Olefin metathesis polymerization catalyst system and curable compositions containing the catalyst system

Abstract

An olefin metathesis polymerization catalyst system is disclosed. The catalyst system includes a metalate as a precatalyst and an aluminum complex as a cocatalyst, the aluminum complex being an alkoxyalkylaluminum halide complex [(OR 1 )(R 2 )AlX 1 ] n [In the formula, OR 1 is an alkoxy ligand derivable from an alcohol having a pKa in the range of 18 to 30, wherein the alkoxy is optionally functionalized, and further wherein n is an integer in the range of 1 to 3; R 2 is an alkyl group, and X 1 is a halide. A method of making a molded article of a curable composition that includes a catalyst system is disclosed. The method includes providing a curable composition by combining in a mold a cyclic olefin and an olefin metathesis polymerization catalyst system, subjecting the composition to conditions that promote an olefin metathesis reaction of the cyclic olefin in the closed mold, and removing the cured composition from the mold to obtain a molded article.

Description

FIELD OF THE INVENTION

[0001] The present invention relates to an olefin metathesis polymerization catalyst based on a metalate as a precatalyst and an aluminum complex as a cocatalyst, which has improved properties over existing catalysts in particular. Such catalysts are widely used in the ring-opening metathesis polymerization (ROMP) of cyclic olefins such as dicyclopentadiene (DCPD). Background of the Invention

[0002] The preparation of polymers by ring-opening metathesis polymerization (ROMP) of cyclic olefins is well known in the art. A good example is the production of polydicyclopentadiene polymer (PDCPD) by using dicyclopentadiene as the monomer and a metathesis catalyst system containing a precatalyst and a cocatalyst. Other monomers that can be used are monocyclic olefins having three or more carbon atoms and one or more double bonds. Polycycloolefins containing norbornene groups can also be used in ROM polymerization. The precatalyst is generally selected from molybdenum and tungsten compounds, and the cocatalyst is usually selected from organometallic compounds. Examples of such organometallic compounds are alkylaluminums (or aluminum alkyls) and alkylaluminum halides.

[0003] U.S. Patent No. 4,923,936 describes heteropolymetallate metathesis catalysts for the polymerization of cyclic olefins. Polymerization of cyclic olefins by ring opening is achieved in the presence of a metathesis catalyst system composed of an organoammonium, organophosphonium, organoarsonium, heteropolymolybdate, or heteropolytungstate precatalyst and a metathesis cocatalyst. Polymerization proceeds by ring opening of the cyclic olefin, resulting in a polymer with backbone unsaturation. The described precatalysts are soluble in the monomer and preferably have low sensitivity to air and moisture. A cocatalyst selected from organometallic compounds and other materials is used in conjunction with the disclosed precatalyst to polymerize cyclic olefins by polymerization, such as solution or bulk (solvent-free) polymerization. Many cocatalysts have been described and tested in polymerization reactions.

[0004] The above-mentioned pre-catalyst / co-catalyst combinations have disadvantages. For example, known catalyst systems are quite sensitive to humidity and moisture, which affects the reactivity of the catalyst and prevents complete monomer conversion. For this reason, it is desirable to provide a co-catalyst that will initiate the polymerization reaction relatively quickly, allowing relatively high monomer conversions to be reached before final catalyst decomposition occurs.

[0005] Known precatalysts generally have too slow initiation, resulting in relatively low monomer conversions, especially when short cycle times on the order of seconds to minutes are required. As a result, it appears difficult, if not impossible, to mold cycloolefin molded articles having an average thickness of less than 3 mm. Another consequence of the relatively slow initiation is that the flash portion of the molded article (such flash portion is, by definition, thin-walled, sometimes on the order of one-tenth of a millimeter) may not be fully cured. This is a significant drawback, as flash removal becomes technically difficult. This is very time-consuming and is usually undesirable given the relatively fast cure achievable in the polymerization of cycloolefins.

[0006] The addition of chlorinating agents such as tetrachlorosilane (SiCl4) has been proposed to partially overcome the slow initiation of some catalyst systems. However, this (or similar) compound is very sensitive to moisture and can lead to the formation of undesirable substances, such as corrosive compounds (HCl). These compounds can be harmful to molds used to produce molded articles from curable compositions containing the catalyst system, and to health and the environment in general. Summary of the Invention

[0007] The present invention provides an improved catalyst system for ROM polymerization reactions, comprising a metalate-based pre-catalyst and a novel co-catalyst, which catalyst system at least partially overcomes the above-mentioned drawbacks of prior art systems. Another object of the present invention is to provide an improved curable composition comprising a cyclic olefin and the claimed olefin metathesis polymerization catalyst system. Yet another object is to provide a method for producing molded articles of the improved curable composition, and to provide thin-walled molded articles having a minimum or average thickness (excluding optional flash) of 0.2 to 4 mm.

[0008] These and other objects are achieved by the olefin metathesis polymerization catalyst system of claim 1. The catalyst system of the present invention comprises a metalate as a pre-catalyst and an aluminum complex as a co-catalyst, wherein the aluminum complex is an alkoxyalkylaluminum halide complex [(OR 1 )(R 2 )AlX 1 ] n [In the formula, OR 1 is an alcohol HOR with a pKa in the range of 18-30 (calculated considering dimethyl sulfoxide (DMSO) as the solvent). 1 and n is an integer ranging from 1 to 3; and R 2 is an alkyl group, and X 1 is a halide].

[0009] Another aspect of the present invention relates to a curable composition comprising a cyclic olefin and a claimed olefin metathesis polymerization catalyst system.

[0010] Yet another aspect of the present invention is a method for producing a molded article of the claimed curable composition, comprising the steps of: a) providing a curable composition by combining in a mold a cyclic olefin and an olefin metathesis polymerization catalyst system; b) subjecting the composition to conditions promoting an olefin metathesis reaction of the cyclic olefin in a closed mold; c) removing the cured composition from the mold to obtain a molded article; The present invention relates to a method, including:

[0011] In another aspect of the present invention, there is provided a moulded article obtainable by the claimed method, wherein the moulded article has a minimum thickness, the minimum or average thickness of the moulded article being 0.2 to 4 mm, more preferably 0.2 to 3 mm, even more preferably 0.2 to 2 mm, even more preferably 0.2 to 1 mm, and most preferably 0.2 to 0.5 mm, excluding any optional flash.

[0012] Unless defined otherwise (e.g., with respect to pKa), all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used to describe the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0013] According to the present invention, there is provided an olefin metathesis polymerization catalyst system comprising a metalate as a pre-catalyst and an aluminum complex as a co-catalyst, wherein the aluminum complex is an alkoxyalkylaluminum halide complex [(OR 1 )(R 2 )AlX 1 ] n [In the formula, OR 1 is an alkoxy ligand derivable from an alcohol having a pKa in the range of 18 to 30, wherein the alkoxy is optionally functionalized, and further wherein n is an integer in the range of 1 to 3; 2 is an alkyl group, and X 1 is a halide.

[0014] According to a preferred embodiment of the present invention, the alkoxy is functionalized, which in the context of the present disclosure means that the backbone of the alkoxy is substituted with a functional group.

[0015] In particular, it has been found that the claimed alkoxyalkylaluminum halide complexes exhibit much faster initiation rates than known complexes, making it possible to produce cyclic olefin products, such as films, having an average thickness of less than 4 mm. Furthermore, the claimed alkoxyalkylaluminum halide complexes potentially allow substantially complete conversion of the polymerization reaction to be achieved, where "substantially" means preferably greater than 90%, more preferably greater than 95%, even more preferably greater than 98%, and most preferably approximately 100%, given suitable conditions and relative amounts of the catalyst system within the curable composition. This greatly improves the quality of articles molded from cyclic olefin compositions containing the claimed catalyst systems.

