WO2018091664A1 - Catalyseurs latents de polymérisation à action de réticulation de dicyclopentadiène (dcpd) - Google Patents

Catalyseurs latents de polymérisation à action de réticulation de dicyclopentadiène (dcpd) Download PDF

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WO2018091664A1
WO2018091664A1 PCT/EP2017/079625 EP2017079625W WO2018091664A1 WO 2018091664 A1 WO2018091664 A1 WO 2018091664A1 EP 2017079625 W EP2017079625 W EP 2017079625W WO 2018091664 A1 WO2018091664 A1 WO 2018091664A1
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partially
branched
linear
group
ylidenes
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Michael R. Buchmeiser
Julia Beerhues
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Universitaet Stuttgart
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2265—Carbenes or carbynes, i.e.(image)
    • B01J31/2278—Complexes comprising two carbene ligands differing from each other, e.g. Grubbs second generation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/50—Redistribution or isomerisation reactions of C-C, C=C or C-C triple bonds
    • B01J2231/54—Metathesis reactions, e.g. olefin metathesis
    • B01J2231/543—Metathesis reactions, e.g. olefin metathesis alkene metathesis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/64—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/66—Tungsten

Definitions

  • the present invention relates to latent catalysts based on molybdenum or tungsten complexes for the crosslinking polymerization of dicyclopentadiene (DCPD). Further aspects of the present invention relate to the use of these catalysts for the preparation of polymers such as polydicyclopentadienes and to processes for preparing corresponding polymers
  • DCPD dicyclopentadiene
  • Poly-DCPD is a polymeric active ingredient characterized by good chemical resistance, a high glass transition temperature of more than 130 ° C and a high corrosion resistance.
  • a further advantage of poly-DCPD is that this material can be painted or coated by oxidation of the surface after polymerization, without first having to apply a primer to the material or otherwise chemically pretreat the material.
  • a major advantage of poly-DCPD over conventional thermosets, such as polyesters and polyepoxides, is that the latter are relatively brittle, so additives are added, such as rubber or thermoplastic particles, to improve the toughness of these materials have to.
  • poly-DCPD has very good impact strengths and toughness even without additional additives, especially a favorable one
  • Poly-DCPD make a very high-performance thermosets. More recently, poly-DCPD has been used to manufacture large workpieces, such as body parts for tractors and trucks, or to coat industrial electrolysis cells.
  • ring-opening metathesis polymerization converted to poly-DCPD, for example, by the reaction injection molding (reaction injection molding).
  • reaction injection molding a reaction mixture of two components, of which the essential portion consists of endo-DCPD, mixed in an antechamber and then quickly transferred to the mold to completely cure there under heating.
  • a problem with the currently used methods is an unfavorably high reactivity of the catalyst which, in combination with the high reactivity of the DCPD monomer, renders the polymerization difficult to control.
  • a very narrow time window must be observed during the polymerization, so that it is not always possible to produce a uniform mixture and to distribute it evenly, in particular in the case of thin shaped bodies, in the mold.
  • a catalyst system currently used for the manufacture of a plastic called Proxima® (based on DCPD) is based on a conventional Grubbs catalyst. For this product, however, the exact composition of the component used for the plastic is not known.
  • Ethylaluminiumdichlorid with propanol and tetrachlorosilane as part of DCPD-containing component 2 of the catalyst system used.
  • tungsten (IV) chloride and tungsten (IV) oxytetrachloride with nonylphenol are part of component 1, while ethylaluminum chloride is used as cocatalyst of the second component.
  • ruthenium-based catalysts have been proposed for the preparation of poly-DCPD, which can be selectively activated.
  • MR Buchmeiser et al. Choemistry - A European Journal, 2010, 16, 12928-12934 proposed a catalyst which is only active by activation with UV light in the metathesis of DCPD.
  • the light activation allows a targeted initiation of the polymerization, but it is particularly suitable for the modification and functionalization of surfaces, since here an activation with light is easily possible if thin coating to be produced.
  • light-activated catalysts are less suitable.
  • Verpoort et al. describe in J. of Polym. Be. Part A: Polymer Chemistry, 2010, 48, p. 302-310 ruthenium catalysts of the formula shown below, which are inactive to DCPD at room temperature but can be activated by the addition of HCl as cocatalyst.
