WO2018091664A1

WO2018091664A1 - Latent catalysts for crosslinking polymerisation of dicyclopentadiene (dcpd)

Info

Publication number: WO2018091664A1
Application number: PCT/EP2017/079625
Authority: WO
Inventors: Michael R. Buchmeiser; Julia Beerhues
Original assignee: Universität Stuttgart
Priority date: 2016-11-17
Filing date: 2017-11-17
Publication date: 2018-05-24
Also published as: DE102016122096A1

Abstract

The present invention relates to catalysts according to formulae I and II for ring-opening metathesis polymerisation (ROMP) where A¹ stands for NR², A² for CR²R^2' or NR², A³ for N and C for a carbene carbon atom. M is Mo or W in these formulae. The catalysts are particularly suited for the ring-opening metathesis polymerisation of dicyclopentadiene since they are distinguished by a favourable latency and only react with this monomer at high temperatures. Further aspects of the present invention relate to the use of corresponding catalysts for producing polymers by means of ring-opening metathesis polymerisation and methods for producing corresponding polymers, in which polymerisation is started by heating the reaction mixture.

Description

Latent catalysts for the crosslinking polymerization of dicyclopentadiene

(DCPD)

description

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

Metathesis.

State of the art

Poly (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. However, this leads to an increase in production costs and a complication of the polymerization process and has adverse effects on the solvent resistance, the creep behavior and the elastic modulus. In contrast, poly-DCPD has very good impact strengths and toughness even without additional additives, especially a favorable one

Impact strength, on. These properties combined with a high

Rigidity, 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.

According to the methods of the prior art, DCPD is using the

ring-opening metathesis polymerization (ROMP) converted to poly-DCPD, for example, by the reaction injection molding (reaction injection molding). In this case, 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, however, 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. In particular, 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.

Other catalyst systems used are poorly defined in their structure. Thus, for the commercial plastic Telene® tetrakis (tridodecylammonium) octamolybdate as part of the DCPD-containing component 1 and

Ethylaluminiumdichlorid with propanol and tetrachlorosilane as part of DCPD-containing component 2 of the catalyst system used. In the case of the poly-DCPD sold under the trade name Metton®, 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.

In addition to various additives and fillers also often a Lewis base is added. This retards the reaction for a short time to allow for a homogeneous mixture of the components and prior to curing of the polymer filling of the mold. However, the delay in the polymerization is challenging due to the highly reactive catalysts

Process management, so that, especially for the production of larger components, an exact control of the reaction by latent catalysts would be beneficial.

In addition, ruthenium-based catalysts have been proposed for the preparation of poly-DCPD, which can be selectively activated. Thus, MR Buchmeiser et al. (Chemistry - A European Journal, 2010, 16, 12928-12934) proposed a catalyst which is only active by activation with UV light in the metathesis of DCPD.

Although 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. For the technical production of solid components, however, 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.

Acid activation would reduce the use of these catalysts in the

Allow two-component system of the "reaction injection molding". A problem with this catalyst system, however, is that the reaction mixture hardens relatively quickly after mixing the components, so that a fast processing with the associated error sources is required.

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

Function is provided by a pyridyl, imine or alkoxy. As the temperature increases, this chelating function dissolves

Metal center and loses the inhibitory effect after the first metathesis cycle, which allows a delay of the initiation rate at room temperature.

Yet another approach has been to inhibit the dissociation of a phosphine ligand that normally activates the complex. Hafner et al. could this purpose with an arene-ruthenium catalyst an initiator for the

solvent-free ROMP of DCPD at elevated temperature, which can be stored in the monomer at room temperature for a long time (A. Hafner et al., Angew Chem. Int Ed., 1997, 36, 2121-2124). However, this catalyst did not allow sufficiently fast cure times.

An additional problem of the catalysts described in the prior art for the polymerization of DCPD via ROM P is that the thermal latency is usually limited to a relatively short period of time. Against this background, it was the object of the present invention to provide as simple as possible a latent, thermally activatable catalyst for the ROM P,

In particular, DCPD proposes a simple process management based on a one-component system containing all components, ie catalyst and Monomer (eg DCPD) is allowed. A corresponding

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.

While due to the high price of ruthenium and its toxicity catalysts based on molybdenum or tungsten appear to be particularly suitable, currently no suitable thermally activatable catalyst is known for the ROMP.

DESCRIPTION OF THE INVENTION It has surprisingly been found that the objects mentioned above can be achieved by catalysts as specified by claim 1. Accordingly, a first aspect of the present invention relates to a catalyst according to the general formula I or II

II which is characterized in that A ^{1 is} NR ² , A ^{2 is} CR ² R ^{2 '} or NR ² , A ^{3 is} N,

C stands for a carbene carbon atom, 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

Heteroatom in the form of nitrogen, phosphorus, oxygen or sulfur and whose substituents may have the meaning described for R ² , R ² and R ^{2 '} , independently of one another, represent H, a linear, partially cyclic or branched C 1 -C 6 -alkyl-, a linear, partially cyclic or branched C2-C18 alkenyl, a C3-Ci2-cycloalkyl, a linear, partially cyclic or branched Cs-Cioo-polyoxaalkyl, a C ₅ -C 4 -aryl or -heteroaryl radical, a C ₅ -C 14 -aryloxy, a linear, partially cyclic or branched C 1 -C 6 -perfluoroalkyl radical, a linear, partially cyclic or branched C 1 -C 4 -aryl radical; Cis-perchloroalkyl, a linear, partially cyclic or branched partially fluorinated Ci-Cis-alkyl, a linear, partially cyclic or branched partially chlorinated Ci-Cis-alkyl, a perfluorinated or partially fluorinated Ce-Ci4-aryl, a per- or partially chlorinated C5-C14 aryl radical, and when A ¹ and A ^{2 are} each NR ² , R ^{2 may be the} same or different, and wherein the C ₅ -C 4 aryl or heteroaryl radicals and C ₅ -C 14 Aryloxy radicals may be substituted by one or more linear, partially cyclic or branched C 1 -C 6 -alkyl radicals, in particular C 1 -C 7 -alkyl radicals,

M in the formulas I or II stands for Mo or W,

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,

Tetrakis (nonafluoro-tert-butoxy) aluminate, tetrafluoroborate, hexafluorophosphate and hexafluoroantimonate, wherein the substituents on the mono-, bi- or terphenolates in addition to halogen may have the same meaning as R ² , Y oxygen, sulfur, an N- An adamantyl, an N-tert-butyl or a Ce-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 and / or an unsubstituted or substituted phenyl radical may be substituted, whose substituents have the same meaning as R ² ,

