Improved ring-opening metathesis catalyst system for cyclic olefin polymerization

Abstract

An improved catalyst for the polymerization of cyclic olefins. The catalyst has the following structure: v (OR') c*m X (v-c*m-2) =C(R * )2, wherein M v is a Group 5 transition metal having a valence (v) of 5 or a Group 6 transition metal having a valence (v) of 5 or 6; each R' is independently a monovalent organic moiety containing 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 C1-C7 alkyl. The catalyst is particularly useful for ring-opening metathesis polymerization (ROMP).

Description

[Technical Field]

[0001] Cross-reference of related applications This application claims the benefit of priority of U.S. Provisional Application No. 62 / 992002, filed on 19 March 2020, the disclosure of which is incorporated herein by reference. [Background technology]

[0002] background This disclosure relates to a ring-opening metathesis catalyst and the polymerization of cyclic olefins using the same. In organic synthesis, metathesis is a catalytic reaction in which a double bond is recombined between two olefins or alkynes. Ring-opening metathesis polymerization (ROMP) involves the formation of an unsaturated polymer from the ring-opening of one, two, or three or more cyclic olefin comonomers. Generally, cyclic olefin comonomers are strained cyclic olefins that react with a ROMP catalyst to open their rings, relieve the strain, and produce a linear molecule that reacts with other cyclic olefins. However, since individual cyclic olefin comonomers have different degrees of strain, their reactivity with the ROMP catalyst differs. In some cases, the reactivity can differ by orders of magnitude. Therefore, the polymers resulting from the incorporation of individual comonomers are different. For example, US 3,598,796, US 3,631,010, and US 3,778,420 describe copolymerization of cyclopentene and dicyclopentadiene premixed in various media before the addition of a ROMP catalyst.

[0003] The resulting polymer properties (e.g., mechanical properties, processability, etc.) are determined, at least in part, by 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 slow-reactive comonomers in amounts exceeding 50 mol%, would be beneficial. One approach to incorporating more slow-reactive comonomers is presented in US 3,707,520 and US 3,941,757, utilizing a two-step copolymerization process. In the first step, cyclopentene was homopolymerized, followed by the introduction of a more reactive comonomer (second step). The resulting polymer is a block copolymer, which has different properties than when the two comonomers are more homogeneously dispersed throughout the polymer structure. Therefore, the ability to control the amount of each comonomer in the resulting polymer, including incorporating slow-reactive comonomers into the overall polymer structure in amounts exceeding 50 mol% of the polymer, would be beneficial.

[0004] Notable references include US Patent Nos. US 3,598,796, US 3,631,010, US 3,707,520, US 3,778,420, US 3,941,757, US 4,002,815, US 4,239,484, US 8,889,786; US Patent Publication Nos. US 2016 / 0289352, US 2017 / 0247479; Canadian Patent No. CA 1,074,949; Chinese Patent Publication No. 2018 / 8001293; WO Patent Publication No. WO 2018 / 173968; Japanese Patent Application Publication Nos. JP 2019 / 081839A and JP 2019 / 081840A; and Yao, Z. et al. (2012) “Ring-Opening Metathesis Copolymerization of Dicyclopentadiene and Cyclopentene Through Reaction Injection Molding Process,” J. of App. Poly. Sci., v.125(4), pp. 2489-2493 is cited. [Overview of the project]

[0005] Summary of the Invention This provides an improved catalyst for cyclic olefin polymerization. The catalyst has the following structure: M v (OR') c*m X (v-c*m-2) =C(R* ) It may contain a transition metal carbene having 2. In the formula, M v is a Group 5 transition metal having a valence (v) of 5 or a Group 6 transition metal having a valence (v) of 5 or 6; each R’ is independently a monovalent organic component containing 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 C1-C7 alkyl. This catalyst is particularly useful for ring-opening metathesis polymerization (ROMP). Formula: m(R’O) c M u X (u-c) Also provided is a catalyst for cyclic olefin polymerization, which is a reaction product of at least one metal alkoxide having the formula: M v X v and at least one transition metal halide having the formula: M u is a Group 1, Group 2, or Group 13 metal having a valence u; and M v is a Group 5 transition metal having a valence v of 5 or a Group 6 transition metal having a valence v of 5 or 6. Each R’ is independently a monovalent organic component containing 8 to 40 atoms selected from Groups 14 to 17. X is a halogen; c is an integer from 1 to 3; and m is 1 / 3, 1 / 2, 3 / 2, 1, 2, 3, or 4, and c*m ≦ v - 2.

[0006] Also provided is a cyclic olefin polymerization process. The process comprises contacting the cyclic olefin polymerization catalyst according to any one of claims 1 to 18 with at least one cyclic olefin component in a polymerization reactor under conditions sufficient to form a reaction product mixture containing a polymer, an unreacted monomer, a catalyst, and optionally a solvent, in a C4-C 20 cyclic olefin monomer; and recovering the polymer. The process may further include separating the monomer from the reaction product mixture and recycling the monomer to the polymerization reactor; or contacting the recovered catalyst with an activator before recycling it to the polymerization reactor; or a combination thereof. The drawings below are included to illustrate specific aspects of the embodiments and should not be considered exclusive embodiments. The subject matter disclosed can be substantially modified, altered, combined, and equivalent in form and function, as will be apparent to those skilled in the art and those benefiting from this disclosure. [Brief explanation of the drawing]

[0007] [Figure 1] This is a typical 13C NMR spectrum illustrating the chemical shift assignment of the cyclopentene polymer, which is helpful for explanation. [Figure 2] A reaction scheme is shown to help explain the formation of a metal alkoxide (I) from the reaction of dimethylaluminum chloride with 2 equivalents of 4-benzylphenol. [Figure 3] A reaction scheme is shown to help explain the formation of a metal alkoxide (I) from the reaction of dimethylaluminum chloride with 2 equivalents of 4-(diphenylamino)phenol. [Figure 4] Figure 2 shows a reaction scheme that is useful for explaining the formation of a transition metal pre-catalyst (III) from the reaction of a metal alkoxide (I) and a transition metal halide (II) which is tungsten hexachloride (WCl6), followed by the formation of an activated catalyst (V) containing an active metal carbene component. [Figure 5] Figure 3 shows a reaction scheme that is useful for explaining the formation of a transition metal pre-catalyst (III) from the reaction of a metal alkoxide (I) and a transition metal halide (II) which is tungsten hexachloride (WCl6), followed by the formation of an activated catalyst (V) containing an active metal carbene component. [Figure 6] This specification provides a polymerization scheme that is helpful in explaining how to produce polypentenamers from cyclopentene using the catalyst system provided herein. [Modes for carrying out the invention]

[0008] Detailed explanation The following disclosure should be understood as describing several typical embodiments for satisfying various features, structures, and / or functions of the present invention. Typical embodiments of components, arrangements, and stereochemistry are described below for the sake of simplification of this disclosure, but these typical embodiments are provided merely as examples and are not intended to limit the scope of the present invention.

[0009] Definitions and Test Methods In the following discussion and claims, the terms "including" and "comprising" are used in an unrestricted form and should be interpreted as meaning "including, but not limited to." The expression "essentially consisting of..." means that the composition described / claimed contains no other components that substantially alter its properties by more than 5%, and in no case contains any other components up to a level exceeding 3% by mass. The term "or" is intended to encompass both exclusive and inclusive cases; that is, "A or B" is intended to be synonymous with "at least one of A and B" unless expressly otherwise provided herein. The indefinite articles "a" and "an" refer to both singular (i.e., "one") and plural (i.e., one or more) objects, unless the context indicates otherwise. Accordingly, embodiments using "an antioxidant" include embodiments using one, two, or three or more oxidizing agents, unless otherwise specified or the context clearly indicates the use of only one type of oxidizing agent.

[0010] The term "mass%" means mass percentage, such as weight percentage; "vol%" means volume percentage; "mol%" means mole percentage; "ppm" means parts per million; and "ppm wt" and "wppm" are used interchangeably and mean parts per million based on mass. All concentrations in this specification are expressed based on the total amount of the composition in question, unless otherwise specified. The terms "alkyl" and "alkyl group" are used interchangeably herein and refer to a saturated hydrocarbyl group consisting of a carbon atom and a hydrogen atom. Alkyl groups can be linear, branched, cyclic, or substituted cyclic groups. The term "cycloalkyl" or "cycloalkyl group" is interchangeable and refers to a saturated hydrocarbyl group in which one or more carbon atoms form a ring structure. The term "aryl" or "aryl group" is interchangeable and refers to a hydrocarbyl group that contains an aromatic ring structure. For the purposes of this disclosure and the claims herein, a new numbering scheme is used for the groups of the periodic table, as found in Chem. Eng. News, (1985), v.63, pg. 27. Thus, “Group 4 metals” are elements from Group 4 of the periodic table.

