords
substituted
alkyl
unsubstituted
alkoxy
composition according
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PCT/EP1997/000816
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English (en)
Inventor
Andreas MÜHLEBACH
Paul Adriaan Van Der Schaaf
Andreas Hafner
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Ciba Specialty Chemicals Holding Inc.
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Priority to AU20919/97A priority Critical patent/AU2091997A/en
Publication of WO1997032913A1 publication Critical patent/WO1997032913A1/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

Definitions

  • the present invention relates to a solvent-free composition
  • a solvent-free composition comprising a) a Diels-Alder adduct of unsubstituted or substituted 1 ,3-cyclopentadienes and a cycloolefin, which adduct has a low content of unsubstituted or substituted cyclopentadiene, b) if desired, at least one substituted or unsubstituted strained cyclic olefin, and c) a small amount of a ruthenium catalyst for the metathesis polymerization, and to a process, and the use of the composition, for preparing metathesis polymers and mouldings from these polymers.
  • oligocyclopentadienes specifically as Diels- Alder adducts or, more generally, Diels-Alder adducts of 1 ,3-dicyclopentadienes and cycloolefins, always include a certain amount of 1 ,3-dicyclopentadienes, the amount being determined by the equilibrium of the Diels-Alder reaction and in general being significantly more than 0.1 % by weight.
  • the invention provides, firstly, a solvent-free polymerizable composition
  • a solvent-free polymerizable composition comprising a) at least one Diels-Alder adduct of (a1 ) unsubstituted or substituted cycloolefins and (a2) unsubstituted or substituted 1 ,3-cyclopentadienes, which adduct has a low content of unsubstituted or substituted cyclopentadienes, and b) a catalytically active amount of a ruthenium catalyst for metathesis polymerization, which composition comprises, based on the Diels-Alder adduct, not more than 0.1 % by weight of cyclopenta-1 ,3-diene or substituted cyclopenta-1 ,3-diene and from 0.05 to 0.3 % by weight of ruthenium catalyst; with the exception of dicyclopentadiene in combination with 0.3 % by weight (p-cumene)Ru
  • the content of cyclopenta-1 ,3-diene or substituted cyclopenta-1 ,3-diene is determined by means of UV spectroscopy in ethanolic solution (for example with 10 or 12 mg of Diels- Alder adduct per ml) at a ⁇ max of 238 nm by comparing the values found for the molar extinction ⁇ with samples of known 1 ,3-diene content.
  • the content can also be determined in a manner known per se by chromatographic methods (gas chromatography, HPLC [High Pressure Liquid Chromatography]), by comparison with calibration samples of known content.
  • Preferred substituents are C ⁇ -C 6 alkyl, C ⁇ -C 4 alkoxy, C 5 cycloalkyl or C 6 cycloalkyl, phenyl, benzyl, -CH 2 F, -CHF 2 , -CF 3 , -CH 2 CI, -CHCI 2 , -CCI 3 , F, Cl, -CN and -C(O)O-C ⁇ -C 18 alkyl.
  • alkyl substituents since then the Diels-Alder adducts are composed entirely of only C and H.
  • alkyl are methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, and the isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl.
  • a large number of Diels-Alder adducts of unsubstituted or substituted 1 ,3-cyclopentadienes with unsubstituted or substituted cycloolefins are known and many are commercially available, or they can be prepared in a known manner by a Diels-Alder reaction of unsubstituted or substituted 1 ,3-cyclopentadienes with unsubstituted or substituted cycloolefins.
  • cycloolefins may be the compounds indicated below under formula II, containing hydrocarbon rings, including the preferences and substitutions indicated.
  • the cycloolefins may be those containing 3 to 12, preferably 5 to 8, ring carbon atoms, and they may be fused ring systems having 2 to 8 and, preferably, 2 to 5 rings, bridged ring systems having 2 to 8 and, preferably, 2 to 5 rings, or fused and bridged ring systems having 2 to 8 and, preferably, 2 to 5 rings.
  • the individual rings can be substituted as indicated above for the Diels-Alder adducts, or aromatic hydrocarbon rings, especially unsubstituted benzene or benzene substituted as indicated above, can be fused onto the individual rings.
  • cycloolefins examples include cyclopropene, cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclooctatetraene, cyclononene, cyclononadiene, cyclononatriene, cyclodecene, cyclodecadiene, cyclodecatriene, cyclododecene, cyclododecadi ⁇ ne, cyclododecatriene, cyclododecatetraene, bicyclo[3.3.0]oct-6-ene, bicyclo[3.3.0]oct-1 ,6- diene, bicyclo[3.4.0]non-7-ene, bicyclo
  • a preferred subgroup comprises Diels-Alder adducts of cyclopentadienes, of which a large number are known and commercially available (they are obtained, for example, in the course of petroleum distillation), or which can be prepared in a known manner by a Diels- Alder reaction of cyclopentadienes with cyclopentadienes, or with Diels-Alder adducts of cyclopentadienes (oligocyclopentadienes).
  • Diels-Alder adducts may be of the formula I
  • p is 0 or a number from 1 to 100, preferably 1 to 50, particularly preferably 1 to 20, and especially preferably 1 to 10, it being possible for the adduct to be substituted as indicated above for the Diels-Alder adducts, in particular by C ⁇ -C 6 alkyl groups.
  • Diels-Alder adducts comprises those of unsubstituted or substituted norbomenes or norbomadienes with unsubstituted or substituted 1 ,3- cyclopentadienes.
  • Particular preferred Diels-Alder adducts are those of the formula la
  • q is preferably a number from 1 to 20, more preferably 1 to 10 and, with particular preference, 1 to 5, and the Diels-Alder adducts are unsubstituted or are substituted by, preferably, d-Cealkyl.
  • the Diels-Alder adducts can be used alone or together with comonomeric strained cycloolefins which differ from the Diels-Alder adducts and which may be present, for example, in proportions of up to 60 % by weight, preferably up to 40 % by weight and, with particular preference, up to 20 % by weight, based on the overall mixture of monomers.
  • comonomers it is possible to establish desired properties of the metathesis polymers.
  • the cyclic olefins can be monocyclic or polycyclic fused and/or bridged and/or linked ring systems, for example with from two to four rings, which are unsubstituted or substituted and can contain heteroatoms such as, for example, O, S, N or Si in one or more rings and/or can contain fused aromatic or heteroaromatic rings, for example o-phenylene, o- naphthylene, o-pyridinylene or o-pyrimidinylene.
  • the individual cyclic rings may include 3 to 16, preferably 3 to 12 and, with particular preference, 3 to 8 ring members.
  • the cyclic olefins may include further nonaromatic double bonds, preferably from 2 to 4 such additional double bonds depending on ring size.
  • the ring substituents involved are those which are inert; in other words, those which do not adversely affect the chemical and thermal stability of the ruthenium and osmium catalysts.
  • the cycloolefins are strained rings or ring systems. Particular preference is given to individual rings and ring systems having 5 to 8 carbon atoms in the ring.
  • cyclic olefins contain more than one double bond, for example 2 to 4 double bonds, or mixtures are used of strained cycloolefins having one double bond and strained cycloolefins having at least two double bonds, for example 2 to 4 double bonds, then depending on the reaction conditions, on the chosen monomer and on the amount of catalyst it is also possible for crossiinked polymers to form.