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

partially fluorinated Ce-Ci4-aryleneoxy, a per- or partially chlorinated Ce-Ci4-aryleneoxy, a per- or partially brominated Ce-Ci4-aryleneoxy, a Cs-Ci4-arylene thio, a per- or partially fluorinated C6-Ci4-Arylenthio -, a per- or partially chlorinated Ce-Ci4- Arylene thio-, a per- or partially brominated C 6 -C 14 -arylene thio- or a C 12 -C 16 -arylene-NR ² -, a perfluorinated or partially fluorinated C 6 -C 14 -arylene-NR ² -, a perchlorinated or partially chlorinated C 6 -C 14 Arylene-NR ² -, a per- or partially brominated Ce-Ci4-arylene-NR ² -, a C6-Ci4-arylene-PR ² -, a per- or partially fluorinated C6-Ci4-arylene-PR ² -, a per- or partially chlorinated C 6 -C 14 -arylene-PR ² -, a per- or partially brominated Ce-C 1-4 -arylene-PR ² -, a carboxyl or a thiocarboxyl or a dithiocarboxyl group and

R ¹ and R ^{1 '} in the formulas I to II, independently of one another, H or a

aliphatic or aromatic radical, in particular a linear or branched Ci-Cis alkyl group, or an unsubstituted or mono- or polysubstituted Ce-Ci4-aryl group, wherein the substituents have the meanings given for R ² . Furthermore, the invention relates to the use of these catalysts for the preparation of polymers by ring-opening metathesis polymerization (ROMP), a

Process for the preparation of corresponding polymers as well

Polydicyclopentadiene, which is prepared by a corresponding method. Preferred embodiments of the catalysts according to the invention emerge from the claims 2 to 8, while the claims 10 and 11 preferred

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. The

Stimulation of the catalysts is generally carried out by heating the catalyst in admixture with the monomer / monomer to be polymerized. When in the

Therefore, in the context of this invention, it is meant a "latent catalyst" or a "latent-action catalyst", it is to be understood that the catalyst inherently possesses the property of latency without the need for any modifications. The term "catalyst according to the formula I or II" is therefore equivalent to the statement "latent catalyst according to the formula I or II" and "catalyst according to the formula I or II with latent action". For the inventive carbene complexes of the general formulas I and II, it is preferred if defined for the substituents R ₂ and R ₂ 'linear, teilcyclische or branched Ci-Cis-alkyl group mentioned as Ci-Cio-alkyl group, preferably a Ci-C ₇ - Alkyl group, and in particular as Ci-C ₄ alkyl group, is present.

Particularly suitable are methyl, ethyl and propyl groups.

The linear, partially cyclic or branched C ₂ -Cis-alkenyl group is

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. For the 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. If the substituent 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. In this context, phenyl, naphthyl or ferrocenyl have been found to be particularly suitable.

As substituted or unsubstituted 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.

Likewise, 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.

Likewise, 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.

Likewise, 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.

In a preferred embodiment, the Cs-C4-aryl or -heteroaryl radicals mentioned above and Cs-C4-aryloxy radicals having one or more linear, partially cyclic or branched C 1 -C 6 -alkyl radicals,

in particular Ci-C7-alkyl radicals, be substituted. When A ¹ and A ^{2 are} each NR ² , R ² and R ^{2 'may be the} same or different.

In general, 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. In the event that 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. In the context of the present invention, A ^{1 is} NR ² , while 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. In addition, the heterocyclic 5- to 7-membered ring has at least one further heteroatom, which may be a nitrogen, phosphorus, oxygen or sulfur atom. The

In this case, 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. In addition, the heterocyclic ring B may be substituted, for example, with phenyl or with another preferably aromatic ring form a bicyclic or polycyclic system. For example, the ring B may be a benzo-fused, naphthannated, phenanthrene or anthraquinone fused 5- to 7-membered ring.

In the context of the present invention, it has proven particularly expedient for ring B to be 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. Of these, in turn, 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.

For the ring B, it is further preferred if 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. As special 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.

If 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.

If 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.

If 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.

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

Trichloroacetate, trifluoroacetate, pentafluoropropionate, heptafluorobutyrate, and pentafluorobenzoate. 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.

In general, 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. For the substituents X ¹ and X ² , in particular weakly coordinating substituents, such as trifluoromethanesulfonate, tetrakis (3,5-bis (trifluoromethyl) phenyl) borate, hexafluorophosphate and hexafluoroantimonate substituents have been found to be particularly useful. In addition, you can

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 preferably X ¹ or X ^{2 are selected} in formulas I to II from Ci-Cie alkoxides, in particular from Ci-C7-alkoxides, and trifluoromethanesulfonate.

As substituent Y, the substituents mentioned in the above are suitable. For preferred embodiments of these substituents, the following applies: 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. Alkyl radicals, in particular C 1 -C 8 -alkyl radicals, C 1 -C 6 -alkyloxy radicals, in particular C 1 -C 8 -alkyloxy radicals, where methoxy or 2-propoxy groups are particularly preferred, or an unsubstituted or substituted phenyl radical Rest, whose

Substituents may have the same meaning as indicated for R ² , may be substituted.

Particularly preferred 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. Further preferred substituents Y are N-alkyl radicals in which the

