WO2021113503A1 - Polymers prepared by ring opening metathesis polymerization - Google Patents

Abstract

A method of ring-opening metathesis polymerization (ROMP) may comprise: contacting a first cyclic olefin comonomer to the reaction mixture over time at a rate of 0.01 mol% per minute to 25 mol% per minute based on a total amount of the second cyclic olefin comonomer added to the reaction mixture to produce a polymer, wherein a final mol to mol ratio of first cyclic olefin comonomer to second cyclic olefin comonomer added to the reaction mixture is 1:1 to 500:1; and wherein the second cyclic olefin comonomer has a higher reactivity with the metathesis catalyst than the first cyclic olefin comonomer.

Description

POLYMERS PREPARED BY RING OPENING METATHESIS POLYMERIZATION

INVENTORS: Alexander V. Zabula, Carlos R. Lopez-Barron, Alan A. Galuska, Xiao-Dong Pan, Mika L. Shiramizu, Yong Yang, Mark K. Davis, Lubin Luo, Sarah J. Mattler, and Shuhui Kang

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to USSN 62/943619, filed December 4, 2019, and EP 20164133.9 filed March 19, 2020, herein incorporated by reference.

BACKGROUND

[0002] The present disclosure relates to ring-opening metathesis polymerization.

[0003] In organic synthesis, a metathesis reaction is a catalytic reaction in which recombination of the double bonds occurs between two kinds of olefins or alkynes. Ringopening metathesis polymerization (ROMP) involves the formation of unsaturated polymers from the ring opening of one, two, or more cyclic olefin comonomers. Generally, the cyclic olefin comonomers are strained cyclic olefins that react with a ROMP catalyst to open and relieve the strain, which produces linear molecules that react with other cyclic olefins. However, individual cyclic olefin comonomers have different degrees of strain and, therefore, have different reactivities with the ROMP catalyst. In some instances, said reactivities can be orders of magnitude different. Consequently, the incorporation of individual comonomers is different in the resultant polymer.

[0004] For example, US 3,598,796, US 3,631,010 and US 3,778,420 describe the copolymerization of pre-mixed cyclopentene and dicyclopentadiene in various media before adding the ROMP catalyst. The resultant polymers are block copolymers or/and cross-linked copolymers.

[0005] The properties of the resultant polymer (e.g., mechanical properties, processability, and the like) depends, at least in part, on the relative amounts of each comonomer in the polymer. Accordingly, the ability to control the amount of each comonomer in the resultant polymer, including incorporation of the slower reacting comonomer at greater than 50 mol% of the polymer, would be advantageous.

[0006] One approach to incorporating more of the slower reacting comonomer is presented in US 3,707,520 and US 3,941,757 where two-stage copolymerization process was employed. In the first step, cyclopentene was homopolymerized before introducing a more reactive comonomer (second step). The resultant polymers were block copolymers, which has different properties than if the two comonomers where dispersed more homogenously throughout the polymer structure. [0007] Accordingly, the ability to control the amount of each comonomer in the resultant polymer, including incorporation of the slower reacting comonomer at greater than 50 mol% of the polymer, throughout the polymer structure would be advantageous. [0008] References of interest include US patent numbers: 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 numbers: US 2016/0289352, US 2017/0247479; Canadian patent number: CA 1,074,949; Chinese Pat. Pub. No. 2018/8001293; WO patent publication number WO 2018/173968, Japanese patent application publication numbers 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. SUMMARY OF THE INVENTION [0009] The present disclosure relates to methods of ring-opening metathesis polymerization (ROMP) that allows for tailoring the incorporation of cyclic olefin comonomers having different ROMP catalyst reactivities, including incorporation of each of the comonomers at substantially equal amounts in the resultant copolymer. [0010] This invention relates to a method of the invention comprising: contacting a first cyclic olefin comonomer to the reaction mixture over time at a rate of 0.01 mol% per minute to 25 mol% per minute based on a total amount of the second cyclic olefin comonomer added to the reaction mixture to produce a polymer, wherein a final mol to mol ratio of first cyclic olefin comonomer to second cyclic olefin comonomer added to the reaction mixture is 1:1 to 500:1; and wherein the second cyclic olefin comonomer has a higher reactivity with the metathesis catalyst than the first cyclic olefin comonomer. [0011] This invention also relates to a polymer having (a) a mol ratio of a first cyclic olefin comonomer-derived unit to a second cyclic olefin comonomer-derived unit of 3:1 to 100:1 and (b) a ratio of cis to trans of 50:50 to 5:95. [0012] This invention also relates to a polymer having (a) a δ at a G* of 50 kPa of 30° to 60° and/or (b) a g’_vis of 0.50 to 0.91. BRIEF DESCRIPTION OF THE DRAWINGS [0013] The following figures are included to illustrate certain aspects of the embodiments, and should not be viewed as exclusive embodiments. The subject matter disclosed is capable of considerable modifications, alterations, combinations, and equivalents in form and function, as will occur to those skilled in the art and having the benefit of this disclosure.

[0014] FIGURE 1 (FIG. 1) is a copolymer with ¹³C NMR assignments for determining the DCPD cis/trans ratio.

[0015] FIGURE 2 (FIG. 2) is a copolymer with ¹H NMR assignments for determining the mol% NBE.

[0016] FIGURE 3 (FIG. 3) is an in situ catalyst synthesis and polymerization scheme.

[0017] FIGURE 4 (FIG. 4) is small amplitude oscillatory (SAOS) data for a linear homopolymer, a long chain branching cyclopentene/dicyclopentadiene copolymer, and a linear cyclopentene/dicyclopentadiene copolymer.

[0018] FIGURE 5 (FIG. 5) is a van Gurp Palmen plot for a linear homopolymer, a long chain branching cyclopentene/dicyclopentadiene copolymer, and a linear cyclopentene/dicyclopentadiene copolymer.

[0019] FIGURE 6A (FIG. 6A) is 4-detector gel permeation chromatography (GPC 4D) data for a linear homopolymer.

[0020] FIGURE 6B (FIG. 6B) is GPC 4D data for a long chain branching cyclopentadiene/dicyclopentadiene copolymer.

[0021] FIGURE 6C (FIG. 6C) is GPC 4D data for a linear cyclopentadiene/dicyclopentadiene copolymer.

DETAILED DESCRIPTION

[0022] The present disclosure relates to methods of ROMP that allows for tailoring the incorporation of cyclic olefin comonomers having different ROMP reactivities, including incorporation of each of the comonomers that are substantially equal amounts and distributed throughout in the resultant copolymer. More specifically, the methods of the present disclosure may comprise adding the cyclic olefin comonomer with the higher reactivity to the reaction mixture over time. For example, a method of the present disclosure can comprise: contacting a first cyclic olefin comonomer with a metathesis catalyst to produce a reaction mixture; and adding a second cyclic olefin comonomer to the reaction mixture over time at a rate of 0.01 mol% per minute to 25 mol% per minute based on a total amount of the second cyclic olefin comonomer added to the reaction mixture to produce a polymer, wherein a final mol to mol ratio of first cyclic olefin comonomer to second cyclic olefin comonomer added to the reaction mixture is 1 : 1 to 500: 1 ; and wherein the second cyclic olefin comonomer has a higher reactivity with the metathesis catalyst than the first cyclic olefin comonomer. [0023] The present disclosure also relates to the polymers resulting from the foregoing methods. For example, the resultant polymer may comprise: a mol ratio of a first cyclic olefin comonomer-derived unit to a second cyclic olefin comonomer-derived unit of 3:1 to 100:1 and having a ratio of cis to trans of 50:50 to 5:95. Said polymer may have long chain branching (LCB) characterized by g’_vis of 0-50 to 0.91 and/or a d at a G* of 50 kPa of 30° to 60°, each described in more detail herein. As these polymers have a new composition, the properties of the polymer may lend themselves to new applications.

Definitions and Test Methods

[0024] The new notation for the Periodic Table Groups is used as described in Chemical and Engineering News, v.63(5), pg. 27 (1985).

[0025] Unless otherwise indicated, room temperature is 25 °C.

[0026] DCPD is dicyclopentadiene.

[0027] An “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.

[0028] A “polymer” has two or more of the same or different mer units. A “homopolymer” is a polymer having mer units that are the same. The term “polymer” as used herein includes, but is not limited to, homopolymers, copolymers, terpolymers, etc. The term “polymer” as used herein also includes impact, block, graft, random, and alternating copolymers. The term “polymer” shall further include all possible geometrical configurations unless otherwise specifically stated. Such configurations may include isotactic, syndiotactic, and random symmetries.

[0029] As used herein, unless specified otherwise, the term “copolymer(s)” refers to polymers formed by the polymerization of at least two different monomers (i.e., mer units). For example, the term “copolymer” includes the copolymerization reaction product of two or more different cyclic olefins like cyclopentene and dicyclopentadiene. Polymer and copolymer compositions herein may be described by the constituent mer units as -derived units. For example, a copolymer that is a reaction product of cyclopentene and dicyclopentadiene may be described as a copolymer comprising cyclopentene-derived units and dicyclopentadiene- derived units. More generally, terms like first cyclic olefin comonomer-derived units to second cyclic olefin comonomer-derived units may be used.

[0030] “Different” as used to refer to monomer mer units indicates that the mer units differ from each other by at least one atom or are different isomerically.