  • the cycloolefins are of the formula II
  • X and Xi independently of one another are -O-, -S-, -CO-, -SO-, -SO 2 -, -O-C(O)-, -C(O)-O-, -C(O)-NR 5 -, -NR 10 -C(O)-, -SO 2 -O- or -O-SO 2 -;
  • R R 2 and R 3 independently of one another are d-C 12 alkyl, C ⁇ -C 12 perfluoroalkyl, phenyl or benzyl;
  • R 4 and R 13 independently are C ⁇ -C 20 alkyl, C ⁇ -C 2 ohaloalkyl, d-C 20 hydroxyalkyl, C 3 -C 8 cycloalkyl, C 6 -C ⁇ 6 aryl or C 7 -C 16 aralkyl;
  • R 5 and R 10 independently of one another are hydrogen, d-C 12 alkyl, phenyl or benzyl, the alkyl groups being in turn unsubstituted or substituted by d-d 2 alkoxy or C 3 -C 8 cycloalkyl;
  • R 6 , R and R 8 independently of one another are C C ⁇ 2 alkyl, d-C 12 perfluoroalkyl, phenyl or benzyl;
  • M is an alkali metal
  • Mi is an alkaline earth metal; and u is 0 or 1 ; it being possible for the alicyclic ring formed with Qt to contain further nonaromatic double bonds;
  • Q 2 is hydrogen, d-C 20 alkyl, d-C 2 ohaloalkyl, d-C 12 alkoxy, halogen, -CN or Rn-X 2 -;
  • Rn is C C 2 oalkyl, d-C 20 haloalkyl, d-C 2 ohydroxyalkyl, C 3 -C 8 cycloalkyl, C 6 -C ⁇ 6 aryl or
  • X 2 is -C(O)-O- or -C(O)-NR 12 -;
  • R 9 is hydrogen, C ⁇ -C ⁇ 2 alkyl, phenyl or benzyl.
  • Fused-on alicyclic rings preferably contain 3 to 8, particularly preferably 5 to 8 and, with a special preference, 5 or 6 ring carbon atoms.
  • alkyl, alkenyl and alkynyl groups can be straight- chain or branched. The same also applies to the alkyl moiety, or each alkyl moiety, of al ⁇ koxy, alkylthio, alkoxycarbonyl and other alkyl-containing groups. These alkyl groups contain preferably 1 to 12, more preferably 1 to 8 and, with particular preference, 1 to 4 carbon atoms. These alkenyl and alkynyl groups preferably contain 2 to 12, more preferably 2 to 8 and, with particular preference, 2 to 4 carbon atoms.
  • Alkyl comprises, for example, methyl, ethyl, i-propyl, n-propyl, n-butyl, i-butyl, t-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals.
  • Hydroxyalkyl comprises, for example, hydroxymethyl, hydroxyethyl, 1-hydroxyisopropyl, 1 -hydroxy-n-propyl, 2-hydroxy-n-butyl, 1-hydroxy-iso-butyl, 1-hydroxy-secondary-butyl, 1 -hydroxy-tertiary-butyl and the hydroxy derivatives of the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals.
  • Haloalkyl comprises, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2- chloroethyl, 2,2,2-trichloroethyl and halogenated, especially fluorinated or chlorinated alkanes, such as, for example, halogen derivatives of the isopropyl, n-propyl, n-butyl, iso- butyl, sec-butyl and tert-butyl radicals and of the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octa
  • Alkenyl comprises, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl, n-octadec-2-enyl and n-octadec-4-enyl.
  • Cycloalkyl is preferably C 5 -C 8 cycloalkyl, especially C 5 cycloalkyl or C 6 cycloalkyl. Some examples are cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Cyanoalkyl comprises, for example, cyanomethyl(methylcarbonitrile), cyanoethyl(ethylcarbonitrile), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl, 1 -cyano- iso-butyl, 1 -cyano-sec-butyl, 1 -cyano-tert-butyl and the various isomeric cyanopentyl and cyanohexyl radicals.
  • Aralkyl contains preferably 7 to 12 carbon atoms and, with particular preference, 7 to 10 carbon atoms and is, for example, phenyl-d-C 6 alkyl or phenyl-C ⁇ -C 4 alkyl.
  • the particular radical may, for example, be benzyl, phenethyl, 3-phenylpropyl, ⁇ -methylbenzyl, phenbutyl or ⁇ , ⁇ -dimethylbenzyl.
  • Aryl contains preferably 6 to 10 carbon atoms. It may, for example, be phenyl, pentaline, indene, naphthalene, azulene or anthracene.
  • Heteroaryl contains preferably 4 or 5 carbon atoms and one or two heteroatoms from the group consisting of O, S and N. It may, for example, be pyrrole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, purine or quinoline.
  • Heterocycloalkyl contains preferably 4 or 5 carbon atoms and one or two heteroatoms from the group consisting of O, S and N. It may, for example, be oxiran, azirin, 1 ,2-oxathiolane, pyrazoline, pyrrolidine, piperidine, piperazine, morpholine, tetrahydrofuran or tetrahydrothio- phene.
  • Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, i-butyloxy and t-butyloxy.
  • Alkali metal in the context of the present invention is to be understood as meaning lithium, sodium, potassium, rubidium or caesium, especially lithium, sodium or potassium.
  • Alkaline earth metal in the context of the present invention is to be understood as meaning beryllium, magnesium, calcium, strontium or barium, especially magnesium or calcium.
  • halogen means fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.
  • the novel composition comprises compounds of the formula II in which
  • the novel composition comprises norbornene and norbornene derivatives, norbornadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene or cyclo- dodecene.
  • norbornene derivatives particular preference is given to those which are alternatively of the formula III
  • X 3 is -CHRie-, oxygen or sulfur
  • R ⁇ and R 15 independently of one another are hydrogen, -CN, trifluoromethyl, (CH 3 ) 3 Si-O-,
  • R 16 and R 17 independently of one another are hydrogen, C C 12 alkyl, phenyl or benzyl; or of the formula IV
  • X 4 is -CHR 19 -, oxygen or sulfur
  • R 19 is hydrogen, d-C ⁇ alkyl, phenyl or benzyl
  • R 18 is hydrogen, d-C 6 alkyl or halogen; or of the formula V
  • X 5 is -CHR 22 -, oxygen or sulfur
  • R 22 is hydrogen, C ⁇ -C ⁇ 2 alkyl, phenyl or benzyl
  • R 20 and R 21 independently of one another are hydrogen, CN, trifluoromethyl, (CH 3 ) 3 Si-O-,
  • R 23 is hydrogen, d-C ⁇ 2 alkyl, phenyl or benzyl
  • X 6 is -CHR 2 -, oxygen or sulfur
  • R 24 is hydrogen, Crd 2 alkyl, phenyl or benzyl; Y is oxygen or — R '2, c 5 and /
  • R 25 is hydrogen, methyl, ethyl or phenyl.
  • Another preferred subgroup of comonomers comprises those composed only of carbon and hydrogen.
  • Ro can, for example, be an epoxide, acrylate or methacrylate group which is attached covalently via a bridge group or directly to the cyclooctene.