Carbon atom in the direct vicinity of the nitrogen a quaternary

Is carbon atom. Examples of such N-alkyl radicals are the N-tert-butyl or the N-adamantyl radical. Particularly preferred 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. For preferred embodiments of the substituent Z, the following applies: 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 and in particular a tetrafluorophenyl-2-enoxy group; the partially fluorinated C6-C4-aryleneoxy group is preferably a partially fluorinated Ce Cio-aryleneoxy group and in particular a fluorophenyl-2-en-oxy group; the perchlorinated Ce-Ci4-aryleneoxy group is preferably a perchlorinated Ce-Cio-aryleneoxy group and in particular a tetrachlorophenyl-2-en- oxygruppe; the partially chlorinated Ce-Ci4-aryleneoxy group is preferably a partially chlorinated Ce-Cio-aryleneoxy group and in particular a chlorophenyl-2-en- oxygruppe; the perbrominated Ce-Ci4-aryleneoxy group is preferably a perbrominated Ce-Cio-aryleneoxy group and in particular a tetrabromophenyl-2-en oxygruppe; the partially brominated C6-C16-aryleneoxy group is preferably a partially brominated Cs-Cio-aryleneoxy group and in particular a bromophenyl-2-enoxy group; the C ₆ -C ₄ arylene thio group is preferably a C ₆ -C 10 arylene thio group and especially a 2-phenylene thio group; the perfluorinated C6-Ci4-arylene thio group is preferably a perfluorinated Cs-Cio-Arylenthio group and in particular a tetrafluorophenyl-2-enothio group; the partially fluorinated C6-Ci4-arylenethio group is preferably a partially fluorinated Ce Cio-Arylenthio group and in particular a fluorophenyl-2-en-thio group; the perbrominated C6-Ci4-arylenethio group is preferably a perbrominated Cs-Cio-arylenethio group and especially a tetrabromophenyl-2-enothio group; the partially brominated Ce-Ci4-arylenethio group is preferably a partially brominated Ce-Cio-Arylenethio group and in particular a bromophenyl-2-enothio group; the perchlorinated Ce-Ci4-arylenethio group is preferably a perchlorinated Ce-Cio-Arylenthio group and in particular a Tetrachlorphenyl-2-en-thio group; the partially chlorinated Ce-Ci4-arylenethio group is preferably a partially chlorinated Ce-Cio-Arylenethio group and in particular a chlorophenyl-2-enothio group; the Ce-Ci4-arylene-NR ² group is preferably a Ce-Cio-arylene-NR ² group and in particular an N-methylphenyl-2-ene or N-ethylphenyl-2-ene group; the perfluorinated Ce-Ci4-arylene-NR ² group is preferably a perfluorinated Ce-Cio-arylene-NR ² group and in particular an N-methyltetrafluorophenyl-2-ene or N-ethyltetrafluorophenyl-2-engruppe; the partially fluorinated C 6 -C 14 arylene-NR ² group is preferably a partially fluorinated C 3 -C 10 -arylene-NR ² group and in particular an N-methylfluorophenyl-2-ene or N-ethylfluorophenyl-2-engroup; the perchlorinated C 6 -C ₄ -arylene-NR ² group is preferably a perchlorinated Cs-Cio-arylene-NR ² group and in particular an N-methyltetrachlorophenyl 2-ene or N-ethyltetrachlorophenyl-2-engroup; the partially chlorinated C 6 -C ₄ -arylene-NR ² group is preferably a partially chlorinated C 3 -C 10 -arylene-NR ² group and in particular an N-methylchlorophenyl-2-enyl or N-ethylchlorophenyl-2-ene group; the perbrominated C 6 -C ₄ -arylene-NR ² group is preferably a perbromated C 3 -C 10 -arylene-NR ² group and in particular an N-methyltetrabromophenyl-2-ene or N-ethyltetrabromophenyl-2-ene group; the partially brominated C 6 -C ₄ -arylene-NR ² group is preferably a partially brominated C 3 -C 10 -arylene-NR ² group and in particular an N-methylbromophenyl-2-ene or N-ethylbromophenyl-2-ene group; the C ₆ -C ₄ -arylene-PR ² group is preferably a Ce-Cio-arylene-PR ² group and in particular a P-methylphenyl-2-ene, P-phenyl-phenyl-2-ene or P Ethylphenyl-2-engroup; the perfluorinated C 6 -C ₄ -arylene-PR ² group is preferably a perfluorinated C 6 -C 10 -arylene-PR ² group and in particular a P-methyltetrafluorophenyl-2-ene, perfluoro-P-phenyl-phenyl-2-ene or P-ethyltetrafluorophenyl-2-ene group; the partially fluorinated C 6 -C ₄ -arylene-PR ² group is preferably a partially fluorinated C 3 -C 10 -arylene-PR ² group and in particular a P-methylfluorophenyl-2-en- or P-ethylfluorophenyl-2-engroup; perchlorinated the _Cs-Ci-4 arylene PR ² group is preferably a perchlorinated Cs-Cio-arylene-PR ² group and in particular a P-Methyltetrachlorophenyl- 2-ene or P-Ethyltetrachlorophenyl-2-engruppe; the partially chlorinated C6-Ci4-arylene-PR ² group is preferably a partially chlorinated Cs-Cio-arylene-PR ² group and in particular a P-methylchlorophenyl-2-en- or P-ethylchlorophenyl-2-engruppe; the perbrominated C6-Ci ₄ -arylene-PR ² group is preferably a perbrominated Cs-Cio-arylene-PR ² group and in particular a p-Methyltetrabromphenyl- 2-ene or P-Ethyltetrabromphenyl-2-engruppe; the partially brominated C ₆ -C 14 -arylene-PR ² group is preferably a partially brominated C 3 -C 10 -arylene-PR ² group and in particular a P-methylbromophenyl-2-ene or P-ethylbromophenyl-2-engroup.

The substituents R ¹ and R ^{1 '} come within the scope of the present invention

Catalysts the task to provide a metal alkylides available that is both stable on the one hand, but on the other hand sufficiently metathesis.

Particularly suitable substituents R ¹ and R ^{1 '} are therefore, in addition to R ^1' = H, are large alkyl or aryl radicals which ensure good steric shielding of the metal alkylidene. Accordingly, it is preferred that R ^{1 is} not hydrogen, while R ^{1 'represents} a hydrogen atom. This is particularly useful

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.

It has been found to be particularly advantageous if 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 , In addition, it has to be advantageous

when C ₁ -C ₆ -alkyl group is a C ₁ -C 10 -alkyl group and C ₆ -C ₄ -aryl is a C 1 -C 10 -aryl aryl group. As a particularly favorable R ¹ , tert-butyl, an unsubstituted or substituted phenyl, ferrocenyl or CMe ₂ Ph can be given. A further aspect of the present invention, as already indicated above, deals with the use of the catalyst according to the invention for the preparation of polymers by a ring-opening metathesis polymerization (ROM P). The polymers thus prepared can be used, for example, as matrix polymers for fibrous matrix composites, as compatibilizers or as base polymers for fibers. Preferred monomers for the preparation of corresponding

Polymers include cyclic olefins such as cyclobutene, cyclopentene,

Dicyclopentadiene, cyclohexene, cycloheptene, cis-cyclooctene, cyclooctatetraene,

[2.3.0] bicycloheptene and norbornene, as well as derivatives thereof. 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

in which 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 thiadiazol-2-ylidenes, mono- or polysubstituted thiadiazolin-2-ylidenes and mono- or polysubstituted tetrahydrotriazole-2-ylidenes ylidene selected heterocycle, and preferably a 1,3-disubstituted imidazol-2-ylidene,

where the 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. For this use, it is preferred if the N-heterocyclic carbene complex according to one of the general formulas I or II as 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 . Most preferably, the substituent Y is N-tert-butyl, N-2,6-dimethylphenyl, N-2,6-dichlorophenyl or N-2- (tert-butyl) phenyl.

Furthermore, the use is preferably the use of an 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.

In the above-described use, the above-mentioned monomers can be used.

A particular advantage of the catalysts of the invention according to the above is that they are particularly highly reactive

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.

