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WO1996016102A1 - Procede de polymerisation thermique d'olefines cycliques - Google Patents

Procede de polymerisation thermique d'olefines cycliques Download PDF

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Publication number
WO1996016102A1
WO1996016102A1 PCT/EP1995/004358 EP9504358W WO9616102A1 WO 1996016102 A1 WO1996016102 A1 WO 1996016102A1 EP 9504358 W EP9504358 W EP 9504358W WO 9616102 A1 WO9616102 A1 WO 9616102A1
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Prior art keywords
alkyl
unsubstituted
substituted
alkoxy
phenyl
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PCT/EP1995/004358
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German (de)
English (en)
Inventor
Paul Adriaan Van Der Schaaf
Andreas Hafner
Andreas MÜHLEBACH
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Ciba Specialty Chemicals Holding Inc.
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Priority to AU39274/95A priority Critical patent/AU3927495A/en
Publication of WO1996016102A1 publication Critical patent/WO1996016102A1/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 process for the polymerization of cyclic olefins by thermal ring opening metathesis polymerization using catalytic amounts of a molybdenum or tungsten catalyst which contains at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent containing no hydrogen atom in the ⁇ -position , and support with a layer containing these olefins together with a catalytic amount of this catalyst.
  • reaction injection molding processes Another disadvantage is the strong heating of the reaction mixture by the heat of reaction, which places very high technical demands on a controlled reaction temperature. Adherence to a polymer specification is difficult and the mold release is insufficient, so that mold release agents usually have to be used or poor surface properties have to be accepted.
  • Tanielan et al. [Tanielan, C, Kieffer, R., Harfouch, A., Tetrahedron Letters 52: 4589-4592 (1977)] describe the W (CO) 6 / CCl 4 catalyst system, which after irradiation with UV light for the metathesis polymerization of Cyclopentene and norbornene can be used. Metal carbonyls are volatile and toxic, so that their use makes complex protective measures necessary for physiological reasons. In addition, a radical addition reaction is observed as a competitive reaction with the formation of monomeric 1-chloro-2-trichloromethyl-cycloalkanes.
  • This catalyst system has the serious disadvantage that it has only a low storage stability as a ready-to-use formulation, the carbonyl compound is physiologically questionable and that Tolerance to functional groups in cycloolefins is too low.
  • WO 93/13171 describes air- and water-stable one-component and two-component catalysts based on molybdenum and wolfiram compounds containing carbonyl groups as well as ruthenium and osmium compounds with at least one polyene ligand for thermal metathesis polymerization and a photoactivated metathesis polymerization of strained cycloolefins, especially norbornene and norborne derivatives. Other polycyclic - especially uncondensed polycyclic cycloolefins are not mentioned.
  • the one-component catalysts used for the ruthenium compounds namely [(C 6 H 6 ) Ru (CH 3 CN) 2 Cl] + PF 6 - and
  • Petasis and Fu describe the thermal ring-opening metathesis polymerization of norbornene using biscyclopentadienyl-bis (trimethylsilyl) methyl-titanium (IV) as a thermally active catalyst.
  • compositions of strained cycloolefins and a one-component catalyst can be thermally polymerized if the composition contains a molybdenum (VI) or Wolf ⁇ am (VI) compound in which at least two optionally substituted alkyl groups are bonded to the metal, the substituent not having a hydrogen atom contains in the ⁇ -position.
  • these thermally stable compounds have proven to be effective catalysts for thermal ring opening metathesis polymerization, and despite the catalytic activity at room temperature, the storage stability of mixtures of cycloolefins and the catalysts is retained for up to about one month.
  • the compositions can be readily made at room temperature and then at elevated temperature after practically all Shaping processes are processed.
  • compositions are further distinguished by long pot lives, a controlled course of the reaction (avoidance of overheating of the reaction mixture), and very good mold release properties and surface properties.
  • the compositions are easy to prepare (simple mixing, advantageously with exclusion of moisture). There is also no need to use solvents.
  • the catalysts which are thermally stable per se, are very reactive catalysts after being mixed with strained cycloolefins when heated, which is to be regarded as surprising. The reactivity is so high that surprisingly a large number of optionally substituted monomers can be polymerized alone or as a mixture with at least two cycloolefins.
  • the polymers are also characterized by low or no odor, which indicates that complete polymerization is achieved and the polymers contain at most small amounts of starting monomers.
  • the present invention relates to a process for the thermal polymerization of a cyclic olefin or at least two different cyclic olefins in the presence of a metal compound as a catalyst, which is characterized in that a ring-opening metathesis polymerization is carried out at a temperature of more than 50 ° C.