  • Fused and/or bridged and/or linked olefinically unsaturated ring systems are generally prepared by means of Diels-Alder reactions. They should be able to be melted without decomposition, which for the purposes of the invention means that strained cycloolefins can be melted and the catalyst can be dissolved. In the case of thermally unstable strained cycloolefins it may therefore be necessary to dissolve the catalyst under pressure. Where the reaction temperature is above the decomposition point of the strained cycloolefin, it is advisable to employ pressure techniques in order to avoid the monomers decomposing prior to polymerization.
  • the amount of unsubstituted or substituted 1 ,3-dicyclopentadiene is preferably not more than 0.08 % by weight, more preferably not more than 0.06 % by weight, particularly preferably not more than 0.04 % by weight and, with special preference, not more than 0.02 % by weight.
  • the Diels-Alder adducts with a content of 1 ,3-cyclopentadienes can be purified by methods which are generally known.
  • the adducts can be treated with basic compounds, for example Grignard compounds, alkali metal hydroxides or alkali metal carbonates, or, preferably, with basic zeolites.
  • the 1 ,3-cyclopentadienes can also be removed by reaction with dienophiles (see EP-A-0 359 186), for example maleimide.
  • the amount of ruthenium catalysts depends essentially on their reactivity. More active catalysts are preferably used in the region of the lower limits, and less active catalysts in the region of the upper limits.
  • the range of amounts is preferably from 0.05 to less than 3 % by weight, more preferably from 0.1 to less than 0.3 % by weight, particularly preferably from 0.1 to 0.25 % by weight, and with special preference from 0.1 to 0.2 % by weight.
  • Ruthenium catalysts for ring-opening metathesis polymerization are known and can be prepared by known methods. Catalysts of this kind are, for example, disclosed in
  • the catalysts are, with particular preference, one-component catalysts with no cocatalysts.
  • the ruthenium catalysts may be mono- or polynuclear and may, for example, include 1 , 2 or 3 ruthenium atoms.
  • the polymerization can be initiated either thermally or by means of actinic radiation, since ruthenium catalysts are known for both methods. Also possible is a combination of photolytic and thermal polymerization. Preference is given, however, to thermal polymerization, especially with regard to the use of casting resins.
  • Photocatalysts are described in WO 95/07310. They may be thermally stable ruthenium compounds containing at least one photolabile ligand attached to the ruthenium atom, with the remaining coordination sites being occupied by non-photolabile ligands. Preference is given to ruthenium(ll) compounds containing non-nucleophilic anions, for example halides, PF 6 , AsF 6 , SbF 6l BF 4 and sulfonate anions.
  • Thermally stable denotes that 0.33 % by weight of catalyst in ethanolic solution containing 20 % by weight monomer, at 50 °C in the dark over 96 hours, forms not more than 0.2 % by weight and, preferably, not more than 0.1 % by weight of polymer.
  • a photolabile ligand is defined as a ligand which is cleaved off from the catalyst under irradiation with light in the visible or ultraviolet range, and forms a catalytically active species from the ruthenium compound.
  • photolabile ligands are N 2 , monocyclic, polycyclic or fused arenes or heteroarenes, or aromatic and aliphatic nitriles. Specific examples are benzene, biphenyl, naphthalene, anthracene, pyrene, thiophene, acetonitrile, propionitrile, butyronitrile, benzonitrile and benzylnitrile.
  • a non-photolabile ligand (also strongly bonding ligand) is not cleaved off in the course of irradiation with light in the visible or ultraviolet range.
  • ligands are solvating, organic and inorganic compounds containing heteroatoms selected from the group consisting of O, S and N, or cyclopentadienyls or indenyls, examples being H 2 O, H 2 S, NH 3 , alcohols and thiols, ethers, thioethers, sulfoxides, sulfones, ketones, carboxylates and carboxamides, lactones and lactames, and also amines.
  • photoactive ruthenium catalysts are Ru(CH 3 CN) 6 (tosylate) , Ru(C 6 H 6 ) 2 (tosylate) 2 , [(C 6 H 6 )(chrysene)]BF 4 , Ru(benzonitrile) 6 (CF 3 SO 3 ) 2 , Ru(C 6 H 6 )(CH 3 - CN) 3 (PF 6 ) 2 , Ru(C 6 H 6 )(CH 3 OH) 3 (PF 6 ) 2 .
  • Chrysene is
  • those which are particularly suitable contain phosphine ligands.
  • phosphine ligands Particular preference is given to divalently cationic ruthenium compounds containing at least one phosphine group and in total from two to five ligands attached to the ruthenium atom, and containing acid anions for charge compensation.
  • a monophosphine can be attached once, twice or three times and a diphosphine once to the metal atom.
  • the ruthenium catalysts there are preferably 1 to 4, more preferably 1 to 3 and, with particular preference, 2 ligands attached.
  • the phosphine ligands are preferably of the formulae VII and Vila,
  • R 26 , R 27 and R 2B independently of one another are H, C ⁇ -C 20 alkyl, d-C 2 oalkoxy, unsubstituted or d-C ⁇ alkyl-, d-C 6 haloalkyl- or d-C 6 alkoxy-substituted C -C ⁇ 2 cycloalkyl or cycloalkoxy, or unsubstituted or d-C 6 alkyl-, d-C 6 haloalkyl- or C -C 6 alkoxy-substituted C 6 -C ⁇ 6 aryl or C 6 -C 16 aryloxy, or unsubstituted or d-C 6 alkyl-, d-C 6 haloalkyl- or C C 6 alkoxy- substituted C 7 -C ⁇ 6 aralkyl or C 7 -d 6 aralkyloxy; the radicals R 26 and R 27 together are unsubstituted or Ci
  • Z 1 is linear or branched, unsubstituted or C C 4 alkoxy-substituted C 2 -C 2 alkylene, unsubstituted or d-C 4 alkyl- or d-C alkoxy-substituted 1 ,2- or 1 ,3-cycloalkylene of 4 to 8 carbon atoms, or is unsubstituted or d-C alkyl- or d-C 4 alkoxy-substituted 1 ,2- or 1 ,3-heterocycloalkylene with 5 or 6 ring members and a heteroatom from the group consisting of O and N.
  • radicals R 26 , R 27 and R 28 are preferably identical radicals. Preference is given, furthermore, to sterically bulky radicals, for examples branched alkyl, especially ⁇ -branched alkyl, or cyclic radicals. Hydrocarbon radicals are particularly preferred.
  • Alkyl R 26 , R 27 and R 28 can be linear or branched and contain preferably 1 to 12, more preferably 1 to 8 and, with particular preference, 1 to 6 carbon atoms.
  • alkyl are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, the isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and eicosyl.
  • Preferred examples are methyl, ethyl, n- and i-propyl, n-, i- and t- butyl, 1 -, 2- or 3-pentyl and 1-, 2-, 3- or 4-hex
  • R 26 , R 27 and R 28 are substituted, the substituents are preferably d-C 4 alkyl, C ⁇ -C 4 haloaikyl or C ⁇ -C 4 alkoxy.
  • Halogen is preferably Cl and, with particular preference, is F.
  • preferred substituents are methyl, methoxy, ethyl, ethoxy and trifluoromethyl.
  • R 26 , R 27 and R 28 are preferably substituted from one to three times.
  • R 26 , R 27 and R 28 are cycloalkyl, they are preferably C 5 -C 8 cycloalkyl and, particularly preferably, C 5 cycloalkyl or C 6 cycloalkyl. Some examples are cyclobutyl, cycloheptyl, cyclooctyl and, in particular, cyclopentyl and cyclohexyl. Examples of substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrif luoromethyl- and tristrifluoromethylcyclopentyl and -cyclohexyl.
