Improved ring-opening metathesis catalyst system for cyclic olefin polymerization

Abstract

The present disclosure provides an improved catalyst for the polymerization of cyclic olefins. The catalyst comprises a transition metal carbene having the following structure: v (OR') c*m X (v‑c*m‑2) =C(R*)2, where M v is a Group 5 transition metal with a valence of 5 (v-valence) or a Group 6 transition metal with a valence of 5 or 6 (v-valence); each R' is independently a monovalent organic moiety comprising 8 to 40 atoms selected from Groups 14 to 17; c is an integer from 1 to 3; m is 1 / 3, 1 / 2, 1, 3 / 2, 2, 3, or 4, and c*m≤v-2; X is a halogen; and each R* is independently H or a C1-C7 alkyl group. The catalyst is particularly useful for ring-opening metathesis polymerization (ROMP).

Description

[0001] Inventors: Alexander V. Zabula, Lubin Luo, Robert Halbach, Jo Ann M. Canich, Carlos R. Lopez-Barron, Alan A. Galuska

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims priority to U.S. Provisional Application No. 62 / 992002, filed on March 19, 2020, the disclosure of which is incorporated herein by reference.

[0004] background

[0005] The present disclosure relates to ring-opening metathesis catalysts and cyclic olefin polymerization using the ring-opening metathesis catalysts. In organic synthesis, metathesis reaction is a catalytic reaction in which a double bond is reorganized between two olefins or alkynes. Ring-opening metathesis polymerization (ROMP) involves the formation of unsaturated polymers by the ring-opening reaction of one, two or more cyclic olefin comonomers. Typically, the cyclic olefin comonomer is a strained cyclic olefin that reacts with the ROMP catalyst to open and release the strain, which produces a linear molecule that reacts with other cyclic olefins. However, each cyclic olefin comonomer has varying degrees of strain and therefore has different reactivity with the ROMP catalyst. In some cases, the reactivity can be orders of magnitude different. Therefore, the binding rate of each comonomer in the resulting polymer is different.

[0006] For example, US Pat. Nos. 3,598,796, 3,631,010 and 3,778,420 describe the copolymerization of cyclopentene and dicyclopentadiene in various media, which are premixed before the addition of the ROMP catalyst. The resulting polymers are block copolymers and / or crosslinked copolymers.

[0007] The properties of the resulting polymer (e.g., mechanical properties, processability, etc.) depend, at least in part, on the relative amounts of each comonomer in the polymer. Therefore, the ability to control the amount of each comonomer in the resulting polymer (including incorporating slower reacting comonomers at greater than 50 mol% of the polymer) would be advantageous.

[0008] US Pat. No. 3,707,520 and US Pat. No. 3,941,757 propose a method for incorporating more slowly reacting comonomers using a two-stage copolymerization process. In the first step, cyclopentene is homopolymerized before the more reactive comonomer is introduced (in the second step). The resulting polymer is a block copolymer having different properties than if the two comonomers were more evenly dispersed throughout the polymer structure.

[0009] Therefore, the ability to control the amount of each comonomer in the resulting polymer, including incorporating slower reacting comonomers into the overall polymer structure at greater than 50 mole percent of the polymer, would be advantageous.

[0010] References of interest include U.S. Patent Nos. 3,598,796, 3,631,010, 3,707,520, 3,778,420, 3,941,757, 4,002,815, 4,239,484, and 8,889,786; U.S. Patent Publication Nos. 2016 / 0289352 and 2017 / 0247479; Canadian Patent No. CA1,074,949; Chinese Patent Publication No. 2018 / 8001293; WO Patent Publication No. WO 2018 / 173968; Japanese Patent Application Publication Nos. JP2019 / 081839A and JP2019 / 081840A; and Yao, Z. et al. (2012) “Ring-Opening Metathesis Copolymerization of Dicyclopentadiene and Cyclopentene Through Reaction Injection MoldingProcess,” J. of App. Poly. Sci., v. 125(4), pp. 2489–2493. SUMMARY OF THE INVENTION

[0012] The present disclosure provides an improved catalyst for the polymerization of cyclic olefins. The catalyst may include a transition metal carbene having the following structure: v (OR') c*m X (v-c*m-2) =C(R * )2, where M v is a Group 5 transition metal having a valence of 5 (v) or a Group 6 transition metal having a valence of 5 or 6 (v); each R' is independently a monovalent organic moiety comprising 8 to 40 atoms selected from Groups 14 to 17; c is an integer from 1 to 3; m is 1 / 3, 1 / 2, 1, 3 / 2, 2, 3, or 4, and c*m≤v-2; X is a halogen; and each R * The catalyst is particularly useful for ring-opening metathesis polymerization (ROMP).

[0013] The present disclosure also provides a catalyst for the polymerization of cyclic olefins, which is at least one compound having the formula m(R'O) c M u X (u-c) A metal alkoxide and at least one having the formula Mv X v The reaction product of transition metal halides. u is a Group 1, 2 or 13 metal of valence u; and M v is a Group 5 transition metal with a valence of five (v) or a Group 6 transition metal with a valence of five or six (v). Each R' is independently a monovalent organic moiety comprising 8 to 40 atoms selected from Groups 14 to 17. X is a halogen; c is an integer from 1 to 3; and m can be 1 / 3, 1 / 2, 3 / 2, 1, 2, 3, or 4, and c*m≤v-2.

[0014] The present disclosure also provides a method for the polymerization of cyclic olefins. The method may include: reacting a cyclic olefin polymerization catalyst described herein with a C4-C4 olefin containing at least one cyclic olefin moiety. 20 Cyclic olefin monomers are contacted in a polymerization reactor under conditions sufficient to form a reaction product mixture comprising a polymer, unreacted monomer, catalyst, and optionally a solvent; and the polymer is recovered. The method may further comprise: separating the monomer from the reaction product mixture and recycling the monomer to the polymerization reactor; or contacting the recovered catalyst with an activator and then recycling it to the polymerization reactor; or a combination thereof.

[0015] BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The present disclosure includes the following drawings to illustrate certain aspects of the embodiments, and the drawings should not be construed as exclusive embodiments. The disclosed subject matter is capable of considerable modification, alteration, combination, and equivalent substitution in form and function, as will be made by those skilled in the art having the benefit of this disclosure.

[0017] Figure 1 is an exemplary graph showing chemical shift assignments for illustrative cyclopentene polymers. 13 CNMR spectrum.

[0018] Figure 2 An illustrative reaction scheme for the formation of metal alkoxides (I) from the reaction of dimethylaluminum monochloride with 2 equivalents of 4-benzylphenol is shown.

[0019] Figure 3 An illustrative reaction scheme for the formation of metal alkoxides (I) from the reaction of dimethylaluminum monochloride with two equivalents of 4-(diphenylamino)phenol is shown.

[0020] Figure 4 Shown by Figure 2An illustrative reaction scheme for the reaction of a metal alkoxide (I) with a transition metal halide (II) which is tungsten hexachloride (WCl6) to form a transition metal procatalyst (III) and then an activated catalyst (V) having an active metal carbene moiety.

[0021] Figure 5 Shown by Figure 3 An illustrative reaction scheme for the reaction of a metal alkoxide (I) with a transition metal halide (II) which is tungsten hexachloride (WCl6) to form a transition metal procatalyst (III) and then an activated catalyst (V) having an active metal carbene moiety.

[0022] Figure 6 Depicted are illustrative polymerization routes for preparing ring-opening polycyclopentene from cyclopentene using the catalyst systems provided herein.

[0023] Detailed description

[0024] It should be understood that the following disclosure describes several exemplary embodiments for implementing the different features, structures and / or functions of the present invention. Exemplary embodiments of components, arrangements and configurations are described below to simplify the present disclosure; however, these exemplary embodiments are provided only as examples and are not intended to limit the scope of the present invention.

[0025] Definition and test methods

[0026] In the following discussion and in the claims, the terms "comprising" and "including" are used in an open-ended manner and, thus, should be interpreted to mean "including but not limited to." The phrase "consisting essentially of" means that the described / claimed composition does not include any other component that would materially alter a property by more than 5% of that property, and in any case does not include any other component at a level greater than 3% by mass.

[0027] Unless the context clearly states otherwise, the term "or" is intended to cover both exclusive and inclusive cases, ie, "A or B" is intended to be synonymous with "at least one of A and B."

[0028] The indefinite articles "a" and "an" refer to both the singular (i.e., "one / an") and the plural (i.e., one or more / one or more) unless the context clearly indicates otherwise. Thus, embodiments using "an antioxidant" include embodiments in which one, two, or more antioxidants are used, unless specified to the contrary or the context clearly indicates that only one antioxidant is used.

[0029] The term "mass %" means percent by mass, such as percent by weight, "vol %" means percent by volume, "mol %" means percent by mole, "ppm" means parts per million, and "ppm wt" and "wppm" are used interchangeably and mean parts per million by weight. Unless otherwise indicated, all concentrations herein are expressed based on the total amount of the composition in question.

[0030] The terms "alkyl" and "alkyl group" are used interchangeably herein and refer to a saturated hydrocarbon group consisting of carbon and hydrogen atoms. An alkyl group can be linear, branched, cyclic, or substituted cyclic.