  • a catalytic amount of at least one molybdenum (VI) or tungsten (VI) compound which contains at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent containing no hydrogen atom in the ⁇ -position.
  • the other valences of molybdenum and tungsten are preferably saturated with neutral ligands, which are known in large numbers.
  • the number of neutral ligands can also exceed the stoichiometrically possible number (solvates).
  • the molybdenum (VI) and tungsten (VI) compounds have a very high activity.
  • the cyclic olefins can be monocyclic or polycyclic fused or bridged ring systems, for example with two to four rings, which are unsubstituted or substituted and heteroatoms such as O, S, N or Si in one or more rings and / or may contain condensed aromatic or heteroaromatic rings such as o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene.
  • the individual cyclic rings can contain 3 to 16, preferably 3 to 12 and particularly preferably 3 to 8 ring members.
  • the cyclic olefins can contain further non-aromatic double bonds, depending on the ring size preferably 2 to 4 such additional double bonds.
  • the ring substituents are those which are inert, that is to say which do not impair the chemical stability of the molybdenum (VI) and tungsten (VI) compounds.
  • the cycloolefins are strained rings or ring systems.
  • crosslinked polymers can also form, depending on the reaction conditions, the monomer chosen and the amount of catalyst.
  • the cycloolefins correspond to formula I.
  • Q 1 is a radical with at least one carbon atom, which together with the
  • R j , R 2 and R 3 independently of one another are C 1 -C 12 alkyl, C 1 -C 12 perfluoroalkyl, phenyl or
  • R 4 and R 13 are independently C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 1 -C 20 hydroxyalkyl,
  • R 5 and R 10 independently of one another are hydrogen, C 1 -C 12 alkyl, phenyl or benzyl, the alkyl groups in turn being unsubstituted or substituted by C 1 -C 12 alkoxy or C 3 -C 8 cycloalkyl;
  • R 6 , R 7 and R 8 independently of one another are C 1 -C 12 alkyl, C 1 -C 12 perfluoroalkyl, phenyl or
  • M stands for an alkali metal and M 1 for an alkaline earth metal
  • u represents 0 or 1
  • Q 2 is hydrogen, C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 1 -C 12 alkoxy, halogen, -CN,
  • R 11 represents -X 2 -
  • R 11 is C 1 -C 20 alkyl, C 1 -C 20 haloalkyl, C 1 -C 10 hydroxyalkyl, C 3 -C 8 cycloalkyl,
  • X 2 is -C (O) -O- or -C (O) -NR 12 -;
  • R 12 represents hydrogen, C 1 -C 12 alkyl, phenyl or benzyl
  • R 9 represents hydrogen, C 1 -C 12 alkyl, phenyl or benzyl.
  • Fused-on alicyclic rings preferably contain 3 to 8, particularly preferably 4 to 7 and particularly preferably 5 or 6 ring C atoms.
  • alkyl, alkenyl and alkynyl groups can be straight-chain or branched. The same also applies to the or each alkyl part of alkoxy, alkylthio, alkoxycarbonyl and other alkyl-containing groups. These alkyl groups preferably contain 1 to 12, more preferably 1 to 8 and particularly preferably 1 to 4 carbon atoms. These alkenyl and alkynyl groups preferably contain 2 to 12, more preferably 2 to 8 and particularly preferably 2 to 4 carbon atoms.
  • Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals.
  • Hydroxyalkyl includes, for example, hydroxymethyl, hydroxyethyl, 1-hydroxyisopropyl, 1-hydroxy-n-propyl, 2-hydroxy-n-butyl, 1-hydroxy-iso-butyl, 1-hydroxy-sec-butyl, 1-hydroxy-tert-butyl as well as the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals.
  • Haloalkyl includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-trichloroethyl as well as halogenated, especially fluorinated or chlorinated alkanes, such as for example the isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl , Undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
  • alkenyl includes 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, n-octadec-4-enyl.
  • Cycloalkyl is preferably C 5 -C 8 cycloalkyl, especially C 5 or C 6 cycloalkyl. Some examples are cyclopropyl, dimethylcyclopropyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Cyanoalkyl includes, for example, cyanomethyl (methyl nitrile), cyanoethyl (ethyl nitrile), 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 hexyl radicals.
  • Aralkyl preferably contains 7 to 12 carbon atoms and particularly preferably 7 to 10 carbon atoms.