[0011] Unless otherwise indicated, substituent means 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 nonhydrogen group, and / or at least one carbon atom and the hydrogen atom bonded to it are replaced by a different group. Preferably, the substituent is a heteroatom or heteroatom-containing group in which at least one hydrogen atom is replaced by at least one functional group, such as halogens (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 * Substituted in the third order or at least one heteroatom, e.g., halogens (Cl, Br, I, F), O, S, Se, Te, NR * PR * AsR * SbR * , BR* , SiR * 2. GeR * 2. SnR * 2. PbR * The second is a group inserted into a hydrocarbyl group. Here, R * These are independently hydrogen or hydrocarbyl. For the purposes of this specification, “heteroatom” refers to nonmetallic or metalloid atoms from groups 13, 14, 15, and 16 of the periodic table, which typically replace carbon atoms. For example, pyridine is a heteroatom-containing form of benzene. Halogens refer to atoms from group 17 of the periodic table.

[0012] The terms "radical," "hydrocarbyl group," or "hydrocarbyl" are interchangeable and refer to a group consisting only of hydrogen and carbon atoms. A hydrocarbyl group can be saturated or unsaturated, linear, branched, cyclic or acyclic, aromatic or aromatic. The substituted hydrocarbyl group is a heteroatom or heteroatom-containing group in which at least one hydrogen atom is present, 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 * Substituted in the third order or at least one heteroatom, e.g., halogens (Cl, Br, I, F), O, S, Se, Te, NR * PR * AsR * SbR * , BR * , SiR * 2. GeR * 2. SnR * 2. PbR * The second is a group inserted into a hydrocarbyl group. Here, R* These are independently hydrogen or hydrocarbyl.

[0013] In some embodiments, the hydrocarbyl group is independently methyl, ethyl, ethenyl, 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, hexadecenyl, heptadecenyl, oc Selected from isomers of tadecenyl, nonadecenyl, eicocenyl, heneicocenyl, dococenyl, tricocenyl, tetracocenyl, pentacocenyl, hexacocenyl, heptacocenyl, octacocenyl, nonacocenyl, triacontinyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octinyl, noninyl, desinyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecenyl, eicosinyl, heneicosinyl, docosinyl, tricosinyl, tetracosinyl, pentacosinyl, hexacocensyl, heptacosinyl, octacosinyl, nonacocensyl, and triacontinyl. This also includes saturated, partially unsaturated, and aromatic ring isomers in which the group can undergo further substitution of the types described above. Examples include phenyl, methylphenyl, benzyl, methylbenzyl, naphthyl, cyclohexyl, cyclohexenyl, and methylcyclohexyl. In this disclosure, when a group is listed, it refers to that group and all other groups that are formed when that type of group undergoes the above substitutions.The listed alkyl, alkenyl, and alkynyl groups include all isomers, including appropriate cyclic isomers. 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 cyclobutyl and cyclopropyls); and 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 (and cyclobutenyl and cyclopropenyl). A substituted cyclic compound includes all isomers; for example, methylphenyl includes ortho-methylphenyl, meta-methylphenyl, and para-methylphenyl; and dimethylphenyl includes 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-diphenylmethyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl.

[0014] The term “C n A "group" or compound refers to a group or compound containing a total of n carbon atoms. Therefore, "C m -C n A group or compound refers to a group or compound containing a total number of carbon atoms in the range of m to n. Therefore, C1-C 50 Alkyl alkyl groups refer to alkyl groups containing a total of 1 to 50 carbon atoms. The term "olefin" is instead called "alkane," and refers to an unsaturated hydrocarbon compound having a hydrocarbon chain containing at least one carbon-carbon double bond in its structure, which does not constitute part of an aromatic ring. Olefins may be linear, branched, or cyclic. For the purposes of this specification and the claims appended herein, when a polymer or copolymer is referred to as containing a cyclic olefin, it includes, but is not limited to, cyclic pentene (cC5), cyclic pentadiene, and other cyclic C6-C9 hydrocarbons and their dienes, and the cyclic olefin present in the unsaturated polymer or copolymer is a polymer of a cyclic olefin. “Polymer” has two or more identical or different monomer units. “Homopolymer” is a polymer having identical monomer units. “Copolymer” is a polymer having two or more monomer units that are different from each other. “Different” as used to refer to monomers means that the monomers have at least one atom that is different from each other or isomerically different. Oligomers are low molecular weight, e.g., 21,000 g / mol or less (preferably 10,000 g / mol or less) M n The polymer is having, and / or a small number of mer units, for example, 100 or fewer mer units (preferably 75 or fewer mer units).

[0015] The term "cyclic olefin" refers to any cyclic species that contains at least one ethylenically double bond within the ring. The atoms in the ring may be optionally substituted. The ring may contain any number of carbon atoms and / or heteroatoms. In some cases, a cyclic olefin may contain more than one ring. The ring may contain at least 3, at least 4, at least 5, at least 6, at least 7, at least 8, or 9 or more atoms. Non-limiting examples of cyclic olefins include cyclopentene, cyclohexene, norbornene, dicyclopentadiene, bicyclo compounds, oxabicyclo compounds, etc., all of which may be optionally substituted. "Bicyclo compounds" is a classification of compounds consisting only of two rings sharing two or more atoms. Unless otherwise specified, the term “substantially all” in relation to molecules refers to at least 90 mol% (e.g., at least 95 mol%, at least 98 mol%, at least 99 mol%, or even 100 mol%). Unless otherwise specified, the term “substantially absent” with respect to a particular component means that the concentration of that component in the composition is 10 mol% or less (for example, 5 mol% or less, 3 mol% or less, 1 mol% or less, or about 0%) based on the total amount of the composition.

[0016] The terms “catalyst” and “catalytic compound” are used interchangeably and refer to compounds that have the ability to induce catalytic activity and / or accelerate a chemical reaction with little or no poisoning / consumption. In this specification, a catalyst may also be described as a catalytic precursor, precatalytic compound, or transition metal compound, and these terms are used interchangeably. A catalytic compound may induce catalytic activity alone or in combination with an activator. When a catalytic compound induces catalytic activity in combination with an activator, the catalytic compound is often called a precatalyst or catalytic precursor. A “catalytic system” is a combination of at least one catalytic compound, at least one activator, an optional co-activator, and an optional support material, and a catalytic system can polymerize one or more monomers to form a polymer. All numerical values ​​in the detailed description and claims of this application are indicated values ​​modified by “about” or “approximately,” taking into account experimental errors and variations that a person skilled in the art would expect. In this disclosure, unless otherwise specified, percentages refer to mass percentages expressed as "wt%".

[0017] In this disclosure, all molecular weight data is in g·moles. -1The units are as follows. Unless otherwise indicated, the molecular weight and distribution of the oligomer or polymer material present in this disclosure are determined using gel permeation chromatography utilizing the Tosoh EcoSEC High Temperature GPC system (GPC-Tosoh EcoSEC; Tosoh Bioscience LLC). GPC can be used to determine the Mw, Mn and / or Mw / Mn of polypentenamers using a high-temperature gel permeation chromatograph equipped with a differential refractive index (DRI) detector. Three high-temperature TSK gel columns (Tosoh GMHHR-H(20)HT2) are used. The nominal flow rate is 1.0 mL / min and the nominal injection volume is 300 μL. Various transfer lines, columns, and a double-flow differential refractometer are housed in an oven maintained at 160 °C. The mobile phase solvent for the experiment is prepared by dissolving 1.2 grams of butylated hydroxytoluene as an oxidizing agent in 4 liters of Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB). This TCB mixture is then filtered through a 0.1 μm Teflon® filter. The TCB is then degassed using an online degasser before entering the GPC instrument. The polydispersity index (PDI) of a material is also called the molecular weight distribution (MWD), and therefore M w / M n It is the ratio of . For the purposes of this specification, the trans:cis ratio of polymers is considered standard according to technically well-known methods. 13 It can be measured using 13C NMR technology. Prepare the sample using 66.67 mg / ml CDCl3 (deuterated chloroform) in a 10 mm tube. 13 The 13C NMR spectrum was measured using a Bruker 600 MHz cryoprobe with inverse gated decoupling, a 20-second delay, a 90° pulse, and 512 transients. Assignments are based on those from 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. [ka]