  • R 26 , R 27 and R 28 are aryl, they are preferably C 6 -C 12 aryl and, particularly preferably, phenyl or naphthyl.
  • substituted aryl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl- and tristrifluoromethylphenyl.
  • R 26 , R 2 and R 28 are aralkyl, they are preferably C 7 -C, 3 aralkyl, the alkylene group in the aralkyl preferably being methylene.
  • the aralkyl is benzyl.
  • substituted aralkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl- and tristrifluoromethylbenzyl.
  • Examples of unsubstituted or substituted, fused or unfused tetra- and pentamethylene attached to the phosphorus atom are
  • R a is d-C 6 alkyl, cyclohexyl, benzyl or unsubstituted or mono- or di- C ⁇ -C 4 alkyl- substituted phenyl.
  • Z ⁇ as linear or branched alkylene is preferably 1 ,2-alkylene or 1 ,3-alkylene having preferably 2 to 6 carbon atoms, for example ethylene, 1 ,2-propylene or 1 ,2-butylene.
  • Examples of Zi as cycloalkylene are 1 ,2- and 1 ,3-cyclopentylene and 1 ,2- or 1 ,3-cyclo- hexylene.
  • Examples of Z ⁇ as heterocycloalkylene are 1 ,2- and 1 ,3-pyrrolidine, 1 ,2- and 1,3- piperidine, and 1 ,2- and 1 ,3-tetrahydrofuran.
  • the phosphine ligands are of the formula VII in which R 26 , R 27 and R 28 independently of one another are H, d-C 6 alkyl, unsubstituted or d-dalkyl- substituted cyclopentyl or cyclohexyl, or unsubstituted or d-C 4 alkyl-, C 1 -C 4 alkoxy- or trifluoromethyl-substituted phenyl, or unsubstituted or C ⁇ -C 4 alkyl-, d-C 4 -alkoxy- or trifluoromethyl-substituted benzyl.
  • phosphine ligands of the formula VII are (C 6 H 5 )H 2 P, (3-CH 3 -6-t-C 4 H 9 -C 6 H 3 ) 3 P, (3-CH 3 -6-t-C 4 H 9 -C 6 H 3 ) 3 P, PH 3 , (2,6-di-t-C 4 H 9 -C 6 H 3 ) 3 P, (2,3-di-t-C 4 H 9 -C 6 H 3 ) 3 P, (2,4-di-t-C 4 H 9 -C 6 H 3 ) 3 P, (2,4-di-CH 3 -C 6 H 3 ) 3 P, (2,6-di-CH 3 -C 6 H 3 ) 3 P, (2-CH 3 -6-t-C 4 H 9 -C 6 H3)3p, (CH 3 ) 3 P, (2-i-C 3 H 7 -C 6 H 4 ) 3 P, (3-i-C 3 H 7 -
  • Particularly preferred phosphines are tri-i-propylphosphine, tri-t-butylphosphine, tricyclo- pentylphosphine and tricyclohexylphosphine.
  • Ligands for the ruthenium compounds to be used in accordance with the invention are organic or inorganic compounds, atoms or ions which are coordinated to a metal centre.
  • ligands used with particular advantage are selected, for example, from a group of ligands (A) consisting of nitrogen (N 2 ); unsubstituted or OH-, d-C alkyl-, d-C alkoxy-, C 6 -C ⁇ 2 aryl- or halo-substituted monocyclic, polycyclic or fused arenes having 6 to 24, preferably 6 to 18 and, with particular preference, 6 to 12 carbon atoms; unsubstituted or C ⁇ -C 4 alkyl-, C ⁇ -C 4 alkoxy- or halo-substituted monocyclic heteroarenes; fused heteroarenes; fused arene-heteroarenes having 3 to 22, preferably 4 to 16 and, in particular, 4 to 10 carbon atoms and 1 to 3 heteroatoms selected from the group consisting of O, S and N; and unsubstituted or d-C 4 alkyl-, d-C 4 alkoxy
  • the preferred substituents are methyl, ethyl, methoxy, ethoxy, fluorine, chlorine and bromine.
  • the arenes and heteroarenes are preferably substituted by from one to three radicals. Among the heteroarenes, the electron-rich heteroarenes are preferred.
  • Some examples of arenes and heteroarenes are benzene, 4-isopropyltolyl, biphenyl, naphthalene, anthracene, acenaphthene, fluorene, phenanthrene, pyrene, chrysene, fluoroanthrene, furan, thiophene, pyrrole, pyridine, ⁇ -pyran, ⁇ -thiopyran, pyrimidine, pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazines, thianthren
  • Preferred arenes and heteroarenes are unsubstituted or substituted benzene, naphthalene, 4-isopropyltolyl, thiophene and benzothiophene.
  • Very particular preference is given to the arene benzene or a benzene substituted by 1 to 3 C C 4 alkyls, for example toluene, xylene, trimethylbenzene, isopropylbenzene, tertiary-butylbenzene or 4-isopropyltolyl.
  • the heteroarene is preferably thiophene.
  • the nitriles can be substituted, for example, by methoxy, ethoxy, fluorine or chlorine; the nitriles are preferably unsubstituted.
  • the alkyl nitriles are preferably linear. Some examples of nitriles are acetonitrile, propionitrile, butyronitrile, pentylnitrile, hexylnitrile, cyclopentyl- and cyclohexylnitrile, benzonitrile, methylbenzonitrile, benzylnitrile and naphthylnitrile.
  • the nitriles are preferably linear C ⁇ -C 4 alkylnitriles or benzonitrile. Among the alkylnitriles, acetonitrile is particulariy preferred.
  • the ligands of group (A) are N 2 , unsubstituted or mono- to tri- C ⁇ -C alkyl-substituted benzene, thiophene, benzonitrile or acetonitrile.
  • Additional ligands may be present, selected for example from the group of ligands (B) consisting of solvating inorganic and organic compounds which contain the heteroatoms O, S or N and which are frequently also used as solvents; and unsubstituted or C ⁇ -C 4 alkyl-, C ⁇ -C alkoxy-, (d-C 4 alkyl) 3 Si- or (d-C alkyl) 3 SiO-substituted cyclopentadienyl or indenyl.