[0031] As used herein, when a polymer is referred to as “comprising, consisting of, or consisting essentially of’ a monomer or monomer-derived units, the monomer is present in the is said to have a “cyclopentene” content of 35 wt% to 55 wt%, it is understood that the mer unit in the copolymer is derived from cyclopentene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer. [0032] The mol ratio of first cyclic olefin comonomer-derived units to second cyclic olefin comonomer-derived units is determined using ¹H NMR where the different chemical shift of a hydrogen atom can be associated with each comonomer. Then, the relative intensity of the NMR associated with said hydrogens provides a relative concentration of each of the comonomers. [0033] The ratio of cis to trans in a polymer is determined by ¹³C NMR using the relevant olefinic resonances. A carbon in a cis configuration has a smaller NMR chemical shift than a carbon in a trans configuration. The exact chemical shift will depend on the other atoms the carbon is bonded to and a configuration of such bond, but by way of non-limiting example, 1-ethyl-3,4-dimethylpyrrolidine-2,5-dione has cis carbon atoms with a ¹³C chemical shift of about 12.9 ppm for trans carbons and a ¹³C chemical shift of about 11.2 ppm for cis carbons. Then, the relative intensity of the NMR associated with said cis and trans carbons provides a relative concentration of each of the comonomers. [0034] Unless otherwise indicated, NMR spectroscopic data of polymers were recorded in a 10 mm tube on a cryoprobe with a field of at least 600 MHz NMR spectrometer at 25°C using deuterated chloroform (CDCl₃) solvent to prepare a solution with a concentration of 30 mg/mL for ¹H NMR and 67 mg/mL for ¹³C NMR. ¹H NMR was recorded using a 30° flip angle RF pulse, 512 transients, with a delay of 5 seconds between pulses. ¹³C NMR was recorded using a 90° pulse, inverse gated decoupling, a 60 second delay, and 512 transients. Samples were referenced to the residual solvent signal of CDCl₃ at 77.16 ppm for ¹³C and 7.26 ppm for ¹H. Assignments for DCPD (dicyclopentadiene) composition and cis/trans ratio were based on Benjamin Autenrieth et. al. (2015) “Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of endo-Dicyclopentadiene by Molybdenum and Tungsten Catalysts,” Macromolecules, v.48, pp.2480-2492. Assignments for cyclopentene (cC5) compositions and cis/trans ratio were based on Dounis, P. et. al. (1995) “Ring-Opening Metathesis Polymerization of Monocyclic Alkenes using Molybdenum and Tungsten Alkylidene (Schrock-type) Initiators and ¹³C Nuclear Magnetic Resonance Studies of the Resulting Polyalkenamers,” Polymer, v.36(14), pp. 2787-2796, and cC5-DCPD copolymer assignments were based on Dragutan, V. et. al. (2010) Green Metathesis Chemistry: Great Challenges in the polymer chain were uniform enough that there is no observable blockiness. [0035] For example, mol% DCPD was calculated from ¹H NMR using the aliphatic region: DCPD (H4) at 3.22 ppm, cC5=(_I5-3ppm–8*DCPD)/6; DCPD*100/(cC5+DCPD)=mol%, mol% cC5 is 1−DCPD or cC5*100/(DCPD+cC5). [0036] cC5 cis/trans ratio was determined from ¹³C NMR of the vinylene double bond region with the trans peak at 130.47 ppm and cis centered at 129.96 ppm. DCPD and norbornene (NBE) contribution to the region was considered negligible. [0037] DCPD cis/trans ratio was determined from ¹³C NMR of the C₂ and C₅ peaks per FIG.1 combined with trans at 47-45.5 ppm and cis at 42.2-41.4 ppm. Both values divided by 2 due to 2 carbons. %Trans=trans*100/(trans+cis) and vice versa. [0038] Mol% NBE was calculated from ¹H NMR using the aliphatic region per FIG. 2 where A and B’s designations: NBE (A) at 2.88 ppm, NBE (mol%) = 100*(I_A/(I_B + I_A). [0039] 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. Molecular weight distribution (MWD) is defined to be M_w divided by M_n. Unless otherwise noted, 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_n) and long chain branching indices were determined by using a Polymer Char GPC-IR, equipped with four in-line detectors, an 18-angle light scattering (“LS”) detector, a viscometer and a differential refractive index detector (“DRI”). Three Agilent PLgel 10 µm Mixed-B LS columns were used for the GPC tests herein. The nominal flow rate was 0.5 mL/min, and the nominal injection volume was 200 µL. The columns, viscometer and DRI detector were contained in ovens maintained at 40°C. The tetrahydrofuran (THF) solvent with 250 ppm antioxidant butylated hydroxytoluene (BHT) was used as the mobile phase. The given amount of polymer samples were weighed and sealed in standard vials. After loading the vials in the auto sampler, polymers were automatically dissolved in the instrument with 8 mL added THF solvent at 40°C for about two hours with continuous shaking. The concentration, C, at each point in the chromatogram was calculated from the baseline-subtracted DRI signal, I_DRI, using the following equation: C = K_DRII_DRI /(dn/dc), where K_DRI is a constant determined by calibrating the DRI, and (d_n/d_c) is the incremental refractive index of polymer in THF solvent. [0040] The conventional molecular weight was determined by combining universal calibration relationship with the column calibration, which was performed with a series of monodispersed polystyrene (PS) standards ranging from 300 g/mol to 12,000,000 g/mol. The molecular weight “M” at each elution volume was calculated with following equation:

where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, a_PS = 0.7362 and K_PS = 0.0000957 while “a” and “K” for the samples were 0.725 and 0.000291, respectively. [0041] 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 determined using the following equation:

Here, ΔR(θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, “c” is the polymer concentration determined from the DRI analysis, A₂ is the second virial coefficient, P(θ) is the form factor for a mono-disperse random coil, and K_o is the optical constant for the system, as set forth in the following equation:

where N_A is Avogadro’s number, and (dn/dc) is the incremental refractive index for the system, which takes the same value as the one obtained from the DRI method, and the value of “n” is 1.40 for THF at 40°C and λ = 665 nm. For the samples used in this test, the dn/dc is measured as 0.1154 by DRI detector. [0042] A four capillaries viscometer with a Wheatstone bridge configuration was used to determine the intrinsic viscosity [η] from the measured specific viscosity (η_S) and the concentration “C”. η_s = C[η] + 0.3(C[η])². [0043] The average intrinsic viscosity, [η]_avg, of the sample was calculated using the following equation:

where the summations are over the chromatographic slices, i, between the integration limits. [0044] The branching index (g’_vis or simply g’) is defined as the ratio of the intrinsic viscosity of the branched polymer to the intrinsic viscosity of a linear polymer of equal molecular weight. The branching index g' is defined mathematically as:

[0045] The Mv is the viscosity-average molecular weight based on molecular weights determined by LS analysis. The Mark-Houwink parameters α and k used for the reference linear polymer are 0.725 and 0.000291, respectively. [0046] All the concentration is expressed in g/cm³, molecular weight is expressed in g/mol, and intrinsic viscosity is expressed in dL/g unless otherwise noted. [0047] The small amplitude oscillatory shear (SAOS) data can be transformed into discrete relaxation spectra using the procedure in Bird, R. B. et al. (1987) Dynamics of Polymeric Liquids, Volume 1, Fluid Mechanics, 2nd Edition, John Wiley and Sons, pages 273-275. The storage and loss moduli are the simultaneously least squares that fit with the functions:

at the relaxation times λ_k = 0.01, 0.1, 1, 10, and 100 seconds (sec). Therefore, the sums are from k=1 to k=5. The sum of the η_k’s is equal to the zero shear viscosity, η₀. An indication of high levels of branched structure is a high value of η₅, corresponding to the relaxation time of 100 sec, relative to the zero shear viscosity. The viscosity fraction of the 100 sec relaxation time is η₅ divided by the zero shear viscosity, η₀. Chains with long relaxation times cannot relax during the cycle time of the SAOS experiment and lead to high zero shear viscosities. [0048] Shear thinning is characterized by the decrease of complex viscosity with increasing frequency. One way to quantify the shear thinning is to use a ratio of the difference between the complex viscosity at a frequency of 0.1 rad/s and the complex viscosity at a frequency of 100 rad/s to the complex viscosity at a frequency of 0.001 rad/sec when the complex viscosity is measured at 80°C. The larger this ratio, the higher is the degree of shear thinning. This ratio is the typical output of the SAOS experiments. Polymer viscosity is conveniently measured in poise (dyne·sec/square centimeter) or Pa·s (1 Pa·s=10 poises) at frequencies within a range from 0.001 rad/sec to 628 rad/sec and at 80°C under a nitrogen atmosphere using a dynamic mechanical spectrometer, such as the Advanced Rheometrics Expansion System (ARES). Generally, a high degree of shear thinning indicates a polymer is readily processable in high shear fabrication processes, for example, by injection molding. [0049] For the determinations of phase angle and degree of shear thinning of polymers and blends via SAOS, a circular sample with a diameter of 25 mm was die-cut from the compression-molded plaque with a thickness of about 2 mm. The sample was mounted between the 25-mm diameter parallel plates in a rheometer ARES-G2 (TA Instruments). The test temperature was 800°C and the strain applied was 1%. The complex modulus (G*), the phase angle (δ), and the complex viscosity (η*) were measured as the frequency is varied from 0.001 to 628 rad/s. [0050] The phase or loss angle δ, is the inverse tangent of the ratio of G″ (the shear loss modulus) to G′ (the shear storage modulus). For a typical linear polymer, the phase angle at low frequencies (or long times) approaches 90° because the chains can relax in the melt, adsorbing energy and making G″ much larger than G′. As frequencies increase, more of the chains relax too slowly to absorb energy during the shear oscillations, and G′ grows relative to G″. In contrast, a branched chain polymer relaxes very slowly even at temperatures well above the melting temperature of the polymer, because the branches need to retract before the chain backbone can relax along its tube in the melt. This polymer never reaches a state where all its chains can relax during a shear oscillation, and the phase angle never reaches 90° even at the lowest frequency, ω, of the experiments. These slowly relaxing chains lead to a higher zero shear viscosity. Long relaxation times lead to a higher polymer melt strength or elasticity. [0051] One way to quantify the degree of shear thinning (DST) is to use the following ratio: DST = [η^∗(0.0011 rads/sec) − η^∗(100 rads/sec)]/η^∗(0.1 rads/sec) where η*(0.001 rads/sec) and η*(100 rads/sec) are the complex viscosities at frequencies of 0.001 rads/sec and 100 rads/sec, respectively, measured at 80°C. This ratio is used to measure the degree of shear thinning of the polymeric materials discussed in the various tables of this invention. The larger this ratio, the higher the degree of shear thinning polymers exhibiting shear thinning behaviors are easily processed in high shear rate fabrication methods, such as injection molding. [0052] The complex modulus (G*) is equal to [(G')^{2 +} (G'')²] ^1/2. The plot of phase angle (δ) versus the complex modulus is known as the van Gurp-Palmen plot (See M. van Gurp, J. Palmen (1998) Rheol. Bull., v.67, pp. 5-8). The values of δ listed in the various tables of this invention are those at a G* of 50 kPa. The lower this δ, the higher is the melt elasticity or melt strength. Compositions and Methods [0053] As used herein, when referring to cyclic olefin comonomer herein, the second cyclic olefin comonomer or combination of comonomers has a higher reactivity with the metathesis catalyst than the first cyclic olefin comonomer. Reactivity for a comonomer with a metathesis catalyst depends on the metathesis catalyst. The reactivity of an individual cyclic olefin comonomer with a metathesis catalyst can be determined by performing separate reactions with the individual cyclic olefin comonomers alone under the same reaction conditions (e.g., same temperature, same pressure, same mol ratio of ROMP catalyst to cyclic olefin monomer, and the like), which are the same reaction conditions as the reaction of interest. The comonomer with the higher reactivity (e.g., higher % yield over the same time that is time sufficient to illustrate a difference in the two reactivities) is the second cyclic olefin comonomer in the reaction of interest.