[0031] The terms "cycloalkyl" or "cycloalkyl group" interchangeably refer to a saturated hydrocarbon group in which the carbon atoms form one or more ring structures.

[0032] The terms "aryl" or "aryl group" refer interchangeably to a hydrocarbyl group that contains an aromatic ring structure therein.

[0033] For purposes of this disclosure and the appended claims, the new numbering scheme for the Periodic Table Groups is used as in Chemical and Engineering News, Vol. 63, p. 27 (1985). Thus, a "Group 4 metal" is an element from Group 4 of the Periodic Table.

[0034] Unless otherwise indicated, a substituted group is a group in which at least one atom is replaced by a different atom or group. Thus, a substituted alkyl group may be an alkyl group in which at least one hydrogen atom is replaced by a hydrocarbyl group, a halogen, any other non-hydrogen group, and / or at least one carbon atom and the hydrogen atom attached thereto are replaced by a different group. Preferably, a substituted group is a group in which at least one hydrogen atom has been replaced by a heteroatom or a heteroatom-containing group, preferably at least one functional group such as a halogen (Cl, Br, I, F), NR * 2. OR * , SeR * ,TeR * , PR * 2. AsR * 2. SbR * 2, SR * , BR * 2. SiR * 3.GeR * 3. SnR * 3. PbR * 3, etc., or at least one heteroatom such as halogen (Cl, Br, I, F), O, S, Se, Te, NR * , PR * , AsR *, SbR * , BR * , SiR * 2.GeR * 2. SnR * 2. PbR * 2 etc. have been inserted into the hydrocarbon group, where R * are independently hydrogen or a hydrocarbyl group.

[0035] For purposes of this disclosure, "heteroatom" refers to a nonmetal or metalloid atom from Groups 13, 14, 15, and 16 of the Periodic Table of the Elements, typically replacing a carbon atom. For example, pyridine is a heteroatom-containing form of benzene. Halogen refers to an atom from Group 17 of the Periodic Table of the Elements.

[0036] The terms "hydrocarbyl radical," "hydrocarbyl group," or "hydrocarbyl" interchangeably refer to a group consisting solely of hydrogen and carbon atoms. A hydrocarbyl group can be saturated or unsaturated, linear, branched, cyclic or acyclic, aromatic or non-aromatic.

[0037] Substituted hydrocarbon groups are groups in which at least one hydrogen atom has been replaced by a heteroatom or a group containing a heteroatom, preferably at least one functional group such as halogen (Cl, Br, I, F), NR * 2. OR * , SeR * ,TeR * , PR * 2. AsR * 2. SbR * 2, SR * , BR * 2. SiR * 3.GeR * 3. SnR * 3. PbR * 3, etc., or at least one heteroatom such as halogen (Cl, Br, I, F), O, S, Se, Te, NR * , PR * , AsR * , SbR * , BR * , SiR * 2.GeR * 2. SnR * 2. PbR * 2 etc. have been inserted into the hydrocarbon group, where R * are independently hydrogen or a hydrocarbyl group.

[0038] In some embodiments, the hydrocarbyl groups are independently selected from methyl, ethyl, vinyl, and propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecanyl, decadecyl, decene Isomers of heptaenyl, octaenyl, nonadecenyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecanyl, octadecynyl, nonadecenyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, triacontenyl. Also included are isomers of saturated, partially unsaturated, and aromatic cyclic structures, wherein the groups may additionally undergo substitutions of the above types. Examples include phenyl, methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl, methylcyclohexyl, etc. For purposes of this disclosure, when a group is listed, it is intended to indicate that group type and all other groups formed when that group type undergoes substitution as defined above. Lists of alkyl, alkenyl and alkynyl groups include all isomers, including cyclic isomers where appropriate, for example, butyl includes n-butyl, 2-methylpropyl, 1-methylpropyl, tert-butyl and cyclobutyl (and similar substituted cyclopropyls); pentyl includes n-pentyl, cyclopentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl and neopentyl (and similar substituted cyclobutyls and cyclopropyls); butenyl includes 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and the E and Z forms of 2-methyl-2-propenyl (as well as cyclobutenyl and cyclopropenyl). The cyclic compounds having substitution include all isomeric forms, for example, methylphenyl includes o-methylphenyl, m-methylphenyl and p-methylphenyl; dimethylphenyl includes 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl and 3,5-dimethylphenyl.

[0039] The term "C n "A group or compound is a group or compound containing a total of n carbon atoms. Therefore, "Cm -C n "A group or compound is a group or compound containing a total number of carbon atoms in the range of m to n. Thus, C1-C 50 The alkyl group refers to an alkyl group containing a total number of carbon atoms in the range of 1 to 50.

[0040] The term "olefin" (or "alkene") refers to an unsaturated hydrocarbon compound having a hydrocarbon chain containing at least one carbon-carbon double bond in its structure, wherein the carbon-carbon double bond does not form part of an aromatic ring. Olefins can be linear, branched or cyclic.

[0041] For the purposes of this specification and the appended claims, when a polymer or copolymer is referred to as comprising a cyclic olefin (including but not limited to cyclopentene (C-C5), cyclopentadiene and other cyclic C6-C9 hydrocarbons and their dienes), the cyclic olefin present in such an unsaturated polymer or copolymer is the polymerized form of the cyclic olefin. A "polymer" has two or more monomeric units that are the same or different. A "homopolymer" is a polymer having identical monomeric units. A "copolymer" is a polymer having two or more monomeric units that are different from each other. "Different" when used to refer to monomers indicates that the monomers differ from each other by at least one atom or are isomerically different. An oligomer is a polymer having a low molecular weight, such as 21,000 g / mol or less (preferably 10,000 g / mol or less). n and / or polymers with a low number of mer units, such as 100 mer units or less (preferably 75 mer units or less).

[0042] The term "cyclic olefin" refers to any cyclic substance containing at least one olefinic double bond in the ring. The atoms of the ring can be optionally substituted. The ring can contain any number of carbon atoms and / or heteroatoms. In some cases, the cyclic olefin can contain multiple rings. A ring can contain at least 3, at least 4, at least 5, at least 6, at least 7, at least 8 or more atoms. Non-limiting examples of cyclic olefins include cyclopentene, cyclohexene, norbornene, dicyclopentadiene, bicyclic compounds, oxabicyclic compounds, etc., all of which are optionally substituted. "Bicyclic compound" is a class of compounds consisting only of two rings, and the two rings have two or more common atoms.

[0043] Unless otherwise specified, the term "substantially all" with respect to a molecule means at least 90 mol% (e.g., at least 95 mol%, at least 98 mol%, at least 99 mol% or even 100 mol%).

[0044] Unless otherwise specified, the term "substantially free" with respect to a particular component means that the concentration of this component in the relevant composition is not greater than 10 mol % (e.g., not greater than 5 mol %, not greater than 3 mol %, not greater than 1 mol % or about 0%, within the scope of the relevant measurement framework), based on the total amount of the relevant composition.

[0045] The terms "catalyst" and "catalyst compound" are used interchangeably and refer to a compound that can initiate catalysis and / or promote a chemical reaction with little or no poisoning / consumption. In the description herein, a catalyst can be described as a catalyst precursor, a procatalyst compound or a transition metal compound, and these terms are used interchangeably. A catalyst compound can be used alone to initiate catalysis, or can be used in combination with an activator to initiate catalysis. When a catalyst compound is combined with an activator to initiate catalysis, the catalyst compound is often referred to as a procatalyst or catalyst precursor. A "catalyst system" is a combination of at least one catalyst compound, at least one activator, an optional co-activator and an optional support, wherein the system can polymerize one or more monomers to form a polymer.

[0046] All numerical values ​​in this detailed description and claims are modified by the indicated value of "about" or "approximately", and take into account experimental error and variations that would be expected by a person of ordinary skill in the art.

[0047] In this disclosure, unless otherwise specified, percentages are by weight, expressed as "wt %."

[0048] In this disclosure, all molecular weight data are in g·mol -1 Unless otherwise indicated, the molecular weight and molecular weight distribution of oligomeric or polymeric materials in this disclosure were determined using gel permeation chromatography using a Tosoh EcoSEC high temperature GPC system (GPC-Tosoh EcoSEC; Tosoh Bioscience LLC). GPC can be used to determine the Mw, Mn, and Mw / Mn of ring-opened polycyclopentene using the high temperature gel permeation chromatograph equipped with a differential refractive index detector (DRI). Three high temperature TSK gel columns (Tosoh GMHHR-H(20)HT2) were used. The nominal flow rate was 1.0 mL / min and the nominal injection volume was 300 μL. The various transfer lines, columns, and dual flow differential refractometer were housed in an oven maintained at 160°C. The mobile phase solvent for the experiments was prepared by dissolving 1.2 g of butylated hydroxytoluene as an antioxidant in 4 L of Aldrich reagent grade 1,2,4-trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.1 μm Teflon filter. The TCB was then degassed using an online degasser before entering the GPC instrument.