  • it can be benzyl, phenethyl, 3-phenylpropyl, ⁇ -methylbenzyl, phenbutyl or ⁇ , ⁇ -dimethylbenzyl.
  • Aryl preferably contains 6 to 10 carbon atoms. It can be, for example, phenyl, pentaline, indene, naphthalene, azuline or anthracene.
  • Heteroaryl preferably contains 4 or 5 carbon atoms and one or two heteroatoms from the groups O, S and N. It can be, for example, pyrrole, furan, thiophene, oxazole, thiazole, pyridine, pyrazine, pyrimidine, pyridazine, indole, purine or Trade quinoline.
  • Heterocycloalkyl preferably contains 4 or 5 carbon atoms and one or two heteroatoms from the group O, S and N. It can be, for example, oxirane, azirine, 1,2-oxathiolane, pyrazoline, pyrrolidine, piperidine, piperazine, morpholine, tetrahydrofuran or Act tetrahydrothiophene.
  • Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, i-butyloxy, sec-butyloxy and t-butyloxy.
  • Alkali metal in the context of the present invention is to be understood as lithium, sodium, potassium, rubidium and cesium, in particular lithium, sodium and potassium.
  • alkaline earth metal is to be understood as meaning beryllium, magnesium, calcium, strontium and barium, in particular magnesium and calcium.
  • halogen, fluorine, chlorine, bromine and iodine is preferably to be understood as fluorine, chlorine and bromine.
  • Compounds of the formula I which are particularly suitable for the process according to the invention are those in which Q 2 is hydrogen.
  • Q 1 is a radical with at least one carbon atom, which together with the
  • X and Xj independently of one another for -O-, -S-, -CO-, -SO-, -SO 2 -, -OC (O) -, -C (O) -O-, -C (O) -NR 5 -, -NR 10 -C (O) -, -SO 2 -O- or -O-SO 2 -;
  • R 1 , R 2 and R 3 independently of one another are C 1 -C 6 alkyl, C 1 -C 6 perfluoroalkyl, phenyl or benzyl;
  • M stands for an alkali metal and M 1 for an alkaline earth metal
  • R 4 and R 13 independently of one another are C 1 -C 12 alkyl, C 1 -C 12 haloalkyl,
  • R 5 and R 10 independently of one another hydrogen, C 1 -C 6 alkyl, phenyl or benzyl
  • alkyl groups in turn unsubstituted or substituted by C 1 -C 6 alkoxy or C 3 -C 6 cycloalkyl;
  • R 6 , R 7 and R 8 independently of one another are C 1 -C 6 alkyl, C 1 -C 6 perfluoroalkyl, phenyl or Represent benzyl;
  • u represents 0 or 1
  • Q 2 is hydrogen, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 6 alkoxy, halogen, -CN, R 11 -X 2 -;
  • R 11 is C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 hydroxyalkyl, C 3 -C 6 cycloalkyl,
  • X 2 is -C (O) -O- or -C (O) -NR 12 -;
  • R 12 represents hydrogen, C 1 -C 6 alkyl, phenyl or benzyl
  • R 9 is hydrogen, C 1 -C 6 alkyl, phenyl or benzyl.
  • Q 1 is a radical with at least one carbon atom, which together with the
  • -CH CQ 2 group forms a 3- to 10-membered alicyclic ring which optionally contains a heteroatom selected from the group consisting of silicon, oxygen, nitrogen and sulfur, and which is unsubstituted or with halogen, -CN, -NO 2 , R 1 R 2 R 3 Si-, -COOM, -SO 3 M, -PO 3 M, -COO (M 1 ) 1/2 , -SO 3 (M 1 ) 1/2 , -PO 3 (M 1 ) 1 / 2 , C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl, C 1 -C 4 cyanoalkyl,
  • C 3 -C 6 cycloalkyl, phenyl, benzyl or R 4 -X- is substituted; or in which an alicyclic, aromatic or heteroaromatic ring which is unsubstituted or by is optionally fused onto adjacent carbon atoms
  • R 1 , R 2 and R 3 independently of one another are C 1 -C 4 alkyl, C 1 -C 4 perfluoroalkyl, phenyl or benzyl;
  • M stands for an alkali metal and M 1 for an alkaline earth metal
  • R 4 and R 13 independently of one another are C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 hydroxyalkyl or C 3 -C 6 cycloalkyl;
  • X and X 1 independently of one another are -O-, -S-, -CO-, -SO- or -SO 2 -;
  • R 6 , R 7 and R 8 independently of one another are C 1 -C 4 alkyl, C 1 -C 4 perfluoroalkyl, phenyl or
  • the process according to the invention is particularly suitable for the polymerization of norbornene and norbornene derivatives.