  • a strategy for preparing a thermal latent catalyst in the literature has been to introduce a chelating alkylidene ligand into Grubbs first and second generation catalysts, the chelating catalyst being a Catalyst
  • Metal center loses the inhibitory effect after the first metathesis cycle, which allows a delay of the initiation rate at room temperature.
  • DCPD proposes a simple process management based on a one-component system containing all components, ie catalyst and Monomer (eg DCPD) is allowed.
  • ie catalyst and Monomer eg DCPD
  • One-component system should also have a sufficient shelf life ("pot life") within which there is no appreciable polymerization and thus no change in viscosity. Nevertheless, when activated, the catalyst should have a sufficiently high activity to allow a cured polymer to be obtained in a short time.
  • a first aspect of the present invention relates to a catalyst according to the general formula I or II
  • a 1 is NR 2
  • a 2 is CR 2 R 2 ' or NR 2
  • a 3 is N
  • the ring B is an unsubstituted or a mono- or polysubstituted 5- to 7-membered ring, in addition to A 1 , A 2 and A 3 at least one other
  • X 1 or X 2 in formulas I to II are identical or different and from the group comprising Ci-Cie carboxylates, Ci-Cis alkoxides, fluorinated Ci-Cie alkoxides, Ci-Cie mono- or polyhalogenated carboxylates, a - or poly-substituted Ce-cis mono-, bi- or terphenolates, trifluoromethanesulfonate, trifluoroacetate, non-coordinating anions, in particular tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, tetrakis (pentafluorophenyl) borate,
  • Z is a linear, partially cyclic or branched C 1 -C 10 -alkyleneoxy, a linear, partially cyclic or branched C 1 -C 10 -alkylenethio, a linear, partially cyclic or branched C 1 -C 10 -alkylene NR 2 -, a C 3 -C 10 -aryleneoxy- , a per- or
  • the invention relates to the use of these catalysts for the preparation of polymers by ring-opening metathesis polymerization (ROMP), a
  • Embodiments of the application theory of the invention and the claims 13 to 15 represent preferred embodiments of the method of the invention.
  • the above catalysts are "latent" in terms of ring-opening metathesis polymerization, i. that they do not initiate metathesis polymerization at ambient temperature (25 ° C) without external stimulation.
  • Stimulation of the catalysts is generally carried out by heating the catalyst in admixture with the monomer / monomer to be polymerized.
  • Particularly suitable are methyl, ethyl and propyl groups.
  • the linear, partially cyclic or branched C 2 -Cis-alkenyl group is
  • C 2 -Cio-alkenyl group suitably in the form of a C 2 -Cio-alkenyl group, in particular in the form of a C 2 -C 7 -alkenyl group and preferably in the form of butenyl or hexenyl before.
  • C3-Ci 2 cycloalkyl group it is preferred if this in the form of a C3-C 6 - cycloalkyl group present.
  • Suitable groups in this context are cyclopentyl and cyclohexyl.
  • R 2 or R 2 ' is a linear, partially cyclic or branched Ce-Cioo-polyoxaalkyl radical, it is advantageous if it is in the form of a Ce-Cao-Polyoxaalkyl-rest and in particular in the form of a Ce -Cis-polyoxaalkyl residue is present.
  • Suitable radicals are, for example, methyloxyethyl or methyloxyethyloxy.
  • the substituted or unsubstituted C 1 -C 12 -aryl or -Heteroarylrest is preferably in the form of a Ce-Ci-aryl or -Heteroarylrests, in particular a Ce-Cio-aryl or -Heteroaryl residue before.
  • phenyl, naphthyl or ferrocenyl have been found to be particularly suitable.
  • C 5 -C 4 -aryloxy radicals C 6 -C 4 -aryloxy radicals and in particular Ce-Cio-aryloxy radicals are preferred.
  • Particularly suitable unsubstituted aryloxy radicals are phenyloxy or naphthyloxy.
  • the linear, partially cyclic or branched Ci-Cis-perfluorinated alkyl radical is in particular in the form of a Ci-Cio-perfluorinated alkyl radical, preferably in the form of a C1-C7 perfluorinated alkyl radical, and particularly preferably in the form of a Ci-C Perfluoroalkyl radical, with trifluoromethyl as the remainder being most preferred.
  • the linear, partially cyclic or branched Ci-Cis-perchlorinated alkyl radical in particular in the form of a Ci-Cio-perchlorinated alkyl radical, preferably in the form of a Ci-C7-perchlorinated alkyl radical and particularly preferably in the form of a Ci C -perchloroalkyl radical, with trichloromethyl being the most preferred radical.