[0054] The reactivity of the second cyclic olefin comonomer (k₂) may be 2 times or greater, 2 times to 100 times greater, or 5 times to 100 times greater, or 5 times to 25 times greater, or 10 times to 50 times greater than the reactivity of the first cyclic olefin comonomer (ki), where k₂=k₁*(2 or greater). To quantify the relative reactivities, under the same reaction conditions the percent yield over 5 minutes is the k value for the respective comonomers.

[0055] A method of the present disclosure can include contacting a first cyclic olefin comonomer with a metathesis catalyst optionally in the presence of an activator to produce a reaction mixture and adding a second cyclic olefin comonomer to the reaction mixture over time. The reaction mixture may also include a diluent.

[0056] The reaction may be carried out over a period of time, which may be from 1 minute to 48 hours, or 1 minute to 20 hours, or 5 minutes to 3 hours, or 10 minutes to 1 hour.

[0057] Before addition of the second cyclic olefin comonomer, the reaction may continue for a time period (e.g., 1 second to 15 minutes, or 5 seconds to 10 minutes, or 30 seconds to 5 minutes).

[0058] Addition of the second cyclic olefin comonomer to the reaction mixture can be over time in any suitable method. For example, the second cyclic olefin comonomer can be added to the reaction mixture in small batches over time (e.g., dropwise or in larger-scale reactions as individual bolus additions). In another example, the second cyclic olefin comonomer can be added to the reaction mixture continuously over time. In yet another example, a combination of the foregoing may be used.

[0059] The reaction mixture is preferably mixed (e.g., stirred) at a sufficient rate to incorporate the addition of the second cyclic olefin comonomer evenly into the entire reaction mixture quickly. This facilitates synthesis of a more polymer product that has a more homogeneous chemical composition between individual polymer molecules and within an individual polymer molecule.

[0060] An addition rate of the second cyclic olefin comonomer to the reaction mixture over time may be from 0.01 mol% per minute to 25 mol% per minute based on a total amount of the second cyclic olefin comonomer added to the reaction mixture. Other suitable addition rates of the second cyclic olefin comonomer to the reaction mixture may be from 1 mol% per minute to 10 mol% per minute, from 0.01 mol% per minute to 1 mol% per minute, from 0.1 mol% per minute to 5 mol% per minute, or from 5 mol% per minute to 25 mol% per minute. The addition rates can be uniform or tunable over the ROMP process. The addition of more reactive monomers can be slower at the beginning of the reaction and faster at the end or vice versa. [0061] After addition of the second cyclic olefin comonomer, the reaction may continue for a time period (e.g., 1 minute to 5 hours, or 1 minute to 1 hour, or 1 minute to 30 minutes) before quenching the reaction. [0062] A mol ratio of first cyclic olefin comonomer to second cyclic olefin comonomer added to the reaction mixture may be 1:1 to 500:1. Other suitable mol ratios of first cyclic olefin comonomer to second cyclic olefin comonomer added to the reaction mixture may be 5:1 to 250:1, 1:1 to 100:1, 1:1 to 10:1, 5:1 to 50:1, 50:1 to 250:1, or 100:1 to 500:1. [0063] A mol ratio of metal in the catalyst to total comonomer may be 1:1 to 1000:1. Other suitable mol ratios of metal in the catalyst to total comonomer 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. [0064] The temperature of the reaction may be -50°C to 200°C, or -25°C to 100°C, or -10°C to 25°C. [0065] The pressure of the reaction may be from 0 MPa to 50 MPa, or 0 MPa to 25 MPa, or ambient pressure to 10 MPa. [0066] Cyclic olefins suitable for use as comonomers in the methods of the present disclosure may be strained or unstrained (preferably strained); monocyclic or polycyclic (e.g., bicyclic); and optionally include hetero atoms and/or one or more functional groups. [0067] Examples of cyclic olefins suitable for use as comonomers 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, dimethyl norbornene carboxylate, norbornene-exo-2,3-carboxylic anhydride, and their respective homologs and derivatives, and substituted derivatives therefrom. Illustrative examples of suitable substituents 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. Metathesis Catalyst Compounds

[0068] Catalysts suitable for use in conjunction with the methods described herein are any catalysts capable of performing ROMP. In embodiments of the invention, the catalyst is a tungsten or ruthenium metal complex-based metathesis catalyst.

[0069] In embodiments according to the instant invention, a process to form a cyclic olefin polymerization catalyst comprises: i) contacting a metal alkoxide (Ilia) with a transition metal halide (IV) to form a transition metal precatalyst (Villa) according to the general formula: m (R' O)_cM^uX_(u-c) + M^vX_v → M^v(OR^,)_c*_mX_(v-c*m-2)X₂ (Ilia) (IV) (Villa) ii) contacting the transition metal precatalyst (Villa) with a metal alkyl activator (A) to form the activated catalyst comprising a transition metal carbene moiety M^v=C(R*)₂ according to the general formula:

M^v(OR')_c*mX_(v-c*m-2)X₂ + n M^uR_aX_(u-a) → M^v(OR')_c*mX_(v-c*m-2)=C(R*)₂ (Villa) (A) (V) wherein

M^u is a Group 1, 2, or 13 metal of valance u, preferably Li, Na, Ca, Mg, Al, or Ga; c is from 1 to 3 and ≤ u; m = 1/3, 1/2, 1, 2, 3, or 4 and c*m ≤ v-2; a is 1, 2, or 3 and a < u; n is a positive number but a*n is in between 2 to 10;

M^v is a Group 5 or 6 transition metal of valance v;

X is halogen, each R’ is independently a monovalent hydrocarbyl comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table; each R is independently a C₁ to C₈ alkyl; each R* is independently H or a C₁ to C₇ alkyl; and each Z is independently halide or a C₁ to C₈ alkyl radical.

[0070] Accordingly, embodiments described herein may include Group 1 and Group 2 mono-alkoxides (e.g., Li(OR’) or Mg(OR’)X), Group 2 metal and Group 13 metal dialkoxides (e.g., Mg(OR')₂ and Al(OR’)₂X), and Group 13 trialkoxide (e.g., Al(OR’)₃), wherein R’ is independently a monovalent hydrocarbyl comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table, and X is halogen_. In any embodiment, metal alkoxide (Ilia) may comprise (a) a Group 1 metal, e.g., NaOR’ (u = 1, c =1, d = 0); (b) a Group 2 metal, e.g., Mg(OR’)Cl (u = 2, c=1, d = 1), or Mg(OR’)₂ (u=2, c=2, u = 0); or (c) a Group 13 metal, e.g., Al(OR’)Cl₂ (u = 3, c = 1, d = 2), Al(OR’)₂Cl (u = 3, c = 2, d = 1), or Al(OR’)₃ (u = 3, c = 3, d = 0). [0071] In embodiments of the invention, the metal alkoxide (IIIa) is formed by contacting a compound comprising a hydroxyl functional group (I) with a Group 1 or Group 2 metal hydride M^u*(H)u according to the general formula: c R’OH + M^u*(H)_u → (R’O)_cM^u*X_(u-c) (I) (IIIa) wherein M^u* is a Group 1 or 2 metal of valance u*, preferably Na, Li, Ca, or Mg; c is 1 or 2 and c is ≤ u*; X is halogen; and each R’ is independently a monovalent hydrocarbyl comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table. [0072] In embodiments of the invention, the metal alkoxide (IIIa) is formed by contacting a compound comprising a hydroxyl functional group (I) with the metal alkyl activator (A) to form the metal alkoxide (IIIa) according to the general formula: a R’OH + M^uR_aX_(u-a) → M^u(OR’)_aX_(u-a) (I) (A) (IIIa) wherein each R’ is independently a monovalent hydrocarbyl comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table; M^u is a Group 1, 2, or 13 metal of valance u, preferably Li, Na, Ca, Mg, Al, or Ga; a is 1, 2, or 3; a is ≤ u; and each R is independently a C₁ to C₈ alkyl. [0073] In embodiments of the invention, the process further comprises contacting a mixture of metal alkoxides with one or more ligand donors (D) under conditions sufficient to crystalize and isolate the metal alkoxide (IIIa) as one or more dimeric coordinated metal alkoxide-donor composition according to the general structure (XXV-GD₂):