  • norbornene derivatives those are particularly preferred which either have the formula II
  • R 14 and R 15 independently of one another are hydrogen, -CN, trifluoromethyl, (CH 3 ) 3 Si-O-,
  • R 16 and R 17 are independently hydrogen, C 1 -C 12 alkyl, phenyl or benzyl;
  • R 19 is hydrogen, C 1 -C 12 alkyl, phenyl or benzyl
  • R 18 is hydrogen, C 1 -C 6 alkyl or halogen
  • R 22 hydrogen, C 1 -C 12 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, C 1 -C 12 alkyl, phenyl or benzyl
  • R 24 is hydrogen, C 1 -C 12 alkyl, phenyl or benzyl
  • Y is oxygen or
  • R 25 is hydrogen, methyl, ethyl or phenyl.
  • the molybdenum (VI) and tungsten (VI) compounds to be used according to the invention can be those which contain one metal atom or two metal atoms connected via a single, double or triple bond.
  • the methyl group or monosubstituted methyl group bonded to the metal is bonded as a ligand at least twice, particularly preferably two to five times and particularly preferably two or three times.
  • the group attached to the metal atom preferably corresponds to formula VII,
  • R 26 , R 27 and R 28 independently of one another are C 1 -C 10 alkyl which is unsubstituted or substituted by C 1 -C 10 alkoxy, or R 26 and R 27 have this meaning and R 28 is C 6 -C 10 Aryl or C 4 -C 9 heteroaryl which is unsubstituted or substituted by C 1 -C 6 alkyl or C 1 -C 6 alkoxy; and R 29 , R 30 and R 31 independently of one another are C 1 -C 18 alkyl, C 5 or C 6 cycloalkyl, or phenyl or benzyl which is unsubstituted or substituted by C 1 -C 6 alkyl or C 1 -C 6 alkoxy mean.
  • R 26 to R 31 are alkyl, this can be linear or branched and preferably contain 1 to 8 and particularly preferably 1 to 4 carbon atoms. If R 1 to R 31 are aliyl, it is preferably phenyl or naphthyl.
  • R in formula VII is aryl, it is preferably phenyl or naphthyl. If R in formula VII is heteroaryl, it is preferably pyridinyl, furanyl, thiophenyl or pyrrolyl.
  • R 26 to R 31 are methyl, ethyl, methoxy and ethoxy in the context of the definitions. Examples of the radicals R 26 to R 31 have previously been given among the compounds of the formula I.
  • the group R in formula VII denotes H, -C (CH 3 ) 3 , -C (CH 3 ) 2 C 6 H 5 , phenyl which is unsubstituted or substituted by methyl, ethyl, methoxy or ethoxy, -CF 3 or -Si (CH 3 ) 3 .
  • Secondary amines are preferably those of the formula R 34 R 35 N-, in which R 34 and R 35 independently of one another are linear or branched C 1 -C 18 -alkyl, C 5 - or C 6 -cycloalkyl, unsubstituted or with C 1 -C 6 -Alkoxy or halogen substituted benzyl or phenylethyl or (C 1 -C 6 alkyl) 3 Si; or together mean tetramethylene, pentamethylene or 3-oxapentane-1,5-diyl.
  • the alkyl preferably contains 1 to 12 and particularly preferably 1 to 6 carbon atoms.
  • Some examples are dimethyl, diethyl, di-n-propyl, di-i-propyl, di-n-butyl, methyl-ethyl, dibenzyl, benzyl-methyl, diphenyl, phenyl-methylamino and Di (trimethylsilyl) amino.
  • Halogen as a further ligand on the metal atoms or as a substituent is preferably fluorine or chlorine and particularly preferably chlorine.
  • the cyclopentadienyl can be unsubstituted or substituted with one to five C 1 -C 4 alkyl, especially methyl or -Si (C 1 -C 4 alkyl), especially -Si (CH 3 ) 3 .
  • Bridged cyclopentadienyls are especially those of the formula R 36 -AR 36 , in which R 36 is unsubstituted or with one to five C 1 -C 4 -alkyl, especially methyl, or -Si (C 1 -C 4 -alkyl)
  • -Si (CH 3 ) 3 represents substituted cyclopentadienyl and A represents -CH 2 -, -CH 2 -CH 2 -,
  • Ethers as neutral ligands can be dialkyl ethers with 2 to 8 C atoms or cycü ether with 5 or 6 ring members. Some examples are diethyl ether, methyl ethyl ether, diethyl ether, di-n-propyl ether, di-i-propyl ether, di-n-butyl ether, ethylene glycol dimethyl ether, tetrahydrofuran and dioxane.