Since 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

Polydicyclopentadienen. For this monomer comes the for the

Catalysts according to the invention found favorable latency with particular advantage for carrying. Accordingly, a preferred use relates to the use of

specified catalysts for the preparation of polydicyclopentadiene. Other monomers in which the latency of the catalysts described has particular benefit are [2.2.1] hept-2-enes, which may be substituted or unsubstituted. Accordingly, another preferred

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 particularly preferred aspect of this usage theory is the

Preparation of dicyclopentadienes in the form of a coating which, as mentioned above, has the advantage of being directly printable with simultaneously high impact strength and toughness.

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:

(i) contacting a catalyst as specified above with a cyclic monomer containing one or more double bonds, (ii) heating the reaction mixture to a temperature sufficient to initiate the polymerization reaction.

With respect to this process, it is preferred if 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. On the other hand, 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. As a suitable maximum temperature, 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. As a suitable amount of catalyst, 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. Furthermore, 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

Compared to classical Grubbs catalysts

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

Compounds 1- (2,6-diisopropylphenyl) -4-phenyl-1 H, 2,3-triazole, 1- (2,6-diisopropylphenyl) -3-isopropyl-4-phenyl-1 H -1,2, 3-triazolium trifluoromethanesulfonate, 1- (2,6-diisopropylphenyl) -3-isopropyl-4-phenyl-1 H, 2,3-triazol-5-ylidene, 1,3-dimethyltetrazolylidene silver chloride, 2,6-bis (triisopropylphenyl) phenyl -l-iodide, 2,6-bis (2,4,6-triisopropylphenyl) -l-phenol (22), 2,6-bis (triisopropylphenyl) -l-lithium phenoxide, Mo (N-2,6-Me ₂ - C 6 H 3) ₂ Cl ₂ (DM E), Mo (N-tert-Bu) ₂ Cl ₂ (DME), Mo (N-2,6-Me ₂ -C 6 H 3) 2 (CH ₂ CMe ₂ Ph) 2, Mo (N -tert-Bu) 2 (CH ₂ CMe ₂ Ph) 2, Mo (N-2,6-Me ₂ -C 6 H 3) (CH ₂ CMe ₂ Ph) (OSO ₂ CF 3) 2 (DM E) were prepared according to known literature procedures.

Unless otherwise stated, all reaction steps were conducted in the absence of oxygen and moisture under N ₂ or Ar either by Schlenk technique or in inert gas boxes (MBraun LabMaster 130) in dry glassware. The deuterated solvent CD ₂ Cl ₂ was dried over P2O5 and vacuum transferred, benzene was dried over Na and distilled.

Diethyl ether, n-pentane TH F and CH ₂ Cl ₂ were by means of a

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.

Structure of the prepared Mo catalysts:

11 12 13 14

15 16 17 18

Example 1 (Preparation of Mo (N-tert-Bu) (1- (2,6-diisopropylphenyl) -3-isopropyl-4-phenyl-1H, 2,3-triazol-5-ylidene) (CHCMe ₂ Ph) (OTf) ₂ (II))

Molybdenum (tert-butylimido) (neophyliden) bis-triflate. DME (146 mg, 0.213 mmol, 1.0 eq.) And l, 2,3-triazol-4-ylidene (74.0 mg, 0.213 mmol, 1.0 eq.) Were each dissolved in benzene (0.4 ml) and combined with stirring. After 16 hours, the resulting precipitate was filtered off and washed with benzene. The solid was dissolved in a little dichloromethane and overlaid with pentane. After decanting the solvent and drying the

Solid under vacuum, II (112 mg, 0.119 mmol, 56%) was obtained as colorless crystals. 1 H-NMR (400, 13 MHz, CD ₂ Cl ₂ ): (isomers 1: 0.08) <5 = 13.76 (s, 1 H, alkylidene-H, J _CH = 128 Hz), 12.82 (s, 0.08H), 7.89-7.63 (m, 5H, aryl-H), 7.53 (t, J = 7.5Hz, 1H, aryl-H), 7.35 (d, J = 7.8Hz, 1H, aryl-H), 7.28-7.12 (m, 3H, aryl-H), 7.09-6.90 (m, 3H, aryl-H , 5.91 (s, 0.08 H), 5.14-4.90 (m, 1 H, N-CH- (CH ₃ ) ₂ ), 4.37 (s, 0.08 H), 3.18- 2.87 (m, 1H, aryl-CH (CH ₃ ) ₂ ), 1.89-1.73 (m, 3H, alkyl-H), 1.65 (s, 3H, alkyl) H), 1.44 (d, 3 = 6.6Hz, 3H, alkyl-H), 1.36-1.21 (m, 3H, alkyl-H), 1.11-0.81 ppm (m , 22 H, alkyl-H); ¹⁹ F NMR (376.46 M Hz, CD ₂ Cl ₂ ): δ = -77.26 (CF ₃ SO ₃ ), -77.81 ppm (CF ₃ SO ₃ ); ¹³ C-NMR (100.61 MHz,

CD ₂ Cl ₂ ): <5 = 311.3 (H = C (CH ₃ ) ₂ Ph, 171.6 (CMcarbene), 148.2, 147.3, 146.4, 146.3, 136.6, 132.7, 132.2, 131.5, 129.9, 128.8, 127.2, 127.0, 126.6, 125.7, 124.9, 120, 1 (q, J = 318 Hz , CF ₃ ), 75.9 (N - CH ₃ ), 55.4 ((CH ₃ ) ₂ Ph), 34.8, 30.2, 29.3, 29.2, 28.3, 26.4, 26.0, 23.7, 22.6, 20.9 ppm; C, H, N analysis (%) for C39H50F6M0N4O6S2: calc .: C, 49.57, H, 5.33; N, 5.93; gef. C, 49.42, H, 5.33, N, 5.94.