wherein M^u is a

Group 1, 2, or 13 metal of valance u, preferably Li, Na, Ca, Mg, Al, or Ga; each R’ is independently a monovalent hydrocarbyl comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table; each L is R’O-, alkyl R as defined for structure A, or halide X; each D is any O or N containing organic donor selected from ethers (e.g., dialkyl ethers, cyclic ethers), ketones, amines (e.g., trialkyl amines, aromatic amines, cyclic amines, and heterocyclic amines (e.g., pyridine)), nitriles (e.g., alkyl nitriles and aromatic nitriles), and any combination thereof (preferably, tetrahydrofuran, methyl-tertbutyl ether, a C1-C4 dialkyl ether, a C₁-C₄ trialkyl amine, and any combination thereof); and n is 1, 2, 3, or 4. [0074] In embodiments of the invention, a process to form a cyclic olefin polymerization catalyst comprises contacting an alkyl-metal alkoxide (IIIb) with a transition metal halide (IV) in a reaction mixture to form the activated catalyst (V) comprising a transition metal carbene moiety M^v=C(R^*)₂ according to the general formula: x M^ub(OR’)aR(u-a) + M^vXv → M^v(OR’)x*aX(v-x*a-2)=C(R*)2 (IIIb) (IV) (V) wherein M^ub is a Group 2 or 13 metal of valance u, preferably Ca, Mg, Al, or Ga, most preferably Al; a is 1 or 2 but < u; x is 1/2 or 1, 2, 3, or 4 but x*a < or = v-2; M^v is a Group 5 or 6 transition metal of valance v; X is halogen; each R’ is independently a monovalent hydrocarbyl comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table; each R is independently a C₁ to C₈ alkyl; and each R* is independently H or a C₁ to C₇ alkyl. [0075] In embodiments of the invention, the reaction mixture further comprises a metal alkyl activator (A) according to the formula M^uR_aX_(u-a) , wherein M^u is a Group 1, 2, or 13 metal of valance u, preferably Li, Na, Ca, Mg, Al, or Ga; a is 1, 2, or 3; a ≤ u; and when present, X is halogen. [0076] In embodiments of the invention, M^v is W, Mo, Nb, or Ta. In some embodiments, two or more R’O- ligands are connected to form a single bidentate chelating moiety. [0077] In one or more embodiments of the invention, a process to form a cyclic olefin polymerization catalyst comprises: (i) and (iia) or (i), (iib1), and (iib2): i) contacting a compound comprising a hydroxyl functional group (I) with an alkyl aluminum compound (II) to form an aluminum precatalyst (III) and the corresponding residual (Q1 + Q2) according to the general formula: m R’OH + AlR_a Y_(3-a) → Al(OR’)_mY_(3-m) + a HR (m-a) HY (I) (II) (III) (Q1) (Q2) wherein m is 1 or 2; a is 1 or 2; each Z is independently H or a C₁ to C₈ alkyl; each R’ is independently a monovalent hydrocarbyl comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table; and each Y is a C₁ to C₈ alkyl, halogen, or an alkoxy hydrocarbyl moiety represented by - OR⁵, wherein each R⁵ is a C₁ to C₂₀ alkyl radical and wherein Y = C₁ to C₈ alkyl; iia) contacting the aluminum precatalyst (III) with a transition metal halide (IV) to form an activated carbene containing cyclic olefin polymerization catalyst (V) comprising a transition metal carbene moiety M^v=C(R^*)₂ according to the general formula: y Al(OR’)_mY_(3-m) + M^vX_v → M^v(OR’)_y*mX_(v-y*m-2)=C(R*)₂ (III) (IV) (V) wherein each R* is independently H or a C₁ to C₇ alkyl; or iib1) contacting the aluminum precatalyst (III) with a transition metal halide (IV) to form a transition metal precatalyst, (VIII) according to the general formula: y Al(OR’)_mY_(3-m) + M^vX_v → M^v(OR’)_y*mY_(3-m)X_(v-m(y-1)-5)X₂ (III) (IV) (VIII) wherein m = 1, 2, or 3; y = 1/3, 1/2, 1, 2, 3, or 4; y*m + 3-m ≤ v-2; and iib2) contacting the transition metal precatalyst, (VIII) with a metal alkyl activator (A) to form the activated carbene containing cyclic olefin polymerization catalyst (V) comprising a transition metal carbene moiety M^v=C(R^*)2 according to the general formula: M^v(OR’)_y*mY_(3-m)X_(v-m(y-1)-5)X₂ + M^uR_aX_(u-a) → M^v(OR’)_y*mY_(3-m)X_(v-m(y-1)-5)=C(R*)₂ (VIII) (A) (V) wherein R* is a hydrogen or C₁-C₇ alkyl. [0078] Embodiments in which R* is C₁-C₇ alkyl are preferred because activators in which R* is an alkyl having 8 or more carbon atoms are not capable of directly activating the transition metal halide. [0079] In one or more embodiments of the invention wherein a=3 such, the alkyl aluminum compound (II) is a trialkyl-aluminum (IX) and the residual is an alkane HR according to the general formula: m R’OH + AlR₃ → Al(OR’)_mR_(3-m) + m HR (alkane) (I) (IX) (III) (Q) wherein m = 1 or 2; and each R is independently a C₁ to C₈ alkyl radical. [0080] In embodiments of the process, the aluminum precatalyst (III) is a dimer represented by structure (III-D) which is reacted with the transition metal halide (IV) to form the activated carbene containing cyclic olefin polymerization catalyst (V) according to the general formula:

wherein each R is C₁ to C₈ alkyl; each R* is independently hydrogen or C₁ to C₇ alkyl; and each R’ is independently a monovalent hydrocarbyl comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table, or two or more of R’ are connected to form a bidentate chelating ligand. [0081] In embodiments where a=2 and Y is halogen, the alkyl aluminum compound (II) is a dialkyl aluminum halide (VI), and the aluminum precatalyst is a di-halo tetrakis alkoxide aluminum dimer (VII) according to the general formula:

; [0082] Then, the di-halo tetrakis alkoxide aluminum dimer (VII) is contacted with the transition metal halide (IV) to form a di-halo transition metal precatalyst (VIII) according to the general formula:

wherein the di-halo transition metal precatalyst (VIII) is contacted with a metal alkyl activator (A) to form the activated carbene containing cyclic olefin polymerization catalyst (V) according to the general formula:

wherein a = 1, 2, or 3; and a is ≤ u. [0083] In one or more embodiments of the invention, a molar ratio of M^v to M^u-R in metal alkyl activator M^uR_aX_(u-a) is from 1 to 2 to 1 to 15. In one or more embodiments the alkoxy ligand R’O- comprises a C₇ to C₂₀ aromatic moiety and wherein the O atom directly bonds to the aromatic ring; the compound comprising a hydroxyl functional group (I) is a bidentate dihydroxy chelating ligand (X’); the alkyl aluminum compound (II) is a dialkyl aluminum halide (VI), and the aluminum precatalyst (III) is an aluminum alkoxide mono-halide (XI) according to the general formula:

wherein R¹ is a direct bond between the two rings or a divalent hydrocarbyl radical comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table; R² through R⁹ are each independently a monovalent hydrocarbyl radicals comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table, or two or more of R² through R⁹ join together for form a ring having 40 or less atoms from Groups 14, 15, and/or 16 of the periodic table.