[0016] Furthermore, it has been found that flash areas in articles molded from cyclic olefin compositions containing the claimed catalyst system also substantially cure. This is surprising, since catalyst systems are generally thought to prematurely decompose in these flash areas when the temperature rises too high. As a result, it has been found that flash removal is much easier than with current systems.

[0017] Further improved catalyst systems according to embodiments are provided wherein the alcohol has a pKa in the range of 20 to 28, more preferably 21 to 27, and most preferably 22 to 26. This preferred acidity range of the alcohol further enhances the desirable properties of articles molded using the cyclic olefin compositions containing the catalyst system.

[0018] In this application, when ranges are given, they are intended to include the endpoints given in the range.

[0019] The claimed alkoxyalkylaluminum halide complexes may be obtained by introducing alkoxy groups into the corresponding dialkylaluminum halides. This can be achieved either by using alcohols or by other methods. The present invention provides an alkoxyalkylaluminum halide complex containing an alkoxy group in the range of 18-30. 1 The dialkylaluminum halide is treated with alcohol before adding it to the system [(OR 1 )(R 2 )AlX 1 ] n Dialkylaluminum halide (R 2 )2AlX 1 of alcohol 1 The reaction with is preferably carried out in the absence of water by providing a nitrogen atmosphere and mixing the two components to obtain the isolated monomer, dimer, or trimer, or mixture thereof. However, another embodiment is where the aluminum complex is a dialkylaluminum halide (R 2 )2AlX 1 Alcohol for 1 The present invention relates to a catalyst system obtained by reacting in situ with an alkoxyalkylaluminum halide complex. Preferred alcohols provide alkoxyalkylaluminum halide complexes that are soluble in cyclic olefin monomers. In such embodiments, bulk polymerization of curable compositions comprising cyclic olefins and the claimed olefin metathesis polymerization catalyst system is possible without the need for additional solvents.

[0020] It should be noted that, according to the present invention, the alkoxy ligands can be derived from alcohols HOR1 having a pKa in the range of 18 to 30. Preferably, the alkoxy ligands are derived from alcohols. However, the alkoxy ligands can also be derived from aldehydes and / or ketones, resulting in alkoxyalkylaluminum halide complexes of similar or identical structure as claimed.

[0021] It should be noted that the aluminum complex cocatalyst in its dimeric or trimeric form may consist of cis and trans stereoisomers and may be used as a mixture of these stereoisomers. Furthermore, in the case of chiral alcohols, both enantiomers and their racemic mixtures may be used to form the aluminum complex cocatalyst. The use of a racemic mixture of chiral alcohols results in the formation of additional stereoisomers of the aluminum complex cocatalyst, all of which are effective in producing a catalytic system with improved properties. Chiral alcohols may have more than one stereoelement, for example, they may include diastereomers.

[0022] The alkoxy groups in the cocatalyst appear to function by suppressing the reducing power of the corresponding dialkylaluminum halide cocatalyst by replacing some of the alkyl groups on the aluminum. The reduced reducing power of the alkoxyalkylaluminum halide cocatalyst results in an extended pot life, allowing for convenient mixing of various ingredients at room temperature before initiating the polymerization reaction and subsequent polymerization.

[0023] The resulting alkoxyalkylaluminum halide has the formula [(OR 1 )(R 2 )AlX 1 ] n As used herein, R 1 is an alkyl group having about 1 to 18 carbon atoms, and R 2 X is also an alkyl group having 1 to 18 carbon atoms. 1 represents a halogen selected from chlorine, iodine, bromine, and fluorine, of which chlorine is preferred.

[0024] In another embodiment of the present invention, R 2 is an alkyl group, and X 1 is chlorine (Cl).

[0025] In yet another embodiment, the catalyst system is characterized in that n=2.

[0026] In another embodiment, the alkoxy ligand OR in the catalyst system 1 is a compound in which the alkoxy ligand is a primary or secondary alcohol HOR 1 Aryloxyalkylaluminum halides may also be added to the claimed catalyst system. The aryloxy groups may be derived, for example, from (sterically unhindered) phenols and resorcinol. However, in another useful embodiment, the alcohol HOR 1 is an aliphatic alcohol and the aluminum complex does not contain an aryloxy ligand. In this embodiment, the alkoxy may also be functionalized.

[0027] The inventors have found that alcohol 1 It has been discovered that the steric bulkiness of the alcohol HOR can play an essential role in the performance of the catalyst system and can be used to improve it for the purposes of the present invention. Therefore, a preferred embodiment of the present invention is to use an alcohol HOR 1 The present invention provides a catalyst system having steric bulk defined by an XCA cone angle in the range of 160 to 200°, more preferably 170 to 190°.

[0028] The inventors further investigated the alcohol HOR 1 R 1 It has been discovered that the Lewis basicity of optional heteroatoms and functional groups present in the amines can also have an effect on the desired properties. To characterize the Lewis basicity of such optional heteroatoms and functional groups, the inventors have introduced the GLB descriptor, which is the Gibbs free energy (kcal / mol) of association of a suitable model compound of such optional heteroatoms and functional groups to AlCl3 as a model Lewis acid. GLB is defined in full detail below. Thus, another preferred embodiment is a amine compound containing an alcohol OR 1 Preferably, the heteroatoms and / or functional groups present therein have a GLB descriptor of greater than -12, more preferably greater than -10, even more preferably greater than -8, and most preferably greater than -6.

[0029] The presence of some functional groups in the alcohol can accelerate decomposition of the cocatalyst, which is less desirable, for example, depending on the rate of decomposition. Such alcohols may even prevent the desired ROMP reaction from proceeding. Less desirable, and therefore less preferred, or even more preferably excluded, functionalized alcohols include benzyl alcohol and / or alcohols containing a -CHF functional group.

[0030] In addition to the cocatalyst, the metathesis polymerization catalyst system of the present invention includes a metalate as a precatalyst capable of metathesis ring-opening polymerization of cyclic olefin monomer units. Such precatalysts may include complexes having a transition metal atom as a central atom and containing multiple ions, atoms, and / or compounds bonded thereto. Transition metal atoms may be advantageously used, including tantalum, molybdenum, tungsten, ruthenium, vanadium, and osmium.

[0031] A very suitable catalyst is one in which the metalate is a molybdate, a tungstate, or a mixture thereof, preferably a molybdate. Molybdates and tungstates have the formula: [R 3 4N] z [R 4 3NH] (2y-6x-z) M x O y where M represents either molybdenum or tungsten, and x and y represent the number of M and O atoms in the molecule based on the oxidation states of molybdenum +6, tungsten +6, and oxygen −2; R 3 and R 4 The moieties may be the same or different and are selected from hydrogen atoms, alkyl and alkylene groups having 1 to 20 carbon atoms, and alicyclic groups having 5 to 16 carbon atoms. The above formula encompasses any quaternary:tertiary ammonium ratio.

[0032] Quaternary ammonium may include compounds formulated as follows: [R 3a R 3b R 3c R 3d N] +

[0033] Tertiary ammonium may include compounds formulated as follows: [R 4a R 4b R 4c HN] +

[0034] When the metalate is soluble in the hydrocarbon reaction solvent and / or the cyclic olefin monomer, R 4 Portion size should not be too small. 4 When the moieties are all the same, each preferably has from 5 to 18 carbon atoms. 4 If the moieties are all different, each preferably has from 4 to 18 carbon atoms.

[0035] Specific examples of suitable metalates, such as molybdates and tungstates, include tridodecylammonium molybdate and tridodecylammonium tungstate, methyltricaprylammonium molybdate and methyltricaprylammonium tungstate, tri(tridecyl)ammonium molybdate and tri(tridecyl)ammonium tungstate, and trioctylammonium molybdate and trioctylammonium tungstate.