[0018] 1. The olefinic group (γ) peak is trans at 130.3 ppm and cis at 129.8 ppm; 2. The α-position is present at 32.2 ppm in trans / cis (tc), 32.07 ppm in trans / trans (tt), 26.9 ppm in cis / cis (cc), and 26.74 ppm in cis / trans (ct); 3. At the β position, cis / cis (cc) is present at 29.86 ppm, cis / trans (trans / cis) (ct+tc) at 29.7 ppm, and trans / trans (tt) at 29.54 ppm; 4. Trans = tt + .5 * (ct + tc); 5. Sys = cc + .5 * (ct + tc); and 6. n is the number of repetition units. The average trans and cis compositions are obtained by averaging the calculation results for each of the above groups 1-3 (i.e., γ, α, and β). In this specification, the term "γ" refers to a (CH=CH) group. Typical 13 The 13C NMR spectrum is shown in Figure 1, which is typical and illustrates the chemical shift assignment of the cyclopentene polymer, which is helpful in the explanation. 13 This is a 1C NMR spectrum.

[0019] For the purposes of this specification, small-scale polymerization conversion rates are monitored and, as instructed, using a Bruker 400MHz instrument. 1 It can be evaluated by 1H NMR. The pulse program zgcw30 can be used with D1=60 seconds and ns=2 or 4. CDCl3 may be the lock solvent. The chemical shift of the double bond proton of the cyclopentene monomer is approximately 5.75 ppm, and the chemical shift of the double bond proton of the polypentenamer is approximately 5.53 ppm. The integral (I) is 5.45-6.00 ppm. m+p These two chemical shifts can be covered using ), and by setting this to 100%, the total cyclopentene can be represented. 4.55~5.60 ppm integral (I p+RS ) is the right side of cyclopentene 13It is attributed to the overlap integral of the polypentenamer with the C satellite chemical shift. To subtract the contribution of the C satellite from the overlap integral, the left C satellite with a similar intensity to that of cyclopentene is integrated from 5.93 ppm to 5.97 ppm (I 13 ) and the conversion rate C can be calculated as follows: C = (I 13 - I LS ) / I P+RS . LS m+p If it is found that I LS is zero, an appropriate 13 C decoupling program is specified.

[0020] M n is the number-average molecular weight, M w is the mass-average molecular weight, and M z is the z-average molecular weight. The molecular weight distribution (MWD) is defined as M w divided by M n . Unless otherwise specified, all molecular weight units (e.g., M w , M n , M z ) are g / mol or kDa (1,000 g / mol = 1 kDa). The molecular weight distribution, molecular weight moments (M w , M n , M w / M nAnd the long-chain branching index is determined by using Polymer Char GPC-IR equipped with four in-line detectors, an 18-angle light scattering (“LS”) detector, a viscometer, and a differential refractive index (“DRI”) detector. Three Agilent PLgel 10μm Mixed-B LS columns are used for the GPC test herein. The nominal flow rate can be 0.5 mL / min, and the nominal injection volume is 200 μL. The columns, viscometer, and DRI detector are housed in an oven maintained at 40 °C. A tetrahydrofuran (THF) solvent containing 250 ppm 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 loading the vial into the autosampler, the polymer is automatically dissolved in the instrument by adding 8 mL of THF solvent and continuously shaking at 40 °C for about 2 hours. The concentration C at each point of the chromatogram is obtained from the DRI signal I DRI from which, the following formula: C = K DRI I DRI / (d n / d c ), is used for calculation, where K DRI is a constant determined by calibrating the DRI, and (d n / d c ) is the refractive index increment of the polymer in the THF solvent.

[0021] The normal molecular weight can be determined by combining the universal calibration relationship with column calibration performed with a series of monodisperse polystyrene (PS) standards in the range of 300 g / mol to 12,000,000 g / mol. The molecular weight “M” at each elution volume can be calculated using the following formula.

Equation

[0022] In the formula, the variable with the subscript “PS” represents polystyrene, and the variable without a subscript relates to the test sample. In this method, a PS = 0.7362 and K PS= 0.0000957, and the values ​​of "a" and "K" for the sample are 0.725 and 0.00029, respectively.

[0023] 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 can be identified using the following formula.

number

[0024] Here, ΔR(θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, "c" is the polymer concentration determined from the DRI analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coil, and K o is the optical constant of the system, expressed by the following formula.

number

[0025] In the formula, N A is Avogadro's number, and (dn / dc) is the refractive index increment of the system. Considering it to be the same value as the one obtained from the DRI method, the value of "n" is 1.40 for THF at 40°C and λ=665nm. For the sample used in this test, dn / dc was measured to be 0.1154 by the DRI method. Measured specific viscosity (η S From the ) and concentration "C", the intrinsic viscosity [η] can be determined using a Wheatstone bridge configuration 4-capillary viscometer as shown in the following formula: η s =C[η]+0.3(C[η]) 2 . Throughout this specification, the following abbreviations may also be used: Bu is butyl, n-Bu is n-butyl, i-Bu is isobutyl, t-Bu is tertiary butyl, pt-Bu is para-tertiary butyl, Et is ethyl, Me is methyl, p-Me is para-methyl, Ph is phenyl, Pr is propyl, i-Pr is isopropyl, n-Pr is n-propyl, RT is room temperature (i.e., about 23°C), THF is tetrahydrofuran, and tol is toluene.

[0026] A detailed explanation is provided below. Each attached claim defines a separate invention, which is intended to include, for the purpose of infringement, equivalents to the various elements or limitations specified in the claim. Depending on the context, all references to “invention” may refer to only certain specific embodiments. Otherwise, references to “invention” may refer to the subject matter described in one or more, but not necessarily all, claims. Each invention is described in further detail below, including specific embodiments, variants, and examples, but the invention is not limited to these specific embodiments, variants, or examples, which are included so that a person skilled in the art can construct and use the invention in combination with publicly available information and technology. This disclosure provides novel pre-catalysts and catalyst systems, including those particularly useful for ring-opening metathesis polymerization (ROMP) of cyclic olefins such as cyclopentene and dicyclopentadiene (DCPD) and mixtures thereof. The catalysts provided herein have an expanded range of aromatic ligands. In some cases, the catalysts may also include one or more heteroatoms in the ligands. Such catalyst frameworks have demonstrated significantly higher activity than previous ones without these ligands. Such substantial improvements in catalytic activity reduce material (catalyst, activator) and process costs. High catalytic activity also reduces the amount of catalyst residue left after polymerization. These novel catalysts also possess low toxicity, avoiding the generation of catastrophic highly hazardous substances (SHS) upon contact with moisture.

[0027] catalyst This catalyst comprises at least one metal alkoxide (I) and at least one transition metal halide (II), and can form a transition metal pre-catalyst (III) of the following general formula. m(R'O) c M u X (u-c) +M v X v →M v (OR') c*m X (v-c*m-2) X2 (I) (II) (III) The transition metal pre-catalyst (III) is then contacted with at least one metal alkyl activator (IV) to form the transition metal carbene component M v =C(R * An activated catalyst (V) of the following general formula, including 2, can be formed. M v (OR') c*m X (v-c*m-2) X2 +nM u R a X (u-a) →M v (OR') c*m X (v-c*m-2) =C(R * )2 (III) (IV) (V) During the ceremony: M u is a group 1, group 2, or group 13 metal with valence u, preferably M u is Li, Na, Ca, Mg, Al, or Ga; c is 1 to 3 and ≤ u; m = 1 / 3, 1 / 2, 1, 3 / 2, 2, 3, or 4 and c*m ≤ v-2; a is 1, 2, or 3 and a ≤ u; n is a positive number, and a*n is between 2 and 10; M v These are, respectively, group 5 or group 6 transition metals having a valence (v) of 5 or 6, preferably v is 6, and M v It is tungsten (W); X is a halogen, Each R' is independently a monovalent organic component comprising 8 to 40 atoms (preferably 12 to 40 atoms; more preferably 18 to 40 atoms) selected from groups 14 to 17 of the periodic table, and may contain one or more heteroatoms; Each R is independently a C1-C8 alkyl; and Each R * These are independently H or C1-C7 alkyl.