  • Nitriles as neutral ligands can be aliphatic or aromatic nitriles with 1 to 12, preferably 1 to 8, carbon atoms. Some examples are acetonitrile, propionitrile, butyl nitrile, benzonitrile and benzyl nitrile.
  • Tertiary amines and phosphines as neutral ligands can be those with 3 to 24, preferably 3 to 18, carbon atoms.
  • Some examples are trimethylamine and phosphine, triethylamine and phosphine, tri-n-propylamine and phosphine, tri-n-butylamine and phosphine, triphenylamine and phosphine, tricyclohexylamine and phosphine, phenyldimethylamine and phosphine, benzyldimethylamine and phosphine , 3,5-dimethyl phenyldimethylamine and phosphine.
  • Halogen as a substituent for the radicals R 32 and R 33 is preferably fluorine and particularly preferably chlorine.
  • the substituents alkyl, alkoxy or alkoxy in the alkoxymethyl or -ethyl preferably contain 1 to 4 and in particular 1 or 2 carbon atoms. Examples are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, methoxy, ethoxy, n- and i-propyloxy and n-, i- and t-butyloxy.
  • R 32 and R 33 preferably contain 1 to 12, particularly preferably 1 to 8, and particularly preferably 1 to 4 C atoms. It is preferably branched alkyl.
  • Some examples of R 32 are methoxy, ethoxy, n- and i-propyloxy, n-, i- and t-butyloxy, hexafluoro-i-propyloxy and hexa- and perfluorobutyloxy.
  • substituted phenyl and benzyl for R 32 and R 33 are p-methylphenyl or benzyl, p-fluoro- or p-chlorophenyl or -benzyl, p-ethylphenyl or -benzyl, pn- or i-propylphenyl or -benzyl, pi -Butylphenyl or benzyl, 3-methylphenyl or benzyl, 3-i-propylphenyl or benzyl, 3,5-dimethylphenyl or benzyl, 3,5-i-propylphenyl or benzyl, 3,5-n- or -t-butylphenyl and -benzyl.
  • R 33 particularly preferably represents phenyl which is unsubstituted or substituted by C 1 -C 4 -alkyl or C 1 -C 4 -alkoxy.
  • Tungsten compounds especially one of the formulas VIII to VIIIc wonn
  • radicals R 39 to R 43 represent a radical -CH 2 -R of the formula VII, RH, -CF 3 , -CR 26 R 27 R 28 , -SiR 29 R 30 R 31 , unsubstituted or with
  • R 26 , R 27 and R 28 independently of one another are C 1 -C 10 alkyl which is unsubstituted or substituted by C 1 -C 10 alkoxy, or R 26 and R 27 have this meaning and R 28 is C 6 -C 10 Aryl or C 4 -C 9 heteroaryl which is unsubstituted or substituted by C 1 -C 6 alkyl or C 1 -C 6 alkoxy; and
  • R 29 , R 30 and R 31 independently of one another are C 1 -C 18 alkyl, C 5 - or C 6 cycloalkyl, or phenyl or benzyl which is unsubstituted or substituted by C 1 -C 6 alkyl or C 1 -C 6 alkoxy mean;
  • R 39 to R 43 are secondary amino with 2 to 18 C atoms, R 32 O or R 32 S, halogen, cyclopentadienyl or bridged biscyclopentadienyl or a neutral ligand, in which the R 32 independently of one another is unsubstituted or with C 1 -C 6 - Alkoxy or halogen substituted linear or branched C 1 -C 18 alkyl, unsubstituted or substituted by C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halogen substituted C 5 - or C 6 cycloalkyl, unsubstituted or with C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkoxymethyl, C 1 -C 6 alkoxyethyl, di (C 1 -C 6 alkyl) amino, di (C 1 -C 6 alkyl) amino C 1 -C 3 alkyl or halogen
  • R 39 to R 44 represent a radical of the formula VII -CH 2 -R, or
  • R 39 and R 40 represent a radical of the formula VII -CH 2 -R
  • R 43 and R 44 together independently represent R 32 -O- or halogen, or
  • R 39 and R 40 represent a radical of the formula VII -CH 2 -R
  • R, R 32 and R 33 have the meanings given above. The above preferences apply to R, R 32 and R 33 .