  • B consisting of solvating inorganic and organic compounds which contain the heteroatoms O, S or N and which are frequently also used as solvents
  • unsubstituted or C ⁇ -C 4 alkyl-, C ⁇ -C alkoxy-, (d-C 4 alkyl) 3 Si- or (d-C alkyl) 3 SiO-substituted cyclopentadienyl or indenyl unsubstituted or C ⁇ -C 4 alkyl-, C ⁇
  • Examples of such compounds are H 2 O, H 2 S, NH 3 ; unhalogenated or halogenated, especially fluorinated or chlorinated, aliphatic or cycloaliphatic alcohols or mercaptans having 1 to 18, preferably 1 to 12 and particularly preferably 1 to 6 carbon atoms, aromatic alcohols or thiols having 6 to 18, preferably 6 to 12 carbon atoms, araliphatic alcohols or thiols having 7 to 18, preferably 7 to 12 carbon atoms, open-chain or cyclic and aliphatic, araliphatic or aromatic ethers, thioethers, sulfoxides, sulfones, ketones, aldehydes, carboxylates, lactones, unsubstituted or N-C ⁇ -C 4 -mono- or -dialkylated carboxamides having 2 to 20, preferably 2 to 12 and especially 2 to 6 carbon atoms, and unsubstituted or N-C r C -
  • Further examples of the group of ligands (B) are methanol, ethanol, n- and i-propanol, n-, i- and t-butanol, 1 ,1 ,1 -trif I uoroethanol, bistrifluoromethyl methanol, tristrifluoromethylmethanol, pentanol, hexanol, methyl or ethyl mercaptan, cyclopentanol, cyclohexanol, cyclohexyl mercaptan, phenol, methylphenol, fluorophenol, phenyl mercaptan, benzyl mercaptan, benzyl alcohol, diethyl ether, dimethyl ether, diisopropyl ether, di-n- or di-t-butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, diethyl thioether, te
  • the primary amines can be of the formula R 29 NH , the secondary amines of the formula R 2 9R 30 NH and the tertiary amines of the formula R 29 R 3 oR 3 iN, in which R 29 is C C ⁇ 8 alkyl, unsubstituted or C ⁇ -C 4 alkyl- or C ⁇ -C 4 alkoxy-substituted C 5 cycloalkyl or C 6 cycloalkyl, or unsubstituted or d-C alkyl- or C r C 4 alkoxy-substituted C ⁇ -Ci ⁇ aryl or C 7 -C 12 aralkyl, R ⁇ independently is as defined for R 29 , or R 29 and R 30 together are tetramethylene, pentamethylene, 3-oxa-1 ,5-pentylene or -CH 2 -CH 2 -NH-CH 2 -CH 2 - or -CH 2 -CH 2 -N(d-C 4 alky
  • the alkyl contains preferably 1 to 12 and particularly preferably 1 to 6 carbon atoms.
  • the aryl contains preferably 6 to 12 carbon atoms and the aralkyl contains preferably 7 to 9 carbon atoms.
  • Examples of amines are methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, triethyl-, methyl-ethyl-, dimethyl-ethyl, n-propyl- , di-n-propyl-, tri-n-butyl-, cyclohexyl-, phenyl- and benzylamine, and also pyrrolidine, N-methylpyrrolidine, piperidine, piperazine, morpholine and N-methylmorpholine.
  • the ligands of group (B) are H 2 O, NH 3 , unsubstituted or partially or completely fluorinated d-C 4 alkanols, or cyclopentadienyl, indenyl, allyl, methallyl or crotyl. Very particular preference is given to H 2 O, NH 3 , cyclopentadienyl, indenyl, methanol and ethanol.
  • the Ru and Os catalysts to be used in accordance with the invention comprises arenes or heteroarenes as ligands, phosphine groups, and anions for charge compensation.
  • they include an arene group as ligand, a tertiary phosphine group, and mono- or divalent anions for charge compensation.
  • Suitable anions of organic or inorganic acids are hydride (H ), halide (for example F “ , Cl “ , Br “ and I ), the anion of an oxygen acid, and BF 4 " , PF 6 ⁇ SbF 6 " or AsF 6 " .
  • H hydride
  • halide for example F “ , Cl “ , Br “ and I
  • BF 4 " PF 6 ⁇ SbF 6 " or AsF 6 "
  • the abovementioned ligands cyclopentadienyl, indenyl, allyl, methallyl and crotyl are anionic and thus also serve for charge compensation.
  • Suitable anions are CrC ⁇ 2 -, preferably d-C 6 - and, with particular preference, d-C alcoholates, which in particular are branched, and are, for example, of the formula R x R y R z C-O " in which R x is H or d-C ⁇ 0 alkyl, R y is C r C ⁇ 0 alkyl and R z is d-C 10 alkyl or phenyl, and the sum of the carbon atoms of R x , R y and R z is at least 2, preferably at least 3, and up to 10. Examples are, in particular, i-propyloxy and t-butyloxy.
  • Some examples are i-propyl, i- and t-butyl, phenyl, benzyl, 2-methyl-, 2,6-dimethyl-, 2-i-propyl-, 2-i-propyl-6-methyl-, 2-t-butyl-, 2,6-di-t-butyl- and 2-methyl-6-t-butylphenyl acetylide.
  • the anions of oxygen acids may for example be sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a C ⁇ -C 8 carboxylic acid, for example formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, sulfonates, for example methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate), unsubstituted or C ⁇ -C 4 alkyl-, C C alkoxy or halo-, especially fluoro-, chloro- or bromo-, substituted phenylsulfonate or benzylsulfonate, for example tosylate, mesylate, brosy
  • the ruthenium compounds are of one of the formulae VIM to Vllld
  • R 32 is a phosphine ligand of the formula VII or Vila;
  • Me is Ru; n is 1, 2 or 3;
  • Z is the anion of an inorganic or organic acid
  • Li is a ligand of group A, the ligands Li in formula VI Id being identical or different, and
  • L 2 is a ligand of group B.
  • R 32 , Li and L 2 are subject to the preferences and definitions indicated above for the phosphines of the formulae VII and Vila. ln the formulae VIII to Vllld, n is preferably 1 or 2, and especially 1. R 32 is subject to the preferences indicated for the phosphine ligands of the formulae VII and Vila; in particular, it comprises tertiary phosphines.
  • the ruthenium compounds used in the novel process are of one of the formulae IX to IXd
  • Z T and Z 2 independently of one another are H “ , cyclopentadienyl, Cl ' , Br “ , BF 4 ' , PF 6 " , SbF 6 ' ,
  • R 26 , R 27 and R 28 independently of one another are d-C 6 alkyl, unsubstituted or mono- to tri- d-C 4 alkyl-substituted cyclopentyl or cyclohexyl or cyclopentyloxy or cyclohexyloxy, or unsubstituted or mono- to tri-d-C 4 alkyl-substituted phenyl or benzyl or phenyloxy or benzyloxy;
  • L is unsubstituted or mono- to tri-d-C alkyl-, -C ⁇ -C 4 alkoxy-, -OH-, -F- or -Cl-substituted
  • C 6 -C 6 arene or C 5 -C 16 heteroarene or d-C 6 alkyl-CN, benzonitrile or benzylnitrile, with the ligands Li in formula IXd being identical or different;
  • L 2 is H 2 O or d-C 6 alkanol. If the preparation of the ruthenium catalysts is carried out in solvents which are able to coordinate onto a metal atom, for example alkanols, then solvated Ru-cation complexes may be formed, the use of which is included in the context of the novel composition.
  • ruthenium compounds to be used in accordance with the invention are: (C 6 Hn) 2 HPRu(4-isopropyltolyl)CI 2 , (C 6 H, ⁇ ) 3 PRu(4- isopropyltolyl)CI 2 , (C 6 Hn) 3 PRu(4-isopropyltolyl)(Tos) 2 , (C 6 Hn)3PRu(4-isopropyltolyl)Br 2 , (CeHii)3PRu(4-isopropyltolyl)CIF, (CeHii)3PRu(CeH e )(Tos)2, (C ⁇ H, 1 )3PRu(CH3-C ⁇ H 5 )(Tos)2, (C 6 H 11 ) 3 PRu(C 10 H 8 )(Tos) 2 , (i-C 3 H 7 ) 3 PRu(4-isopropyltolyl)
  • the abovementioned ruthenium catalysts are preferably employed in an amount of from 0.15 to 0.3 % by weight.