[0036] An embodiment of the present invention is a halogen compound M x X y R z[wherein M is tungsten (W), molybdenum (Mo), titanium (Ti), or silicon (Si), preferably Si; X is fluoride (F), chloride (Cl), bromide (Br), or iodide (I), preferably Cl; R is O, an O-alkyl group, an O-phenyl group, an alkyl group, or a phenyl group; and x, y, and z may be 1 to 10. The catalyst system according to this embodiment preferably further comprises a halogen compound selected from the group consisting of silicon alkyl chloride Si x Cl y R z [wherein R is O, an O-alkyl group, or an alkyl group, and x, y, and z can be 1 to 10], and is contained in an amount of 0 to 3 mass % relative to the total amount of the catalyst system.

[0037] An important advantage of the catalyst system of the present invention is that it can be used in combination with a further halogen compound M x X y R z A particularly preferred embodiment provides a catalyst system in which the alkylchlorosilane comprises tetrachlorosilane, and the catalyst system comprises at most 0.15 wt. % of tetrachlorosilane (SiCl), based on the total amount of the catalyst system, more preferably at most 0.12 wt. %, even more preferably at most 0.10 wt. %, and most preferably at most 0.06 wt. % of tetrachlorosilane (SiCl).

[0038] Even more preferably, the catalyst system does not contain tetrachlorosilane. Embodiments containing up to 0.06% by weight of an additional halogen compound, particularly SiCl, exhibit reduced sensitivity to moisture. Furthermore, the release of corrosive compounds such as HCl is reduced or even completely prevented.

[0039] In yet another useful embodiment, the catalyst system comprises an alkoxy ligand OR 1is functionalized with a halogen. The halogen is, for example, chlorine (Cl) or fluorine (F), preferably fluorine (F). The latter embodiment is preferred because some cocatalysts may undergo slight decomposition during the polymer molding operation and may release compounds upon reaction with moisture. While the compounds released in this embodiment are non-carcinogenic, in other embodiments some of these compounds are classified as carcinogenic, making the release of these substances into the atmosphere particularly problematic.

[0040] In yet another catalyst system according to an embodiment of the present invention, the alkoxy ligand OR 1 is an alcohol HOR selected from 1,1,1-trifluoro-2-propanol, 1,1-difluoro-2-propanol, and 1-chloro-2-propanol 1 It is a derivative of

[0041] A particularly preferred catalyst system according to the present invention comprises molybdate as precatalyst and [Al(1,1,1-trifluoro-2-propoxy)](Cl)(C2H5) as cocatalyst. n Includes [n=1 or 2].

[0042] Another aspect of the present invention relates to a curable composition comprising a cyclic olefin and a claimed olefin metathesis polymerization catalyst system.

[0043] The cyclic olefin used in the present invention comprises cyclic olefin monomer units that can be prepared to form a cyclic olefin polymer obtained by polymerization of the cyclic olefin monomer units. In principle, any polymer of cyclic olefin monomer units known in the art may be used in the present invention. The cyclic olefin polymer comprises cyclic monomer units of a saturated cyclic hydrocarbon (cycloalkane) structure and / or an unsaturated cyclic hydrocarbon (cycloalkene) structure. The number of carbon atoms forming the cyclic structure in the monomer unit is not particularly limited, but in a preferred embodiment, it is in the range of 4 to 30, more preferably 5 to 20, and most preferably 5 to 15.

[0044] The amount of cyclic olefin monomer units in the cyclic olefin polymer may be selected within a wide range, but is preferably 50% by weight or more, more preferably 70% by weight or more, and most preferably 90% by weight or more, excluding any filler in the composition. Combinations of different cyclic monomers may also be used. The cyclic olefin polymer of the composition may optionally comprise an addition polymer of cyclic olefin monomer units copolymerized with another olefin monomer and / or may comprise a ring-opening polymer of cyclic olefin monomer units, the latter being preferred.

[0045] The cyclic olefin monomer unit forms a cyclic structure of carbon atoms and carbon-carbon double bonds, and examples thereof include, but are not limited to, norbornene-based monomer units and monocyclic monomer units. The cyclic olefin monomer unit is preferably a norbornene-based monomer unit. Norbornene-based monomer units include those having a norbornene ring, such as 2-norbornene, norbornadiene, and other bicyclic compounds; dicyclopentadiene (DCPD), dihydrodicyclopentadiene, and other tricyclic compounds; tetracyclododecene, ethylidenetetracyclododecene, phenyltetracyclododecene, and other tetracyclic compounds; tricyclopentadiene and other pentacyclic compounds; tetracyclopentadiene and other heptacyclic compounds; alkyl-substituted compounds, such as methyl, ethyl, propyl, and butyl-substituted compounds; alkylidene-substituted compounds, such as ethylidene-substituted compounds; aryl-substituted compounds, such as phenyl and tolyl-substituted compounds; and derivatives thereof having, for example, epoxy groups, methacryl groups, hydroxyl groups, amino groups, carboxyl groups, cyano groups, halogen atoms, and the like. The cyclic olefin preferably contains a dicyclopentadiene unit.

[0046] Monocyclic cyclic olefin monomer units may also be used, and suitable examples thereof include cyclobutene, cyclopentene, cyclooctene, cyclododecene, 1,5-cyclooctadiene, and other monocyclic olefins, as well as polar group-containing substituted compounds and derivatives such as those listed as examples of norbornene-based monomer units. Such cyclic olefin monomers may be used alone or in combination with one another or multiple types. Suitable linear olefin monomer units that may be polymerized via addition polymerization with the above-mentioned cyclic olefin monomer units include, but are not limited to, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 2-pentene, and 1,4-hexadiene. The amount of linear olefin monomer units used is preferably less than 50% by weight, more preferably less than 20% by weight, and even more preferably less than 10% by weight, based on the total amount of the cyclic olefin and linear olefin monomer units.

[0047] In addition to the cyclic olefin monomer units, the curable composition further comprises a claimed cyclic olefin metathesis polymerization catalyst system, preferably in an amount of 30 to 1000 ppm based on the total weight of the composition. This corresponds to a preferred amount of about 0.01 to 100 mmol of metalate per mole of total monomer, preferably 0.1 to 10 mmol of metalate per mole of total monomer. The molar ratio of alkoxy or aryloxyalkyl aluminum halide to metalate is not particularly critical and may be selected from the range of about 1:10 to about 200:1, preferably 2:1 to 40:1, for alkoxy or aryloxyalkyl aluminum halide to metalate.

[0048] The olefin metathesis polymerization catalyst system may be used in any suitable form, including a form in which it is dissolved or suspended in a solvent. Suitable solvents include linear aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, or liquid paraffin, and alicyclic hydrocarbons such as cyclopentane, cyclohexane, alkyl-substituted cyclohexane, di- and tricycloheptane, and cyclooctane, as well as aromatic hydrocarbons such as benzene, toluene, xylene, and the like; nitrogen-containing solvents such as nitromethane, nitrobenzene, and acetonitrile; and oxygen-containing solvents such as diethyl ether and tetrahydrofuran, to name a few. As already mentioned above, the olefin metathesis polymerization catalyst system is preferably dissolved in the cyclic olefin monomer.

[0049] The curable composition may also preferably include a catalyst retarder capable of extending shelf life before curing begins. Polymerization reaction retarders are well known in the art and may include, but are not limited to, phosphite compounds.