[0028] In certain embodiments, at least one metal alkoxide (I) may be or comprise a group 2 metal (e.g., Mg(OR')2), a group 13 metal dialkoxide (e.g., Al(OR')2X), or a group 13 metal trialkoxide (e.g., Al(OR')3). In certain embodiments, metal alkoxide (I) may comprise a group 1 metal, e.g., NaOR'(u=1, c=1); a group 2 metal, e.g., Mg(OR')Cl(u=2, c=1) or Mg(OR')2(u=2, c=2); or a group 13 metal, e.g., Al(OR')Cl2(u=3, c=1), Al(OR')2Cl(u=3, c=2), or Al(OR')3(u=3, c=3).

[0029] In certain embodiments, each R' of at least one metal alkoxide(I) is independently a linear, branched, or aromatic hydrocarbon. Each R' may 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, carboalkoxyl, and halogen. Metal alkoxides (I) can be formed by contacting a compound containing a hydroxyl functional group (FI) with a metal alkyl activator (IV) to form a metal alkoxide (I) of the following general formula. cR'OH+M u R c X (u-c) →cHR+(R'O) c M u X (u-c) (FI) (IV) (I) Metal alkoxides (I) are compounds containing a hydroxyl functional group (FI) according to the following general formula, and are classified as Group 1 or Group 2 metal halides M. u* (H) u It can also be formed by contact with it. cR'OH+M u* (H) u →(R'O) c M u* X (u-c) (FI) (I) In the formula, M u* is a Group 1 or Group 2 metal with a valence of u*, preferably M u These are Na, Li, Ca, or Mg; c is either 1 or 2, and c is ≤ u*; X is a halogen; and Each R' is independently a monovalent hydrocarbyl containing 8 to 40 atoms (preferably 12 to 40 atoms; more preferably 18 to 40 atoms) selected from groups 14 to 17 of the periodic table, and may contain one or more heteroatoms.

[0030] In a particular embodiment, the metal alkoxide catalyst (I) can be represented by one or more of the following general structures A to C. [ka]

[0031] In the formula, Hal is F, Cl, Br, or I; E is either O or S; Ar 1 is an aryl group; Ar 2 is an aryl group; M is a Group 5 or Group 6 transition metal having a valence v of 5 or 6, preferably a Group 6 transition metal, more preferably Mo or W; R 3 C1-C 10Alkyl, alkylene, alkyldiyl, silylene, silyldiyl, germylene, germyldiyl, O, S, NAr 2 , or PAR 2 Preferably a methylene group; For group 6 metals in oxidation state +6, n=1 to 4, and since n+m=6, m=2 to 5, preferably n=2 and m=4 (structure B) or n=4 and m=2 (structure C); and For group 5 and group 6 metals with an oxidation state of +5, n=1 to 3, and since n+m=5, m=2 to 4.

[0032] In a particular embodiment, the activation catalyst (V) can be represented by one or more of the following general structures D to F. [ka]

[0033] In the formula, R 1 is H, alkyl, or aryl; and R 2 is H, alkyl, or aryl, preferably R 1 and R 2 Both are hydrogen. Figure 2 shows a reaction scheme useful for explaining the formation of metal alkoxide(I) from the reaction of dimethylaluminum chloride with 2 equivalents of 4-benzylphenol. Figure 3 shows a reaction scheme useful for explaining the formation of metal alkoxide(I) from the reaction of dimethylaluminum chloride with 2 equivalents of 4-(diphenylamino)phenol. Considering the metal alkyl activator (IV) in more detail, M u is a group 1, group 2, or group 13 metal with valence u, preferably Li, Na, Ca, Mg, Al, or Ga; R is a C1-C8 alkyl; c is 1, 2, or 3; c ≤ u; and if present, X is a halogen. The metal alkyl activator (IV) may also be an alkylaluminum. A suitable alkylaluminum activator has the following general formula: AlR *r (Y) 3-r In the formula, R * The elements are C1-C8 alkyl, and each Y is hydrogen, halogen, or -OR 5 And each R 5 C1-C 20 It is a hydrocarbyl group, and when optionally present, it is two or more R 5 These atoms combine to form a ring having 40 or fewer atoms from groups 14, 15, and / or 16 of the periodic table; r is 1 to 3.

[0034] Figure 4 shows a reaction scheme that helps explain the formation of a transition metal pre-catalyst (III) from the reaction of the metal alkoxide (I) in Figure 2 with the transition metal halide (II), which is tungsten hexachloride (WCl6), and then the formation of an activated catalyst (V) having an active metal carbene component. Figure 5 shows a reaction scheme that helps explain the formation of a transition metal pre-catalyst (III) from the reaction of the metal alkoxide (I) in Figure 3 with a transition metal halide (II) which is tungsten hexachloride (WCl6), and then the formation of an activated catalyst (V) having an active metal carbene component.

[0035] Optional carrier material In embodiments of this specification, the catalyst system may include an inert support material. Preferably, the support material is a porous support material, such as talc and inorganic oxides. Other support materials include zeolites, clays, organic clays, or any other organic or inorganic support material, or mixtures thereof. Preferably, the carrier material is an inorganic oxide in a pulverized form. Suitable inorganic oxide materials for use in catalyst systems as used herein include Group 2, Group 4, Group 13, and Group 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica or alumina include magnesia, titania, and zirconia. However, other suitable carrier materials, such as pulverized functionalized polyolefins, such as pulverized polyethylene, can be used. Particularly useful carrier materials include magnesia, titania, zirconia, montmorillonite, phyllosilicates, zeolites, talc, and clay. Combinations of these carrier materials, such as silica-chromium, silica-alumina, and silica-titania, may also be used. Preferred carrier materials include Al2O3, ZrO2, SiO2, and combinations thereof, more preferably SiO2, Al2O3, or SiO2 / Al2O3.

[0036] The support material is most preferably an inorganic oxide, approximately 10 to approximately 700 m 2 Preferably, the surface area is within the range of / g, the pore volume is within the range of about 0.1 to about 4.0 cc / g, and the average particle size is within the range of about 5 to about 500 μm. More preferably, the surface area of ​​the carrier material is about 50 to about 500 m 2 The particle size is within the range of / g, with a pore volume of approximately 0.5 to approximately 3.5 cc / g and an average particle size of approximately 10 to approximately 200 μm. Most preferably, the surface area of ​​the carrier material is approximately 100 to approximately 400 m². 2 The pore volume is within the range of / g, with a pore volume of approximately 0.8 to approximately 3.0 cc / g and an average particle size of approximately 5 to approximately 100 μm. The average pore size of the carrier material useful in the present invention is within the range of 10 to 1000 Å, preferably 50 to approximately 500 Å, and most preferably 75 to approximately 350 Å. In some embodiments, the carrier material is amorphous silica with a high surface area (surface area = 300 m²). 2 / gm;1.65cm 3This is the pore volume per gm. Preferred silica is commercially available from Davison Chemical Division of WR Grace and Company under the trade names Davison® 952 or Davis® 955. In other embodiments, DAVISON® is used.

[0037] The carrier material should be dry, i.e., free from absorbent water. Drying of the carrier material can be achieved by heating or calcining at about 100°C to about 1000°C, preferably at least about 600°C. When the carrier material is silica, it is heated at at least 200°C, preferably about 200°C to about 850°C, most preferably about 600°C; and for about 1 minute to about 100 hours, about 12 hours to about 72 hours, or about 24 hours to about 60 hours. The calcined carrier material must have at least some reactive hydroxyl (OH) groups to produce the supported catalyst system of the present invention. The calcined carrier material is then contacted with at least one polymerization catalyst comprising at least one catalyst compound and an activator. A support material having reactive surface groups, typically hydroxyl groups, is slurryed in a nonpolar solvent, and the resulting slurry is contacted with a solution of catalyst and activator. In some embodiments, the support material slurry is first contacted with the activator for a period ranging from about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. The solution of the catalyst compound is then contacted with the isolated support / activator. In some embodiments, the supported catalyst system is generated in situ. In alternative embodiments, the support material slurry is first contacted with the catalyst compound for a period ranging from about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. The slurry of the supported catalyst compound is then contacted with the activator solution.