  • the ruthenium compounds to be used in accordance with the invention are known or can be prepared by known and analogous techniques starting from the metal halides (for example MeX 3 or [Me-areneX 2 ] 2 ) by reaction with phosphines and ligand-forming agents.
  • the metal halides for example MeX 3 or [Me-areneX 2 ] 2
  • ruthenium compounds are ruthenium carbenes with two phosphine ligands and two halogen atoms.
  • They can preferably be of the formula X or Xa or mixtures of compounds of the formulae X and Xa *o,
  • Me is ruthenium
  • T T and T 2 independently of one another are a tertiary phosphine, or Ji and T 2 together are a ditertiary diphosphine;
  • T 3 is H, d-C 12 alkyl; C 3 -C 8 cycloalkyl, C 3 -C 7 heterocycloalkyl with one or two heteroatoms selected from the group consisting of -O-, -S- and -N-, C 6 -C 14 aryl, or C 4 -C 15 heteroaryl with one to three heteroatoms selected from the group consisting of -O-, -S- and -N-, which are unsubstituted or substituted by Ci-CealkyI, C ⁇ -C ⁇ 2 haloalkyl, d-C ⁇ 2 alkoxy, C 6 -C ⁇ oaryl,
  • T is unsubstituted or mono- to tri-d-C 4 alkyl-, -C ⁇ -C 4 haloalkyl-, -C C 4 alkoxy-, -OH-, -F-, -Cl- or -Br-substituted C 6 -C ⁇ 6 arene or C -d 5 heteroarene, and
  • Xo ⁇ and X 02 independently of one another are halogen.
  • Xo ⁇ and X0 2 in the formulae X and Xa are preferably F, Cl or Br, more preferably Cl or Br, and, with particular preference, are each Cl.
  • T 3 is a hydrogen atom or is a hydrocarbon radical defined in the context of the invention, having 1 to 16 carbon atoms, more preferably 1 to 12 carbon atoms.
  • Alkyl T 3 can preferably contain 1 to 8 and, with particular preference, 1 to 6 carbon atoms. Some examples of alkyl are methyl, ethyl and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. With particular preference, T 3 is linear d-C 4 alkyl.
  • Cycloalkyl T 3 can preferably contain 5 to 8 carbon atoms. Cyclopentyl and cyclohexyl are particularly preferred.
  • Heterocycloalkyl T 3 can preferably contain 4 or 5 carbon atoms and preferably one heteroatom selected from the group consisting of -O-, -S- and -N-. Some examples are tetrahydrofuranyl, pyrrolidinyl, piperazinyl and tetrahydrothiophenyl.
  • Aryl T 3 can preferably contain 6 to 10 carbon atoms. Preferred examples are naphthyl and, in particular phenyl.
  • Heteroaryl T 3 can preferably contain 4 or 5 carbon atoms and one or two heteroatoms selected from the group consisting of -O-, -S- and -N-. Some examples are furanyl, thiophenyl, pyrrolyl, pyridinyl and pyrimidinyl.
  • Preferred substituents for T 3 are methyl, ethyl, methoxy, ethoxy, trichloromethyl, tri ⁇ fluoromethyl, phenyl, phenyloxy, F and Cl.
  • T 3 is H, C ⁇ -C 4 alkyl, cyclopentyl, cyclohexyl, phenyl or naphthyl, which are unsubstituted or substituted by C ⁇ -C alkyl, C ⁇ -C alkoxy, C ⁇ -C haloalkyl, phenyl, F or CI.
  • T in formula Xa contains as arene preferably 6 to 12 carbon atoms, and as heteroarene preferably 4 to 11 carbon atoms and preferably 1 to 3 heteroatoms from the group consisting of O, S and N.
  • substituents of T are methyl, ethyl, n- or i- propyl, n-, i- or t-butyl, methoxy, ethoxy, trifluoromethyl, F and Cl.
  • Preferred arenes and heteroarenes are benzene, toluene, xylene, trimethylbenzene, naphthalene, biphenyl, anthracene, acenaphthene, fluorene, phenanthene, pyrene, chrysene, fluoroanthrene, furan, thiophene, pyrrole, pyridine, ⁇ -pyran, ⁇ -xhiopyran, pyrimidine, pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, isoxazole, isothiazole, quinoline, isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, tri
  • More preferred arenes and heteroarenes are benzene, naphthalene, cumene, thiophene and benzthiophene.
  • a very particularly preferred arene is benzene or an d- dalkyl-substituted benzene, for example toluene, xylene, isopropylbenzene, tertiary- butylbenzene or cumene; a particularly preferred heteroarene is thiophene.
  • the phosphine group T, and T 2 preferably comprises tertiary phosphines, or ditertiary diphosphines having 3 to 40, more preferably 3 to 30 and, particularly preferably, 3 to 24 carbon atoms.
  • tertiary phosphine or ditertiary diphosphine groups are subject to the same embodiments and preferences as indicated beforehand under the formulae VII and Vila.
  • a preferred subgroup of the compounds of the formulae X and Xa comprises those of the formulae Xb and Xc,
  • R 9 is ⁇ -branched C 3 -C 8 alkyl, unsubstituted or C C 4 alkyl-, C ⁇ - dhaloalkyl-, C ⁇ -C 4 alkoxy-, halo- or -NO 2 -substituted C 5 -C 8 cycIoalkyl, or unsubstituted or d- dalkyl-, C ⁇ -C haloalkyl-, C C 4 alkoxy-, halo- or -NO 2 -substituted C 6 -C ⁇ 0 aryl
  • T 3 is H, d- C 6 alkyl, unsubstituted or d-C alkyl-, d-C 4 haloalkyl-, C C -alkoxy-, halo- or -NO 2 - substituted C 5 -C 8 cycloalkyl, or unsubstituted or C ⁇ -C 4 alkyl- C
  • the ruthenium carbene catalysts are preferably employed in amounts of from 0.05 to 0.2 % by weight.
  • the compounds of the formula X are known and their preparation is described by P. Schwab et al. in Angew. Chem. (1995), 107, No. 18, pages 2179 to 2181.
  • the preparation of the dinuclear compounds of the formula Xa for example, can be carried out by reacting 2 equivalents of a compound of the formula X with one equivalent of a conventional compound of the formula
  • novel composition in which X 02 , Me and T 4 are as defined for formula Xa, in the presence of an inert solvent.
  • novel composition may additionally include further open-chain comonomers which form copolymers with the strained cycloolefins. If, say, dienes are also used, it is possible for crossiinked polymers to be formed.
  • comonomers are olefinically mono- or di-unsaturated compounds, such as olefins and dienes from the group consisting of ethene, propene, butene, pentene, hexene, heptene, octene, decene, dodecylene, cyclohexene (which is known not to form metathesis polymers on its own), acrylic and methacrylic acid, their esters and amides, vinyl ethers, vinyl esters, vinyl chloride, vinylidene chloride, styrene, butadiene, isoprene and chlorobutadiene. If volatile comonomers are used, pressure techniques are frequently necessary. If nonvolatile comonomers are used, therefore, there may be process advantages.