[0050] The composition may also contain a chain transfer agent, such as a linear olefin having a substituent. Suitable chain transfer agents include vinylnorbornene, 1-hexene, 2-hexene, and other aliphatic olefins; styrene, divinylbenzene, and other vinyl aromatic olefins; olefins having alicyclic hydrocarbon groups such as vinylcyclohexane; vinyl ethers; methyl vinyl ketone; and substituted (meth)acrylic acids and their salts, such as vinyl (meth)acrylate, allyl (meth)acrylate, and allyl trivinyl silane; allyl methyl divinyl silane, allyl dimethyl vinyl silane, and 4-vinyl aniline. Such chain transfer agents may be used alone or in combination and are generally added in an amount ranging from 0.01 to 10 parts by weight, preferably from 0.1 to 5 parts by weight, per 100 parts by weight of the cyclic olefin monomer units.

[0051] Other additives, such as flame retardants, light stabilizers, pigments, dyes, pigments and other pigments, and, for example, blowing agents, may be added to the composition. Suitable flame retardants include, but are not limited to, phosphorus, nitrogen, and halogen-containing flame retardants, for example, metal hydroxides such as aluminum hydroxide, and antimony compounds such as antimony trioxide.

[0052] In a preferred embodiment, filler can be added to the composition of the present invention.Both inorganic and organic fillers can be used without limitation, but inorganic fillers are preferred.Suitable inorganic fillers include, for example, iron, copper, nickel, gold, silver, aluminum, lead and tungsten metal particles; carbon particles, for example, carbon black, graphite, activated carbon, carbon microballoons, etc.; inorganic oxide particles, for example, silica, alumina, titanium oxide, iron oxide, zinc oxide, magnesium oxide, etc.; inorganic carbonate particles, for example, calcium carbonate and magnesium carbonate; calcium sulfate; inorganic silicate particles, for example, talc, clay, mica, kaolin, fly ash, montmorillonite, calcium silicate and glass microparticles; and titanate, aluminum nitride and silicon carbide particles.

[0053] Suitable organic fillers include, for example, wood, starch, lignin, organic pigments, and polymer particles, such as particles of polystyrene, polyamide, polyolefin (e.g., polyethylene and polypropylene), polyvinyl chloride, elastomers, and / or waste polymers. Functional fillers, such as piezoelectric ceramics, fillers that change static / conductive properties (e.g., carbon nanotubes), and rheology modifiers, can also be added. The fillers may be sized.

[0054] The composition may also contain reinforcing fibers. Suitable reinforcing fibers can be selected from a wide range. For example, inorganic fibers such as glass fibers, carbon fibers, and graphite fibers, alumina fibers, tungsten fibers, molybdenum fibers, titanium fibers, steel fibers, boron fibers, silicon carbide fibers, and silica fibers can be used. Other suitable fibers include organic fibers such as aramid fibers, ultra-high molecular weight polyethylene fibers, liquid crystal and other polyester fibers, as well as natural fibers and reinforcing materials. Preferred reinforcing fibers include glass fibers and carbon fibers, of which E-glass, R-glass, S-glass, and S2-glass fibers are most preferably used.

[0055] The reinforcing fibers can be applied in any physical form, i.e., as mono- and multifilaments, in the form of strands and yarns, as woven fabrics or according to other fabric structures, as staple or continuous fibers, or in the form of pre-impregnated sheets ("prepregs"). Any combination of different types of fibers is also possible. The amount of reinforcing fibers may be chosen within wide limits, but suitable amounts are generally in the range of 30-70% by volume.

[0056] In yet another aspect of the present invention, there is provided a method for producing a molded article of the claimed curable composition, comprising the steps of: a) providing a curable composition by combining in a mold a cyclic olefin and an olefin metathesis polymerization catalyst system; b) subjecting the composition to conditions promoting an olefin metathesis reaction of the cyclic olefin in a closed mold; c) removing the cured composition from the mold to obtain a molded article; A method is provided, comprising:

[0057] Methods for producing molded articles include, but are not limited to, those formed by modern manufacturing techniques such as casting, centrifugal casting, pultrusion, injection pultrusion, rotational molding, and open molding. In embodiments of the present invention, a method is provided that includes injecting a composition into a closed mold, where reinforcing fibers may be provided in the mold prior to injecting the composition. Other suitable techniques include reaction injection molding (RIM), resin transfer molding (RTM), vacuum-assisted resin infusion (VARI), Seeman Composite Resin Infusion Molding (SCRIMP), reinforced reaction injection molding (RRIM), structural reaction injection molding (SRIM), thermal expansion transfer molding (TERM), resin injection recirculation molding (RICM), pneumatically controlled resin infusion (CAPRI), and the like.

[0058] The step of subjecting the composition to conditions promoting the olefin metathesis reaction of the cyclic olefin involves heating the mold and composition to a suitable curing temperature, optionally at a pressure greater than 0.1 MPa, for a suitable time interval. In an embodiment of the method, the heating temperature ranges from room temperature (RT) to 200°C, more preferably from 30°C to 100°C, and even more preferably from 60°C to 80°C. The heating time preferably ranges from 1 to 60 minutes, more preferably from 2 to 30 minutes, and even more preferably from 5 to 10 minutes. The pressure applied during molding may be selected according to the manufacturing method used and may be as low as 0.1 to 0.5 MPa, for example, when using RTM. Vacuum or reduced pressure may also be used.

[0059] Molded articles may be used in a variety of applications, including, but not limited to, aerospace, marine, automotive, sporting goods, electrical, medical, and military components. Particularly preferred applications involve molded articles in the form of films. Polymer films are defined as thin, continuous materials with relatively low thicknesses, typically from 10 μm to a maximum of 4 mm. They are typically provided in rolls.

[0060] A particularly useful embodiment provides a process in which the molded article after step c) has a glass transition temperature Tg equal to or higher than the mold temperature, preferably greater than 60°C, more preferably greater than 80°C, even more preferably greater than 100°C, and most preferably greater than 120°C. The inventors have surprisingly found that it is possible to produce cyclic olefin articles having the claimed properties. The catalyst system of the present invention has also been found to make it possible to produce parts comprising a flash portion having a relatively high Tg. This embodiment greatly facilitates flash portion removal, an additional step in preferred embodiments of the process further comprising a flash portion removal step.

[0061] The methods and claimed catalyst systems of the present invention may be used to produce improved molded articles. In one embodiment, a molded article is obtainable by the method and is characterized in that, excluding any flash, the minimum or average thickness of the molded article is 0.2 to 4 mm, more preferably 0.2 to 2 mm, even more preferably 0.2 to 1 mm, and most preferably 0.2 to 0.5 mm. An example of such a molded article includes a film. In another embodiment, a molded article is obtainable by the method and includes a flash, and has a glass transition temperature Tg greater than 60°C, more preferably greater than 80°C, even more preferably greater than 100°C, and most preferably greater than 120°C. [Example]

[0062] The present invention will be more specifically described with reference to examples and comparative experiments, but is not limited to these examples. It should be noted that in the examples and comparative experiments, "parts" and "%" are based on mass unless otherwise specified. The present invention will be further described by the following figures. [Brief explanation of the drawings]

[0063] [Figure 1]FIG. 1 is a graph of XiMo cone angle as a steric parameter introduced in accordance with an embodiment of the present invention to characterize the steric bulkiness of alkoxide ligands in both transition metal and main group metal complexes. [Figure 2] Figure 2 is a graph showing polydicyclopentadiene yield as a function of time for DCPD ROMP catalyzed by the system pMo / [(ClCH)CHOAlEtCl] in D8 toluene at 25 °C ([Mo] / [Al] / [DCPD] = 0.00025, 0.001, 0.033 mol / L). [Figure 3] Figure 3 is a graph showing polydicyclopentadiene yield as a function of time for DCPD ROMP catalyzed by the system pMo / [(rac)-(CF)MeCHOAlEtCl] in D8 toluene at 25 °C ([Mo] / [Al] / [DCPD] = 0.00025, 0.001, 0.033 mol / L). [Figure 4] FIG. 4 is a graph showing the kinetic curves of FIGS. 2 and 3 combined into one graph for comparison.