Example 2 (Mo (N ^t Bu) (l- (2,6-diisopropylphenyl () -3-isopropyl-4-phenyl-lH-l, 2,3-triazol-5-ylidene) CHCMe ₂ Ph) (OTf) (O ^t Bu) (12))

II (60.0 mg, 63.5 μιτιοΙ, 1.0 equiv.) And Lithiumferfbutanolat (5, 1 mg, 6.37 μΜοΙ, 1.0 equiv.) Each were dissolved or suspended in dichloromethane (2 ml) and cooled to -30 ° C. With stirring, the molybdenum precursor solution was added slowly to the lithium salt suspension. After 72 hours, the solution was concentrated to 1 ml, filtered and dried in vacuo. The resulting solid was washed with n-pentane and then with a little diethyl ether. In

Diethyl ether / dichloromethane was crystallized 12 (26 mg, 29.9 μΜοΙ, 47%) at -30 ° C. * H-NM R (400, 13 M Hz, CD ₂ CI _2): <5 = 11.84 (s, 1H, alkylidene-H, J _CH = 120 Hz), 7.69 (t, J = 7 , 7Hz, 2H, aryl-H), 7.58 (t, J = 7.7Hz, 2H, aryl-H), 7.47 (dd, J = 7.9Hz, 2H, aryl-H) , 7.27-7.13 (m, 5H, aryl-H), 7.05 (dd, J = 7.8, 1.9Hz, 2H, aryl-H), 4.72 (hept, J = 6.6Hz, N-CH- (CH ₃ ) ₂ , 1H), 2.25 (2 x hept, J = 6.9Hz, aryl-CH- (CH ₃ ) ₂ , 2H), 1.63 (d, J = 6.6Hz, 3H, alkyl-H), 1.50 (d, J = 6.6Hz, 3H, alkyl-H), 1.45-1.32 (m, 12H, Alkyl H), 1.20 (s, 12 H, alkyl H), 1.09 (d, 3 = 6.8 Hz, 3H, alkyl H), 1.03 ppm (s, 9H, alkyl). H); ¹⁹ F NM R (376.46 MHz, CD 2 Cl 2): δ = -78.88 ppm (CF ₃ SO ₃ ); ¹³ C-NM R (100.61 MHz, CD 2 Cl 2): δ = 290.3

(CH = C (CH ₃ ) ₂ Ph), 166.9, 148, 1, 146.6, 144.7, 144.2, 134.6, 131.8, 131, 1, 129.6, 129, 2, 127.4, 125.7, 125.2, 124.6, 124.5, 124.2, 120.3 (q, J = 323 Hz, CF ₃ ), 83.4, 74.4, 31 , 3, 31.0, 29.9, 29.4, 28.5, 24.4, 24, 1, 21.8, 21.7, 21.7, 21.6, 21.6 ppm; C, H, N analysis (%) for C4 ₂ H ₅ 9F ₃ MoN ₄ 04S: calc.: C, 58.05, H, 6.84, N, 6.56; gef. C, 58.09, H, 6.73, N, 6.85.

Example 3 (Mo (N-2,6-Me ₂ -C ₆ H ₃ ) (l, 3,4-triphenyl-4,5-dihydro-1H, 2,4-triazole-5-ylidene) (CHCMe ₂ Ph) (OTf) ₂ (13))

Mo (N-2,6-Me2-C ₆ H ₃₎ (CHCMe ₂ Ph) (OTf) 2 (DM E) (0.400 g, 0.5437 mmol) was dissolved in 8 ml of benzene. A benzene solution (1 ml) of 1, 3,4-triphenyl-4,5-dihydro-1H-1, 2,4-triazol-5-ylidene (0.162 g, 0.5437 mmol) was added and the

resulting mixture was stirred for 18 h. The benzene was then removed in vacuo and the residue was washed with diethyl ether and dried in vacuo. 13, a yellow solid was obtained (0.360 g, 81%). * H NMR (CD ₂ Cl ₂ ): δ 14.37 (s, 1 H, CHCMe ₂ Ph), 14.08 (s, 0.57H, CHCMe ₂ Ph), 8.09-6.24 (m, 35H, ArH), 1.95-0.78 (s, 18H, Me); ¹⁹ F NMR (CD 2 Cl 2): δ - 77.41, 77.46 (d,

CF3SO3); -77.79, -77.85 (d, CF3SO3). ¹³ C NMR (CD2CI2): δ 322.9 (CHCMe ₂ Ph), 320.7 (CHCMe ₂ Ph), 186.0 (CN _ca rben), 185.0 (CN _ca rben), 146.8 (C _ipS o), 139.6 (Cortho),

135.3 (Caryl), 132.7 (Caryl), 132.3 (Caryl), 132, 1 (Caryl), 131.9 (Caryl), 131.6 (Caryl), 131.3 (Caryl), 130 , 7 (Caryl), 130.5 (Caryl), 129.8 (Caryl), 129.6 (Caryl), 129.0 (Caryl), 128.5 (Caryl), 128.2 (Caryl), 127, 3 (Caryl), 126.8 (Caryl), 123.2 (CF ₃ ), 120, 1 (q, CF ₃ , J

= 319 Hz), 57.8 (CMe ₂ Ph), 57.4 (CMe ₂ Ph), 30.7 (CMe ₂ Ph), 28.0 (CMe ₂ Ph), 27.2 (CMe ₂ Ph), 19.4 (CH ₃ ), 18.2 (CH ₃ ). Example 4 (Mo (/ V-t Bu) (CHC Me2Ph) (OTf) ₂ (1,3-dimesityl imidazol-2-ylidene) 14)

Mo (/ V-t Bu) (CHC Me2Ph) (OTf) ₂ (dme) (130 mg, 0.19 mmol) was dissolved in toluene (4 mL) and a solution of 1,3-dimesityl-imidazol-2-ylidene (57.7 mg , 0.19 mmol) in toluene (1 mL) was added. The reaction mixture was stirred at room temperature overnight. The solvent was then removed and the residue was dissolved in dichloromethane and filtered through Celite to remove formed imidazolium salt. The filtrate was concentrated and treated with diethyl ether and pentane until cloudy. The product was isolated in the form of yellow crystals in 68% yield. Two isomers were observed. The sum of the integrals of the two alkylidene signals was normalized to 1. ¹ H NM R (CDCl ₃ , 400 MHz): δ = 13.62 (s, 0.55H, Mo = CH), 11.35 (s, 0.45H, Mo = CH), 7.30- 7.28 (m, 1H), 7.23- 7.15 (m, 5H), 7.12-7.08 (m, 2H), 7.04 (s, 1H), 6.96 (s, 1H), 6.94 (s, 1H), 2.39-2.30 (m, 6H, IMes) , 2:18 to 2:07 (m, 12H, IMes), 1.68-1.61 (m, 6H, C (CH ₃₎ ₂ Ph), 1:24 to 1:14 (m, 9H, O-tBu) ppm. ¹⁹ F NM R (CDCI ₃ , 376 MHz): δ = - 76.12 (s, 3F), -76.70 (s, 3F) ppm.