[0084] In one or more embodiments of the invention, the process may further comprises: i) contacting two equivalents of the aluminum alkoxide mono-halide (XI) with the transition metal halide (IV) to form a transition metal halo bis-alkoxide catalyst precursor (XII) according to the general formula:

and ii) contacting the transition metal halo bis-alkoxide catalyst precursor (XII) with a trialkyl aluminum compound (IX) to form the activated carbene containing cyclic olefin polymerization catalyst (XIII) according to the general formula:

[0085] In other embodiments of the invention, the process may further comprise: i) contacting one equivalent of the aluminum alkoxide mono-halide (XI) with a transition metal halide (IV) to form a transition metal halo alkoxide catalyst precursor (XIV) according to the general formula:

and ii) contacting the transition metal halo alkoxide catalyst precursor (XIV) with a trialkyl aluminum compound (IX) to form the activated carbene containing cyclic olefin polymerization catalyst (XV) according to the general formula:

[0086] In one or more embodiments of the process, the compound comprising a hydroxyl functional group (I) is a bidentate dihydroxy chelating ligand (X’); the alkyl aluminum compound (II) is a trialkyl aluminum (IX), and the aluminum precatalyst (III) is an alkyl aluminum alkoxide (XX) according to the general formula:

wherein R¹ is a direct bond between the two rings or a divalent hydrocarbyl radical comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table; R² through R⁹ are each independently a monovalent hydrocarbyl radicals comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table, or two or more of R² through R⁹ join together for form a ring having 40 or less atoms from Groups 14, 15, and/or 16 of the periodic table. [0087] In embodiments, the process further comprises contacting two equivalents of the aluminum-alkyl alkoxide (XX) with a transition metal halide (V) to form the activated carbene containing cyclic olefin polymerization catalyst (XXI) according to the general formula:

[0088] In embodiments of the invention, the process further comprises contacting one equivalent of the aluminum- alkyl alkoxide (XX) with a transition metal halide (V) to form the activated carbene containing cyclic olefin polymerization catalyst (XXIa) according to the general formula:

[0089] In embodiments of the process, the compound comprising a hydroxyl functional group (I) is a mixture comprising a bidentate dihydroxy chelating ligand (X') and a monodentate hydroxy ligand (XVI); the alkyl aluminum compound (II) is a trialkyl aluminum (IX), and the aluminum precatalyst (III) is an aluminum tri-alkoxide (XVII), the process further comprising: i) forming the aluminum tri-alkoxide (XVII) according to the general formula:

ii) contacting the aluminum tri-alkoxide (XVII) with a transition metal halide (IV) to form a transition metal alkoxide catalyst precursor (XVIII) according to the general formula:

and iii) contacting the transition metal alkoxide catalyst precursor (XVIII) with a trialkyl aluminum compound (IX) to form the activated carbene containing cyclic olefin polymerization catalyst (XIX) according to the general formula:

wherein M^v is a Group 5 or Group 6 transition metal of valance v; X is halogen; R¹ is a direct bond between the two rings of the bidentate ligand, or a divalent hydrocarbyl radical comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table; each of R² through R¹⁴ is independently, a hydrogen, a monovalent radical comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table, a halogen, or two or more of R² through R⁹ and/or two or more of R¹⁰ through R¹⁴ join together to form a ring comprising 40 atoms or less from Groups 14, 15, and 16 of the periodic table.

[0090] In embodiments of the invention, the compound comprising a hydroxyl functional group (I) is an aromatic compound comprising a phenoxy hydroxyl group Ar-OH (XXIV); the alkyl aluminum compound (II) is an alkyl aluminum halide, and the aluminum precatalyst (III) is a mixture of aluminum alkoxides (XXVa), (XXVb), and (XXVc), the process further comprising: i) forming the mixture of aluminum alkoxides (XXVa), (XXVb), and (XXVc) according to the general formula:

wherein x is from 1 to 2; and ii) contacting the mixture of metal alkoxides with one or more ligand donors (D) under conditions sufficient to crystalize and isolate the metal alkoxide (Ilia) as one or more dimeric coordinated metal alkoxide-donor composition according to the general structure (XXV- GD₂):

wherein M^u is a Group 1, 2, or 13 metal of valance u, preferably Li, Na, Ca, Mg, Al, or

Ga; each R’ is independently a monovalent hydrocarbyl comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table; each L is R’O-, alkyl R as defined for structure A, or halide X; each D is any O or N containing organic donor selected from ethers (e.g., dialkyl ethers, cyclic ethers), ketones, amines (e.g., trialkyl amines, aromatic amines, cyclic amines, and heterocyclic amines (e.g., pyridine)), nitriles (e.g., alkyl nitriles and aromatic nitriles), and any combination thereof (preferably, tetrahydrofuran, methyl-tertbutyl ether, a C₁-C₄ dialkyl ether, a C₁-C₄ trialkyl amine, and any combination thereof); and n is 1, 2, 3, or 4.

[0091] Another example of catalysts suitable for use in conjunction with the methods described herein may include, but are not limited to:

(i) a catalyst represented by the (XXVI):

where M is a group 8 metal, preferably Os or Ru, preferably Ru;

X and X¹ are, independently, any anionic ligand, preferably a halogen (preferably chlorine), an alkoxide or a triflate, or X and X¹ may be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear-ring system of up to 30 non-hydrogen atoms;

L and L¹ are, independently, a neutral two electron donor, preferably a phosphine or a N-heterocyclic carbene, L and L¹ may be joined to form a single ring of up to 30 non-hydrogen atoms or a multinuclear-ring system of up to 30 non-hydrogen atoms;

L and X may be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear-ring system of up to 30 nonhydrogen atoms;

L¹ and X¹ may be joined to form a multidentate monoanionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear-ring system of up to 30 nonhydrogen atoms; and

R¹ and R² may be different or the same and may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl; and/or

(ii) a catalyst represented by (XXVII):

where M* is a Group 8 metal, preferably Ru or Os, preferably Ru;

X* and X^1* are, independently, any anionic ligand, preferably a halogen (preferably chlorine), an alkoxide or an alkyl sulfonate, or X* and X^1* may be joined to form a dianionic group and may form a single ring of up to 30 non-hydrogen atoms or a multinuclear-ring system of up to 30 non-hydrogen atoms;

L* is N— R**, 0, P — R , or S, preferably N— R** or O (R** is a C₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl, preferably methyl, ethyl, propyl or butyl); R^* is hydrogen or a C₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl, preferably methyl;

R^1*, R^2*, R^3*, R^4*, R^5*, R^6*, R^7*, and R^8* are, independently, hydrogen or a C₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl, preferably methyl, ethyl, propyl or butyl, preferably R^1*, R^2*, R^3*, and R^4* are methyl; each R^9* and R^13* are, independently, hydrogen or a C₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl, preferably a C₂ to C₆, hydrocarbyl, preferably ethyl;

R^10*, R^11*, R^12* are, independently hydrogen or a C₁ to C₃₀ hydrocarbyl or substituted hydrocarbyl, preferably hydrogen or methyl; each G, is, independently, hydrogen, halogen or C₁ to C₃₀ substituted or unsubstituted hydrocarbyl (preferably a C₁ to C₃₀ substituted or unsubstituted alkyl or a substituted or unsubstituted C₄ to C₃₀ aryl); and where any two adjacent R groups may form a single ring of up to 8 non-hydrogen atoms or a multinuclear-ring system of up to 30 non-hydrogen atoms; and/or (iii) a Group 8 metal complex represented by (XXVIII):

wherein M" is a Group 8 metal (preferably M is ruthenium or osmium, preferably ruthenium); each X" is independently an anionic ligand (preferably selected from the group consisting of halides, alkoxides, aryloxides, and alkyl sulfonates, preferably a halide, preferably chloride);

R"¹ and R"² are independently selected from the group consisting of hydrogen, a C₁ to C₃₀ hydrocarbyl, and a C₁ to C₃₀ substituted hydrocarbyl (preferably R"¹ and R"² are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert- butyl, sec -butyl, cyclohexyl, and cyclooctyl);

R"³ and R"⁴ are independently selected from the group consisting of hydrogen, C₁ to C₁₂ hydrocarbyl groups, substituted C₁ to C₁₂ hydrocarbyl groups, and halides (preferably R"³ and R"⁴ are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert-butyl, sec-butyl, cyclohexyl, and cyclooctyl); and

L" is a neutral donor ligand, preferably L" is selected from the group consisting of a phosphine, a sulfonated phosphine, a phosphite, a phosphinite, a phosphonite, an arsine, a stibine, an ether, an amine, an imine, a sulfoxide, a carboxyl, a nitrosyl, a pyridine, a thioester, a cyclic carbene, and substituted analogs thereof; preferably a phosphine, a sulfonated phosphine, an N-heterocyclic carbene, a cyclic alkyl amino carbene, and substituted analogs thereof (preferably L" is selected from a phosphine, an N-heterocyclic carbene, a cyclic alkyl amino carbene, and substituted analogs thereof); and/or

(iv) a Group 8 metal complex represented by (XXIX):

wherein M" is a Group 8 metal (preferably M is ruthenium or osmium, preferably ruthenium); each X" is independently an anionic ligand (preferably selected from the group consisting of halides, alkoxides, aryloxides, and alkyl sulfonates, preferably a halide, preferably chloride);

R"¹ and R"² are independently selected from the group consisting of hydrogen, a C₁ to C₃₀ hydrocarbyl, and a C₁ to C₃₀ substituted hydrocarbyl (preferably R"¹ and R"² are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert- butyl, sec -butyl, cyclohexyl, and cyclooctyl);

R"³, R"⁴, R"⁵, and R"⁶ are independently selected from the group consisting of hydrogen, C₁ to C₁₂ hydrocarbyl groups, substituted C₁ to C₁₂ hydrocarbyl groups, and halides (preferably R"³, R"⁴, R"⁵, and R"⁶ are independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, sec -butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, octyl, cyclooctyl, and substituted analogs and isomers thereof, preferably selected from the group consisting of tert-butyl, sec -butyl, cyclohexyl, and cyclooctyl).

[0092] Additional examples of catalysts suitable for use in conjunction with the methods described herein are available in US Patent No. 8,227,371and US Patent Pub. Nos. US 2012/0077945 and US 2019/0040186, each of which is incorporated herein by reference. The catalysts may be zeolite-supported catalysts, silica-supported catalysts, and alumina- supported catalysts.

[0093] Two or more catalysts may optionally be used including combinations of the foregoing catalysts.