[0049] The polydispersity index (PDI) (also called molecular weight distribution (MWD)) of a material is the molecular weight distribution of w / M n ratio.

[0050] For purposes of this disclosure, the trans:cis ratio of a polymer can be determined by standard methods known in the art. 13 CNMR technique measurements: Samples were prepared in 10 mm tubes at a concentration of 66.67 mg / ml CDCl3 (deuterated chloroform). 13 C NMR spectra were measured on a Bruker 600 MHz cryogenic probe using inverse gated decoupling, a 20 s delay, a 90° pulse, and 512 transients. Peak assignments were based on those reported in O. Dereli et al. (2006) European Polymer Journal, v. 42, pp. 368-374. Three different positions were used for the calculation of trans / cis composition:

[0051]

[0052] 1. Olefin group (γ) peak, where the trans form is at 130.3 ppm and the cis form is at 129.8 ppm;

[0053] 2. α-position, where trans / cis (tc) is at 32.2 ppm, trans / trans (tt) is at 32.07 ppm, cis / cis (cc) is at 26.9 ppm, and cis / trans (ct) is at 26.74 ppm;

[0054] 3. β-position, where cis / cis (cc) is at 29.86 ppm, cis / trans (trans / cis) (ct+tc) is at 29.7 ppm, and trans / trans (tt) is at 29.54 ppm;

[0055] 4. trans = tt + 0.5*(ct + tc);

[0056] 5. cis = cc + 0.5*(ct + tc); and

[0057] 6.n is the number of repeating units.

[0058] The calculations for each of the above groups 1-3 (i.e., γ, α, and β) are averaged to obtain the average trans and cis compositions. As used herein, the term "γ" refers to a (CH=CH) group. Exemplary 13 C NMR spectrum is shown in Figure 1 , which is an exemplary diagram showing chemical shift assignments for illustrative cyclopentene polymers. 13 C NMR spectrum.

[0059] In terms of the present disclosure, it is possible to use 1 H NMR methods were used as indicated using a Bruker 400 MHz instrument to monitor and estimate small-scale polymerization conversions. Pulse program zgcw30 was used with D1 = 60 s and ns = 2 or 4. CDCl3 was used as the lock solvent. The chemical shift of the double bond protons of the cyclopentene monomer was approximately 5.75 ppm, and the chemical shift of the double bond protons of the ring-opened polycyclopentene was approximately 5.53 ppm. The integral (I) from 5.45 to 6.00 ppm was used. m+p ) can be used to overlay the two chemical shifts and can be set to 100% to represent total cyclopentene. The integral (I p+RS ) is designated as the right side of the ring-opening polycyclopentene superimposed cyclopentene 13 C satellite chemical shift. To deduct the 13 The C satellite contribution can be found from 5.93 to 5.97 ppm to the left of cyclopentene of similar intensity. 13 C satellite chemical shift integration (I LS ), and the conversion rate C is calculated as follows: C = (I P+RS –I LS ) / I m+p .

[0060] When I found LS When it is zero, the appropriate 13 C decoupling procedure.

[0061] M n is the number average molecular weight, M w is the weight average molecular weight, and M z is the z-average molecular weight. The molecular weight distribution (MWD) is defined as w Divide by M n Unless otherwise indicated, all molecular weight units (e.g., M w , M n , M z ) is g / mol or kDa (1,000 g / mol = 1 kDa). Polymer Char GPC-IR was used to determine molecular weight distribution and molecular weight moment (M w , M n , M w / M n) and long chain branching index, the chromatograph is equipped with four online detectors, namely an 18-angle light scattering ("LS") detector, a viscometer and a differential refractive index detector ("DRI"). Three Agilent PLgel 10μm Mixed-BLS columns are used for the GPC tests in this article. The nominal flow rate can be 0.5mL / min and the nominal injection volume is 200μL. The column, viscometer and DRI detector are contained in an oven maintained at 40°C. Tetrahydrofuran (THF) solvent containing 250ppm of the antioxidant butylated hydroxytoluene (BHT) can be used as the mobile phase. A given amount of polymer sample is weighed and sealed in a standard vial. After the vial is loaded into the autosampler, the polymer is automatically dissolved in the instrument at 40°C with 8mL of added THF solvent under continuous shaking for about 2 hours. The concentration C at each point of the chromatogram is calculated from the baseline-subtracted DRI signal I using the following formula DRI Calculation: C = K DRI I DRI / (d n / d c ), where K DRI is a constant determined by correcting the DRI, and (d n / d c ) is the refractive index increment of the polymer in THF solvent.

[0062] Conventional molecular weight can be determined by combining a universal calibration relationship with a column calibration using a series of monodisperse polystyrene (PS) standards ranging from 300 g / mol to 12,000,000 g / mol. The molecular weight "M" for each elution volume can be calculated using the following equation:

[0063]

[0064] The variables with the subscript "PS" represent polystyrene, while the variables without the subscript represent the test sample. In this method, a PS =0.7362 and K PS =0.0000957, while the “a” and “K” of the sample are 0.725 and 0.000291 respectively.

[0065] The LS molecular weight, M, at each point in the chromatogram can be determined by analyzing the LS output using the Zimm model for static light scattering and using the following formula:

[0066]

[0067] Here, ΔR(θ) is the hyper-Rayleigh scattering intensity measured at the scattering angle θ, “c” is the polymer concentration determined by DRI analysis, A2 is the second virial coefficient, P(θ) is the morphology factor of the monodisperse random coils, and K o is the optical constant of the system stated in the following formula:

[0068]

[0069] where N A is Avogadro's number, and (dn / dc) is the refractive index increment of the system, which takes the same value as that obtained by the DRI method, and the value of "n" is 1.40 for THF at 40°C and λ = 665 nm. For the sample used in this test, dn / dc was determined by the DRI detector to be 0.1154.

[0070] A four-capillary viscometer with a Wheatstone bridge structure can be used to measure the specific viscosity (η S ) and concentration "C" are used to determine the intrinsic viscosity [η] as follows: ηs = C[η] + 0.3(C[η]) 2 .

[0071] The following abbreviations may also be used in this specification: Bu is butyl, n-Bu is n-butyl, i-Bu is isobutyl, t-Bu is tert-butyl, pt-Bu is p-tert-butyl, Et is ethyl, Me is methyl, p-Me is p-methyl, Ph is phenyl, Pr is propyl, i-Pr is isopropyl, n-Pr is n-propyl, RT is room temperature (i.e., approximately 23° C.), THF is tetrahydrofuran, and tol is toluene.

[0072] A detailed description will now be provided. Each of the appended claims defines a separate invention, which is deemed for infringement purposes to include equivalents to the various elements or limitations specified in the claims. Depending on the context, all references to the "invention" may in some cases refer to only certain specific embodiments. In other cases, it will be recognized that references to the "invention" will refer to the subject matter recited in one or more, but not necessarily all, of the claims. Each of the inventions is described in more detail below, including specific embodiments, variations, and examples, but the invention is not limited to these embodiments, variations, or examples. These embodiments, variations, and examples are included in this disclosure to enable one of ordinary skill in the art to make and use the invention when combining the information in this disclosure with publicly available information and technology.

[0073] The present disclosure provides novel procatalysts and catalyst systems comprising the procatalysts, which are particularly useful for the ring-opening metathesis polymerization (ROMP) of cyclic olefins including cyclopentene and dicyclopentadiene (DCPD) and mixtures thereof. The catalysts provided herein have extended aromatic ligands and optionally may include one or more heteroatoms in the ligands. Such catalyst frameworks have been shown to be significantly more active than their predecessors that do not have the same ligands. This significant increase in catalyst activity reduces material (catalyst, activator) costs and process expenses. High catalyst activity also reduces the amount of catalyst residue remaining after polymerization. These novel catalysts also have low toxicity and avoid the production of lethal, highly hazardous substances (SHS) when in contact with moisture.

[0074] catalyst

[0075] The catalyst may include at least one metal alkoxide (I) and at least one transition metal halide (II) to form a transition metal procatalyst (III) according to the following general formula:

[0076]

[0077] The transition metal procatalyst (III) can then be contacted with at least one metal alkyl activator (IV) to form a transition metal carbene moiety M comprising the following general formula: v =C(R * )2 activated catalyst (V):

[0078]

[0079] in:

[0080] M u is a u-valent Group 1, 2 or 13 metal, preferably M u is Li, Na, Ca, Mg, Al, or Ga;

[0081] c is in the range of 1-3 and ≤ u;

[0082] m = 1 / 3, 1 / 2, 1, 3 / 2, 2, 3, or 4, and c*m ≤ v-2;

[0083] a is 1, 2, or 3 and ≤ u;

[0084] n is a positive number and a*n is in the range of 2-10;

[0085] M v is a Group 5 or 6 transition metal having a valence of 5 or 6 (v), preferably v is 6 and M v is tungsten (W);

[0086] X is a halogen,

[0087] Each R' is independently a monovalent organic moiety comprising 8-40 (preferably 12-40; more preferably 18-40) atoms selected from Groups 14-17 of the Periodic Table, and which may include one or more heteroatoms;

[0088] Each R is independently C1-C8 alkyl; and

[0089] Each R * are independently H or C1-C7 alkyl.