  • R 39 , R 40 and R 41 represent a radical of the formula VII are particularly preferred, the radical of the formula VII particularly preferably being -CH 2 -Si (C 1 -C 4 Alkyl) 3 .
  • Molybdenum or tungsten compounds of the formulas IX, IXa or IXb are very particularly preferably used in the process according to the invention
  • R 33 denotes phenyl or phenyl substituted with 1 to 3 C 1 -C 4 alkyl or C 1 -C 4 alkoxy,
  • R 41 unsubstituted or fluorine-substituted linear or particularly branched
  • R 42 has the same meaning as R 41 or represents F, Cl or Br.
  • R 41 particularly preferably represents branched alkoxy which is optionally partially or completely substituted by F, for example i-propyloxy, i- and t-butyloxy, hexafluoropropyloxy and
  • R 42 is preferably Cl.
  • a preferred subgroup in the case of the molybdenum and tungsten compounds are those in which at least one halogen from the group Cl, Br and I is bonded to the metal atom if two of the radicals of the formula VII represent the group -CH 2 -SiR 29 R 30 R 31 , the above preferences apply to R 29 , R 30 and R 31 .
  • molybdenum and tungsten compounds are:
  • the molybdenum and tungsten compounds to be used according to the invention are known or can be prepared by known and analogous processes from the corresponding optionally substituted metal halides by means of Grignard reactions [Schrock, RR, Murdzeck, JS, Bazan, GC, Robbins, J., DiMare, M., O'Regan, M., J. Am. Chem. Soc, 112: 3875-3886 (1990)].
  • the process according to the invention can be carried out in the presence of an inert solvent.
  • An inert solvent means that the choice of solvent depends on the reactivity of the molybdenum and tungsten compounds, for example that protically polar solvents are not used if substitution reactions such as the replacement of halogen by alkoxy are to be expected.
  • Suitable inert solvents are, for example, protic-polar and aprotic solvents, which can be used alone or in mixtures of at least two solvents.
  • examples are: ethers (dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl or dimethyl ether, ethylene glycol monoethyl or diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether), halogenated hydrocarbons (methylene chloride, chloroform, 1,2-dichloroethane, 1,1,1-trichloro , 1,2,2-tetrachloroethane), carboxylic acid esters and lactones (ethyl acetate, methyl propionate, ethyl benzoate, 2-methoxyethyl acetate, ⁇ -butyrolactone, ⁇ -valerolactone, pivalolactone), carboxamides and lactams (N, N
  • Preferred solvents are aliphatic and aromatic hydrocarbons and mixtures of such solvents.
  • compositions of an optionally substituted cycloolefin and catalyst used in the process according to the invention are often insensitive to oxygen, which means storage and reaction management without protective gas.
  • oxygen means storage and reaction management without protective gas.
  • exclusion of moisture is recommended, i.e. the use of dry reaction and storage conditions.
  • the monomers of the formula I and catalysts used for the process according to the invention can be stored either separately or together as a mixture, since the catalyst used has a particularly high stability.
  • the mixture Before the thermal polymerization, the mixture can be stored as a ready-to-use formulation, which is advantageous for the large-scale application of the process according to the invention. Because of the sensitivity to light, the storage is expedient, particularly in UV light, with exclusion of light.
  • composition according to the invention can additionally contain further non-volatile open-chain comonomers which form copolymers with the strained cycloolefins. If, for example, dienes are also used, crosslinked polymers can form.
  • Some examples of such comonomers are olefinically mono- or di-unsaturated compounds such as olefins and dienes from the group pentene, hexene, heptene, octene, decene, dodecylene, acrylic and methacrylic acid, their esters and amides, vinyl ethers, styrene, butadiene, isoprene and chlorobutadiene.
  • the other olefins capable of metathesis polymerization are, for example, in the composition according to the invention in an amount of up to 80% by weight, preferably 0.1 to 80% by weight, more preferably 0.5 to 60% by weight and particularly preferably 5 to 40% by weight .% Contain, based on the total amount of compounds of the formula I and other olefins capable of metathesis polymerization.
  • the polymerizable composition to be used according to the invention can contain formulation auxiliaries.
  • the compounds specified above as solvents are suitable as such.
  • auxiliaries are antistatic agents, antioxidants, light stabilizers, plasticizers, dyes, pigments, fillers, reinforcing fillers, lubricants, adhesion promoters, viscosity-increasing agents and mold release agents.