[0094] Optionally, an activator can be included with the catalyst. Examples of activators suitable for use in conjunction with the methods described herein include, but are not limited to, aluminum alkyls (e.g., triethylaluminum), organomagnesium compounds, and the like, and any combination thereof. [0095] The reaction can be carried out as a solution polymerization in a diluent. Diluents for the methods described herein should be non-coordinating, inert liquids. Examples of diluents suitable for use in conjunction with the methods described herein may include, but are not limited to, straight and branched-chain hydrocarbons (e.g., isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof); cyclic and alicyclic hydrocarbons (e.g., cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof such as ISOPAR™(synthetic isoparaffins, commercially available from ExxonMobil Chemical Company)); perhalogenated hydrocarbons (e.g., perfluorinated C₄-C₁₀ alkanes, chlorobenzene, and aromatic); alkyl substituted aromatic compounds (e.g., benzene, toluene, mesitylene, and xylene); and the like, and any combination thereof.

[0096] The reaction mixture can include diluents at 60 vol% or less, or 40 vol% or less, or 20 vol% or less, based on the total volume of the reaction mixture.

[0097] Generally, quenching compounds that stop the polymerization reaction are antioxidants, which may be dispersed in alcohols (e.g., methanol or ethanol). Examples of quenching compounds may include, but are not limited to, butylated hydroxytoluene, IRGANOX™ antioxidants (available from BASF), and the like, and any combination thereof. [0098] The quenching compounds can be added to the reaction mixture at 0.05 wt% to 5 wt%, or 0.1 wt% to 2 wt% based on the weight of the polymer product.

[0099] In the ROMP process, the preparation of the ROMP catalyst and/or the copolymerization may be carried out in an inert atmosphere (e.g., under a nitrogen or argon environment) to minimize the presence of air and/or water.

[0100] Further, the ROMP process may be carried out in a continuous reactor or batch reactors.

[0101] Polymers of the present disclosure may have a mol 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. As previously discussed, previous methods where the second cyclic olefin comonomer is added in full, the second cyclic olefin comonomer incorporates to a greater degree than the first cyclic olefin comonomer. Accordingly, incorporation of the first cyclic olefin comonomer to a degree greater than a 3:1, 4:1, 5:1, or especially a 6: 1 mol ratio of first cyclic olefin comonomer-derived units to second cyclic olefin comonomer-derived units was previously unattainable.

[0102] The ratio of cis to trans in the polymers of the present disclosure may 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 targeted cis/trans ratio may be achieved by appropriate selection of ROMP catalysts and activators, catalyst: activator ratios, catalyst:monomer ratios, concentrations of reagents, solvents and mixtures of solvents, process temperature, and reaction times, and any combination thereof.

[0103] Polymers of the present disclosure may have a Mw 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. [0104] Polymers of the present disclosure may have a Mn 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.

[0105] Polymers of the present disclosure may have a MWD of 1 to 10, or 1 to 5, or 2 to 4, or 1 to 3.

[0106] The long chain branching (LCB) can be qualitatively characterized by the analysis of the van Gurp-Palmen (vGP) plot according to the method described by Trinkle et al. (Rheol. Acta 41, 103, 2002). The vGP plot is a plot of the loss angle versus the magnitude of the complex modulus (|G*|) measured by dynamic oscillatory rheology in the linear viscoelastic regime. A linear polymer is characterized by a monotonic decreasing dependence of the loss angle with |G* | in the vGP plot and a long chain branched polymer has a shoulder or a minimum in the vGP plot.

[0107] Polymers of the present disclosure having a long chain branching structure may have a δ at a G* of 50 kPa of 30° to 60°, or 30° to 50°, or 30° to 40°. Polymers of the present disclosure having a linear structure may have a δ at a G* of 50 kPa of 65° to 80°, or 70° to 80°, or 70° to 75°.

[0108] Additionally, the level of LCB can be quantified by the GPC method with triple detector via the branching index (g'_vis) described herein. The polymers of the present disclosure having long chain branching may have a g'_vis of 0-5 to 0.91, 0.5 to 0.8, or 0.6 to 0.8, or 0.7 to 0.91. The polymers of the present disclosure having a linear structure may have a g' _vis of 0.92 to 1.0, 0.92 to 0.95, or 0.95 to 0.99, or 0.95 to 1.0.

[0109] The polymers of the present disclosure having a long chain branching structure may have (a) a δ at a G* of 50 kPa of 30° to 60°, or 30° to 50°, or 30° to 40° and/or (b) a g'_vis of 0.5 to 0.91, 0.5 to 0.8, or 0.6 to 0.8, or 0.7 to 0.91 and one or more of (c) a mol 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, (d) a ratio of cis to trans of 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 for both comonomer entities, (e) a Mw 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, (f) a Mn 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, and (g) a MWD of 1 to 10, or 1 to 5, or 2 to 4, or 1 to 3.

[0110] The polymers of the present disclosure having a linear structure may have (a) a δ at a G* of 50 kPa of 65° to 80°, or 70° to 80°, or 70° to 75° and/or (b) a g’_vis of 0-92 to 1.0, 0.92 to 0.95, or 0.95 to 0.99, or 0.95 to 1.0 and one or more of (c) a mol 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, (d) a ratio of cis to trans of 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 for both comonomer entities, (e) a Mw 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, (f) a Mn 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, and (g) a MWD of 1 to 10, or 1 to 5, or 2 to 4, or 1 to 3.

[0111] The properties of the polymers described herein may depend, at least in part, on the composition of the catalyst, the composition of the comonomers, the rate of addition of the second cyclic olefin comonomer, the reaction temperature, and the reaction time. By way of nonlimiting example, a slower rate of addition of the second comonomer in combination with high concentration of the first cyclic olefin comonomer may lead to a higher amount of first cyclic olefin comonomer-derived units in the resultant polymer.

Example Embodiments

[0112] A first nonlimiting example embodiment of the present disclosure is a method comprising: contacting a first cyclic olefin comonomer with a metathesis catalyst to produce a reaction mixture; and adding a second cyclic olefin comonomer to the reaction mixture over time at a rate of 0.01 mol% per minute to 25 mol% per minute based on a total amount of the second cyclic olefin comonomer added to the reaction mixture to produce a polymer, wherein a final mol to mol ratio of first cyclic olefin comonomer to second cyclic olefin comonomer added to the reaction mixture is 1:1 to 500:1; and wherein the second cyclic olefin comonomer has a higher reactivity with the metathesis catalyst than the first cyclic olefin comonomer. The first nonlimiting example embodiment may further include one or more of the following: Element 1 : wherein the polymer has a g’ _vis of 0-50 to 0.91 and/or a δ at a G* of 50 kPa of 30° to 60°; Element 2: wherein the polymer has a g’_vis of 0.92 to 1.0 and/or a δ at a G* of 50 kPa of 65° to 80°; Element 3: wherein contacting the first cyclic olefin comonomer with the metathesis catalyst is in the presence of an activator; Element 4: wherein the reaction mixture further comprises a diluent at 60 vol% or less based on a total volume of the reaction mixture; Element 5: the method further comprising: reacting the first cyclic olefin comonomer with the metathesis catalyst in the reaction mixture for 1 second to 15 minutes before adding the second cyclic olefin comonomer; Element 6: wherein adding the second cyclic olefin comonomer to the reaction mixture over time is in batches over time; Element 7: wherein adding the second cyclic olefin comonomer to the reaction mixture over time is continuous over time; Element 8: wherein a rate at which adding the second cyclic olefin comonomer to the reaction mixture occurs changes over time; Element 9: the method further comprising: quenching the reaction mixture after adding the total amount of the second cyclic olefin comonomer to the reaction mixture; Element 10: wherein quenching is 1 minute to 5 hours after adding the total amount of the second cyclic olefin comonomer to the reaction mixture; Element 11: wherein the polymer has a mol ratio of first cyclic olefin comonomer-derived units to second cyclic olefin comonomer-derived units of 3:1 to 100:1; Element 12: wherein the polymer has a ratio of cis to trans of 50:50 to 5:95; Element 13: wherein the polymer has a weight average molecular weight of 1 kDa to 1,000 kDa; Element 14: wherein the polymer has a number average molecular weight of 0.5 kDa to 500 kDa; and Element 15: wherein the polymer has a molecular weight distribution of 1 to 10; and Element 16: wherein the first and second olefin comonomer- derived units are different and each selected from the group consisting of: cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene,

5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbornene, norbomadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, cis-5-norbomene-endo-2,3-dicarboxylic anhydride, dimethyl norbornene carboxylate, and norbornene-exo-2,3-carboxylic anhydride. Example of combinations include, but are not limited to, Element 1 or Element 2 in combination with one or more of Elements 11-16; Element 1 or Element 2 in combination with one or more of Elements 3-10 and, optionally, in further combination with one or more of Elements 11-16; one or more of Elements 11-16 in combination with one or more of Elements 3-10; two or more of Elements 11-16 in combination; and two or more of Elements 3-10 in combination.

[0113] A second nonlimiting example embodiment of the present disclosure is a polymer comprising: a mol ratio of a first cyclic olefin comonomer-derived unit to a second cyclic olefin comonomer-derived unit of 3:1 to 100:1 and having a ratio of cis to trans of 50:50 to 5:95. The second nonlimiting example embodiment may further include one or more of the following: Element 1; Element 2; Element 11; Element 12; Element 13; Element 14; Element 15; and Element 16. Examples of combinations include, but are not limited to, Element 1 or Element 2 in combination with Element 11 and/or Element 12; Element 1 or Element 2 in combination with one or more of Elements 13-15; Element 1 or Element 2 in combination with Element 16; Element 1 or Element 2 in combination with one or more of Elements 11-16; two or more of Elements 11-16 in combination.