Example 5 (Mo (/ V-2,6-Me 2 C ₆ H 3) (CHC Me 2 Ph) (OTf) 2 (1,3-dimesityl-imidazol-2-ylidene) 15) The synthesis was carried out according to a literature procedure and will be described here for simplicity once mentioned. Mo (/ V-2,6-Me 2 C ₆ H 3) (CHC Me 2 Ph) (OTf) 2 (dme) (503 mg, 0.7 mmol) was dissolved in toluene (5 mL) and a solution of 1.3. Dimesityl-imidazol-2-ylidene (208.3 mg, 0.7 mmol) in toluene (3 mL) was added. The solution was stirred for three hours and then the solvent was removed. The residue was washed with diethyl ether and the remaining yellow solid was crystallized from a mixture of dichloromethane and diethyl ether. The product was in the form of yellow crystals in 84% Isolated yield. The analytical data corresponded to those described in the literature. * H NM R (CD2CI2, 400 MHz): δ = 13.18 (s, 1H, Mo = CH), 7.24-7.18 (m, 4H), 7.18-7.09 (m, 2H), 7.05-7.03 (m, 2H ), 6.99 (s, 2H), 6.95 (br s, 2H), 2.64 (s, 3H), 2.25 (s, 6H), 2.12 (s, 6H), 1.97 (s, 3H), 1.95 (s, 6H ), 1.79 (s, 3H), 1.29 (s, 3H) ppm. ¹⁹ F NM R (CD2CI2, 376 M Hz): δ = -74.94 (s, 3F), -76.54 (s, 3F) ppm.

Example 6 (Mo (/ V-2-t Bu-C ₆ H ₄ ) (CHC Me 2 Ph) (OTf) 2 (1,3-dimesityl-imidazol-2-ylidene) 16)

Mo (A / -2-t Bu-C ₆ H ₄ ) (CHC Me ₂ Ph) (OTf) ₂ (dme) (130 mg, 0.17 mmol) was dissolved in toluene (5 mL) and cooled to -35 ° C. A cold (-35 ° C) solution of 1,3-dimesityl-imidazol-2-ylidene (51.9 mg, 0.17 mmol) was added. After five hours, the solvent was removed and the residue crystallized from a mixture of dichloromethane, diethyl ether and pentane. The product was isolated in the form of yellow crystals in 72% yield. * H NMR (CDCl 3, only signals of the major isomer are given (syn), 400 MHz): δ = 14.30 (s, Mo = CH), 7.31-7.29 (m, 1H), 7.23-7.10 (m, 8H), 6.99-6.95 (m, 3H), 6.87-6.85 (m, 2H), 6.55 (s, 2H), 2.28 (s, 6H, IMes), 2.19 (s, 6H, IMes), 1.89 (s, 6H, IMes ), 1.41 (s, 3H, C (CH ₃ ) ₂ Ph), 1.35 (s, 3H, C (CH ₃ ) ₂ Ph), 1.34 (s, 9H, o-tBu) ppm. ¹⁹ F NM R (CDCI ₃ , only signals of the major isomer are given (syn), 376 MHz): δ = - 74.36 (s, 3F), -76.31 (s, 3F) ppm.

Example 7 (Mo (/ V-2,6-Cl 2 C ₆ H ₃ ) (CHCMe ₃ ) (OTf) 2 (1,3-dimesityl-imidazol-2-ylidene) 17)

The synthesis was carried out according to a literature specification and will be recited here for the sake of simplicity. Mo (/ V-2,6-Cl2C ₆ H ₃₎ (CHCMe ₃₎ (OTf) 2 (dme) (400 mg, 0.6 mmol) was dissolved in toluene (5 mL) and a solution of 1,3-Dimesityl- Imidazol-2-ylidene (170.0 mg, 0.6 mmol) in toluene (3 mL) was added. The solution was stirred for four hours and then the solvent was removed. The residue was washed with diethyl ether and the remaining yellow solid was crystallized from a mixture of dichloromethane and diethyl ether. The product was isolated as yellow crystals in 77% yield. The analytical data corresponded to those described in the literature. Both syn and anti isomer were observed. In the following, only the signals of the major isomer (syn) are listed. * H NMR (CDCb, 400 MHz): δ = 13.30 (s, 1H, Mo = CH), 7.26 (s, 2H), 7.24-7.21 (m, 2H, ArH, / V-2,6-Cl 2 -C ₆ H _3), 7:17 to 7:13 (m, 1 H, ArH, / V-2,6-Cl2-C ₆ H _3), 6.82 (s, 2H), 6.72 (s, 2H), 2:08 (s, 6H), 1.87 (s, 6H), 1.78 (s, 6H), 0.79 (s, 9H, CMe ₃ ) ppm. ¹⁹ F NM R (CDCb, 376 MHz): δ = -76.11 ppm.

Example 8 (Mo (/ V-t Bu) (CHC Me2Ph) (OTf) ₂ (1, 3,4-phenyl-1,2,4-triazol-5-ylidene) 18)

Mo (/ V-tBu) (CHCMe2Ph) (OTf) ₂ (dme) (150 mg, 0.22 mmol) was dissolved in toluene (3 mL) and a solution of l, 3,4-triphenyl-l, 2,4- Triazol-5-ylidene (64.9 mg, 0.22 mmol) in toluene (1 mL) was added. The reaction mixture was stirred at room temperature overnight. The solvent was then removed and the residue was dissolved in dichloromethane and filtered through Celite to remove triazolium salt formed. The filtrate was concentrated and treated with diethyl ether and pentane until cloudy. The product was isolated in the form of light yellow crystals in 61% yield. There were two isomers

observed. The sum of the integrals of the alkylidene signals was normalized to 1. * H NM R (CDCb, 400 M Hz): δ = 13.92 (s, 0.21H, Mo = CH), 13.69 (s, 0.79H, Mo = CH, syn, ^ CH = 122.14 Hz), 8.14 (d, 1H, 3JH H = 7.7Hz), 7.94-7.90 (m, 2H), 7.77-7.73 (m, 2H), 7.67-7.61 (m, 2H), 7.46-7.28 (m, 5H), 7.25-7.16 ( m, 5H), 7.10 (t, 1 H, ³ J _HH = 7.7 Hz), 7.02-7.00 (m, 2H), 6.44 (d, 1 H, ³ J _HH = 7.7 Hz), 3.48 (q, 2H, ³ J _HH = 7.0 Hz, CH3CH2O, 0.5 eq. Et ₂ 0), 1.42 and 1.36 (2 s, 3H,

C (CH ₃ ) ₂ Ph), 1.27 and 1.22 (2 s, 3H, C (CH ₃ ) ₂ Ph), 1.21 (t, 3H, ³ J _HH = 7.0 Hz, CH ₃ CH ₂ O, 0.5 eq. Et ₂ O), 0.91 and 0.88 (2 s, 9H, / V-tBu) ppm. ¹⁹ F NM R (CDCb, 376 MHz): δ = -76.98-77.01 (m, 3F), -77.58-77.70 (m, 3F) ppm.