[0038] The mixture of catalyst, activator, and support is heated to about 0°C to about 70°C, preferably about 23°C to about 60°C, and preferably at room temperature. The contact time is typically about 0.5 hours to about 24 hours, about 2 hours to about 16 hours, or about 4 hours to about 8 hours. A suitable nonpolar solvent is one in which all of the reactants used herein, namely the activator and catalyst compound, are at least partially soluble and which is a liquid at the reaction temperature. Preferred nonpolar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, but a variety of other materials may be used, including cycloalkanes such as cyclohexane, benzene, toluene, and aromatic compounds such as ethylbenzene.

[0039] polymerization The catalysts provided herein can be used in ring-opening metathesis polymerization (ROMP) to produce polymers comprising one or more polyalkenamers, such as polypentenamers. These polymers may include cyclic olefin homopolymers and / or cyclic olefin copolymers. Figure 6 shows a polymerization scheme useful for illustrating the production of polypentenamers from cyclopentene. 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 in solution. However, for the sake of simplicity and ease of explanation, the polymerization process for producing polypentenamers using the catalyst described herein will be further described in relation to solution polymerization in a diluent, and the reaction mixture may contain one or more diluents in amounts of 60 vol% or less, or 40 vol% or less, or 20 vol% or less, based on the total volume of the reaction mixture. Suitable diluents may include non-coordinating, inert liquids. Examples of suitable diluents, but not limited to, include: linear 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, e.g., ISOPAR® (synthetic isoparaffin, commercially available from ExxonMobil Chemical Company)); and total halogenated hydrocarbons (e.g., total fluorine-substituted C4-C 10Examples include alkanes, chlorobenzenes, and aromatic compounds; alkyl-substituted aromatic compounds (e.g., benzene, toluene, mesitylene, and xylene), and any combination thereof.

[0040] The preparation of the catalyst and / or copolymerization may be carried out in an inert atmosphere (e.g., under a nitrogen or argon atmosphere) to minimize the presence of air and / or water. Polymerization is carried out in a polymerization reactor under conditions sufficient to form a reaction mixture containing the polymer, monomer, catalyst, and possibly diluent, with one or more C4-C4 compounds. 20 This may include contacting a cyclic olefin monomer. The polymer, catalyst, and optionally the solvent can be recovered from the reaction product mixture. At least a portion of the recovered catalyst, unreacted cyclic olefin monomer, and optionally the solvent can be recycled back into the polymerization reactor. The reaction temperature may be -50°C to 200°C, or -25°C to 100°C, or -10°C to 25°C. The reaction pressure may be 0 MPa to 50 MPa, or 0 MPa to 25 MPa, or ambient pressure to 10 MPa. The reaction may take place over a period of time of 1 minute to 48 hours, or 1 minute to 20 hours, or 5 minutes to 3 hours, or 10 minutes to 1 hour. A suitable molar ratio of metal to total comonomer in the catalyst may be 1:1 to 1000:1. Other suitable molar ratios of metal to total comonomer in the catalyst may be 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.

[0041] The cyclic olefins may be strained or not (preferably strained); monocyclic or polycyclic (e.g., bicyclic); and may optionally contain 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, dimethylnorbornene carboxylate, norbornene-exo-2,3-carboxylic anhydride, and their respective homologs and derivatives, and substituted derivatives. Examples that are helpful in describing appropriate functional groups include, but are not limited to, hydroxyl, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxyl, and halogen.

[0042] Cyclic olefins are further classified by the following general formula: [ka] One or more C4-C structures including at least one annular structure having 20 Cyclic diolefin; and / or

[0043] The following general formula: [ka] One or more functionalized C4-C molecules containing at least one cyclic structure 20A cyclic diolefin may be included as a comonomer in the reaction product mixture, where each functional group (FG) is essential to and / or suspended from the corresponding cyclic structure, and each FG is independently a 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 It is a hydrocarbyl group, where r is 1 or more, and when present, s is 1 or more; preferably the comonomer includes norbornene, ethylidenenorbornene, dicyclopentadiene, or a combination thereof.

[0044] In one or more embodiments of the present invention, the cyclic olefin polymerization process is further described below: (I) Controlling the reaction temperature between -35°C and 100°C; controlling the amount of monomer recycled into the reactor; using monomer as a reaction solvent; or a combination thereof to control the polymer M w and / or controlling the transformer-sys ratio; (II) After forming the activated catalyst species at a temperature of approximately 5°C or lower, the reaction temperature is raised to a temperature of less than 100°C; (III) To reduce the molecular weight of the polymer in the product mixture by incorporating a certain amount of olefin, preferably α-olefin, preferably α-olefin containing at least one heteroatom-containing functional group, into a cyclic olefin monomer; (IV) Using two or more cyclic olefin polymerization catalysts in the same or different reactors, the following: i) Multimodal M w Profile; ii) Transformer greater than 1: cis-molecule ratio; iii) Trans-to-cis-molecule ratio less than 1 To produce polymers exhibiting; and / or (V) Producing heterophasic copolymers using multiple sequentially connected reactors. Includes.

[0045] In one or more embodiments of the present invention, the olefin comonomer has the following general formula: CH2=CH-(CH2) n -CH3; CH2=CH-[(CH2) n (FG) s ]-CH3; and / or CH2=CH-(CH2) n -FG; In the formula, when present, each FG is independently a 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 It is a hydrocarbyl group; n is 1 or greater; and if present, s is 1 or greater. In one or more embodiments of the present invention, transition metal M v Based on the total amount of catalyst present, it is preferably present in the catalyst at an amount of 0.1 wt% to 30 wt%. In some embodiments, the transition metal M is present in the supported catalyst. v and the molar ratio of aluminum (M v :Al) is an existing M v Based on the total number of moles of aluminum, the ratio is preferably 1:1000 to 4:10. If desired, the polymerization reaction can be stopped using one or more quenching compounds. Suitable quenching compounds may be one or more antioxidants that can be dispersed in an alcohol (e.g., methanol or ethanol), or may include such antioxidants. Examples of quenching compounds, but not limited to, butylated hydroxytoluene (BHT), IRGANOX® antioxidant (available from BASF), and any combination thereof. Quenching compounds may be added in amounts of 0.05 wt% to 5 wt%, or 0.1 wt% to 2 wt%, based on the total mass of the polymer product.

[0046] Polymer properties The properties of the resulting polymer may depend, at least in part, on the catalyst composition, the (co)monomer composition, the comonomer addition rate, the reaction temperature, and the reaction time. When two cyclic olefin comonomers are used, the resulting copolymer may have molar ratios of units derived from the first cyclic olefin comonomer to units derived from the second cyclic olefin comonomer 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 necessary, a higher concentration of the first cyclic olefin comonomer may be combined with a slower addition rate of the second cyclic olefin comonomer to increase the concentration of units derived from the first cyclic olefin comonomer in the resulting polymer. The cis-to-trans ratio in the resulting polymer can be 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 for both comonomer entities. The target cis / trans ratio can be achieved by the appropriate selection of catalyst and activator, catalyst:activator ratio, catalyst:monomer ratio, reagent concentration, solvent and solvent mixture, process temperature, and reaction temperature, as well as any combination thereof. The resulting polymers are M, ranging from 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 It may have. The resulting polymers are M, ranging from 0.5kDa to 500kDa, or 1kDa to 250kDa, or 10kDa to 250kDa, or 50kDa to 250kDa, or 100kDa to 500kDa. n It may have. The polymers of this disclosure may have MWDs of 1 to 10, or 1 to 5, or 2 to 4, or 1 to 3.

[0047] Furthermore, the LCB level is determined by the GPC method using a triple detector, with the branching index (g' vis It can be quantified using the branching exponent (g'). vis Alternatively, g') is defined as the ratio of the intrinsic viscosity of a branched polymer to the intrinsic viscosity of a linear polymer of equal molecular weight. The branching exponent g' is mathematically defined as follows:

number

[0048] Mv is the viscosity-average molecular weight based on molecular weight determined by LS analysis. The Mark-Houwink parameters α and k used for the reference linear polymer were 0.725 and 0.000291, respectively. The polymers of the present disclosure having long-chain branching have g' values ​​of 0.5-0.91, 0.5-0.8, or 0.6-0.8, or 0.7-0.91. vis The polymers of this disclosure having a linear structure may have g' of 0.92-1.0, 0.92-0.95, or 0.95-0.99, or 0.95-1.0. vis It may have. The resulting polymer having a long-chain branched structure is (a) g' of 0.5-0.91, 0.5-0.8, or 0.6-0.8, or 0.7-0.91. vis, and (b) molar ratios of units derived from the first cyclic olefin comonomer to units derived from the second cyclic olefin comonomer in the order 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) for both comonomer entities, 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: (d) A systolic to transformer ratio of 25-25:75, or 40:60-5:95, or 30:70-5:95, or 20:80-5:95, or 20:80-10:90, or 100:0, (d) M of 1kDa-1,000kDa, or 10kDa-1,000kDa, or 100kDa-1,000kDa, or 250kDa-750kDa, or 250kDa-550kDa w (e) M of 0.5kDa to 500kDa, or 1kDa to 250kDa, or 10kDa to 250kDa, or 50kDa to 250kDa, or 100kDa to 500kDa n (f) may have one or more MWDs of 1-10, or 1-5, or 2-4, or 1-3.