  • the fillers can be present in surprisingly high proportions without adversely affecting the polymerization, for example in amounts of up to 70% by weight, preferably 1 to 70% by weight, more preferably 5 to 60% by weight, particularly preferably 10 up to 50 wt .-% and particularly preferably 10 to 40 wt .-%, based on the composition.
  • Some case Games are glass and quartz in the form of powders, spheres and fibers, metal 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, feldspar, tonides such as Chinaclay, rock flour, whiskers, carbon fibers, plastic fibers or powder and soot.
  • Viscosity-increasing agents are, in particular, metathesis polymers which have olefinically unsaturated groups and can be incorporated into the polymer during the polymerization. Such metathesis polymers are known and can be purchased, for example, under the trade name Vestenamere®. Other viscosity-increasing agents are polybutadiene, polyisoprene or polychlorobutadiene, and copolymers of butadiene, isoprene and chloroprene with olefins. The viscosity-increasing agents can be present in an amount of 0.1 to 50, preferably 1 to 30, and particularly preferably 1 to 20% by weight, based on the composition.
  • catalytic amounts preferably mean an amount of 0.001 to 20 mol%, particularly preferably 0.01 to 15 mol% and very particularly preferably 0.01 to 10 mol%, based on the amount of the monomer.
  • the method according to the invention is preferably carried out at a temperature of at least 60 ° C. and more preferably at least 70 ° C.
  • the method according to the invention is carried out at temperatures from 60 ° C. to 300 ° C., preferably 60 ° C. to 250 ° C., particularly preferably 60 ° C. to 200 ° C and particularly preferably 70 ° C to 160 ° C.
  • After the polymerization it may be advantageous to post-heat the polymers at elevated temperatures, for example from 80 ° C. to 200 ° C.
  • cycloolefins to be used according to the invention are tensioned rings.
  • cyclohexene cannot generally be homopolymerized using olefin metathesis.
  • This exception is known to the person skilled in the art and is described, for example, in Ivin [Ivin, K.J. in: Ivin, K.J., Saegusa, T. (ed.), Ring-Opening Polymerization 1: 139-144 Elsevier Applied Science Publishers, London and New York (1984)].
  • the polymers produced by the process according to the invention can be homopolymers or copolymers with a statistical distribution of the structural units, graft polymers or block polymers, and also crosslinked polymers of this type. They can have an average molecular weight (Mw) of, for. B. 500 to 2 million daltons, preferably 1000 to 1 million daltons (determined by GPC by comparison with narrowly distributed polystyrene standards).
  • Mw average molecular weight
  • the process according to the invention can be used to produce thermoplastically deformable materials for the production of moldings of all types and coatings. Shaping and polymerization are advantageously combined in solvent-free reactive systems, it being possible to use processing methods such as, for example, injection molding, extrusion, polymerizations in predetermined forms (if appropriate under pressure).
  • the polymers produced according to the invention can have very different properties. Some are characterized by very high oxygen permeability, low dielectric constants, good heat stability and low water absorption. Others have excellent optical properties such as high transparency and low refractive indices. The low shrinkage is particularly noteworthy. Therefore, they can come in very different technical
  • the polymers produced according to the invention are distinguished as layers on the surfaces of support materials by a high adhesive strength.
  • the coated materials are also characterized by a very high surface smoothness and gloss.
  • the good mechanical properties the low shrinkage and high impact strength are particularly noteworthy, but also the thermal resistance.
  • the ease of demolding and the high resistance to solvents should also be mentioned.
  • polymers are suitable for the production of medical devices, implants or contact lenses; for the production of electronic components; as a binder for paints; as curable compositions for model making or as adhesives for bonding substrates with low surface energies (e.g. Teflon, polyethylene and polypropylene), and as a polymerizable composition in stereolithography.
  • the polymers produced according to the invention can also be used for the production of lacquers, it being possible on the one hand to use clear (transparent) and even pigmented compositions. Both white and colored pigments can be used.
  • the production of moldings by thermoplastic molding processes for everyday articles of all kinds should be mentioned.
  • the polymerizable compositions to be used according to the invention are suitable also for the production of protective layers.
  • Another object of the invention is a variant of the method according to the invention for the production of coated materials on substrates, in which a composition of cyclic olefin, catalyst and optionally solvent is applied as a layer on a support, for example by dipping, brushing, pouring. , Rolling, knife or centrifugal casting, optionally removing the solvent, and heating the layer for polymerization. With this method, surfaces of substrates can be modified.
  • Another object of the present invention is a carrier material which is coated with an oligomer or polymer according to the invention and which contains a crosslinking agent.