[0090] In certain embodiments, the at least one metal alkoxide (I) may be or may include a Group 2 metal dialkoxide (e.g., Mg(OR')2), a Group 13 metal dialkoxide (e.g., Al(OR')2X), and a Group 13 metal trialkoxide (e.g., Al(OR')3). In certain embodiments, the metal alkoxide (I) may include a Group 1 metal, such as NaOR' (u=1, c=1); a Group 2 metal, such as Mg(OR')Cl (u=2, c=1) or Mg(OR')2 (u=2, c=2); or a Group 13 metal, such as Al(OR')Cl2 (u=3, c=1), Al(OR')2Cl (u=3, c=2), or Al(OR')3 (u=3, c=3).

[0091] In certain embodiments, each R' in the at least one metal alkoxide (I) is independently a linear, branched or aromatic hydrocarbon group. Each R' can also be functionalized with one or more groups selected from hydroxyl, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, alkoxycarbonyl and halogen.

[0092] The metal alkoxide (I) can be formed by contacting a compound (FI) comprising a hydroxyl functional group with a metal alkyl activator (IV) to form the metal alkoxide (I) according to the following general formula:

[0093]

[0094] The metal alkoxide (I) can also be prepared by reacting a compound (FI) containing a hydroxyl group with a Group 1 or Group 2 metal hydride M u* (H) u The contacts are formed according to the following general formula:

[0095]

[0096] Among them, M u* is a u* valence Group 1 or Group 2 metal, preferably M uis Na, Li, Ca, or Mg;

[0097] c is 1 or 2 and c≤u*;

[0098] X is a halogen; and

[0099] Each R' is independently a monovalent hydrocarbon group comprising 8-40 (preferably 12-40; more preferably 18-40) atoms selected from Groups 14-17 of the Periodic Table, which may include one or more heteroatoms.

[0100] In certain embodiments, the metal alkoxide procatalyst (I) may be represented by one or more of the following general structures AC:

[0101]

[0102] Wherein: Hal is F, Cl, Br or I;

[0103] E is O or S;

[0104] Ar 1 is an aryl group;

[0105] Ar 2 is an aryl group;

[0106] M is a Group 5 or 6 transition metal having a valence of 5 or 6 (v-valence), preferably a Group 6 transition metal, more preferably Mo or W;

[0107] R 3 It is C1-C 10 Alkyl, alkylene, alkanediyl, silylene, silanediyl, germylene, germanediyl, O, S, NAr 2 , or PAr 2 , preferably a methylene group;

[0108] For Group 6 metals in oxidation state +6, n = 1-4, m = 2-5 and n + m = 6, preferably n = 2 and m = 4 (Structure B) or n = 4 and m = 2 (Structure C); and

[0109] For Group 5 and Group 6 metals in oxidation state +5, n=1-3, m=2-4 and n+m=5.

[0110] In certain embodiments, the activated catalyst (V) may be represented by one or more of the following general structures DF:

[0111]

[0112] where R 1 is H, alkyl, or aryl; and R 2is H, alkyl, or aryl, preferably R 1 and R 2 It's all hydrogen.

[0113] Figure 2 An illustrative reaction scheme for forming the metal alkoxide (I) from the reaction of dimethylaluminum monochloride with 2 equivalents of 4-benzylphenol is shown. Figure 3 An illustrative reaction scheme for forming the metal alkoxide (I) from the reaction of dimethylaluminum monochloride with 2 equivalents of 4-(diphenylamino)phenol is shown.

[0114] Considering the metal alkyl activator (IV), M in more detail u It can be a u-valent Group 1, 2 or 13 metal, preferably Li, Na, Ca, Mg, Al, or Ga; R is a C1-C8 alkyl; c is 1, 2, or 3; c≤u; and X, when present, is a halogen. The metal alkyl activator (IV) can also be an aluminum alkyl. Suitable aluminum alkyl activators have the general formula:

[0115] AYR * r (Y) 3-r

[0116] where R * is C1-C8 alkyl, each Y is hydrogen, halogen, or -OR 5 , where each R 5 Independently C1-C 20 Hydrocarbyl, optionally when present R 5 Two or more of are linked together to form a ring having up to 40 atoms from Groups 14, 15 and / or 16 of the Periodic Table of the Elements; and r is 1-3.

[0117] Figure 4 Shown by Figure 2 An illustrative reaction scheme for the reaction of a metal alkoxide (I) with a transition metal halide (II) which is tungsten hexachloride (WCl6) to form a transition metal procatalyst (III) and then an activated catalyst (V) having an active metal carbene moiety.

[0118] Figure 5 Shown by Figure 3 An illustrative reaction scheme for the reaction of a metal alkoxide (I) with a transition metal halide (II) which is tungsten hexachloride (WCl6) to form a transition metal procatalyst (III) and then an activated catalyst (V) having an active metal carbene moiety.

[0119] Optional support material

[0120] In some embodiments of the present disclosure, the catalyst system may include an inert support material. Preferably, the support material is a porous support material, such as talc and an inorganic oxide. Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support materials, or mixtures thereof.

[0121] Preferably, the support material is an inorganic oxide in finely divided form. Suitable inorganic oxide materials for use in the catalyst systems herein include Group 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be used alone or in combination with the silica or alumina are magnesium oxide, titanium dioxide, zirconium oxide, and the like. However, other suitable support materials may be used, such as finely divided functionalized polyolefins, such as finely divided polyethylene. Particularly useful supports include magnesium oxide, titanium dioxide, zirconium oxide, montmorillonite, phyllosilicates, zeolites, talc, clays, and the like. In addition, combinations of these support materials may be used, such as silica-chromium, silica-alumina, silica-titania, and the like. Preferred support materials include Al2O3, ZrO2, SiO2, and combinations thereof, more preferably SiO2, Al2O3, or SiO2 / Al2O3.

[0122] Preferably, the support material (most preferably an inorganic oxide) has a 2 / g–about 700m 2 / g surface area, about 0.1 cm 3 / g–approximately 4.0cm 3 / g pore volume, and an average particle size of about 5 μm to about 500 μm. More preferably, the surface area of ​​the support material is about 50 m 2 / g–about 500m 2 / g, the pore volume is about 0.5cm 3 / g–approximately 3.5cm 3 / g, and the average particle size is in the range of about 10 μm to about 200 μm. Most preferably, the surface area of ​​the support material is about 100 m 2 / g–about 400m 2 / g, and the pore volume is about 0.8cm 3 / g–approximately 3.0cm 3 / g range, and the average particle size is in the range of about 5μm to about 100μm. The average pore size of the support material that can be used in the present invention is in the range of In the range of about In the range of about In some embodiments, the support material is a high surface area amorphous silica (surface area = 300 m 2 / gm; pore volume = 1.65cm 3 / gm). Preferred silica is manufactured by Davison Chemical Division of WR Graze and Company under the trade name DAVISON TM 952 or DAVISON TM 955 sales. In some other embodiments, DAVISON TM 948.

[0123] The support material should be dry, that is, free of absorbed water. Drying of the support material can be performed by heating or calcining at a temperature of about 100°C to about 1000°C, preferably at least about 600°C. When the support material is silica, it is heated to at least 200°C, preferably about 200°C to about 850°C, and most preferably about 600°C, for a period of about 1 minute to about 100 hours, about 12 hours to about 72 hours, or about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups for use in producing the supported catalyst system of the present invention. The calcined support material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator.

[0124] The support material having reactive surface groups (typically hydroxyl groups) is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a catalyst compound and an activator. In some embodiments, the slurry of the support material is first contacted with the activator for a period of time ranging from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The solution of the catalyst compound is then contacted with a separated support / activator. In some embodiments, the supported catalyst system is generated in situ. In an alternative embodiment, the slurry of the support material is first contacted with the catalyst compound for a period of time ranging from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The slurry of the supported catalyst compound is then contacted with the activator solution.

[0125] The mixture of the catalyst, activator, and support is heated to about 0° C. to about 70° C., preferably to about 23° C. to about 60° C., preferably to room temperature. The contact time is typically in the range of about 0.5 hours to about 24 hours, or in the range of about 2 hours to about 16 hours, or in the range of about 4 hours to about 8 hours.

[0126] Suitable nonpolar solvents are materials in which all of the reactants used herein, i.e., the activator and the catalyst compound, are at least partially soluble and which are liquid at the reaction temperature. Preferred nonpolar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although various other materials may also be used, including cycloalkanes such as cyclohexane, and aromatic hydrocarbons such as benzene, toluene, and ethylbenzene.

[0127] polymerization

[0128] The catalysts provided herein can be used for ring-opening metathesis polymerization (ROMP) to prepare polymers comprising one or more ring-opening polycycloolefins such as ring-opening polycyclopentene. Such polymers can also include cyclic olefin homopolymers and / or cyclic olefin copolymers. Figure 6 An illustrative polymerization route for preparing ring-opening polycyclopentene from cyclopentene is depicted.