  • olefins and dienes from the group consisting of ethene, propene, butene, pentene, hexene, heptene,
  • the further open-chain olefins suitable for the copolymerization are present in the novel composition, for example, in an amount of up to 80 % by weight, preferably from 0.1 to 80 % by weight, more preferably from 0.5 to 60 % by weight and, with particular preference, from 5 to 40 % by weight, based on the overall amount of di- and oligocyclopentadienes and other olefins capable of copolymerization.
  • the novel composition may include formulation auxiliaries.
  • auxiliaries are antistats, antioxidants, light stabilizers, plasticizers, dyes, pigments, fillers, reinforcing fillers, lubricants, adhesion promoters, viscosity-increasing agents, and mould release auxiliaries.
  • the fillers can be present in surprisingly high proportions without any adverse effect on the polymerization, for example in amounts of up to 80 % by weight, preferably from 1 to 70 % by weight, more preferably from 5 to 70 % by weight, particularly preferably from 5 to 60 % by weight and, with special preference, from 10 to 60 % by weight, based on the composition.
  • Fillers and reinforcing fillers for improving the optical, physical, mechanical and electrical properties have been disclosed in large numbers.
  • Some examples are glass and quartz in the form of powders, beads and fibres, metal oxides and semimetal oxides, carbonates such as MgCO 3 , CaCO 3 , dolomite, metal sulfates, such as gypsum and heavy spar, natural and synthetic silicates, such as talc, zeolites, wollastonite, felspars, aluminas, such as china clay, ground minerals, whiskers, carbon fibres, polymer fibres or polymer powders, and carbon black.
  • Viscosity-increasing agents are, in particular, metathesis polymers which contain olefinically unsaturated groups and which, in the course of the polymerization, can be inco ⁇ orated into the polymer.
  • Metathesis polymers of this kind are known and are commercially available, for example, under the trade name Vestenamers".
  • poly-1 ,3-dienes such as polybutadiene, polyisoprene, polychlorobutadiene or copolymers with the underlying dienes and with one or more olefins.
  • Such polymers are likewise commercially available, for example Buna" and Kraton*.
  • the amount of the viscosity-increasing polymers may for example be from 0.1 to 50 % by weight, preferably from 1 to 30 % by weight and, with particular preference, from 1 to 20 % by weight, based on all of the monomers present in the composition.
  • the viscosity-increasing agents serve at the same time to improve the toughness properties of the polymers.
  • the viscosity of the composition can be adjusted to the desired applications over a broad range.
  • novel compositions are outstandingly suitable for the direct production of shaped articles.
  • the individual components can be mixed and brought into the desired shape, since the catalysts dissolve even at room temperature, or with gentle heating, in nonpolar and polar monomers, and therefore permit a sufficient time for processing.
  • the invention additionally provides a process for preparing polymers by metathesis polymerization, which comprises heating or irradiating a solvent-free novel composition, or first irradiating and then heating such a composition.
  • the novel process is subject to the same preferences as for the novel composition.
  • the novel compositions are not very stable on storage, and it is expedient to mix monomers and catalyst not until just before processing.
  • the novel process is expediently conducted such that the mixing operation is associated, prior to polymerization, with a shaping operation, for example a coating or a shaped article. It is possible in principle to employ all known shaping techniques, for example extrusion, injection moulding and compression.
  • the novel compositions are particularly suitable as casting resins with or without the use of pressure, as for example in the RIM (Reaction injection Moulding) technique.
  • Irradiation can be carried out with light having a wavelength ranging from the UV region through the visible region into the near infrared region.
  • Heating can mean a temperature from 0 °C to 300 °C, preferably from room temperature to 300 °C, more preferably from room temperature to 250 °C, particularly preferably from room temperature to 200 °C, and, with particular preference, from 30 to 200 °C.
  • the polymerization times depend essentially on the catalyst activity, and they can range from seconds through minutes up to a number of hours. Polymerization can also be carried out in stages at ascending temperatures.
  • novel process it is possible to produce materials (semi-finished products) for the machining of shaped articles, or, directly, to produce mouldings of all kinds, films, sheets and coatings.
  • novel composition for producing semi-finished products, mouldings and sheets.
  • invention additionally provides mouldings from the novel compositions.
  • the polymers prepared in accordance with the invention may have very different properties. Some are notable for very high oxygen permeability, low dielectric constants, good thermal stability and low water absorption. Others have outstanding optical properties, such as high transparency and low refractive indices. A further quality to be emphasized, in particular, is the low shrinkage.
  • the polymers can therefore be used in widely differing industrial fields. The avoidance of solvents ensures the production of bubble-free mouldings and coatings even at relatively high polymerization temperatures.
  • the novel compositions are notable, as coats on the surface of substrate materials, especially apolar substrate materials, for a high bonding strength. A physical (for example plasma treatment) or chemical treatment (application of adhesion promoters) may further increase the bonding strength.
  • the coated materials are notable for very high surface gloss and surface smoothness.
  • good mechanical properties particular mention should be made of the low shrinkage and the high impact resistance, but also of the thermal stability. Also deserving a mention are the ease of demoulding, in the case of processing in moulds, and the high solvent resistance.
  • monomers it is possible to tailor the desired properties for the end use.
  • crossiinked thermosetting or elastomeric polymers are obtainable.
  • These polymers are suitable for producing medical implements, implants or contact lenses; for producing electronic components; as binders for coating materials; as photocurable compositions for constructing models, or as adhesives for bonding substrates having low surface energies (for example Teflon, polyethylene and polypropylene).
  • novel compositions are particulariy suitable for producing protective coats on substrate materials, and for producing relief images.
  • the invention also provides a variant of the novel process for producing coatings on substrate materials, in which a novel composition is applied as a coat on a substrate, for example by dipping, spreading, flow coating, rolling, knife or spin coating techniques, and the coat is heated for polymerization. This may be followed by further heat treatment. Using this process it is possible to modify or to protect surfaces of substrates.
  • the present invention likewise provides a composition comprising (a) a substrate material, and (b) a coat of a novel composition, which is applied at least to one surface.
  • a substrate material which is coated on at least one surface with a novel composition.
  • the present invention similarly provides a composition comprising (a) a substrate material, and (b) a polymer coat of a novel composition which is applied at least to one surface.
  • suitable substrates are those of glass, minerals, ceramics, plastics, wood, semimetals, metals, metal oxides and metal nitrides.
  • the coat thicknesses are guided essentially by the desired use and may, for example, be from 0.1 to 1000 ⁇ m, preferably from 0.5 to 500 ⁇ m, and, with particular preference, from 1 to 100 ⁇ m.
  • the coated materials are notable for a high bonding strength and good thermal and mechanical properties.
  • novel coated materials can be prepared by known methods, for example spreading, knife coating, flow-coating techniques, such as curtain coating, or spin coating.
  • novel compositions are also suitable for preparing rubber-like or thermoplastic polymers which can be crossiinked still further.
  • the strained cyclopentadienes can include reactive groups, for example (meth)acrylate or epoxide groups, which are attached covalently via a bridge group or directly to the cycloolefin.
  • novel compositions can also be used as heat-curable adhesives for the firm bonding of a wide variety of materials, in which case outstanding peel strengths can be obtained.