  • Another object of the present invention is a carrier material which is coated with an oligomer or polymer according to the invention. These materials are suitable for the production of protective layers or relief images.
  • Suitable crosslinking agents e.g. can be contained in an amount of 0.01 to 20% by weight, especially organic bisazides, especially the commercially available 2,6-bis (4-azidobenzylidene) -4-methyl-cyclohexanone.
  • the present invention furthermore relates to a coated carrier material, which is characterized in that on a carrier a layer composed of (a) a cyclic olefin or at least two different cyclic olefins and (b) a catalytically effective amount of at least one molybdenum (VI) or tungsten (VI) compound which contains at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent containing no hydrogen atom in the ⁇ position, is applied.
  • a layer composed of (a) a cyclic olefin or at least two different cyclic olefins and (b) a catalytically effective amount of at least one molybdenum (VI) or tungsten (VI) compound which contains at least two methyl groups or two monosubstituted methyl groups bonded to the metal, the substituent containing no hydrogen atom in the ⁇ position, is applied.
  • Suitable carrier materials are, for example, those made of glass, minerals, ceramics, plastics, wood, semimetals, metals, metal oxides and metal nitrides.
  • the layer thicknesses depend essentially on the desired use and can e.g. 0.1 to 1000 ⁇ m, preferably 0.5 to 500 ⁇ m, particularly preferably 1 to 100 ⁇ m.
  • the coated materials are characterized by high adhesive strength and good thermal and mechanical properties.
  • coated materials according to the invention can be produced by known methods such as brushing, knife coating, casting processes such as curtain casting or centrifugal casting.
  • coatings particularly good results are often achieved if cycloolefins are used for the thermal ring opening metathesis polymerization which additionally contain 1 to three and preferably a further double bond and which, in the context of the invention, are polycyclic condensed ring systems or those linked directly or via bridge groups.
  • Examples 1 to 6 Polymerization of biscyclopentadiene.
  • the monomer / catalyst mixtures are stable at room temperature (20 ° C.) for at least 3 days, observed on a practically undetectable increase in viscosity.
  • the gelation times are measured with a viscometer and are defined as follows: the beginning of the increase means time for a relative viscosity increase of 10%; End of gelation means time for a relative viscosity increase of 90% of the maximum value.
  • Compound (20) is used as the monomer.

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)

Abstract

L'invention concerne un procédé de polymérisation thermique d'une oléfine cyclique ou d'au moins deux oléfines cycliques différentes en présence d'un composé métal servant de catalyseur. Ce procédé se caractérise en ce qu'on effectue une polymérisation par métathèse avec ouverture du cycle en présence d'un volume catalytique d'au moins un composé molybdène(VI) ou tungstène (VI), qui contient au moins deux groupes méthyle ou deux groupes méthyle monosubstitués, liés au métal, le substituant ne contenant pas d'atome d'hydrogène en position α. Ce procédé s'utilise par exemple pour produire des matières moulées, des revêtements et des corps moulés thermoplastiques.
PCT/EP1995/004358 1994-11-17 1995-11-06 Procede de polymerisation thermique d'olefines cycliques WO1996016102A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU39274/95A AU3927495A (en) 1994-11-17 1995-11-06 Process for the thermal polymerization of cyclical olefins

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CH3462/94 1994-11-17
CH346294 1994-11-17

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WO1996016102A1 true WO1996016102A1 (fr) 1996-05-30

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WO (1) WO1996016102A1 (fr)

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
P.A.VAN DER SCHAAF ET ALL.: "New Ring-opening Methathesis Polymerization Catalyst based on a Five-coordinate Tungsten(VI)Alkylidene Complex Containing an ortho-Chelating Arylamine Ligand;X-ray Structure of [W{C6H4(CH2NMe2)-2}(=NPh)(=CHSiMe3)(CH2SiMe3)]", JOURNAL OF THE CHEMICAL SOCIETY, CHEMICAL COMMUNICATIONS, 1992, LETCHWORTH GB, pages 717 - 719, XP002000035 *
P.A.VAN DER SCHAAF ET ALL.: "Tungsten(VI)Phenylimido Alkylidene Complexes Containing a Monoanionic O,N-Chelating Ligand and Their Isolated Precursor Complexes:X-ray Structures of W(CHSiMe3)3(=NPh)[OCPh2(2-py)] and W(=CHSiMe3)(CH2SiMe3)(=NPh)[OCPh2(2-py)]", ORGANOMETALLICS, vol. 13, no. 12, April 1994 (1994-04-01), US, XP000564434 *

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