[0129] The reaction can be carried out in a continuous reactor or a batch reactor. The reaction can also be carried out in a slurry phase or a solution. However, for simplicity and ease of description, the polymerization method for preparing ring-opening polycyclopentene using the catalyst described herein will be further described with reference to solution polymerization in a diluent, whereby the reaction mixture may include one or more diluents at a concentration of 60% by volume or less, or 40% by volume or less, or 20% by volume or less, based on the total volume of the reaction mixture. Suitable diluents may include non-coordinating inert liquids. Examples of suitable diluents may include, but are not limited to: straight-chain and branched hydrocarbons (e.g., isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof); cyclic and alicyclic hydrocarbons (e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as ISOPAR TM (synthetic isoparaffins, commercially available from ExxonMobil Chemical Company); perhalogenated hydrocarbons (e.g., perfluorinated C4-C 10 alkanes, chlorobenzenes, and aromatic compounds); alkyl-substituted aromatic compounds (such as benzene, toluene, 1,3,5-trimethylbenzene and xylene); and the like, and any combination thereof.

[0130] The preparation of the catalyst and / or the copolymerization can be carried out in an inert atmosphere (e.g., under a nitrogen or argon environment) to minimize the presence of air and / or water. The polymerization can include reacting one or more C4-C4 monomers in a polymerization reactor under conditions sufficient to form a reaction mixture comprising a polymer, a monomer, a catalyst, and an optional diluent. 20 The polymer, catalyst and optional solvent can be recovered from the reaction product mixture. At least a portion of the recovered catalyst, unreacted cyclic olefin monomer and optional solvent can be recycled to the polymerization reactor.

[0131] The temperature of the reaction can be in the range of -50°C to 200°C, or in the range of -25°C to 100°C, or in the range of -10°C to 25°C. The pressure of the reaction can be in the range of 0MPa to 50MPa, or in the range of 0MPa to 25MPa, or in the range of ambient pressure to 10MPa. The reaction can be carried out for a period of time, which can be in the range of 1 minute to 48 hours, or in the range of 1 minute to 20 hours, or in the range of 5 minutes to 3 hours, or in the range of 10 minutes to 1 hour.

[0132] Suitable molar ratios of metal to total comonomers in the catalyst can be from 1:1 to 1000: 1. Other suitable molar ratios of metal to total comonomers in the catalyst can be from 1:1 to 250:1, 1:1 to 50:1, 1:1 to 10:1, 10:1 to 100:1, 50:1 to 250:1, 100:1 to 500:1, or 250:1 to 1000:1.

[0133] The cyclic olefins may be strained or unstrained (preferably strained), monocyclic or polycyclic (e.g., bicyclic), and optionally include heteroatoms and / or one or more functional groups. Examples of cyclic olefins suitable for use as (co)monomers in the methods of the present disclosure include, but are not limited to, cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbornene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, norbornene carboxylic acid dimethyl ester, norbornene-exo-2,3-dicarboxylic anhydride, and their respective homologs and derivatives, and substituted derivatives thereof. Illustrative examples of suitable functional groups include, but are not limited to, hydroxyl, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, alkoxycarbonyl, and halogen.

[0134] The cyclic olefin may further include one or more C-containing cyclic structures of at least one of the following general formulas: 4-20 Cyclic dienes:

[0135] and / or

[0136] One or more functionalized C containing at least one cyclic structure of the general formula 4-20 Cyclic dienes:

[0137]

[0138] As a comonomer incorporated into the reaction product mixture, wherein each functional group (FG) is integral to and / or pendant from the corresponding cyclic structure, and wherein each FG is independently halogen, NR^2, OR^, SeR^, TeR^, PR^2, AsR^2, SbR^2, SR^, BR^2, SiR^3, GeR^3, SnR^3, PbR^3, O, S, Se, Te, NR^, PR^, AsR^, SbR^, BR^, SiR^2, GeR^2, SnR^2, PbR^2, or a combination thereof, and each R^ is independently hydrogen or C1–C 10 a hydrocarbon group, r greater than or equal to 1, and when present s greater than or equal to 1; preferably wherein the comonomer comprises norbornene, ethylidene norbornene, dicyclopentadiene, or a combination thereof.

[0139] In one or more embodiments of the present invention, the cyclic olefin polymerization process further comprises:

[0140] (I) controlling the M of the polymer by controlling the reactor temperature between -35°C and 100°C, controlling the amount of monomer recycled to the reactor, using monomer as a reaction solvent, or a combination thereof w and / or trans:cis ratio;

[0141] (II) forming an active catalyst species at a temperature of less than or equal to about 5°C, and then increasing the reaction temperature to a temperature of less than 100°C;

[0142] (III) introducing an amount of an olefin, preferably an α-olefin, preferably an α-olefin containing at least one heteroatom-containing functional group, into the cyclic olefin monomer to reduce the molecular weight of the polymer in the product mixture;

[0143] (IV) using two or more cyclic olefin polymerization catalysts in the same reactor or in different reactors to produce a polymer exhibiting the following properties:

[0144] i) Multimodal M w curve;

[0145] ii) a trans:cis molar ratio greater than 1;

[0146] iii) a trans:cis molar ratio of less than 1; and / or

[0147] (V) Using multiple reactors connected in series to produce heterophasic copolymers.

[0148] In one or more embodiments of the present invention, the olefin comonomer has the general formula:

[0149] CH2=CH-(CH2) n -CH3;

[0150] CH2=CH-[(CH2) n (FG) s ]-CH3; and / or

[0151] CH2=CH-(CH2) n -FG;

[0152] wherein each FG when present is independently halogen, NR^2, OR^, SeR^, TeR^, PR^2, AsR^2, SbR^2, SR^, BR^2, SiR^3, GeR^3, SnR^3, PbR^3, O, S, Se, Te, NR^, PR^, AsR^, SbR^, BR^, SiR^2, GeR^2, SnR^2, PbR^2, or a combination thereof, and each R^ is independently C1-C 10 a hydrocarbyl group; n is greater than or equal to 1; and s, when present, is greater than or equal to 1.

[0153] In one or more embodiments of the present invention, the transition metal M v It is preferably present in the catalyst at a level of 0.1 wt% to 30 wt%, based on the total amount of catalyst present. In some embodiments, the transition metal M in the supported catalyst v The molar ratio of aluminum (M v :A1) is preferably 1:1000 to 4:10, based on the presence of M v The total number of moles of aluminum is used.

[0154] When desired, one or more quenching compounds may be used to terminate the polymerization reaction. Suitable quenching compounds may be or may include one or more antioxidants, which may be dispersed in an alcohol (e.g., methanol or ethanol). Examples of quenching compounds may include, but are not limited to, butylated hydroxytoluene (BHT), IRGANOX TM Antioxidants (available from BASF), and the like, and any combination thereof.The quenching compound may be added to the reaction mixture at a level of 0.05 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the polymer product.

[0155] Polymer properties

[0156] The properties of the polymer produced may depend, at least in part, on the composition of the catalyst, the composition of the (comonomers), the rate of comonomer addition, the reaction temperature, and the reaction time. If two cyclic olefin comonomers are used, the copolymer produced may have a molar ratio of first cyclic olefin comonomer-derived units to second cyclic olefin comonomer-derived units of 3:1 to 100:1, or 4:1 to 75:1, or 5:1 to 50:1, or 6:1 to 35:1. If desired, a slower addition rate of the second comonomer combined with a higher concentration of the first cyclic olefin comonomer may result in a higher amount of first cyclic olefin comonomer-derived units in the resulting polymer.

[0157] The polymer produced can have a cis to trans ratio for both comonomer entities of 95:5 to 5:95, or 95:5 to 80:20, or 80:20 to 60:40, or 75:25 to 50:50, or 75:25 to 25:75, or 50:50 to 5:95, or 40:60 to 5:95, or 30:70 to 5:95, or 20:80 to 5:95, or 20:80 to 10:90, or 100: 0. The target cis / trans ratio can be achieved by appropriate selection of catalyst and activator, catalyst:activator ratio, catalyst:monomer ratio, reagent concentrations, solvents and solvent mixtures, process temperature, reaction time, and any combination thereof.

[0158] The polymer produced can have an M of 1 kDa to 1,000 kDa, or 10 kDa to 1,000 kDa, or 100 kDa to 1,000 kDa, or 250 kDa to 750 kDa, or 250 kDa to 550 kDa. w .

[0159] The polymer produced may have an M of 0.5 kDa to 500 kDa, or 1 kDa to 250 kDa, or 10 kDa to 250 kDa, or 50 kDa to 250 kDa, or 100 kDa to 500 kDa. n .

[0160] The polymers of the present disclosure may have an MWD of 1 to 10, or 1 to 5, or 2 to 4, or 1 to 3.

[0161] Alternatively, the level of LCB can be determined by GPC using a triple detector method by the branching index (g′ vis ) is quantified. vis The intrinsic viscosity of a branched polymer is defined as the ratio of the intrinsic viscosity of a branched polymer to the intrinsic viscosity of a linear polymer of the same molecular weight. The branching index g' is mathematically defined as follows:

[0162]

[0163] Mv is the viscosity average molecular weight, based on the molecular weight determined by LS analysis. The Mark-Houwink parameters α and k for the reference linear polymer are 0.725 and 0.000291, respectively.