  • the linear, partially cyclic or branched partially fluorinated C 1 -C 6 -alkyl radical is preferably present as a partially fluorinated C 1 -C 10 -alkyl radical, and in particular as a partially fluorinated C 1 -C 7 -alkyl radical.
  • An example of such a radical is trifluoroethyl.
  • the linear, partially cyclic or branched partially chlorinated C 1 -C 6 -alkyl radical is preferably present as a partially chlorinated C 1 -C 10 -alkyl radical and in particular as a partially chlorinated C 1 -C 7 -alkyl radical.
  • An example of such a radical is trichloroethyl.
  • the perfluorinated C5-C14-aryl radical is present in particular as a perfluorinated Ce-Ci4-aryl radical, preferably as a perfluorinated Ce-Cio-aryl radical and particularly preferably in the form of a pentafluorophenyl radical.
  • the partially fluorinated C 5 -C 14 aryl radical is present in particular as a partially fluorinated Ce-C 1-4 aryl radical, preferably as a partially fluorinated Ce-Cio-aryl radical and more preferably in the form of fluorophenyl.
  • the perchlorinated Cs-Ci4-aryl radical is in particular as a perchlorinated Ce-Ci4- aryl radical, preferably as perchlorinated Ce-Cio-aryl radical and more preferably in the form of a Pentachlorophenylrests ago.
  • the partially chlorinated Cs-Ci4-aryl radical is present in particular as a partially chlorinated Ce- Ci4-aryl radical, preferably as a partially chlorinated Ce-Cio-aryl radical and particularly preferably in the form of chlorophenyl.
  • Ci-C7-alkyl radicals be substituted.
  • a 1 and A 2 are each NR 2 , R 2 and R 2 'may be the same or different.
  • R 2 it is preferred for the substituent R 2 , if it is bonded directly to one of the substituents A 1 or A 2 , that it is a substituent other than hydrogen.
  • R 2 and R 2 ' together form a linear or branched C 1 -C 6 -alkylene group, this is preferably present as C 1 -C 7 -alkylene group and particularly preferably in the form of a butylene or pentylene group.
  • a 1 is NR 2
  • a 2 is NR 2 or CR 2 R 2 ' and preferably NR 2 .
  • the ring B is a heterocyclic 5- to 7-membered ring at least one adjacent to the carbenoid carbon (i.e., the carbon atom which is in the form of a carbene)
  • Nitrogen atom and further comprises either another nitrogen atom or quaternary carbon atom.
  • the heterocyclic 5- to 7-membered ring has at least one further heteroatom, which may be a nitrogen, phosphorus, oxygen or sulfur atom.
  • nitrogen atoms or phosphorus atoms are incorporated into a double bond or have a substituent R 2 which is not present in the form of hydrogen, so that the nitrogen or phosphorus atoms in ring B are tertiary amines or phosphines.
  • the heterocyclic ring B may be substituted, for example, with phenyl or with another preferably aromatic ring form a bicyclic or polycyclic system.
  • the ring B may be a benzo-fused, naphthannated, phenanthrene or anthraquinone fused 5- to 7-membered ring.
  • ring B is one selected from the group comprising 1, 2,3-triazol-5-ylidene, 1, 2,4-triazol-3-ylidene or 1, 2 3,4-tetrazol-5-ylidene is a selected heterocycle.
  • 1, 2,3-triazol-5-ylidene, 1, 2,4-triazol-3-ylidene or 1, 2 3,4-tetrazol-5-ylidene is a selected heterocycle.
  • l, 2,3-triazol-5-ylidene and l, 2,4-tetrazol-3-ylidene are preferred; is most preferred as the ring B l, 2,3-triazole-5-ylidene.
  • the ring is mono- or polysubstituted and has one or more substituents which are selected from linear, partially cyclic or branched C 1 -C 6 -alkyl, in particular C 1 -C 7 -alkyl radicals and C 5 -C 4 -aryl or aryl or heteroaryl radicals and C 5 -C 4 -aryloxy radicals which are substituted by one or more linear, partially cyclic or branched C 1 -C 6 -alkyl radicals, in particular C 1 -C 7 -alkyl radicals.
  • Preferred rings B are in the context of the present invention, a 1- (2,6-diisopropylphenyl) -3-isopropyl-4-phenyl-lH-l, 3-triazol-5-ylidene and a 1,3,4-triphenyl-4 , 5-dihydro-lH-l, 2,4-triazole-5-ylidene.