Example 9 (Crosslinking polymerization of dicyclopentadiene)

The catalysts II to 13 (3.5 mg, 4.03 μΜοΙ, 1 eq.) Were dissolved in the glove box under nitrogen atmosphere in dichloromethane (10 μΙ). DCPD (245 mg (II and 13), 266 mg (12), 500 eq each, based on the amount of catalyst) was added and the reaction mixture was stirred for a few seconds to obtain a homogeneous mixture. The exact compositions of the samples are given in Table 1. Table 1

Initiator initiator charge m DCPD

No initiator

(Mmol) (mg) (mole%) (mg)

1 II 3.70 3.5 0.2 245

2 12 4.03 3.5 0.2 266

3 13 3.71 3.5 0.2 245

In each case one sample (about 5 mg) was taken and the crucible for

Performing a dynamic DSC measurement (heating rate 10 ° C / min) in the glovebox. The results of the DSC measurements are shown in Figure 1 versus a corresponding polymerization of DCPD using

RuCl2 (PCy3) 2) CH Ph (R1, Grubbs first generation catalyst) as

Catalyst shown.

In order to determine the swelling behavior of the different polymers, corresponding samples of catalyst and monomer were cured for a reaction time of 60 minutes at the temperature given in Table 2 below and then swollen in toluene for 60 hours. Percent swelling is given by Q = m _q -mo / mo where m _{0 is} the mass of the polymer before swelling and m _{q is} the mass of the polymer after swelling.

Table 2

Initiator T (° C) nio (mg), (mg) Q (%)

1 II 150 ° C 74 225 204

2 12 110 ° C 94 243 159

3 13 140 ° C 77 104 35

3 Rl 50 ° C 88 329 274

Example 10 (Crosslinking polymerization of dicyclopentadiene)

Preparation of Catalyst / Dichloromethane / DCPD Mixtures: Der

Catalyst (1 eq., Ca. 1-3 mg) was suspended in dichloromethane (10 μΙ_) 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.

DSC heating programs:

Temperature scan: 1 minute at 0 ° C

0 ° C to 200 ° C with 10 Kmin ^"1

Isothermal measurement: 30 minutes at constant, catalyst-dependent

Temperature (For each catalyst, a temperature was about 10-20 ° C below the temperature of the exothermic

Maximum of the polymerization selected).

Table 3: Latent ROMP of DCPD using Catalysts 11-17.

Catalyst ■ exo, max [° C]

11 169

12 116

13 149

14 157

15 160

16 149 17 186

Catalyst / dichloromethane / DCPD; 1 eq. / 10 μΙ / 500 eq. (i) Temperature of the exothermic maximum of the DSC curve of the temperature scan measurement (0 ° C for one minute, from 0 ° C to 200 ° C at 10 Kmin ^"1 ). Minute, from 0 ° C to 200 ° C at 10 Kmin ^"

The DSC curves of ROMP of DCPD using catalysts 13-17 are shown in FIG.

The DSC curves of ROMP of DCPD using catalysts 13-16 are shown in FIG. For these measurements, the catalyst / dichloromethane / DCPD ratio was 1 eq / 10 μΙ / 500 eq. Each temperature program consisted of holding the temperature in brackets for 30 minutes. Example 11 (ROM P of 5,6-bis ((pentyloxy) methyl) bicyclo [2.2.1] hept-2-ene)

Preparation of Catalyst / Dichloromethane / Monomer Mixtures: Der

Catalyst (1 eq, ca. 1-3 mg) was suspended in dichloromethane (10 μΙ_) 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.

DSC heating programs:

Temperature scan: 1 minute at 0 ° C

0 ° C to 200 ° C with 10 Kmin ^"1

Isothermal measurement: 30 minutes at constant temperature.

Following: Measurement of a temperature scan to check if a polymerization has taken place. Comparison of the reaction enthalpy obtained with the reference sample, which was not thermally pretreated. Table 4 Latent ROM P of 5,6-bis ((pentyloxy) methyl) bicyclo [2.2.1] hept-2 using catalysts 13, 17 and 18.

13 120 60

17 149 80

18 120 60

Catalyst / dichloromethane / 5,6-bis ((pentyloxy) methyl) bicyclo [2.2.1] hept-2-ene; 1 eq. / 10 pL / 200 eq. (i) temperature of the exothermic peak of the DSC curve of the temperature scan (0 ° C for one minute, from 0 ° C to 200 ° C with 10 Kmin ^"1 ); (ii) maximum temperature after an isothermal measurement in

following measured temperature scan (0 ° C for one minute, from 0 ° C to 200 ° C with 10 Kmin ^"1 ) nor the reference enthalpy (sample without thermal

Pretreatment) becomes free.

The DSC curves of the ROM P of 5,6-bis ((pentyloxy) methyl) bicyclo [2.2.1] hept-2-ene using catalysts 13, 17 and 18 are shown in FIG. 4

played. 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 .

Claims

claims

1. Catalyst according to general formulas I and II for ring-opening metathesis polymerization (ROMP),

characterized in that

A ^{1 is} NR ² , A ^{2 is} CR ² R ^{2 '} or NR ² , A ^{3 is} N, C is a carbene carbon atom, ring B is an unsubstituted or a monosubstituted or polysubstituted 5-7 is a membered ring containing in addition to A ¹ , A ² and A ³ at least one further heteroatom in the form of nitrogen, phosphorus, oxygen or sulfur and its substituents described for R ²

Meaning,

R ² and R ^{2 '} , independently of one another, are H, a linear, partially cyclic or branched C 1 -C 6 -alkyl-, in particular a C 1 -C 7 -alkyl, a linear, partially cyclic or branched C 2 -C alkenyl, in particular one _C2-C7 alkenyl, a C3-Ci2-cycloalkyl, in particular a C3-C ₆ - cycloalkyl, a linear or branched C teilcyclischen Cioo- Polyoxaalkyl-, in particular C ₆ -C3o-Polyoxaalkyl-, a C ₅ -Ci4-aryl or - heteroaryl radical, a C5-Ci4-aryloxy, a linear, partially cyclic or branched Ci-Cis-perfluoroalkyl, in particular Ci-C7-Perfluoralkyl-, a linear, partially cyclic or branched Ci-Cis -Perchloralkyl-,

in particular a C 1 -C 7 -perchloroalkyl, a linear, partially cyclic or branched partially fluorinated C 1 -C 6 -alkyl-, in particular a partially fluorinated C 1 -C 7 -alkyl, a linear, partially cyclic or branched partially chlorinated C 1 -C 6 -alkyl-, in particular a partially chlorinated Ci-C7-alkyl, a perfluorinated or partially fluorinated C6-Ci4-aryl, a per- or partially chlorinated C5-Ci4-aryl- And when A ¹ and A ^{2 are} each NR ² , R ^{2 may be} identical or different, where the C5-C14-aryl or -heteroaryl radicals and C5-C14-aryloxy radicals having one or more linear, partially cyclic or branched C 1 -C 6 -alkyl radicals, in particular C 1 -C 7 -alkyl radicals, may be substituted,