[0164] The disclosed polymers having long chain branching may have a g' of 0.5 to 0.91, 0.5 to 0.8, or 0.6 to 0.8, or 0.7 to 0.91. vis The disclosed polymers having a linear structure may have a g′ of 0.92 to 1.0, 0.92 to 0.95, or 0.95 to 0.99, or 0.95 to 1.0. vis .

[0165] The polymer having a long chain branched structure produced may have (a) a g′ of 0.5 to 0.91, 0.5 to 0.8, or 0.6 to 0.8, or 0.7 to 0.91. vis , and one or more of the following properties: (b) a molar ratio of the first cyclic olefin comonomer-derived units to the second cyclic olefin comonomer-derived units of 3:1 to 100:1, or 4:1 to 75:1, or 5:1 to 50:1, or 6:1 to 35:1, (b) 5:5 to 5:95, or 95:5 to 80:20, or 80:20 to 60:40, or 75:25 to 50:50, or 75:25 to 25:75, or 40:60 to 5:95, or 30:70 to 5:95, or 20:80 to 5:95, or 20:80 to 10:90, or 100:0 cis to trans ratio for both comonomer entities, (d) 1 kDa to 1,000 kDa, or 10 kDa to 1,000 kDa, or 100 kDa to 1,000 kDa, or 250 kDa to 750 kDa, or 250 kDa to 550 kDa w , (e) M of 0.5 kDa to 500 kDa, or 1 kDa to 250 kDa, or 10 kDa to 250 kDa, or 50 kDa to 250 kDa, or 100 kDa to 500 kDa n , and (f) an MWD of 1 to 10, or 1 to 5, or 2 to 4, or 1 to 3.

[0166] The polymer having a linear structure produced may have (a) a g′ of 0.92 to 1.0, 0.92 to 0.95, or 0.95 to 0.99, or 0.95 to 1.0. vis, and one or more of the following properties: (b) a molar ratio of the first cyclic olefin comonomer-derived units to the second cyclic olefin comonomer-derived units of 3:1 to 100:1, or 4:1 to 75:1, or 5:1 to 50:1, or 6:1 to 35:1, (c) 5:5 to 5:95, or 95:5 to 80:20, or 80:20 to 60:40, or 75:25 to 50:50, or 75:25 to 25:75, or 40:60 to 5:95, or 30:70 to 5:95, or 20:80 to 5:95, or 20:80 to 10:90, or 100:0 cis to trans ratio for both comonomer entities, (d) 1 kDa to 1,000 kDa, or 10 kDa to 1,000 kDa, or 100 kDa to 1,000 kDa, or 250 kDa to 750 kDa, or 250 kDa to 550 kDa w , (e) M of 0.5 kDa to 500 kDa, or 1 kDa to 250 kDa, or 10 kDa to 250 kDa, or 50 kDa to 250 kDa, or 100 kDa to 500 kDa n , and (f) an MWD of 1 to 10, or 1 to 5, or 2 to 4, or 1 to 3. Example

[0167] The embodiments discussed and described herein can be further described with the following non-limiting examples. Although the examples are directed to specific embodiments, they should not be considered as limiting in any particular respect. Methods for characterizing samples (NMR and GPC) are included in embodiments 0042-0053.

[0168] Two different catalyst systems were prepared and used to polymerize cyclopentene (C5). Example 1 used a (4-PhCH2C6H4O)2AlCl procatalyst and Example 2 used a (4-(Ph2N)C6H4O)2AlCl procatalyst. Both procatalysts were activated using a WCl6 mixture in toluene and used to polymerize cyclopentene to provide a solid ring-opened polycyclopentene product. A comparative example (Comparative Example 3) using (4-MeC6H4O)2AlCl as a procatalyst is also provided. As summarized in Table 1 below, the polymers produced using the catalyst systems of Examples 1 and 2 provide polymers having a desired cis / trans ratio of about 20 / 80, a narrow MWD (about 2.0), and an M of up to 563 kDa. wHowever, it was surprisingly and unexpectedly found that the activities of the (4-PhCH2C6H4O)-based system (Example 1) and the (4-(Ph2N)C6H4O)-based system (Example 2) were significantly higher than the activities of all other systems. Even more surprisingly and unexpectedly, the activity of the (4-PhCH2C6H4O)-based system (Example 1) was found to be 2,070 g polymer / g W , the activity is based on the activity of the system (4-MeC6H4O) (976g polymer / g W )(Comparative Example 3) is more than twice.

[0169] Example 1: Catalyst based on (4-PhCH2C6H4O)

[0170] Synthesis of (4-PhCH2C6H4O)2AlCl precatalyst (W: monomer ratio of 1:4000). A solution of 4-benzylphenol (60.0 g, 326 mmol) in toluene (350 mL) was slowly added to a solution of dimethylaluminum monochloride (15.06 g, 163 mmol) in toluene (50 mL) over 1 hour under vigorous stirring. The resulting mixture was stirred at 25 ° C for 12 hours, and then n-pentane (100 mL) was added. The resulting mixture was then stirred for another 24 hours. The precipitated solid product was then collected, washed with n-pentane (3×100 mL) and dried in vacuo at 75 ° C for 3 hours.

[0171] Yield: 63.7 g (91.2%) of white solid. 1 H NMR (400MHz, THF-d8, 25°C, ppm): δ7.21-7.09 (8H, m, Ar-H), 6.92 (4H, d, J HH =7.6Hz, Ar-H), 6.78-6.69 (4H, m, Ar-H), 3.82 (4H, s, CH2). 13 CNMR (100.63MHz, THF-d8, 25°C, ppm): δ158.7, 143.1, 130.1, 129.2, 128.7, 126.1, 119.7, 119.6 (Ar-C), 41.7 (CH2).

[0172] Example 1A. Cyclopentene polymerization using the (4-PhCH2C6H4O)2AlCl procatalyst (W:monomer=1:10,000). Solid (4-PhCH2C6H4O)2AlCl (130 mg, 0.303 mmol) was added to a solution of WCl6 (60 mg, 0.151 mmol) in toluene (20 mL). The resulting solution was stirred at ambient conditions for 1 hour. The resulting solution was added to a mechanically stirred mixture (400 rpm) containing cyclopentene (103 g, 1.513 mol), triethylaluminum (35 mg, 0.303 mmol) and toluene (250 mL) at 0°C. The reaction was stirred at 0°C for 3 hours. The active catalyst was then quenched by the addition of 2,6-di-tert-butyl-4-methylphenol (1.0 g) in ethanol / toluene (20 / 80 mL). The resulting solution was poured into ethanol (1 L) under vigorous mechanical stirring.The precipitated polymer was washed with ethanol (3 x 250 mL) and dried with a stream of nitrogen for 3 days.

[0173] Yield: 57.5 g, 56%. Cis / trans ratio: 19 / 81%. M w :563kDa,M w / M n :2.02.

[0174] Example 1B. Cyclopentene polymerization using the (4-PhCH2C6H4O)2AlCl procatalyst (W:monomer=1:4,000). Solid (4-PhCH2C6H4O)2AlCl (288 mg, 0.631 mmol) was added to a solution of WCl6 (125 mg, 0.316 mmol) in toluene (20 mL). The resulting solution was stirred at ambient conditions for 1 hour. The resulting solution was added to a mechanically stirred mixture (400 rpm) containing cyclopentene (85.86 g, 1.263 mol), triethylaluminum (72 mg, 0.632 mmol), and toluene (250 mL) at 0°C. The reaction was stirred at 0°C for 3 hours. The active catalyst was then quenched by the addition of 2,6-di-tert-butyl-4-methylphenol (1.0 g) in ethanol / toluene (20 / 80 mL). The resulting solution was poured into ethanol (1 L) under vigorous mechanical stirring.The precipitated polymer was washed with ethanol (3 x 250 mL) and dried with a stream of nitrogen for 3 days.

[0175] Yield: 77.0 g, 90%. Cis / trans ratio: 18 / 82%. M w :515kDa,M w / M n :1.82.

[0176] Example 1C. Cyclopentene and dicyclopentadiene copolymerization using the (4-PhCH2C6H4O)2AlCl precatalyst (W:monomer=1:4,000). The catalyst was formed in situ by adding solid (4-(PhCH2)C6H4O)2AlCl (865 mg, 2.02 mmol) to a solution of WCl6 (400 mg, 1.01 mmol) in toluene (20 mL). After stirring for 1 hour at ambient conditions, the resulting mixture was added to a 0°C solution containing cyclopentene (first comonomer) (275 g, 4.035 mol), triethylaluminum (230 mg, 2.02 mmol) and toluene (1200 mL). A solution of DCPD (second comonomer) (3.60 g, 27.3 mmol) in toluene (15 mL) was slowly added to the reaction mixture over 35 minutes under vigorous mechanical stirring. After 20 minutes, a solution of 2,6-di-tert-butyl-4-methylphenol (2.00 g, 9.0 mmol) in 100 mL of an ethanol / toluene mixture (1:4, v:v) was added. The resulting mixture was added to ethanol (1 L). The precipitated polymer was washed three times with ethanol (500 mL each time) and dried under vacuum at 55° C. for 4 hours to give 98 g of product.