  • the metal in the catalyst is molybdenum or tungsten, especially molybdenum.
  • At least one of the two substituents X 1 and X 2 is present in the form of a C 1 -C 6 carboxylate, it is preferred if this is a C 1 -C 5 -carboxylate.
  • Particularly suitable carboxylates are acetate, propionate and benzoate.
  • At least one of the two substituents X 1 and X 2 is present in the form of a C 1 -C 6 -alkoxide, it is preferred if this is a C 1 -C 5 -alkoxide.
  • Particularly suitable alkoxides are 2-propoxide and tert-butoxide.
  • At least one of the two substituents X 1 and X 2 is present in the form of a fluorinated C 1 -C 6 -alkoxide, it is preferred if this is a fluorinated C 1 -C 5 -alkoxide.
  • Particularly suitable fluorinated alkoxides are the hexafluoro-2-propoxide and a hexafluoro-tert-butoxide.
  • Ci-Cis-carboxylate If at least one of the two substituents X 1 and X 2 in the form of a mono- or polyhalogenated Ci-Cis-carboxylate, it is preferred if it is a mono- or polyhalogenated Ci-Cs-carboxylate. As particularly suitable mono- or polyhalogenated Ci-Cis carboxylates are
  • Preferred mono-, mono- or polysubstituted mono-, bi- or terphenolates are the 2,6-diphenylphenolate, 2 ', 2 ", 6', 6" -tetrakis (2-propyl) -2,6-diphenylphenolate and the 2 ', 2', 6 ', 6 "-tetramethyl-2,6-diphenylphenolat.
  • the substituents X 1 and X 2 should be weakly or non-coordinating anions and in particular anionic P, B-Al, or Sb-based anions.
  • weakly coordinating substituents such as trifluoromethanesulfonate, tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, hexafluorophosphate and hexafluoroantimonate substituents have been found to be particularly useful.
  • weakly coordinating substituents such as trifluoromethanesulfonate, tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, hexafluorophosphate and hexafluoroantimonate substituents have been found to be particularly useful.
  • Substituents such as fluorinated and non-fluorinated C 1 -C 6 -alkoxides, in particular in the form of C 1 -C 4 -alkoxides used.
  • Particularly suitable alkoxides are ethanolate, 2-propoxide, tert-butoxide, hexafluoro-2-propoxide or hexafluoro-tert-butoxide.
  • Most X 1 or X 2 are selected in formulas I to II from Ci-Cie alkoxides, in particular from Ci-C7-alkoxides, and trifluoromethanesulfonate.
  • the C6-C14-N-aryl radical is preferably in the form of a Ce-Cio-N-aryl radical, where the aryl radical is monosubstituted or polysubstituted by halogen, C 1 -C 6 -N-aryl radical.
  • Substituents may have the same meaning as indicated for R 2 , may be substituted.
  • Y substituents are, in particular 2,6-disubstituted N-aryl radicals, preferably, to name in the form of N-phenyl radicals in which the substituents preferred as alkyl radicals such as tert-butyl, / 'so-propyl or methyl, or as halogens such as chlorine, fluorine or bromine or mixtures thereof.
  • substituents Y are N-alkyl radicals in which the
  • N-alkyl radicals are the N-tert-butyl or the N-adamantyl radical.
  • substituents Y in the context of the present invention are N-2,6-dimethylphenyl, 2,6-bis (2-propyl) phenyl, pentafluorophenyl, N-2,6-dichlorophenyl, 2-tert Butylphenyl, the N-tert-butyl and the N-adamantyl radical.
  • the linear, partially cyclic or branched C 1 -C 10 -alkyleneoxy group is preferably a C 1 -C 3 -alkyleneoxy group and in particular an ethyleneoxy group
  • the linear, partially cyclic or branched C 1 -C 10 -alkylenethio group is preferably a C 1 -C 3 -alkylenethio group and in particular an ethylenethio group
  • the linear, partially cyclic or branched C 1 -C 10 -alkylene NR 2 group is preferably a C 1 -C 3 -alkylene-NR 2 group and in particular an ethylene-NR 2 group
  • the C6-C14 aryleneoxy group is preferably a Ce-Cio-aryleneoxy group, and especially a 2-phenyleneoxy group
  • the perfluorinated C 6 -C 14 -arylenoxy group is preferably a perfluorinated C 1 -C 10 -aryleneoxy group
  • Carbon atom in R 1 which is in direct proximity to the metal alkylidene, a quaternary carbon atom having no hydrogen substituent.