[0064] <Methods and definitions> XiMo cone angle (XCA; degrees) The XiMo cone angle is a steric parameter of alkoxide ligands in d-block and p-block metal complexes, introduced by the present inventors to characterize the steric bulkiness of alkoxide ligands in both transition and main group metal complexes, particularly the claimed aluminum complexes of alkoxide ligands. XCA is adapted from the concept of the Tolman cone angle (C.A. Tolman, J. Am. Chem. Soc., 1970, 92, 2956-2965), a steric parameter widely used for tertiary phosphines coordinated to transition metals. However, in the case of XCA, the original definition has been modified to take into account the different σ-donor symmetry in the case of oxygen donor atoms compared to phosphorus donor atoms.

[0065] XCA is the opening angle of a cone whose apex is the oxygen atom of the alkoxide ligand and whose outer face touches the outermost atom of the alkoxy ligand. 3v Symmetry (RCO - ), the opening angle of one single cone is used as the steric parameter. - ), the corresponding C 3v Symmetrical alkoxides (RCO - , R'3CO - , R”3CO - ) defines the steric bulk of the ligand.

[0066] The step-by-step determination of steric parameters using molecular modeling is disclosed below. The molecular modeling was performed by Dr. Adam Madarasz and Prof. Imre Papai of the Institute of Organic Chemistry of the Hungarian Academy of Sciences. Importantly, unlike the Tolman cone angle, the calculation of the XiMo cone angle does not directly involve the metal to which the alkoxide is coordinated. However, the alkoxide conformation used in the calculation is derived from the optimized structure of the desired metal complex, so the metal and other ligands indirectly affect the calculated cone angle.

[0067] Referring to Figure 1, the steps are as follows: 1. Determine the most stable conformation of the alkoxide ligand in the desired complex. 2. Determine the β angle from the structure. β is the angle between the bond OC and the line segment OA, where A is the outermost atom of the group bonded to CO (to find the β angle, consider the centers of the O, CO, and A atoms). 3. Calculate γ-s from the distance OA and the van der Waals radius r at A: sinγ=r / A. 4. If the three moieties attached to the CO atom of an alkoxide are the same, the alkoxide is C 3vThe steric parameters are given by the C atom from each moiety. 3v It is defined as the average of the cone angles of a symmetric alkoxide. Technically, it is calculated by taking the average of the three β + γ half angles and multiplying the average half angle by 2.

[0068] Bronsted acidity (pKa) of alcohols In the studies related to the present invention, the electronic properties (electron donor ability) of alkoxide ligands toward metals (especially Al) are characterized by the Brønsted acidity of the corresponding alcohol. We hypothesized that the electron donation of the alkoxide oxygen toward metals (especially Al) correlates with the polarity of the OM bond (where M = metal), and with the polarity of the OH bond in the corresponding alcohol, i.e., the Brønsted acidity of the alcohol. pKa values ​​were calculated considering dimethyl sulfoxide (DMSO) as the solvent.

[0069] GLB, Lewis basicity descriptor of the functional groups in the alkoxide skeleton (kcal / mol) The inventors have observed that the Lewis basicity of certain heteroatoms or functional groups present in the backbone of alkoxide ligands has a significant impact on the catalytic performance of the catalyst system. The inventors have introduced the GLB descriptor to characterize the Lewis basicity of such heteroatoms or functional groups. The GLB of said heteroatoms or functional groups is determined by the following reaction: X+AlCl3→[XAlCl3] ΔG(kcal / mol)=GLB is defined as the Gibbs free energy of complex formation between a model compound X with a given heteroatom or functional group as the Lewis base functional group and AlCl3 as the model Lewis acid according to

[0070] Model compounds X are defined as compounds derived from a given heteroatom or functional group in which all free valences of the given heteroatom or functional group are bonded to methyl groups and are listed in Table 1 along with the calculated ΔG-s (GLB-s) of the model Lewis acid-base reaction.

[0071] [Table 1]

[0072] Example 1: Synthesis and characterization of an Al-based cocatalyst of a Mo-based catalyst system for the ring-opening metathesis polymerization of dicyclopentadiene (DCPD) <Method A> It should be noted that diethylaluminum chloride (DEAC) physically exists as a dimer [AlEt2Cl]2, but in terms of stoichiometry the molecule is considered as monomeric AlEt2Cl.

[0073] DEAC (125 μL, 121 mg, 1 mmol) was dissolved in pentane (5 mL) in a 30 mL vial equipped with a magnetic stir bar. The vial was sealed with a septum, which was pierced with a needle to avoid a possible pressure buildup in the vial during the reaction. At room temperature, R dissolved in pentane (5 mL) was 1 OH alcohol (1 mmol) was slowly added dropwise through the septum using a syringe over approximately 15 minutes. Note that in many cases, the evolution of EtH could not be observed visually. The reaction mixture was stirred overnight at room temperature. All volatiles were evaporated under reduced pressure to give the crude product, typically as a colorless oil or white solid. No further purification was attempted, so yields are not given. Nevertheless, mass balances were usually checked, and the masses of the isolated materials were found to be within ±10% of the theoretical yield of the given target. The crude products were analyzed by 1D and 2D NMR techniques and were typically found to be cis,trans-[Al(OR)EtCl]2. They were 1 H, 13 C{ 1 H}, and 19 F{ 1 Characterized by {H} NMR (where applicable).

[0074] Note that the rapid addition of alcohol to DEAC did not change the composition of the cocatalyst.

[0075] Furthermore, in the case of racemic chiral alcohols, the number of stereoisomers of [Al(OR)EtCl] increases, and in most cases, they have not been individually characterized by NMR. It should also be noted that the presence of certain functional groups in the alcohol promotes cocatalyst decomposition. Depending on the rate of decomposition, the decomposing cocatalyst may or may not be characterized by NMR and may or may not be used to promote the desired ROMP reaction. Such structural features were benzyl alcohol or the presence of the -CHF functional group. (Examples 1.2, 1.7)

[0076] <Method B> Similar to Method A, but benzene was used as the solvent for the alcohol.

[0077] <Examples 1.1 to 1.10> Example 1.1. Reaction of 1,3-dichloro-2-propanol (1,3-DCP) with diethylaluminum chloride in 1:1 stoichiometry: The reaction was carried out according to Method A, yielding a white solid. The major product was cis,trans-{Al[OCH(CH2Cl)2]EtCl}2 (cis:trans = 45:55). An unidentified by-product was present in an amount of approximately 10%.

[0078] The NMR characteristics were as follows: cis-dimer 1 H NMR(400MHz,300K,C6D6):(ppm)3.91(m,2H,OCH(CH2Cl)2),3.35(dd,3J=3.4Hz,2J=11.8Hz, 4H,OCH(CHHCl)2),3.2(dd,3J=6.5Hz,2J=11.8Hz,4H,OCH(CHHCl)2),-0.41(s,6H,Al-CH3); 13 C NMR(75MHz,298K,C6D6):(ppm)74.3(OCH(CH2Cl)2),43.4(OCH(CH2Cl)2),-9.45(Al-CH3); 27Al NMR(104MHz,300K,C6D6):(ppm)119(Δ1 / 2=3.2kHz) trans-dimer 1 H NMR(400MHz,300K,C6D6):(ppm)3.84(m,2H,OCH(CH2Cl)2),3.55(dd,3J=3.8Hz,2J=11.5Hz,2H,OCH(CHHCl) )2),3.34(m,4H,OCH(CHHCl)2),3.28(dd,3J=6.0Hz,2J=12.1Hz,2H,OCH(CH2Cl)2),-0.36(s,6H,Al-CH3); 13 C NMR(75MHz,298K,C6D6):(ppm)74.1(OCH(CH2Cl)2),43.8(OCH(CH2Cl)2),-9.65(Al-CH3); 27 Al NMR(104MHz,300K,C6D6):(ppm)119(Δ1 / 2=3.2kHz)

[0079] Example 1.2. Reaction of rac-1-phenylethanol with diethylaluminum chloride in 1:1 stoichiometry: The reaction was carried out according to Method B. A colorless oil was obtained that turned yellow on standing. The major product was a stereoisomer of {Al[OCH(CHOMe)]EtCl}. Several isomers were present but were not individually characterized.