[0177] Yield: 98 g, 35%. 2.4 mol% DCPD. Cis / trans ratio: 20 / 80%. M w :614kDa,M w / M n : 1.70, g'(Z average) 0.93, g'(viscosity average) 0.91.

[0178] Example 2: Catalyst based on (4-(Ph2N)C6H4O)

[0179] Synthesis of (4-(Ph2N)C6H4O)2AlCl precatalyst. A solution of (4-HO-C6H4)NPh2 (452 ​​mg, 1.73 mmol) in toluene (10 mL) was added dropwise to a solution of dimethylaluminum monochloride (80 mg, 0.86 mmol) in toluene (5 mL) at -30°C. After the addition was complete, the reaction mixture was allowed to gradually warm to 25°C over 30 minutes and stirred for an additional 30 minutes. The resulting solution was concentrated to approximately 5 mL. Addition of n-pentane (15 mL) to the solution resulted in the precipitation of an off-white solid, which was collected and dried under vacuum.

[0180] Yield: 418 mg (82.9%) of light green powder. 1H NMR (400 MHz, THF-d8, 25°C, ppm): δ 7.20-7.08 (10H, m, Ar-H), 6.98-6.80 (18H, m, Ar-H). The low solubility of (4-(Ph2N)C6H4O)2AlCl prevented the collection of satisfactory 13 C NMR spectrum.

[0181] Polymerization using the 4-((Ph2N)C6H4O)2AlCl procatalyst (W:monomer=1:4,000): Toluene (20 mL) was added to a mixture of solid (4-(Ph2N)C6H4O)2AlCl (426 mg, 0.731 mmol) and solid WCl6 (145 mg, 0.366 mmol). The resulting solution was stirred at ambient conditions for 1 hour and then added to a mechanically stirred mixture (400 rpm) of cyclopentene (99.7 g, 1.46 mol), triethylaluminum (84 mg, 0.0.731 mmol) and toluene (500 mL) at 0°C. The reaction was stirred at 0°C for 2 hours. The active catalyst was then quenched by the addition of 2,6-di-tert-butyl-4-methylphenol (1.0 g, 4.5 mmol) in ethanol / toluene (20 / 80 mL). The resulting solution was poured into ethanol (1 L) under vigorous mechanical stirring.The precipitated polymer was washed with ethanol (3 x 250 mL) and dried under vacuum for 12 hours.

[0182] Yield: 33.7 g, 33.8%. Cis / trans ratio: 20 / 80%. Mw: 605 kDa, Mw / Mn: 1.44.

[0183] Comparative Example: Catalyst based on (4-MeC6H4O)

[0184] (4-MeC6H4O)2AlCl precatalyst synthesis. In a 500mL round-bottom flask containing a magnetic stirring bar, dimethylaluminum monochloride (21.38g, 231mmol) was dissolved in 250mL toluene. Under vigorous stirring, p-cresol (50g, 462mmol, Sigma-Aldrich) was added dropwise to the dimethylaluminum monochloride solution for 30 minutes. Then, the mixture was allowed to gradually warm to ambient temperature. After further stirring for 3 hours, the mixture was concentrated by purging nitrogen to provide a yellow oily product. Pentane (300mL) was added, and the formed colorless solid was collected by filtration. Washed with pentane (200mL) and dried under vacuum at 60°C for 5 hours, 46.7g (73.0%) of colorless powder was provided. 1H NMR (400MHz, THF-d8, ppm): δ6.89-6.66 (4H, m, Ar-H), 2.18 (3H, s, CH3).

[0185] Comparative Example 3A. Polymerization using the (4-MeC6H4O)2AlCl procatalyst (W:monomer = 1:10,000): Solid (4-MeC6H4O)2AlCl (84 mg, 0.303 mmol) was added to a solution of WCl6 (60 mg, 0.151 mmol) in toluene (20 mL) and stirred at room temperature for 1.0 hour. The resulting mixture was then added to a solution of cyclopentene (103 g, 1.513 mmol) and triethylaluminum (86 mg, 0.757 mmol) in toluene (500 mL) at 0°C with mechanical stirring (400 rpm). After approximately 20 minutes of reaction time, the mixture became viscous. After 3 hours at 0°C, a solution of 2,6-di-tert-butyl-4-methylphenol (1.0 g, 4.5 mmol) in ethanol (20 mL) / toluene (100 mL) was added. The resulting mixture was poured into ethanol (1.5 L) with vigorous mechanical mixing.The formed polymer was washed with ethanol (3 x 500 mL) and dried under vacuum at 50°C for 4 hours.

[0186] Yield: 15.6 g (15.1%); cis: trans ratio: 25 / 75%; M w :464kDa; M w / M n :3.41.

[0187] Comparative Example 3B. Polymerization using the (4-MeC6H4O)2AlCl procatalyst (W:monomer = 1:4,000): Solid (4-MeC6H4O)2AlCl (209 mg, 0.747 mmol) was added to a solution of WCl6 (150 mg, 0.378 mmol) in toluene (20 mL) and stirred at room temperature for 1.0 hour. The resulting mixture was then added to a solution of cyclopentene (103 g, 1.513 mmol) and triethylaluminum (86 mg, 0.757 mmol) in toluene (500 mL) at 0°C with mechanical stirring (400 rpm). After approximately 20 minutes of reaction time, the mixture became viscous. After 3 hours at 0°C, a solution of 2,6-di-tert-butyl-4-methylphenol (1.0 g, 4.5 mmol) in ethanol (20 mL) / toluene (100 mL) was added. The resulting mixture was poured into ethanol (1.5 L) with vigorous mechanical mixing.The formed polymer was washed with ethanol (3 x 500 mL) and dried under vacuum at 50°C for 4 hours.

[0188] Yield: 65.5 g (63.6%); cis: trans ratio: 15 / 85%; M w :490kDa; M w / M n :2.02.

[0189] Table 1. Aggregation summary

[0190]

[0191] In each of the above examples, the molecular weight distribution, molecular weight moment (M w , M n , M w / M n ) and long chain branching index, the chromatograph is equipped with three online detectors, namely an 18-angle light scattering ("LS") detector, a viscometer and a differential refractive index detector ("DRI"). Three Agilent PLgel 10μm Mixed-B LS columns were used for the GPC tests here. The nominal flow rate was 0.5mL / min and the nominal injection volume was 200μL. The column, viscometer and DRI detector were contained in an oven maintained at 40°C. Tetrahydrofuran (THF) solvent containing 250ppm of the antioxidant butylated hydroxytoluene (BHT) was used as the mobile phase. A given amount of polymer sample was weighed and sealed in a standard vial. After the vial was loaded into the autosampler, the polymer was automatically dissolved in the instrument at 40°C with 8mL of added THF solvent under continuous shaking for about 2 hours. The concentration c at each point in the chromatogram was calculated from the baseline-subtracted DRI signal I using the following formula DRI Calculation: c = K DRI I DRI / (d n / d c ), where K DRI is a constant determined by correcting the DRI, and (d n / d c ) is the refractive index increment of the polymer in THF solvent.

[0192] Conventional molecular weight is determined by combining a universal calibration relationship with a column calibration using a series of monodisperse polystyrene (PS) standards ranging from 300 g / mol to 12,000,000 g / mol. The molecular weight "M" for each elution volume is calculated using the following equation:

[0193]

[0194] Variables with the subscript "PS" represent polystyrene, while those without the subscript represent the test sample. In this method, aPS =0.7362 and K PS =0.0000957, while "a" and "K" of the rubber sample, obtained by fitting the logIV vs. logM curve of the linear reference sample (where IV represents intrinsic viscosity), are 0.725 / 0.000291.

[0195] The LS molecular weight, M, at each point in the chromatogram was determined by analyzing the LS output using the Zimm model for static light scattering and using the following formula:

[0196]

[0197] Here, ΔR(θ) is the hyper-Rayleigh scattering intensity measured at the scattering angle θ, “c” is the polymer concentration determined by DRI analysis, A2 is the second virial coefficient, P(θ) is the morphology factor of the monodisperse random coils, and K o is the optical constant of the system stated in the following formula:

[0198]

[0199] where N A is Avogadro's number, and (dn / dc) is the refractive index increment of the system, which takes the same value as that obtained by the DRI method, and the value of "n" is 1.40 for THF at 40°C and λ = 665 nm. For the rubber sample used in this test, dn / dc was determined by the DRI detector to be 0.1154.

[0200] A four-capillary viscometer with a Wheatstone bridge structure was used to measure the specific viscosity (η S ) and concentration "c" determine the intrinsic viscosity [η].

[0201] ηs=c[η]+0.3(c[η]) 2 ,

[0202] Average intrinsic viscosity of the sample [η] avg Use the following formula to calculate:

[0203]

[0204] where the sum is taken over all chromatographic slices i between the integration limits.