[0114] A third nonlimiting example embodiment of the present disclosure is a polymer comprising: a mol ratio of a first cyclic olefin comonomer-derived unit to a second cyclic olefin comonomer-derived unit of 3:1 to 100:1 and having (a) a g’_vis of 0-50 to 0.91 and/or a δ at a G* of 50 kPa of 30° to 60°. The third nonlimiting example embodiment may further include one or more of the following: Element 11; Element 12; Element 13; Element 14; Element 15; and Element 16, including in the combinations described above.

[0115] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the present specification and associated claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the embodiments of the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claim, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. [0116] One or more illustrative embodiments incorporating the invention embodiments disclosed herein are presented herein. Not all features of a physical implementation are described or shown in this application for the sake of clarity.

[0117] While compositions and methods are described herein in terms of “comprising” or "having" various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps.

[0118] This invention relates to a polymer having (a) a mol ratio of a first cyclic olefin comonomer-derived unit to a second cyclic olefin comonomer-derived unit of 3:1 to 100:1 (or 4:1 to 75:1, or 5:1 to 50:1, or 6:1 to 35:1) and (b) a ratio of cis to trans of 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 0:100) and one or more of: (c) a δ at a G* of 50 kPa of 30° to 60° (or 30° to 50°, or 30° to 40°), (d) a g’_vis of 0-5 to 0.91 (0.5 to 0.8, or 0.6 to 0.8, or 0.7 to 0.91), (e) a Mw 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), (f) a Mn 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), and (g) a MWD of 1 to 10 (or 1 to 5, or 2 to 4, or 1 to 3).

[0119] This invention also relates to a polymer having (a) a mol ratio of a first cyclic olefin comonomer-derived unit to a second cyclic olefin comonomer-derived unit of 3:1 to 100:1 (or 4:1 to 75:1, or 5:1 to 50:1, or 6:1 to 35:1) and (b) a ratio of cis to trans of 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 0:100) and one or more of: (c) a δ at a G* of 50 kPa of 65° to 80° (or 70° to 80°, or 70° to 75°), (d) a g’_vis of 0-92 to 1.0 (0.92 to 0.95, or 0.95 to 0.99, or 0.95 to 1.0), (e) a Mw 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), (f) a Mn 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), and (g) a MWD of 1 to 10 (or 1 to 5, or 2 to 4, or 1 to 3).

[0120] This invention also relates to a polymer having (a) a δ at a G* of 50 kPa of 30° to 60° (or 30° to 50°, or 30° to 40°) and/or (b) a g’_vis of 0-5 to 0.91 (0.5 to 0.8, or 0.6 to 0.8, or 0.7 to 0.91) and one or more of: (c) a mol 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), (d) a ratio of cis to trans of 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 for both comonomer entities), (e) a Mw 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), (f) a Mn 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), and (g) a MWD of 1 to 10 (or 1 to 5, or 2 to 4, or 1 to 3).

[0121] This invention also relates to a polymer having (a) a δ at a G* of 50 kPa of 65° to 80° (or 70° to 80°, or 70° to 75°) and/or (b) a g’_vis of 0-92 to 1.0 (0.92 to 0.95, or 0.95 to 0.99, or 0.95 to 1.0) and one or more of: (c) a mol 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), (d) a ratio of cis to trans of 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 for both comonomer entities), (e) a Mw 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), (f) a Mn 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), and (g) a MWD of 1 to 10 (or 1 to 5, or 2 to 4, or 1 to 3). [0122] This invention also relates to methods of producing the polymers to which the invention is related. A method of the invention comprises: contacting a first cyclic olefin comonomer (e.g., cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4- cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbomene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbornadiene, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, dimethyl norbomene carboxylate, norbomene-exo-2,3-carboxylic anhydride, and their respective homologs and derivatives, and substituted derivatives therefrom) with a metathesis catalyst to produce a reaction mixture; and adding a second cyclic olefin comonomer (e.g., cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbomene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, cis-5-norbomene-endo-2,3-dicarboxylic anhydride, dimethyl norbomene carboxylate, norbornene-exo-2,3-carboxylic anhydride, and their respective homologs and derivatives, and substituted derivatives therefrom) to the reaction mixture over time at a rate of 0.01 mol% per minute to 25 mol% per minute (or 1 mol% per minute to 10 mol% per minute, or 0.01 mol% per minute to 1 mol% per minute, or 0.1 mol% per minute to 5 mol% per minute, or 5 mol% per minute to 25 mol% per minute) based on a total amount of the second cyclic olefin comonomer added to the reaction mixture to produce a polymer, wherein a final mol to mol ratio of first cyclic olefin comonomer to second cyclic olefin comonomer added to the reaction mixture is 1:1 to 500:1 (or 5:1 to 250:1, or 1:1 to 100:1, or 1:1 to 10:1, or 5:1 to 50:1, or 50:1 to 250: 1, or 100:1 to 500: 1) and a mol ratio of metal in the catalyst to total comonomer is 1:1 to 1000:1 (or 1:1 to 250:1, or 1:1 to 50:1, or 1:1 to 10:1, or 10:1 to 100:1, or 50:1 to 250:1, or 100: 1 to 500: 1, or 250: 1 to 1000: 1); and wherein the second cyclic olefin comonomer has a higher reactivity with the metathesis catalyst than the first cyclic olefin comonomer. [0123] This invention also relates to a method comprising: contacting a first cyclic olefin comonomer (e.g., cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4- cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbomene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbornadiene, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, dimethyl norbomene carboxylate, norbomene-exo-2,3-carboxylic anhydride, and their respective homologs and derivatives, and substituted derivatives therefrom) with a metathesis catalyst to produce a reaction mixture; and adding a second cyclic olefin comonomer (e.g., cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbornene, norbomadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, cis-5-norbomene-endo-2,3-dicarboxylic anhydride, dimethyl norbornene carboxylate, norbornene-exo-2,3-carboxylic anhydride, and their respective homologs and derivatives, and substituted derivatives therefrom) to the reaction mixture over time at a rate of 0.01 mol% per minute to 25 mol% per minute (or 1 mol% per minute to 10 mol% per minute, or 0.01 mol% per minute to 1 mol% per minute, or 0.1 mol% per minute to 5 mol% per minute, or 5 mol% per minute to 25 mol% per minute) based on a total amount of the second cyclic olefin comonomer added to the reaction mixture to produce a polymer, wherein a final mol to mol ratio of first cyclic olefin comonomer to second cyclic olefin comonomer added to the reaction mixture is 1:1 to 500:1 (or 5:1 to 250:1, or 1:1 to 100:1, or 1:1 to 10:1, or 5:1 to 50:1, or 50:1 to 250: 1, or 100:1 to 500: 1) and a mol ratio of metal in the catalyst to total comonomer is 1:1 to 1000:1 (or 1:1 to 250:1, or 1:1 to 50:1, or 1:1 to 10:1, or 10:1 to 100:1, or 50:1 to 250:1, or 100: 1 to 500: 1, or 250: 1 to 1000: 1); and wherein the second cyclic olefin comonomer has a higher reactivity with the metathesis catalyst than the first cyclic olefin comonomer, and wherein the polymer has (a) a mol ratio of a first cyclic olefin comonomer-derived unit to a second cyclic olefin comonomer-derived unit of 3:1 to 100:1 (or 4:1 to 75:1, or 5:1 to 50:1, or 6:1 to 35:1) and (b) a ratio of cis to trans of 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 0:100) and one or more of: (c) a δ at a G* of 50 kPa of 30° to 60° (or 30° to 50°, or 30° to 40°), (d) a g'_vis of 0.5 to 0.91 (0.5 to 0.8, or 0.6 to 0.8, or 0.7 to 0.91), (e) a Mw 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), (f) a Mn 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), and (g) a MWD of 1 to 10 (or 1 to 5, or 2 to 4, or 1 to 3).

[0124] This invention also relates to a method comprising: contacting a first cyclic olefin comonomer (e.g., cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4- cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbornene, norbomadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbornadiene, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, dimethyl norbornene carboxylate, norbomene-exo-2,3-carboxylic anhydride, and their respective homologs and derivatives, and substituted derivatives therefrom) with a metathesis catalyst to produce a reaction mixture; and adding a second cyclic olefin comonomer (e.g., cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbornene, norbomadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, cis-5-norbomene-endo-2,3-dicarboxylic anhydride, dimethyl norbomene carboxylate, norbornene-exo-2,3-carboxylic anhydride, and their respective homologs and derivatives, and substituted derivatives therefrom) to the reaction mixture over time at a rate of 0.01 mol% per minute to 25 mol% per minute (or 1 mol% per minute to 10 mol% per minute, or 0.01 mol% per minute to 1 mol% per minute, or 0.1 mol% per minute to 5 mol% per minute, or 5 mol% per minute to 25 mol% per minute) based on a total amount of the second cyclic olefin comonomer added to the reaction mixture to produce a polymer, wherein a final mol to mol ratio of first cyclic olefin comonomer to second cyclic olefin comonomer added to the reaction mixture is 1:1 to 500:1 (or 5:1 to 250:1, or 1:1 to 100:1, or 1:1 to 10:1, or 5:1 to 50:1, or 50:1 to 250: 1, or 100:1 to 500: 1) and a mol ratio of metal in the catalyst to total comonomer is 1:1 to 1000:1 (or 1:1 to 250:1, or 1:1 to 50:1, or 1:1 to 10:1, or 10:1 to 100:1, or 50:1 to 250:1, or 100: 1 to 500: 1, or 250: 1 to 1000: 1); and wherein the second cyclic olefin comonomer has a higher reactivity with the metathesis catalyst than the first cyclic olefin comonomer, and wherein the polymer has (a) a mol ratio of a first cyclic olefin comonomer-derived unit to a second cyclic olefin comonomer-derived unit of 3:1 to 100:1 (or 4:1 to 75:1, or 5:1 to 50:1, or 6:1 to 35:1) and (b) a ratio of cis to trans of 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 0:100) and one or more of: (c) a δ at a G* of 50 kPa of 65° to 80° (or 70° to 80°, or 70° to 75°), (d) a g’_vis of 0-92 to 1.0 (0.92 to 0.95, or 0.95 to 0.99, or 0.95 to 1.0), (e) a Mw 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), (f) a Mn 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), and (g) a MWD of 1 to 10 (or 1 to 5, or 2 to 4, or 1 to 3).