  • the novel polymers are particularly notable, in addition to their high bonding strengths, outstanding ease of processing, good surface properties (smoothness, gloss), high crossiinking density and resistance to solvents and other liquids, the novel polymers are particularly notable, in addition, for very good physico- mechanical properties, for example high temperature resistance, breaking strength and flexural strength, and impact resistance, and outstanding electrical properties, for example low conductivities, dielectric constants and loss factors ⁇ and tan ⁇ . Also deserving a mention are the high oxygen permeability and the low water uptake. Polymers composed only of carbon and hydrogen are particularly valuable ecologically, since they can, for example, be completely recycled by pyrolysis or harmlessly incinerated.
  • DCPD Dicyclopentadiene
  • DCPD Commercial grade
  • molecular sieve Union Carbide, type 5A, supplied by Fluka, No. 69849
  • the content of CPD is determined as being 0.06 % by weight.
  • 0.3 % by weight of catalyst A is added, the solid is dissolved with gentle heating, and polymerization is carried out in an aluminium mould in a hot-air oven for 1 h at 80° C, 1 h at 100° C and 2h at 120° C, to give a yellow, transparent, firm plate 4 mm thick and of good impact resistance with a T g of 100° C.
  • Example A1 The procedure of Example A1 is repeated but without storage of the DCPD.
  • the CPD content is 0.2 % by weight.
  • a soft, black, rubber-like moulding with a T g ⁇ room temperature is obtained.
  • Example A2 The procedure of Example A2 is repeated but the DCPD, prior to devolatilization, is stored over a molecular sieve (amount and molecular sieve as in Example A1).
  • the CPD content is 0.02 % by weight.
  • a yellow, transparent plate 4 mm thick of good impact resistance with a Tg ⁇ f 127° C is obtained.
  • Example A2 5 g of technical-grade DCPD are devolatilized as in Example A2, and 0.2 % by weight of catalyst B is added. The CPD content is 0.04 % by weight. Polymerization is carried out as in Example A1 , to give a yellow, transparent plate 4 mm thick of good impact resistance with a T g of 135° C.
  • Example A5 30 mg of CPD are added to the mixture from Example A5, and polymerization is then carried out as in Example A1 , to give a rubber-like product with a strong odour of DCPD, indicating incomplete conversion.
  • Example A5 The procedure for Example A5 is repeated but without devolatilization.
  • the CPD content is 0.2 % by weight.
  • Polymerization is carried out as in Example A1 , to give a yellowish brown plate 4 mm thick with a T g of only 60° C.

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Abstract

L'invention concerne une composition polymérisable exempte de solvant et comprenant: a) au moins un composé d'addition Diels-Alder de (a1) cyclo-olifines non substituées ou substituées et (a2) 1,3-cyclopentadienes non substitués ou substitués, ce composé d'addition ayant une faible teneur en cyclopentadiènes non substitués ou substitués, et b) une quantité catalytiquement active d'un catalyseur de ruthénium pour une polymérisation par métathèse. Cette composition comprend, sur la base d'un composé d'addition Diels-Alder, une teneur en cyclopenta-1,3-diène ou cyclopenta-1,3-diène substitué inférieure à 0,1 % en poids et une teneur en catalyseur de ruthénium comprise entre 0,05 et 0,3 % en poids; à l'exception de dicyclopentadiène en combinaison avec 0,3 % en poids de (4-isopropyltolyl)RuCl2[P(C6H11)3]. Ces compositions peuvent être utilisées pour fabriquer des moulages possédant de très bonnes propriétés mécaniques.
PCT/EP1997/000816 1996-03-04 1997-02-20 Composition polymerisable WO1997032913A1 (fr)

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Cited By (11)

* Cited by examiner, † Cited by third party
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WO2002088220A1 (fr) * 2001-04-30 2002-11-07 Essilor International Compagnie Generale D'optique Photopolymerisation d'episulfures au moyen de complexes metalliques, et realisation de lentilles ophthalmiques par ce procede
EP1165630A4 (fr) * 1999-02-05 2004-07-07 Materia Inc Compositions de polyolefine a densite variable et procedes de production et d'utilisation associes
EP1849806A1 (fr) * 2006-04-20 2007-10-31 Shin-Etsu Chemical Company, Ltd. Polymère fortement perméable à l'oxygène
US8178604B2 (en) 2006-02-02 2012-05-15 3M Innovative Properties Company Solid materials obtainable by ring-opening metathesis polymerization
WO2012110648A1 (fr) 2011-02-17 2012-08-23 Ccp Composites Us Polyester insaturé dépourvu de styrène
US8367858B2 (en) 2009-06-16 2013-02-05 Amyris, Inc. Terephthalic and trimellitic based acids and carboxylate derivatives thereof
US8367859B2 (en) 2009-06-16 2013-02-05 Amyris, Inc. Cyclohexane 1,4 carboxylates
US8415496B2 (en) 2009-06-16 2013-04-09 Amyris, Inc. Biobased polyesters
US8426639B2 (en) 2009-06-16 2013-04-23 Amyris, Inc. Preparation of trans, trans muconic acid and trans, trans muconates
US8431625B2 (en) 2006-12-20 2013-04-30 3M Innovative Properties Company Compositions curable by ring opening metathesis polymerization at low temperatures and their application in the dental field
US8809583B2 (en) 2010-01-08 2014-08-19 Amyris, Inc. Methods for producing isomers of muconic acid and muconate salts

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1165630A4 (fr) * 1999-02-05 2004-07-07 Materia Inc Compositions de polyolefine a densite variable et procedes de production et d'utilisation associes
WO2002088220A1 (fr) * 2001-04-30 2002-11-07 Essilor International Compagnie Generale D'optique Photopolymerisation d'episulfures au moyen de complexes metalliques, et realisation de lentilles ophthalmiques par ce procede
US6592801B2 (en) 2001-04-30 2003-07-15 Essilor International Compagnie Generale D'optique Photopolymerization of episulfides using metal complexes and its use for making ophthalmic lenses
US8178604B2 (en) 2006-02-02 2012-05-15 3M Innovative Properties Company Solid materials obtainable by ring-opening metathesis polymerization
EP1849806A1 (fr) * 2006-04-20 2007-10-31 Shin-Etsu Chemical Company, Ltd. Polymère fortement perméable à l'oxygène
US7741423B2 (en) 2006-04-20 2010-06-22 Shin-Etsu Chemical Co, Ltd. Highly oxygen permeable polymer
US8431625B2 (en) 2006-12-20 2013-04-30 3M Innovative Properties Company Compositions curable by ring opening metathesis polymerization at low temperatures and their application in the dental field
US8415496B2 (en) 2009-06-16 2013-04-09 Amyris, Inc. Biobased polyesters
US8367859B2 (en) 2009-06-16 2013-02-05 Amyris, Inc. Cyclohexane 1,4 carboxylates
US8367858B2 (en) 2009-06-16 2013-02-05 Amyris, Inc. Terephthalic and trimellitic based acids and carboxylate derivatives thereof
US8426639B2 (en) 2009-06-16 2013-04-23 Amyris, Inc. Preparation of trans, trans muconic acid and trans, trans muconates
US8809583B2 (en) 2010-01-08 2014-08-19 Amyris, Inc. Methods for producing isomers of muconic acid and muconate salts
WO2012110648A1 (fr) 2011-02-17 2012-08-23 Ccp Composites Us Polyester insaturé dépourvu de styrène
US8906999B2 (en) 2011-02-17 2014-12-09 Ccp Composites Us Llc Styrene-free unsaturated polyester

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