[0049] The resulting polymer having a linear structure is (a) g' of 0.92-1.0, 0.92-0.95, or 0.95-0.99, or 0.95-1.0. vis , and (b) molar ratios of units derived from the first cyclic olefin comonomer to units derived from the cyclic olefin comonomer 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 for both comonomer entities. (d) A systolic to transformer ratio of ~25:75, or 40:60~5:95, or 30:70~5:95, or 20:80~5:95, or 20:80~10:90, or 100:0, (d) M of 1kDa~1,000kDa, or 10kDa~1,000kDa, or 100kDa~1,000kDa, or 250kDa~750kDa, or 250kDa~550kDa w(e) M of 0.5kDa to 500kDa, or 1kDa to 250kDa, or 10kDa to 250kDa, or 50kDa to 250kDa, or 100kDa to 500kDa n (f) may have one or more MWDs of 1-10, or 1-5, or 2-4, or 1-3. [Examples]

[0050] Examples The embodiments discussed and described herein can be further described using the following non-limiting examples. While the examples relate to specific embodiments, they should not be considered to limit any particular aspect. Methodologies for characterizing samples (NMR and GPC) are included in embodiments 0042 to 0053. Two different catalyst systems were prepared and used to polymerize cyclopentene (cC5). Example 1 used a (4-PhCH2C6H4O)2AlCl precatalyst, and Example 2 used a (4-(Ph2N)C6H4O)2AlCl precatalyst. Both precatalysts were activated with a mixture of WCl6 in toluene and used to polymerize cyclopentene to give a solid polypentenomer product. A comparative example using (4-MeC6H4O)2AlCl as a precatalyst is also provided (Comp.Ex.3). As summarized in Table 1 below, the polymers produced using the catalyst systems of Examples 1 and 2 had a desirable cis / trans ratio of about 20 / 80, a narrow molecular weight (MWD) of about 2.0, and a molecular weight up to 563 kDa. w This yielded polypentenomer products containing [specific compound]. However, surprisingly and unexpectedly, the activity of the system based on (4-PhCH2C6H4O) (Ex. 1) and the system based on (4-(Ph2N)C6H4O) (Ex. 2) was found to be significantly higher than all the other systems. Even more surprisingly and unexpectedly, the activity of the system based on (4-PhCH2C6H4O) (Ex. 1) was 2,070 g. ポリマー / g W Therefore, the activity of the system based on (4-MeC6H4O) (976g ポリマー / g W It was found to be more than twice that of (Comp.Ex. 3).

[0051] Example 1: Catalyst based on (4-PhCH2C6H4O) Synthesis of (4-PhCH2C6H4O)2AlCl pre-catalyst (W:monomer ratio is 1:4000). A solution of 4-benzylphenol (60.0 g, 326 mmol) in toluene (350 mL) was slowly added over 1 hour under vigorous stirring to a solution of dimethylaluminum chloride (15.06 g, 163 mmol) in toluene (50 mL). The resulting mixture was stirred at 25°C for 12 hours, after which n-pentane (100 mL) was added. The resulting mixture was then stirred for a further 24 hours. The precipitated solid product was then collected, washed with n-pentane (3 × 100 mL), and dried in vacuum at 75°C for 3 hours. Yield: 63.7g (91.2%) of white solids. 1 H NMR (400 MHz, THF-d8, 25℃, ppm): δ 7.21-7.09 (8H, m, Ar-H), 6.92 (4H, d, J HH = 7.6 Hz, Ar-H), 6.78-6.69 (4H, m, Ar-H), 3.82 (4H, s, CH2). 13 C NMR (100.63 MHz, THF-d8, 25℃, ppm): δ 158.7, 143.1, 130.1, 129.2, 128.7, 126.1, 119.7, 119.6 (Ar-C), 41.7 (CH2).

[0052] Example 1A: Polymerization of cyclopentene using (4-PhCH2C6H4O)2AlCl pre-catalyst (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 under ambient conditions for 1 hour. The obtained solution was added to a mixture (400 rpm) containing cyclopentene (103 g, 1.513 mol), triethylaluminum (35 mg, 0.303 mmol), and toluene (250 mL), which was mechanically stirred at 0°C. The reaction was stirred at 0°C for 3 hours. Next, the activated catalyst was quenched by adding 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 × 250 mL) and dried under a nitrogen stream for 3 days. Yield: 57.5g, 56%. Cis / Trans ratio: 19 / 81%. M w :563kDa, M w / M n :2.02.

[0053] Example 1B: Polymerization of cyclopentene using (4-PhCH2C6H4O)2AlCl pre-catalyst (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 under ambient conditions for 1 hour. The obtained solution was added to a mixture containing cyclopentene (85.86 g, 1.263 mol), triethylaluminum (72 mg, 0.632 mmol), and toluene (250 mL) that was mechanically stirred at 0°C (400 rpm). The reaction was stirred at 0°C for 3 hours. Next, the activated catalyst was quenched by adding 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 × 250 mL) and dried under a nitrogen stream for 3 days. Yield: 77.0g, 90%. Cis / Trans ratio: 18 / 82%. M w :515kDa, M w / M n :1.82.

[0054] Example 1C: Copolymerization of cyclopentene and dicyclopentadiene using (4-PhCH2C6H4O)2AlCl pre-catalyst (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 under ambient conditions for 1 hour, the resulting mixture was added at 0°C to a 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 another 20 minutes, a solution of 2,6-di-tert-butyl-4-methylphenol (2.00 g, 9.0 mmol) in 100 mL of ethanol / toluene mixture (1:4, v:v, respectively) 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 obtain 98 g of product. Yield: 98g, 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' (vis average): 0.91.

[0055] Example 2: Catalyst based on (4-(Ph2N)C6H4O) Synthesis of (4-(Ph2N)C6H4O)2AlCl pre-catalyst: A solution of (4-HO-C6H4)NPh2 (452 ​​mg, 1.73 mmol) in toluene (10 mL) was added dropwise to a solution of dimethylaluminum chloride (80 mg, 0.86 mmol) in toluene (5 mL) at -30°C. After the addition was complete, the reaction mixture was gradually heated to 25°C over 30 minutes and stirred for another 30 minutes. The resulting solution was concentrated to approximately 5 mL. N-pentane (15 mL) was added to this solution, and the resulting pale blue solid precipitate was collected and vacuum-dried. Yield: 418 mg (82.9%) of light green powder. 1 ¹H NMR (400 MHz, THF-d8, 25℃, 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 is satisfactory. 13 This interferes with the collection of 13C NMR spectra. Polymerization using 4-((Ph2N)C6H4O)2AlCl pre-catalyst (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 under ambient conditions for 1 hour and then added to a mixture containing cyclopentene (99.7 g, 1.46 mol), triethylaluminum (84 mg, 0.0731 mmol), and toluene (500 mL) that was mechanically stirred at 0°C (400 rpm). The reaction was stirred at 0°C for 2 hours. The activated catalyst was then quenched by adding 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 × 250 mL) and dried in vacuum for 12 hours. Yield: 33.7g, 33.8%. Cis / Trans ratio: 20 / 80%. Mw: 605kDa, Mw / Mn: 1.44.