  • Suitable substituents of this quaternary carbon atom include, inter alia, the radicals listed for the substituents R 2 . Based on these specifications, a suitable substituent R 1 can be expertly selected.
  • R 1 in the formulas I and II is tert-butyl, an unsubstituted or substituted phenyl, such as 2- (2-propoxy) phen-1-yl, 2-methoxyphen-1-yl, 2,4,5-trimethoxyphenyl, or ferrocenyl or CMe 2 Ph, wherein the substituents on the phenyl may have the same meaning for as R 2 given, but in particular 2- (2-propoxy) - or 2-methoxy substituents may be ,
  • 2- (2-propoxy) - or 2-methoxy substituents may be advantageous
  • Polymers include cyclic olefins such as cyclobutene, cyclopentene,
  • a particularly suitable monomer in the context of the present invention is dicyclopentadiene.
  • Another aspect of the present invention relates to the use of a catalyst in the form of an N-heterocyclic carbene complex according to one of the general formulas I od
  • a 1 is NR 2
  • a 2 is CR 2 R 2 ' , NR 2 , or S
  • a 3 is N
  • C is a carbene carbon atom
  • ring B is one selected from the group consisting of 1,3-disubstituted imidazol-2-ylidenes, 1,3-disubstituted imidazolin-2-ylidenes, 1,3-disubstituted tetrahydropyrimidin-2-ylidenes, 1,3-disubstituted diazepine-2 ylidenes, 1,3-disubstituted dihydrodiazepin-2-ylidenes, 1,3-disubstituted tetrahydrodiazepin-2-ylidenes, N-substituted thiazol-2-ylidenes, N-substituted thiazolin-2-ylidenes, N-substituted triazol-2-ylidenes , N-substituted dihydrotriazol-2-ylidenes, mono- or polysubstituted triazolin-2-ylidenes, N-substituted thi
  • substituents R 2 and R 2 ' , M, X 1 and X 2 , Y and Z have the abovementioned meaning, for the preparation of polymers by ring-opening metathesis polymerization.
  • substituent Y is an N-adamantyl, an N-tert-butyl, a Cs-Ci4-N-aryl radical, in particular a Ce-Cio-N-aryl radical, wherein the aryl radical is mono- or polysubstituted by halogen, a linear or branched Ci-Cie alkyl, a linear or branched Ci-Cie alkyloxy or an unsubstituted or substituted phenyl radical may be substituted, whose substituents have the same meaning as R 2 .
  • the substituent Y is N-tert-butyl, N-2,6
  • N-heterocyclic carbene complex according to the general formula I.
  • the above-mentioned N-heterocyclic carbene complexes are also used as such in the context of this description. regardless of use for producing polymers by ring-opening metathesis polymerization.
  • Monomers for the ROMP characterized by their latency, i. that they are quasi non-reactive with the monomers at ambient temperature (25 ° C), while heating the reaction mixture allows a controlled polymerization.
  • dicyclopentadiene represents a particularly reactive monomer in the context of ROMP and ruthenium-based catalysts generally do not give any storage-stable mixtures
  • a particularly preferred aspect of the use of the invention relates to the preparation of
  • Catalysts according to the invention found favorable latency with particular advantage for carrying. Accordingly, a preferred use relates to the use of
  • the specified catalysts for the preparation of substituted or unsubstituted poly [2.2.1] hept-2-enes. More preferably, the [2.2.1] hept-2-enes are disubstituted and more preferably substituted at the 5- and 6-positions each with pentyl-oxy-methylene radicals.
  • a further aspect of the present invention relates, as mentioned above, to a process for the preparation of polymers by ring-opening
  • Metathesis polymerization comprising the following steps:
  • the reaction mixture is heated to a temperature of at least 60 ° C, more preferably at least 80 ° C, and most preferably at least 100 ° C.
  • the temperature to which the reaction mixture is heated should not be too high so that unwanted decomposition of the catalyst and / or the polymer can not occur.
  • a temperature of about 250 ° C and preferably at most 200 ° C can be specified in this context.
  • the amount of catalyst involved in the process is not critical. On the one hand, however, the amount should be high enough for the polymerization to proceed quickly enough after activation for the industrial application. On the other hand, the amount of catalyst should be as low as possible from a cost point of view.