[0205] Branching coefficient (g' vis Or simply g') is defined as the ratio of the intrinsic viscosity of a branched polymer to the intrinsic viscosity of a linear polymer of the same molecular weight. The branching index g' is arithmetically defined as:

[0206]

[0207] Wherein Mv is the viscosity average molecular weight, based on the molecular weight determined by LS analysis.The Mark-Houwink parameters k / α used in the reference linear polymer are 0.725 / 0.000291.

[0208] Certain embodiments and features have been described using a set of numerical upper limits and a set of numerical lower limits. It should be understood that ranges including any combination of two values, such as any lower limit combined with any upper limit, any two lower limits combined, and / or any two upper limits combined, are contemplated unless otherwise indicated. Certain lower limits, upper limits, and ranges appear in one or more of the claims below. All numerical values ​​are "about" or "approximately" the indicated value, and take into account experimental error and variations that would be expected by one of ordinary skill in the art.

[0209] Various terms have been defined above. If a term used in a claim is not defined above, it should be given the broadest definition persons in the pertinent art have given that term, as reflected in at least one printed publication or issued patent. In addition, all patents, test procedures, and other documents cited in this application are fully incorporated herein by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions where such incorporation is permitted.

[0210] While the foregoing is directed to embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope of the invention is determined by the claims that follow.

Claims

1. A catalyst for the polymerization of cyclic olefins comprising a transition metal carbene having the following structure (V): M v (OR’) c*m X (v-c*m-2) =C(R * )2 (V), in: M v is a Group 5 transition metal having a valence of 5 or a Group 6 transition metal having a valence of 5 or 6, wherein v represents the valence of the Group 5 or 6 transition metal; Each OR' is independently 4-benzylphenol or 4-(diphenylamino)phenol; c is an integer from 1 to 3; m is 1 / 3, 1 / 2, 1, 3 / 2, 2, 3, or 4, and c*m ≤ v-2; X is a halogen; and Each R * are independently H or C1-C7 alkyl, and wherein the catalyst comprises the reaction product of: A) at least one metal alkoxide (I) having the formula: m(R'O) c M u X (u-c) ;and B) at least one transition metal halide (II) having the formula: M v X v Among them, M u is a Group 1, 2 or 13 metal of u valence, M v , R', c, m and X have the meanings defined above, and said reaction product having been activated by at least one metal alkyl activator (IV), The metal alkyl activator (IV) has the following general formula: u R a X (u-a) , where M u and X have the meanings defined above, a is 1, 2 or 3 and ≤ u, and each R is independently C1-C8 alkyl, or The metal alkyl activator (IV) is an aluminum alkyl having the general formula: AlR * r (AND) 3-r where R * is C1-C8 alkyl, each Y is hydrogen, halogen, or -OR 5 , where each R 5 Independently C1-C 20 Hydrocarbyl, optionally when present R 5 Two or more of are linked together to form a ring having up to 40 atoms from Groups 14, 15 and / or 16 of the Periodic Table of the Elements; and r is 1-3.

2. The catalyst of claim 1, wherein v is 6, M v is tungsten (W), X is chlorine or fluorine, and each R It is aromatic.

3. A cyclic olefin polymerization method, comprising: The cyclic olefin polymerization catalyst according to claim 1 is reacted with a C4-C ... 20 contacting a cyclic olefin monomer in a polymerization reactor under conditions sufficient to form a reaction product mixture comprising polymer, unreacted monomer, catalyst, and optionally solvent; and The polymer is recovered.

4. The method of claim 3, further comprising: separating the monomer from the reaction product mixture and recycling the monomer to the polymerization reactor; contacting the recovered catalyst with an activator and then recycling it to the polymerization reactor; Or a combination of these.

5. The method of claim 3, wherein the polymerization comprises ring-opening metathesis polymerization, and the polymer comprises a ring-opening polycycloolefin, a cyclic olefin copolymer, and / or a cyclic olefin polymer.

6. The process of claim 3, further comprising recovering the catalyst and optionally the solvent from the reaction product mixture; and recycling at least a portion of the recovered catalyst, unreacted monomers and / or optional solvent to the polymerization reactor.

7. The method of claim 3, further comprising: 4-20 Cyclic dienes: One or more functionalized C containing at least one cyclic structure of the general formula 4-20 Cyclic dienes: is incorporated into the reaction product mixture as a comonomer, wherein each FG is integral to and / or pendant from the corresponding cyclic structure, and wherein each FG is independently halogen, NR^2, OR^, SeR^, TeR^, PR^2, AsR^2, SbR^2, SR^, BR^2, SiR^3, GeR^3, SnR^3, PbR^3, O, S, Se, Te, NR^, PR^, AsR^, SbR^, BR^, SiR^2, GeR^2, SnR^2, PbR^2, or a combination thereof, and each R^ is independently hydrogen or C1-C 10 Hydrocarbyl, r is greater than or equal to 1, and when present, s is greater than or equal to 1.

8. The method of claim 7, wherein the comonomer comprises norbornene, ethylidene norbornene, dicyclopentadiene, or a combination thereof.

9. The method of claim 3, further comprising: (I) controlling the M of the polymer by controlling the reactor temperature between -35°C and 100°C, controlling the amount of monomer recycled to the reactor, using the monomer as a reaction solvent, or a combination thereof w and / or trans:cis ratio; (II) forming an active catalyst species at a temperature of 5°C or less, and then increasing the reaction temperature to a temperature of less than 100°C; (III) introducing an amount of olefin into the cyclic olefin monomer to reduce the molecular weight of the polymer in the product mixture; (IV) using two or more cyclic olefin polymerization catalysts in the same reactor or in different reactors to produce a polymer exhibiting the following properties: Multi-peak M w curve; a trans:cis molar ratio of 1; a trans:cis molar ratio greater than 1; a trans:cis molar ratio of less than 1; and / or (V) Using multiple reactors connected in series to produce heterophasic copolymers.

10. The process of claim 9, wherein in step (IV), two or more cyclic olefin polymerization catalysts are used in the same reactor or in different reactors to produce a polymer exhibiting the following properties: Multi-peak M w curve; a trans:cis molar ratio of 1; 2.33-19 trans:cis molar ratio; A trans:cis molar ratio of less than 1.

11. The process according to claim 9, wherein the olefin in (III) is an α-olefin.

12. The process of claim 9, wherein the olefin in (III) is an α-olefin containing at least one heteroatom-containing functional group.

13. The method of claim 3, wherein the olefin comonomer has the general formula: CH2=CH-(CH2) n -CH3; CH2=CH-[(CH2) n (FG) s ]-CH3; and / or CH2=CH-(CH2) n -FG; wherein each FG when present is independently halogen, NR^2, OR^, SeR^, TeR^, PR^2, AsR^2, SbR^2, SR^, BR^2, SiR^3, GeR^3, SnR^3, PbR^3, O, S, Se, Te, NR^, PR^, AsR^, SbR^, BR^, SiR^2, GeR^2, SnR^2, PbR^2, or a combination thereof, and each R^ is independently C1-C 10 hydrocarbon group; n is greater than or equal to 1; and When present, s is greater than or equal to 1.

14. The method of claim 3, wherein the polymer has a g vis .

15. The method of claim 3, wherein the reaction mixture further comprises a diluent at a level of 60 volume % or less, based on the total volume of the reaction mixture.

16. The method of claim 3, wherein the polymer has a cis to trans ratio of 50:50 to 5:

95.

17. The method of claim 3, wherein the polymer has a weight average molecular weight of 1 kDa to 1,000 kDa, and the polymer has a molecular weight distribution of 1 to 10.

18. A method for preparing a catalyst for cyclic olefin polymerization, the method comprising: The following components are reacted to form a reaction product: A) at least one metal alkoxide (I) having the formula: m(R'O) c M u X (u-c) ;and B) at least one transition metal halide (II) having the formula: M v X v in: M u is a Group 1, 2 or 13 metal of valence u; M v is a pentavalent Group 5 transition metal or a penta- or hexavalent Group 6 transition metal, wherein v represents the valence of the Group 5 or 6 transition metal; Each OR' is independently 4-benzylphenol or 4-(diphenylamino)phenol; X is a halogen; and c is an integer from 1 to 3; and The reaction product is activated with at least one metal alkyl activator (IV), wherein the metal alkyl activator (IV) has the following general formula: u R a X (u-a) , where M u and X have the meanings defined above, a is 1, 2 or 3 and ≤ u, and each R is independently a C1-C8 alkyl, or the metal alkyl activator (IV) is an aluminum alkyl having the general formula: AlR * r (Y) 3-r , where R * is C1-C8 alkyl, each Y is hydrogen, halogen, or -OR 5 , where each R 5 Independently C1-C 20 Hydrocarbyl, optionally when present R 5 Two or more of are joined together to form a ring having up to 40 atoms from Groups 14, 15 and / or 16 of the Periodic Table of the Elements; and r is 1-3, and recovering the resulting catalyst having the formula: M v (OR’) c*m X (v-c*m-2) =C(R * )2 (V), where m is 1 / 3, 1 / 2, 1, 3 / 2, 2, 3, or 4, and c*m ≤ v-2; each R * are independently H or C1-C7 alkyl; and M v , R', c and X are as defined above.

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