M in the formulas I or II stands for Mo or W,

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 polysubstituted Ce-cis mono-, bi- or terphenolates,

Trifluoromethanesulfonate, trifluoroacetate, noncoordinating anions, especially tetrakis (3,5-bis (trifluoromethyl) phenyl) borate,

Tetrakis (pentafluorophenyl) borate, tetrakis (nonafluoro-tert-butoxy) aluminate, tetrafluoroborate, hexafluorophosphate and

Hexafluoroantimonat, wherein the substituents on the

Mono-, bi- or terphenolates in addition to halogen may have the same meaning as R ² ,

Y is oxygen, sulfur, an N-adamantyl, an N-tert-butyl or a Ce-Ci4-N-aryl radical, in particular a Ce-Cio-N-aryl radical, where the aryl radical is a or several times with halogen, a linear or branched Ci-Cie

Alkyl, a linear or branched Ci-Cie alkyloxy and / or an unsubstituted or substituted phenyl radical may be substituted, whose substituents have the same meaning as R ² ,

Z is a linear, partially cyclic or branched C 1 -C 10 -alkyleneoxy,

in particular a Ci-Cs-Alkylenoxy-, a linear, partially cyclic or branched Ci-Cio-Alkylenenthio-, in particular a Ci-Cs-Alkylenthio-, a linear, partially cyclic or branched Ci-Cio-alkylene-NR ² -, in particular a Ci -Cs-alkylene-NR ² -, a Ce-Cio-aryleneoxy, a per- or partially fluorinated C ₆ -C 4 -aryleneoxy, a per- or partially chlorinated C ₆ -C 4 -aryleneoxy, a per- or partially brominated Ce Ci4-aryleneoxy, a C6-Ci4-arylene thio, a per- or partially fluorinated C6-Ci4-arylene thio, a per- or partially chlorinated Ce-Ci4-arylene thio, a per- or partially brominated C6-Ci4-arylene thio- or a Ce Ci4-arylene-NR ² -, a per- or partially fluorinated C6-Ci4-arylene-NR ² -, a per- or partially chlorinated C6-Ci4-arylene-NR ² -, a per- or partially brominated Ce-Ci4-arylene-NR ² -, a C6-Ci4-arylene-PR ² -, a per- or partially fluorinated Ce-Ci4- arylene-PR ² -, a per- or partially chlorinated C6-Ci4-arylene-PR ² -, a per- or partially brominated Ce -Ci4-arylene-PR ² -, a carboxyl or a thiocarboxyl or a dithiocarboxyl group, and

R ¹ and R ^{1 '} in the formulas I to II, independently of one another, are H or an aliphatic or aromatic radical, in particular a linear or branched C 1 -C 6 -alkyl group, preferably in the form of a tert-butyl or C -C ₂ Ph Group, or an unsubstituted or mono- or polysubstituted Ce-Ci4-aryl group, wherein the substituents have the meanings given for R ² , preferably in the form of 2- (2-propoxy) phen-1-yl, 2-methoxyphene -l-yl, 2,4,5-trimethoxyphenyl or ferrocenyl.

2. Catalyst according to claim 1, characterized in that it has a

shows latent effect in the polymerization of dicyclopentadiene.

3. A catalyst according to claim 1 or 2, characterized in that the ring B is one of the group comprising 1, 2,3-triazol-5-ylidenes, 1,2,4-triazol-3-ylidene or l, 2,3 , 4-tetrazol-5-ylidene is selected heterocycle.

4. A catalyst according to claim 3, characterized in that the ring B is a l, 2,3-triazole-5-ylidene heterocycle.

5. Catalyst according to one of the preceding claims, characterized

in that the ring B is monosubstituted 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 radicals or heteroaryl radicals and C 5 -C 14 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.

6. Catalyst according to one of the preceding claims, characterized

characterized in that R ¹ in formulas I or II for tert-butyl, a

unsubstituted or substituted phenyl or ferrocenyl or CMe ₂ Ph.

7. Catalyst according to one of the preceding claims, characterized

in that Y in the formulas I and II is an N-adamantyl, an N-tert-butyl or an N-dialkylphenyl radical, in particular an N-2,6-dialkylphenyl radical.

8. Catalyst according to one of the preceding claims, characterized

in that X ¹ or X ² in formulas I to II are selected from C ¹ -C 6 -alkoxides and trifluoromethanesulfonate.

9. Use of a catalyst according to any one of claims 1 to 8 for the preparation of polymers by ring-opening metathesis polymerization.

10. Use of a catalyst in the form of an N-heterocyclic carbene complex according to one of the general formulas I or II

characterized in that

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,

the ring B is one of 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 ylidene, 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 thiadiazol-2-ylidenes, mono- or polysubstituted thiadiazolin-2-ylidenes and mono- or polysubstituted tetrahydrotriazol-2-ylidenes selected heterocycle, and preferably 1,3-disubstituted imidazole-2-ylidenes ylidene, is

where the substituents R ² and R ^{2 '} , M, X ¹ and X ² , Y and Z have the meaning given in claim 1,

for the preparation of polymers by ring-opening metathesis polymerization.

11. Use according to claim 9 or 10 for the preparation of

Polydicyclopentadiene or poly [2.2.1] hept-2-enes, where the poly [2.2.1] -hept-2-enes may be substituted or unsubstituted, and preferably at the 5 and 6-position each with pentyl- oxy-methylene radicals are substituted.

12. Use according to claim 11 for the preparation of polydicyclopentadiene in the form of a coating.

13. Process for the preparation of polymers by ring-opening

Metathesis polymerization comprising:

(i) contacting a catalyst according to any one of claims 1 to 8 or as specified in claim 10 with one or more

Double bonds containing cyclic monomer,

(ii) heating the reaction mixture to a temperature sufficient to start the polymerization reaction.

14. The method according to claim 13, characterized in that the

Reaction mixture to a temperature of at least 60 ° C, preferably at least 80 ° C and particularly preferably at least 100 ° C is heated.

15. The method according to claim 13 or 14, characterized in that the reaction mixture is applied before heating in (ii) as a coating on a substrate.

16. The method according to any one of claims 12 to 15, characterized in that the method as a reaction injection molding method,

Transfer molding process or resin injection process is designed.

17. Polydicyclopentadiene, prepared by a process according to any one of claims 12 to 15.