  • a range of 0.0001 to 5 mol% (based on the molar amount of the monomer (s) used), especially 0.001 to 1 mol%, and particularly preferably 0.05 to 0.5 mol% can be given. It has already been mentioned in the foregoing that coatings can be produced in a simple and favorable manner using the combination of catalyst and monomer according to the invention. As a result, the
  • Reaction mixture in a preferred aspect of the above-described process before heating in (ii) applied as a coating on a substrate there are no relevant ones with regard to the type of substrate
  • Restrictions ie. it may be a metal, a plastic or another substrate, wherein metal and plastic substrates are to be specified as preferred.
  • the method according to the invention can be advantageously designed by being carried out as a reaction injection molding method, transfer molding method or resin injection method. The corresponding processes and their implementation are readily familiar to the person skilled in the art.
  • a final aspect of the present invention finally concerns a
  • Polydicyclopentadiene which is prepared by the method described above. As shown in the following examples, the polycyclopentadienes prepared by such a process are characterized by a
  • Polycyclopentadienes are less swellable, which in turn suggests a higher degree of crosslinking. In turn, in principle, further favorable material properties such. B. derived a higher strength or dimensional stability.
  • the invention will be explained in more detail by way of examples. Examples
  • Solvent cleaning system (PLC, M brown) cleaned. Commercially available reagents were used without further purification.
  • the NMR spectra were recorded using a Bruker 400 spectrometer (400 M Hz for proton, 101 MHz for carbon and 376 MHz for fluorine) at 20 ° C, and calibrated for internal solvent residual signals. The shifts of the signals and are given in ppm.
  • Catalyst (1 eq., Ca. 1-3 mg) was suspended in dichloromethane (10 ⁇ _) and DCPD (500 eq.) Was added. The suspension was stirred for five minutes. Subsequently, the samples for the temperature scan and the isothermal measurements (about 2-5 mg) were weighed into the DSC crucibles. The crucibles were pressed in the glove box. The prepared mixtures were stored for 24 hours at room temperature with stirring to check the viscosity for latency at room temperature.
  • Catalyst (1 eq, ca. 1-3 mg) was suspended in dichloromethane (10 ⁇ _) and became 5,6-bis ((pentyloxy) methyl) bicyclo [2.2.1] hept-2-ene (200 eq.) added. The suspension was stirred for five minutes. Subsequently, the samples for the temperature scan and the isothermal measurements (about 2-5 mg) were weighed into the DSC crucibles. The crucibles were pressed in the glove box. The prepared mixtures were stored at room temperature with stirring to check for latency at room temperature. After 24 hours another sample (about 2-5 mg) was taken and measured in the DSC.
  • the catalyst / dichloromethane / DCPD ratio was 1 eq / 10 pL / 200 eq. with a temperature program of 0 ° C for one minute, from 0 ° C to 200 ° C with 10 Kmin "1 .

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  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne des catalyseurs selon les formules I et II pour la polymérisation par métathèse par ouverture de cycle (ROMP) de dicyclopentadiène, pour lesquels A1 désigne NR2, A2 désigne CR2R2' ou NR2, A3 désigne N et C désigne un atome de carbone-carbène. Dans ces formules, M désigne Mo ou W. L'invention concerne des catalyseurs selon les formules I et II pour la polymérisation par métathèse par ouverture de cycle de dicyclopentadiène, dans la mesure où ils se caractérisent par une latence avantageuse et ne réagissent avec ce monomère qu'à température élevée. D'autres aspects de la présente invention concernent l'utilisation de catalyseurs correspondants pour la production de polymères obtenus par polymérisation par métathèse par ouverture de cycle ainsi qu'un procédé de production de polymères correspondants, pour lesquels la polymérisation est initiée par chauffage du mélange réactionnel.
PCT/EP2017/079625 2016-11-17 2017-11-17 Catalyseurs latents de polymérisation à action de réticulation de dicyclopentadiène (dcpd) Ceased WO2018091664A1 (fr)

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DE102016122096.5A DE102016122096A1 (de) 2016-11-17 2016-11-17 Latente Katalysatoren zur vernetzenden Polymerisation von Dicyclopentadien (DCPD)
DE102016122096.5 2016-11-17

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US10343153B2 (en) 2013-03-14 2019-07-09 Ximo Ag Metathesis catalysts and reactions using the catalysts
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