[0080] Example 1.3. Reaction of 2,4-dimethyl-3-pentanol with diethylaluminum chloride in 1:1 stoichiometry: The reaction was carried out according to Method B, yielding a colorless oil. The major product was cis,trans-[Al(OCHEt2)2]EtCl]2 (cis:trans = 33:67). An unidentified by-product was present in an amount of approximately 27%. The cis isomer was present in an amount of approximately 33%.

[0081] The NMR results were as follows: 1H-NMR (C6D6, 300 MHz): d 0.26 (q, 4H, CHClEt), 0.85 (d, 12H, CHalkoxide), 0.98 (d, 12H, CHalkoxide), 1.34 (t, 6H, CHClEt), 3.43 ppm (t, 2H, OCH). 13 C{ 1 H}-NMR (C6D6, 75 MHz): d 2 (br, CH2Et), 8.9 (CH3Et), 18.6 (CH3 alkoxide), 19.4 (CH3 alkoxide), 31.5 (CH), 89.31 ppm (OCH), trans isomer (approximately 67%). 1 H-NMR (C6D6, 300 MHz): d 0.40 (q, 4H, CHClEt), 0.73 (d, 12H, CHalkoxide), 0.87 (d, 12H, CHalkoxide), 1.00 (d, 12H, CHalkoxide), 1.07 (d, 12H, CHalkoxide), 1.36 (t, 6H, CHClEt), 3.49 ppm (dd, 2H, OCH). 13 C{ 1 H}-NMR (C6D6, 75 MHz): d 2 (br, CH2Et), 8.8 (CH3Et), 17.7 (CH3 alkoxide), 19.2 (CH3 alkoxide), 19.4 (CH3 alkoxide), 20.0 (CH3 alkoxide), 31.2 (CH), 31.9 (CH), 89.26 ppm (OCH).

[0082] Example 1.4. Reaction of (rac)-trans-2-chloro-cyclohexanol with diethylaluminum chloride in 1:1 stoichiometry: The reaction was carried out according to Method B, yielding a white solid. The major product was the stereoisomer of [Al(OR)]EtCl}2 (R = 2-chloro-cyclohexyl). Some stereoisomers were not individually characterized.

[0083] Example 1.5. Reaction of (R)-1-chloro-2-propanol with diethylaluminum chloride in 1:1 stoichiometry: The reaction was carried out according to Method A, yielding a white solid. The major product was cis,trans-{Al[OCH(CHCl)Me]EtCl}(cis:trans=40:60). Unidentified by-products were <5%, and the cis isomer was present in an amount of approximately 40%.

[0084] The NMR results were as follows: 1 H-NMR(C6D6,300MHz):d 0.26(q, H,CH2Et),1.07(d,6H,CH3),1.17(t,6H,CH3Et),2.92&3.15(m,4H,CH2Cl),3.92ppm(m,2H,CH). 13 C{ 1 H}-NMR(C6D6,75MHz):d about 0.9 br(CH2Et),8.47(CH3Et),20.02(CH3),49.34(CH2Cl),72.14 ppm(CH),trans isomer(about 60%) 1 H-NMR(C6D6,300MHz):d 0.31(q,4H,CH2Et),1.07(d,6H,CH3),1.23(t,6H,CH3Et),2.92&3.15(m,4H,CH2Cl),3.86ppm(m,2H,CH). 13 C{ 1 H}-NMR(C6D6,75MHz):d approx. 0.9 br(CH2Et),8.43(CH3Et),19.94(CH3),19.98(CH3),49.28(CH2Cl),49.32(CH2Cl),71.98(CH),72.17ppm(CH).

[0085] Example 1.6. Reaction of 1,3-dimethoxy-2-propanol with diethylaluminum chloride in 1:1 stoichiometry: The reaction was carried out according to Method B, yielding a white solid. The major product was cis,trans-{Al[OCH(CHOMe)]EtCl} (cis:trans = 45:55). The unidentified by-product accounted for approximately 18%, and the cis isomer was present in an amount of approximately 45%.

[0086] The NMR results were as follows: 1 H-NMR (C6D6,300MHz):d 0.20(q,4H,CH2Et),1.32(t,6H,CH3Et),3.02(s,12H,OCH3),3.35&3.40(ABqd,8H,OCH2),4.43ppm(quintet,2H,CH). 13 C{ 1 H}-NMR(C6D6,75MHz):d approx. 0.5 br(CH2Et),9.9(CH3Et),58.7(OCH3),67.2(CH),72.1ppm(OCH2),trans isomer(approximately 55%) 1 H-NMR(C6D6,300MHz):d 0.23(q,4H,CH2Et),1.37(t,6H,CH3Et),3.02(s,12H,OCH3),3.33&3.78(ABqd,4H,OCH2),3.47&3.52(ABqd,4H,OCH2),3.78ppm(dddd,2H,CH). 13 C{ 1 H}-NMR(C6D6,75MHz):d approx. 0.5 br(CH2Et), 9.8(CH3Et), 58.64(OCH3), 58.66(OCH3), 67.6(CH), 71.7(OCH2), 72.1ppm(OCH2).

[0087] Example 1.7. Reaction of 1,3-difluoro-2-propanol with diethylaluminum chloride in 1:1 stoichiometry: The reaction was carried out according to Method B, yielding a colorless oil that began to crystallize in the freezer. Partial decomposition was observed upon standing. The major product was cis,trans-{Al[OCH(CHF)EtCl}(cis:trans=50:50). An unidentified by-product accounted for approximately 10% and was the cis isomer (approximately 50%).

[0088] The NMR results were as follows: 1H-NMR(C6D6,300MHz):d 0.28(q,4H,CH2Et),1.20(t,6H,CH3Et),3.93(ABqdd, 2 J HF =47Hz,J HH =9.9,4.9Hz,8H,CH2F),3.78ppm(t quintet, 3 J HF =20Hz,2H,CH). 13 C{ 1 H}-NMR(C6D6,75MHz):d 8.2(CH3Et),71.5(t,CH),81.3 ppm(dd,J CF =170,6.5Hz,CH2F). trans isomer (approximately 50%) 1 H-NMR(C6D6,300MHz):d 0.31(q,4H,CH2Et),1.24(t,6H,CH3Et),4.02&4.09(ABqdd, 2 J HF =47Hz,J HH =10.5,10.2,5.3,4.3Hz,8H,CH2F),3.65ppm(m,2H,CH). 13 C{ 1 H}-NMR(C6D6,75MHz):d 8.2(CH3Et),71.4(dd,CH),81.0ppm(dd,J CF =170,6.0Hz,CH2F).

[0089] Example 1.8. Reaction of t-butanol with diethylaluminum chloride in 1:1 stoichiometry: The reaction was carried out according to Method B, and colorless crystals were obtained. The main product was cis,trans-[Al(OCMe3)EtCl]2 (cis:trans=30:70). The unidentified by-product accounted for approximately 10%. 1 It was characterized by H NMR resonance.