[0056] Comparative example: Catalyst based on (4-MeC6H4O) Synthesis of (4-MeC6H4O)2AlCl pre-catalyst: Dimethylaluminum chloride (21.38 g, 231 mmol) was dissolved in 250 mL of toluene in a 500 mL round-bottom flask containing a magnetic stirring bar. p-cresol (50 g, 462 mmol, Sigma-Aldrich) was added dropwise to the dimethylaluminum chloride solution over 30 minutes under vigorous stirring. The mixture was then gradually allowed to return to ambient temperature. After further stirring for 3 hours, the mixture was concentrated by purging with nitrogen to obtain a yellow oily product. Pentane (300 mL) was added, and the resulting colorless solid was collected by filtration. The mixture was washed with pentane (200 mL) and dried in vacuum at 60°C for 5 hours to obtain 46.7 g (73.0%) of colorless powder. 1 H NMR (400 MHz, THF-d8, ppm): δ 6.89-6.66 (4H, m, Ar-H), 2.18 (3H, s, CH3).

[0057] Comparative Example 3A: Polymerization using (4-MeC6H4O)2AlCl pre-catalyst (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) under mechanical stirring (rpm 400) at 0°C. After a reaction time of approximately 20 minutes, 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) under vigorous mechanical mixing. The resulting polymer was washed with ethanol (3 × 500 mL) and dried in vacuum at 50°C for 4 hours. Yield: 15.6g (15.1%); Cis:Trans ratio: 25 / 75%; M w :464kDa;M w / M n :3.41.

[0058] Comparative Example 3B: Polymerization using (4-MeC6H4O)2AlCl pre-catalyst (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) under mechanical stirring (rpm 400) at 0°C. The mixture became viscous after about 20 minutes of reaction. 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) under vigorous mechanical mixing. The resulting polymer was washed with ethanol (3 × 500 mL) and dried in vacuum at 50°C for 4 hours. Yield: 65.5g (63.6%); Cis:Trans ratio: 15 / 85%; M w :490kDa;M w / M n :2.02.

[0059] [Table 1]

[0060] In each of the above examples, the molecular weight distribution, molecular weight moment (Mw, Mn, Mw / Mn), and long-chain branching index were determined using Polymer Char GPC-IR equipped with three in-line detectors, an 18-angle light scattering ("LS") detector, a viscometer, and a differential refractive index ("DRI") detector. Three Agilent PLgel 10 μm Mixed-B LS columns were used for the GPC analysis. The nominal flow rate was 0.5 mL / min, and the nominal injection volume was 200 μL. The columns, viscometer, and DRI detector were housed in an oven maintained at 40°C. Tetrahydrofuran (THF) solvent containing 250 ppm butylated hydroxytoluene (BHT) antioxidant was used as the mobile phase. A given volume of polymer sample was weighed and sealed in a standard vial. After loading the vial into the autosampler, the polymer was automatically dissolved in the instrument with 8 mL of added THF solvent by continuous shaking at 40°C for approximately 2 hours. The intensity c of each point in the chromatogram is the DRI signal I with the baseline subtracted. DRI Therefore, the calculation was performed using the following formula. c=K DRI I DRI / (dn / dc) In the formula, K DRI (d) is a constant determined by calibrating the DRI, n / d c ) is the refractive index increment of the polymer in THF solvent.

[0061] The typical molecular weight was determined by combining a universal calibration relationship with column calibration performed using a series of monodisperse polystyrene (PS) standards ranging from 300 g / mol to 12,000,000 g / mol. The molecular weight "M" at each elution volume can be calculated using the following formula.

number

[0062] In the formula, variables with the subscript "PS" represent polystyrene, while variables without a subscript relate to the test sample. In this method, a PS =0.7362 and K PS= 0.0000957, and "a" and "K" for the rubber sample were obtained as 0.725 / 0.000291 by fitting the logIV vs. logM curve for the linear reference sample. In the formula, IV represents the intrinsic viscosity. 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 was identified using the following formula.

number

[0063] Here, ΔR(θ) is the excess Rayleigh scattering intensity measured at the scattering angle θ, "c" is the polymer concentration determined from the DRI analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coil, and K o is the optical constant of the system, expressed by the following formula.

number

[0064] In the formula, N A is Avogadro's number, and (dn / dc) is the refractive index increment of the system. Considering it to be the same value as the one obtained from the DRI method, the value of "n" is 1.40 for THF at 40°C and λ=665nm. For the rubber sample used in this test, dn / dc was measured as 0.1154 by the DRI detector. Measured specific viscosity (η S The intrinsic viscosity [η] was determined from the ) and concentration "c" using a 4-capillary viscometer with a Wheatstone bridge configuration. η s =c[η]+0.3(c[η]) 2 The average intrinsic viscosity [η] of the sample is calculated using the following formula. avg I calculated it.

number

[0065] In the formula, the sum extends over all chromatography slices i between the integration limits. Branching exponent (g') vis Alternatively, g') is defined as the ratio of the intrinsic viscosity of a branched polymer to the intrinsic viscosity of a linear polymer of equal molecular weight. The branching exponent g' is mathematically defined as follows:

number

[0066] In the formula, M v This is the viscosity-average molecular weight based on molecular weight determined by LS analysis. The Mark-Houwink parameter k / α used for the reference linear polymer was 0.725 / 0.000291.

[0067] Specific embodiments and features are described using a set of upper and lower numerical limits. Unless otherwise indicated, it should be understood that ranges are intended to include any combination of any two values, e.g., any combination of any lower and upper limit, any combination of any two lower limits, and / or any combination of any two upper limits. Specific lower limits, upper limits, and ranges appear in one or more of the following claims. All numerical values ​​are designated as "about" or "approximately" values, taking into account experimental errors and variations expected by those skilled in the art. Various terms have been defined above. Unless a term used in a claim is defined above, that term should be given the broadest definition that a person skilled in the art would give to it, as reflected in at least one publication or granted patent. Furthermore, all patents, test procedures, and other documents referenced herein are incorporated by reference to such an extent as to be consistent with this application, and for all jurisdictions in which such incorporation is permitted. The foregoing concerns embodiments of the present invention, but other further embodiments of the present invention can be devised without departing from the basic scope of the present invention, the scope of which is defined by the following claims. This disclosure includes the following embodiments. <Embodiment 1> A catalyst for cyclic olefin polymerization, having the following structure (V): M v (OR') c*m X (v-c*m-2) =C(R * ) 2 (V) It contains a transition metal carbene having the following formula: 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 a monovalent organic component containing 8 to 40 atoms selected from groups 14 to 17; c is an integer between 1 and 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 * H or C 1 ~C 7 It is alkyl. catalyst. <Embodiment 2> v is 6, M v The catalyst according to Embodiment 1, wherein is tungsten (W), X is chlorine or fluorine, and each R' is aromatic. <Embodiment 3> The catalyst according to any one of Embodiments 1 to 2, wherein OR' is 4-benzylphenolate or 4-(diphenylamino)phenolate. <Embodiment 4> A cyclic olefin polymerization process, as follows: A cyclic olefin polymerization catalyst according to any one of Embodiments 1 to 18, comprising C 4 -C 20 Contacting a cyclic olefin monomer with conditions sufficient to form a reaction product mixture containing a polymer, unreacted monomer, catalyst, and possibly a solvent in a polymerization reactor; and To recover the aforementioned polymer. A process that includes this. <Embodiment 5> Furthermore, see below: Separating the monomer from the reaction product mixture and recirculating the monomer back into the polymerization reactor; The recovered catalyst is brought into contact with an activator before being recycled back into the polymerization reactor; or a combination thereof The process described in Embodiment 4, including the process described in Embodiment 4. <Embodiment 6> The process according to any one of Embodiments 4 to 5, wherein the polymerization comprises ring-opening metathesis polymerization, and the polymer comprises a polyalkenamer, a cyclic olefin copolymer, and / or a cyclic olefin polymer. <Embodiment 7> The process according to any one of Embodiments 4 to 6, further comprising recovering the catalyst and optionally the solvent from the reaction product mixture; and recirculating at least a portion of the recovered catalyst, unreacted monomer, and / or optionally the solvent to the polymerization reactor. <Embodiment 8> The following general formula: TIFF0007834652000016.tif2029 One or more C including at least one cyclic structure having 4-20 Cyclic diolefin; and / or The following is a general formula: TIFF0007834652000017.tif2042 One or more functionalizations C containing at least one cyclic structure 4-20 The further step involves incorporating a cyclic diolefin as a comonomer into the reaction product mixture, wherein each FG is essential to and / or suspended from the corresponding cyclic structure, and each FG is independently a 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, where each R^ is independently hydrogen or C 1 -C 10 A hydrocarbyl group, where r is 1 or greater, and where present, s is 1 or greater; preferably the comonomer comprises norbornene, ethylidenenorbornene, dicyclopentadiene, or a combination thereof. The process described in any one of Embodiments 4 to 7. <Embodiment 9> Furthermore, see below: Controlling the reaction temperature between -35°C and 100°C; controlling the amount of monomer recycled into the reactor; using the monomer as the reaction solvent; or a combination thereof to control the M of the polymer w and / or controlling the transformer-sys ratio; After forming the activated catalyst species at a temperature of approximately 5°C or lower, the reaction temperature is raised to a temperature of less than 100°C; To reduce the molecular weight of the polymer in the product mixture by incorporating a certain amount of olefin, preferably α-olefin, preferably α-olefin containing at least one heteroatom-containing functional group, into the cyclic olefin monomer; Using two or more cyclic olefin polymerization catalysts in the same or different reactors, the following can be achieved: Multimodal M w Profile; A transformer-to-cis-molecule ratio of 1; Trans-to-cis-molecule ratios greater than 1, typically 2.33–19; Trans-to-cis-molar ratio less than 1; To produce polymers exhibiting; and / or The process of generating heterogeneous copolymers using multiple reactors connected sequentially. The process described in any one of Embodiments 4 to 8, including the process described in any one of Embodiments 4 to 8. <Embodiment 10> The aforementioned olefin comonomer has the following general formula: CH 2 =CH-(CH 2 ) n -CH 3 ; CH 2 =CH-[(CH 2 ) n (FG) s ]-CH 3 ; and / or CH 2 =CH-(CH 2 ) n -FG Having; In the formula, each FG, if present, is independently a 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^ independently C 1 -C 10 It is a hydrocarbyl group; n is 1 or greater; and s is greater than or equal to 1 if it exists. The process described in any one of Embodiments 4 to 9. <Embodiment 11> The polymer has a concentration of 0.50 to 0.91 g'. vis A process according to any one of embodiments 4 to 10, comprising: <Embodiment 12> The process according to any one of Embodiments 4 to 11, wherein the reaction mixture contains a diluent in an amount of 60 vol% or less based on the total volume of the reaction mixture. <Embodiment 13> The process according to any one of Embodiments 4 to 12, wherein the polymer has a cis-to-trans ratio of 50:50 to 5:95. <Embodiment 14> The process according to any one of Embodiments 4 to 13, wherein the polymer has a mass-average molecular weight of 1 kDa to 1,000 kDa, and the polymer has a molecular weight distribution of 1 to 10. <Embodiment 15> A catalyst for cyclic olefin polymerization, the following: A) Formula: m(R'O) c M u X(u-c) At least one metal alkoxide (I) having and B) Formula:M v X v at least one transition metal halide(II) having The reaction product includes; During the ceremony: M u It is a group 1, group 2, or group 13 metal with valence u; 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 a monovalent organic component containing 8 to 40 atoms selected from groups 14 to 17; X is a halogen; and c is an integer between 1 and 3. catalyst.