[0090] cis isomer (approximately 30%) The NMR results were as follows: 1H-NMR (C6D6, 300MHz):d 0.22(q,CH2-Al),1.18(t,C*H3CH2Al)ppm,1.24ppm(s,CH3-C). trans isomer (approximately 70%) 1 H-NMR (C6D6, 300MHz):d 0.29(q,CH2-Al),1.28(t,C*H3CH2Al),1.23ppm(s,CH3-C).

[0091] Example 1.9. Reaction of 2-trifluoromethyl-2-propanol with diethylaluminum chloride in 1:1 stoichiometry: The reaction was carried out according to Method B, and a white solid was obtained. The major product was cis,trans-[Al(OCMe2CF3)EtCl]2 (cis:trans=30:70). The unidentified by-product accounted for approximately 12%.

[0092] cis isomer (approximately 30%). The NMR results were as follows: 1 H-NMR(C6D6,300MHz):d 0.29(q,4H,CH2Et),1.14(t,6H,CH3Et),1.38ppm(q, 4 J HF =1.1Hz,12H,OC(CH3)2). 19 F-NMR(C6D6,300MHz):d -81.6(septet, 4 J HF =1.1Hz,6F) 13 C{ 1 H}-NMR(C6D6,75MHz):d 1.6(br,CH2Et),7.7(CH3Et),22.81(q, 3 J CF =1.3Hz),79.5(q, 2 J CF =30.6Hz,OC), 25.3ppm(q, 1 J CF =284Hz,CF3). trans isomer (approximately 70%) 1H-NMR(C6D6,300MHz):d 0.26(q,4H,CH2Et),1.18(t,6H,CH3Et),1.28(br,6H,OC(CH3)2),1.31(br,6H,OC(CH3)2). 19 F-NMR(C6D6,300MHz):d-81.1(br,6F) 13 C{ 1 H}-NMR(C6D6,75MHz):d 1.6(br,CH2Et),7.7(CH3Et),22.79(q, 3 J CF =1.3Hz),22.84(q, 3 J CF =1.3Hz),79.1(q, 2 J CF =30.6Hz,OC),125.2ppm(q, 1 J CF =284Hz,CF3).

[0093] Example 1.10. Reaction of 1,1,1-trifluoro-2-propanol with diethylaluminum chloride in 1:1 stoichiometry: The reaction was carried out according to Method B, yielding a white solid. The major products were cis and trans-[Al(OCHMeCF3)EtCl]2 (cis:trans = 53:47). Note that seven stereoisomers were formed from the racemic alcohol, including two enantiomeric pairs. The unidentified by-product accounted for approximately 10%. NMR characterization shows the chemical shift range.

[0094] 1 H-NMR (C6D6, 300 MHz): d 0.22 (4H, CH2Et), 1.02-1.21 (12H, CH3Et and CH3 alkoxide), 3.71-4.00 ppm (2H, CH). 19 F{ 1 H}-NMR(C6D6,300MHz):d -79.34,-79.19,-78.92,-78.87,-78.78,-78.72ppm(CF3). 13 C{ 1H}-NMR (C6D6, 75MHz): d -1.7-1.2 (CH2Et), 7.7-8.0 (CH3Et), 15.6-16.2 (CH3 alkoxide), 69.9-71.8 (OC), 124.2-124.6 ppm (CF3).

[0095] Example 2: Polymerization of DCPD using various cocatalyst systems A general method for in situ cocatalyst synthesis. In a glove box, equimolar amounts of diethylaluminum chloride and alcohol were introduced into 1 kg of a liquid DCPD / TCPD mixture at room temperature. The mixture was stirred at room temperature for 24 hours. The resulting cocatalyst solution in monomer was used in the polymerization experiments listed in Table 2. In most cases, the resulting cocatalyst solution was clear and colorless, except for entries 10 and 14.

[0096] General method for preparation of formulations from isolated complexes The isolated Al alkoxy complex described in Example 1 was introduced into 1 kg of the liquid DCPD / TCPD mixture at room temperature under an inert atmosphere.

[0097] General method for polymerization reaction testing 100 g of the cocatalyst solution obtained using the method described above and 100 g of a polymolybdate solution in a DCPD / TCPD mixture were introduced into a cartridge equipped with a static mixer. The cartridge was conditioned at 30°C for 30 minutes. Injection of the two solutions was carried out using an air gun. Temperature measurement was started immediately after injection.

[0098] Cure time was measured as the time from the end of pouring to 100°C.

[0099] ΔT was calculated as the difference between the maximum temperature and the initial temperature. The temperature difference is an indirect indicator of monomer conversion in bulk conditions. Previous data showed that a ΔT above 184°C corresponds to at least 95% conversion, as judged from TGA analysis.

[0100] [Table 2]

[0101] Examples 2.1 to 2.13 Examples 2.1 to 2.3 (Table 2: Entries 1 to 3) The cocatalyst solutions were stable for up to one year at room temperature under an inert atmosphere. Differences in alcohol descriptors can rationalize the observed differences in initiation rates. 1,1,1-trifluoro-2-propanol exhibited the shortest cure times combined with excellent monomer conversion due to its lowest pKa and XCA and higher GLB values.

[0102] Examples 1a, 3a and 13a The catalytic results obtained using the isolated Al complex and the in situ generated one are identical.

[0103] Example 2.4 (Table 2, entry 4) Reactivity data show rapid initiation but low monomer conversion (ΔT = 149 °C, thus 35 °C below the target value). Because the pKa value of 1-propanol (4) is above 30, the corresponding cocatalyst performs poorly in the ROMP of DCPD.

[0104] Example 2.5 (Table 2, entry 5) The reactivity data show that initiation is very slow under the test conditions, mainly due to the high pKa value. At the same time, the maximum polymerization temperature is high and the ΔT reaches the target value (184°C).

[0105] Examples 2.6 to 2.8 (Table 2, Entries 6 to 8) The catalytic system does not exhibit catalytic activity under the test conditions due to the heteroatoms (O or N) in the alcohol moiety. Heteroatoms have a strong ability to bind to aluminum, blocking their catalytic activity.

[0106] Examples 2.9 to 2.10 (Table 2, Entries 9 and 13) The catalytic system does not show catalytic activity due to the high pKa values ​​of 2,4-dimethylpentan-3-ol (9) and tert-butanol (12).

[0107] Example 2.11 (Table 2, entries 10 and 11). The prepared in situ cocatalyst solution was clear and pale yellow in color. Reactivity data for the freshly prepared cocatalyst show moderate initiation rates and low monomer conversion (ΔT = 150°C, thus 34°C below the target value).

[0108] After two weeks of storage at room temperature under an inert atmosphere, the cocatalyst solution turned yellow and reactivity data showed slower initiation and lower monomer conversion.

[0109] Example 2.12 (Table 2, Entries 14 and 15) The cocatalyst solution obtained using 1-phenylethanol turned orange immediately after the addition of the alcohol. Furthermore, an orange-brown precipitate formed during storage at room temperature under an inert atmosphere. The corresponding aluminum complex undergoes autolysis under the test conditions. The reactivity test was repeated after one month, and a slight temperature increase due to the polymerization reaction was measured (Table 2, entry 15).

[0110] Example 2.13 (Table 2, entry 12) 24 hours after the addition of the alcohol, the cocatalyst turned yellow-orange. A similar autolysis of the aluminum complex was observed in Example 1.7.

[0111] Example 3: Glass Transition Temperature (Tg) of Cured Bulk Samples The Tg values ​​of PDCPD (Table 2, entries 1-4) were measured using DSC (10 mg of polymer, heating rate 10 °C / min). The DSC pan was weighed before and after the test to assess the weight loss during the heating cycle. The weight loss was attributed to the loss of monomer and converted the test sample.

[0112] [Table 3]

[0113] Alcohols 1 and 3, which have low pKa values, formed the cocatalysts that gave the best performance, complete conversion, and high Tg polymers.

[0114] The less acidic and slightly bulkier 1-chloro-2-propanol (2) formed a cocatalyst with reduced activity compared to alcohols 1 and 3.

[0115] The least acidic alcohol, 4, performed poorly, with DSC analysis revealing only 8% monomer conversion and a glass transition temperature of 81°C for the resulting polymer.

[0116] Disappointing results were obtained with alcohol 10 and 13 derivatives bearing benzyl functionality: the interaction between aluminum and the aromatic ring reduced the stability of the corresponding complexes, leading to autolysis.

[0117] Example 5: Glass Transition Temperature (Tg) of Thin Films in the Presence of SiCl 0.1% tetrachlorosilane SiCl4 was added to the cocatalyst solution prepared according to Example 3. Thin films with an average thickness of 0.3 mm were cast in an aluminum mold preheated at 60°C. The mold was opened within 180 seconds after the monomer injection.

[0118] The Tg values ​​were obtained using the DSC method described in Example 3.

[0119] The results are shown in Table 5.

[0120] [Table 4]

[0121] The addition of SiCl4 did not affect the glass transition temperature of the polymers obtained using alcohols 1 and 3. In the cases of 4 and 10, the effect of SiCl4 was positive. However, with 0.1% SiCl4, the target Tg value was not reached under the test conditions.

[0122] Example 6: Comparative kinetic study of the DCPD ROMP reaction catalyzed by the {Molybdenum precatalyst / [(ClCH2)2CHOAlEtCl]2} and {Molybdenum precatalyst / [(CF3)MeCHOAlEtCl]2} systems To obtain further evidence of the influence of the structure of the alcohol additive (i.e., the structure of the alkoxide ligand of the aluminum cocatalyst) on catalytic performance, we recorded kinetic curves (conversion vs. time) for the DCPD ROMP reaction promoted by (ClCH2)2CHOH-derived and rac-(CF3)MeCHOH-derived catalyst systems. In these experiments, the catalyst systems were generated from commercial molybdenum-based precatalysts and the corresponding (ClCH2)2CHOH-derived and rac-(CF3)MeCHOH-derived aluminum cocatalysts, respectively (Scheme 1). The reactions were carried out in NMR test tubes, and they 1 The reactions were followed by H NMR. The reaction conditions were optimized to obtain a clear data set that can serve to show the differences in reaction rates. Note that the conditions chosen may prevent precipitation of the product, obscuring the results.

[0123] Scheme 1. Kinetic study of the DCPD ROMP reaction catalyzed by Mo precatalyst / [(ClCH2)2CHOAlEtCl]2 and Mo precatalyst / [(CF3)MeCHOAlEtCl]2 systems

[0124] [ka]

[0125] Under the applied conditions, the Mo precatalyst / [(CF3)MeCHOAlEtCl]2 catalytic system was found to be significantly more active than the industrially used Mo precatalyst / [(ClCH2)2CHOAlEtCl]2 catalytic system. While the (ClCH2)2CHOH-derived system required more than 95 min to reach 98% conversion (Figure 2), the (rac)-(CF3)MeCHOH-modified catalyst provided 99% conversion in 51 min (Figure 3).

[0126] Plotting the two kinetic curves on the same graph provides even clearer evidence of the difference in activity between the two systems (Figure 4).

[0127] The present invention is not limited to the above-described embodiments, but includes modifications thereof within the scope of the claims appended below.

Claims

1. 1. An olefin metathesis polymerization catalyst system comprising a metalate as a precatalyst and an aluminum complex as a cocatalyst, The aluminum complex is an alkoxyalkyl aluminum halide complex [(OR １ ) (R ２ ) AlX １ ] ｎ [In the formula, OR １ is an alcohol HOR having a pKa in the range of 18-28 (calculated considering dimethyl sulfoxide (DMSO) as the solvent). １ wherein said alkoxy ligand OR 1 is functionalized with a halogen, and further wherein n is an integer ranging from 1 to 3, and R ２ is an alkyl group, and X １ is a halide, and benzyl alcohol and —CH ２ The catalyst system is selected from alcohols containing an F functionality, excluding functionalized alcohols.

2. The alcohol HOR １ 2. The catalyst system of claim 1, wherein the pKa of the catalyst is in the range of 20 to 28.

3. R ２ is an alkyl group, and X １ 3. The catalyst system according to claim 1 or 2, wherein is Cl.

4. 3. The catalyst system of claim 1, wherein the metalate is a molybdate.

5. 3. The catalyst system according to claim 1 or 2, wherein n=2.

6. The alkoxy ligand OR １ is a primary or secondary alcohol HOR １ 3. The catalyst system of claim 1 or 2, derived from

7. The alcohol HOR １ has steric bulkiness defined by an XCA cone angle in the range of 160 to 200°, as disclosed in the section "Methods and Definitions," the XCA cone angle being defined by the opening angle of a cone whose apex is an oxygen atom of the alkoxy ligand and whose outer surface contacts the outermost atom of the alkoxy ligand.

8. Model compound X with the given heteroatom or functional group as the Lewis base functional group and AlCl as the model Lewis acid ３ The following reaction between: X+AlCl ３ →[XAlCl ３ ] ΔG(kcal / mol)=GLB is defined as the Gibbs free energy of complexation with the alcohol HOR １ R １ 3. The catalytic system according to claim 1 or 2, wherein the GLB descriptor (kcal / mol) of the heteroatoms or functional groups present therein is greater than or equal to -12.

9. Alkylchlorosilane Si ｘ Cl ｙ R ｚ wherein R is O, O-alkyl, alkyl, or aryl; and x, y, and z can be 1 to 10, in an amount of 0 to 3% by weight, based on the total amount of the catalyst system.

10. The chlorosilane comprises tetrachlorosilane, and the catalyst system is tetrachlorosilane (SiCl ４ 10. The catalyst system of claim 9, comprising up to 0.15% by weight of hydroxybenzoates, based on the total amount of the catalyst system.

11. 11. The catalyst system of claim 10, which is free of tetrachlorosilane.

12. 3. The catalytic system according to claim 1 or 2, wherein the halogen is chlorine (Cl) or fluorine (F).

13. The alcohol HOR １ 3. The catalytic system according to claim 1, wherein is selected from 1,1,1-trifluoro-2-propanol, 1,1-difluoropropanol, and 1-chloro-2-propanol.

14. The catalyst contains molybdate as a precatalyst and [Al(1,1,1-trifluoro-2-propoxy)(Cl)(C ２ H ５ )] ｎ 3. The catalyst system according to claim 1 or 2, wherein n=1 or 2.

15. A curable composition comprising a cyclic olefin and the olefin metathesis polymerization catalyst system of claim 1 or 2.

16. 16. The curable composition of claim 15, wherein the cyclic olefin comprises dicyclopentadiene.

17. 16. A method for producing a molded article of the curable composition of claim 15, comprising the steps of: a) providing the curable composition by combining the cyclic olefin and the olefin metathesis polymerization catalyst system in a mold; b) subjecting the composition to conditions promoting an olefin metathesis reaction of the cyclic olefin in a closed mold; c) removing the cured composition from the mold to obtain the molded article; A method comprising:

18. 18. The method of claim 17, comprising injecting the composition into the closed mold.

19. 18. The method of claim 17, wherein the molded article after step c) has a glass transition temperature Tg equal to or higher than the mold temperature.

20. The method of claim 19 further comprising removing the flash portion.

21. A molded article obtainable by the method of claim 17, The molded article optionally has a minimum thickness, and said minimum or average thickness of the molded article excluding any flash is from 0.2 to 4 mm.

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