Claims

1. A catalyst for cyclic olefin polymerization, having the following structure (V): M v (OR’) c*m X (v-c*m-2) =C(R * ) 2 (V) It contains a transition metal carbene having the following formula: M v is a group 5 transition metal having a valence v of 5, or a group 6 transition metal having a valence (v) of 5 or 6; Each OR' is independently a monovalent organic component comprising 4-benzylphenolate or 4-(diphenylamino)phenolate and containing 14 to 40 atoms selected from groups 14 to 17; c is an integer between 1 and 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 C 1 -C 7 alkyl catalyst.

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

3. The catalyst according to claim 1, wherein OR' is 4-benzylphenolate or 4-(diphenylamino)phenolate.

4. A cyclic olefin polymerization process, as follows: The cyclic olefin polymerization catalyst according to claim 1 comprises C, which contains at least one cyclic olefin component. 4 -C 20 Contacting a cyclic olefin monomer with conditions sufficient to form a reaction product mixture containing a polymer, unreacted monomer, catalyst, and possibly a solvent in a polymerization reactor; and To recover the aforementioned polymer. A process that includes this.

5. Furthermore, see below: Separating the monomer from the reaction product mixture and recirculating the monomer back into the polymerization reactor; To recover the catalyst from the reaction product mixture; The recovered catalyst is brought into contact with an activator before being recycled back into the polymerization reactor; or a combination thereof The process according to claim 4, including the process described in claim 4.

6. The process according to claim 4, wherein the polymerization comprises ring-opening metathesis polymerization, and the polymer comprises a polyalkenamer, a cyclic olefin copolymer, and / or a cyclic olefin polymer.

7. The process according to claim 4, further comprising recovering the catalyst and optionally the solvent from the reaction product mixture; and recirculating at least a portion of the recovered catalyst, unreacted monomer, and / or optionally the solvent to the polymerization reactor.

8. The following general formula: 【Chemistry 1】 One or more C including at least one cyclic structure having 4-20 Cyclic diolefin; and / or The following is a general formula: 【Chemistry 2】 One or more functionalizations C containing at least one cyclic structure 4-20 The further step involves incorporating a cyclic diolefin as a comonomer into the reaction product mixture, wherein each FG is essential to and / or suspended from the corresponding cyclic structure, and each FG is independently a 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, where each R^ is independently hydrogen or C 1 -C 10 A hydrocarbyl group, where r is 1 or more, and where present, s is 1 or more; optionally the comonomer includes norbornadiene, dicyclopentadiene, or a combination thereof. The process according to claim 4.

9. Furthermore, see below: Controlling the reaction temperature between -35°C and 100°C; controlling the amount of monomer recycled into the reactor; using the monomer as the reaction solvent; or a combination thereof to control the M of the polymer w and / or transformer: controlling the cis ratio; After forming the activated catalyst species at a temperature of approximately 5°C or lower, the reaction temperature is raised to a temperature of less than 100°C; To reduce the molecular weight of the polymer in the reaction product mixture by incorporating a certain amount of olefin, or an α-olefin containing at least one heteroatom-containing functional group, into the cyclic olefin monomer; Using two or more cyclic olefin polymerization catalysts in the same or different reactors, the following can be achieved: multimodal M w Profile; 1 transformer:cis-molecule ratio; Trans-:cis-molecule ratio greater than 1, typically 2.33–19; or Trans-: cis-mol ratio less than 1; To produce polymers that exhibit the following characteristics; and / or The process of generating heterogeneous copolymers using multiple reactors connected sequentially. The process according to claim 4, including the process described in claim 4.

10. Olefins are given by the following general formula: CH 2 =CH-(CH 2 ) n -CH 3 ; CH 2 =CH-[(CH 2 ) n (FG) s ]-CH 3 ; and / or CH 2 =CH-(CH 2 ) n -FG Having; In the formula, each FG, if present, is independently a 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^ independently C 1 -C 10 It is a hydrocarbyl group; n is 1 or greater; and s is greater than or equal to 1 if it exists. The process according to claim 9.

11. The polymer has a concentration of 0.50 to 0.91 g'. vis The process according to claim 4, wherein the reaction product mixture further contains a diluent in an amount of 60 vol% or less based on the total volume of the reaction product mixture, the polymer has a cis-to-trans ratio of 50:50 to 5:95, the polymer has a mass-average molecular weight of 1 kDa to 1,000 kDa, and the polymer has a molecular weight distribution of 1 to 10.

12. A method for producing a catalyst for cyclic olefin polymerization, Formula: m(R'O) c M u X (u-c) A metal alkoxide (I) having the formula: M v X v A step of reacting with at least one transition metal halide(II) having a certain property to form a reaction product, During the ceremony: M u is a group 1, group 2, or group 13 metal with valence u; M v is a group 5 transition metal having a valence v of 5, or a group 6 transition metal having a valence (v) of 5 or 6; Each OR' is independently a monovalent organic component comprising 4-benzylphenolate or 4-(diphenylamino)phenolate and containing 14 to 40 atoms selected from groups 14 to 17; X is a halogen; and The process where c is an integer from 1 to 3, A step of contacting the reaction product with a metal alkyl activator, Structure (V): M v (OR’) c*m X (v-c*m-2) =C(R * ) 2 (V) A step of recovering a catalyst having, m is 1 / 3, 1 / 2, 1, 3 / 2, 2, 3, or 4, and c*m ≤ v-2. Each R * H or C 1 ~C 7 The process includes an alkylation step, A method for manufacturing a catalyst.

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