[0125] This invention also relates to a method comprising: contacting a first cyclic olefin comonomer (e.g., cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4- cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbomene, norbomadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbornadiene, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, dimethyl norbomene carboxylate, norbomene-exo-2,3-carboxylic anhydride, and their respective homologs and derivatives, and substituted derivatives therefrom) with a metathesis catalyst to produce a reaction mixture; and adding a second cyclic olefin comonomer (e.g., cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbomene, norbomadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, cis-5-norbomene-endo-2,3-dicarboxylic anhydride, dimethyl norbomene carboxylate, norbornene-exo-2,3-carboxylic anhydride, and their respective homologs and derivatives, and substituted derivatives therefrom) to the reaction mixture over time at a rate of 0.01 mol% per minute to 25 mol% per minute (or 1 mol% per minute to 10 mol% per minute, or 0.01 mol% per minute to 1 mol% per minute, or 0.1 mol% per minute to 5 mol% per minute, or 5 mol% per minute to 25 mol% per minute) based on a total amount of the second cyclic olefin comonomer added to the reaction mixture to produce a polymer, wherein a final mol to mol ratio of first cyclic olefin comonomer to second cyclic olefin comonomer added to the reaction mixture is 1:1 to 500:1 (or 5:1 to 250:1, or 1:1 to 100:1, or 1:1 to 10:1, or 5:1 to 50:1, or 50:1 to 250: 1, or 100:1 to 500: 1) and a mol ratio of metal in the catalyst to total comonomer is 1:1 to 1000:1 (or 1:1 to 250:1, or 1:1 to 50:1, or 1:1 to 10:1, or 10:1 to 100:1, or 50:1 to 250:1, or 100: 1 to 500: 1, or 250: 1 to 1000: 1); and wherein the second cyclic olefin comonomer has a higher reactivity with the metathesis catalyst than the first cyclic olefin comonomer, and wherein the polymer has (a) a δ at a G* of 50 kPa of 30° to 60° (or 30° to 50°, or 30° to 40°) and/or (b) a g’_vis of 0-5 to 0.91 (0.5 to 0.8, or 0.6 to 0.8, or 0.7 to 0.91) and one or more of: (c) a mol 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), (d) a ratio of cis to trans of 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 for both comonomer entities), (e) a Mw 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), (f) a Mn 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), and (g) a MWD of 1 to 10 (or 1 to 5, or 2 to 4, or 1 to 3).

[0126] This invention also relates to a method comprising: contacting a first cyclic olefin comonomer (e.g., cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4- cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbomene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbornadiene, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, dimethyl norbomene carboxylate, norbomene-exo-2,3-carboxylic anhydride, and their respective homologs and derivatives, and substituted derivatives therefrom) with a metathesis catalyst to produce a reaction mixture; and adding a second cyclic olefin comonomer (e.g., cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbomene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, cis-5-norbomene-endo-2,3-dicarboxylic anhydride, dimethyl norbomene carboxylate, norbornene-exo-2,3-carboxylic anhydride, and their respective homologs and derivatives, and substituted derivatives therefrom) to the reaction mixture over time at a rate of 0.01 mol% per minute to 25 mol% per minute (or 1 mol% per minute to 10 mol% per minute, or 0.01 mol% per minute to 1 mol% per minute, or 0.1 mol% per minute to 5 mol% per minute, or 5 mol% per minute to 25 mol% per minute) based on a total amount of the second cyclic olefin comonomer added to the reaction mixture to produce a polymer, wherein a final mol to mol ratio of first cyclic olefin comonomer to second cyclic olefin comonomer added to the reaction mixture is 1:1 to 500:1 (or 5:1 to 250:1, or 1:1 to 100:1, or 1:1 to 10:1, or 5:1 to 50:1, or 50:1 to 250: 1, or 100:1 to 500: 1) and a mol ratio of metal in the catalyst to total comonomer is 1:1 to 1000:1 (or 1:1 to 250:1, or 1:1 to 50:1, or 1:1 to 10:1, or 10:1 to 100:1, or 50:1 to 250:1, or 100: 1 to 500: 1, or 250: 1 to 1000: 1); and wherein the second cyclic olefin comonomer has a higher reactivity with the metathesis catalyst than the first cyclic olefin comonomer, and wherein the polymer has (a) a d at a G* of 50 kPa of 65° to 80° (or 70° to 80°, or 70° to 75°) and/or (b) a g’_vis of 0-92 to 1.0 (0.92 to 0.95, or 0.95 to 0.99, or 0.95 to 1.0) and one or more of: (c) a mol 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), (d) a ratio of cis to trans of 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 for both comonomer entities), (e) a M_w 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), (f) a Mn 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), and (g) a MWD of 1 to 10 (or 1 to 5, or 2 to 4, or 1 to 3).

[0127] This invention also relates to Embodiment A1, which is a method comprising: contacting a first cyclic olefin comonomer with a metathesis catalyst to produce a reaction mixture; and adding a second cyclic olefin comonomer to the reaction mixture over time at a rate of 0.01 mol% per minute to 25 mol% per minute based on a total amount of the second cyclic olefin comonomer added to the reaction mixture to produce a polymer, wherein a final mol to mol ratio of first cyclic olefin comonomer to second cyclic olefin comonomer added to the reaction mixture is 1:1 to 500:1; and wherein the second cyclic olefin comonomer has a higher reactivity with the metathesis catalyst than the first cyclic olefin comonomer.

[0128] This invention also relates to Embodiment A2, which is the method of Embodiment Al and wherein the polymer has a g’_vis of 0-5 to 0.91 (0.5 to 0.8, or 0.6 to 0.8, or 0.7 to 0.91). [0129] This invention also relates to Embodiment A3, which is the method of Embodiment A1 or A2 and wherein the polymer has a d at a G* of 50 kPa of 30° to 60° (or 30° to 50°, or 30° to 40°).

[0130] This invention also relates to Embodiment A4, which is the method of Embodiment A1 and wherein the polymer has a g’_vis of 0.92 to 1.0 (0.92 to 0.95, or 0.95 to 0.99, or 0.95 to 1.0).

[0131] This invention also relates to Embodiment A5, which is the method of Embodiment A1 or A4 and wherein the polymer has a δ at a G* of 65° to 80° (or 70° to 80°, or 70° to 75°). [0132] This invention also relates to Embodiment A6, which is the method of Embodiment A1 or A2 or A3 or A4 or A5 and wherein contacting the first cyclic olefin comonomer with the metathesis catalyst is in the presence of an activator.

[0133] This invention also relates to Embodiment A7, which is the method of Embodiment A1 or A2 or A3 or A4 or A5 or A6 and wherein the reaction mixture further comprises a diluent at 60 vol% or less based on a total volume of the reaction mixture.

[0134] This invention also relates to Embodiment A8, which is the method of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7 and wherein the method further comprises: reacting the first cyclic olefin comonomer with the metathesis catalyst in the reaction mixture for 1 second to 15 minutes before adding the second cyclic olefin comonomer.

[0135] This invention also relates to Embodiment A9, which is the method of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7 or A8 and wherein adding the second cyclic olefin comonomer to the reaction mixture over time is in batches over time.

[0136] This invention also relates to Embodiment A10, which is the method of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7 or A8 and wherein adding the second cyclic olefin comonomer to the reaction mixture over time is continuous over time.

[0137] This invention also relates to Embodiment All, which is the method of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7 or A8 or A9 or A10 and wherein the method further comprises: quenching the reaction mixture after adding the total amount of the second cyclic olefin comonomer to the reaction mixture and optionally wherein quenching is 1 minute to 5 hours after adding the total amount of the second cyclic olefin comonomer to the reaction mixture.

[0138] This invention also relates to Embodiment A12, which is the method of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7 or A8 or A9 or A10 or A11 and wherein the polymer has a mol ratio of first cyclic olefin comonomer-derived units to second cyclic olefin comonomer-derived units of 3:1 to 100:1. [0139] This invention also relates to Embodiment A13, which is the method of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7 or A8 or A9 or A10 or A11 or A12 and wherein the polymer has a ratio of cis to trans of 50:50 to 5:95.

[0140] This invention also relates to Embodiment A14, which is the method of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7 or A8 or A9 or A10 or A11 or A12 or A13 and wherein the polymer has a weight average molecular weight of 1 kDa to 1,000 kDa. [0141] This invention also relates to Embodiment A15, which is the method of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7 or A8 or A9 or A10 or A11 or A12 or A13 or A14 and wherein the polymer has a molecular weight distribution of 1 to 10.

[0142] This invention also relates to Embodiment B 1, which a polymer comprising: a mol ratio of a first cyclic olefin comonomer-derived unit to a second cyclic olefin comonomer- derived unit of 3:1 to 100:1 and having a ratio of cis to trans of 50:50 to 5:95.

[0143] This invention also relates to Embodiment B2, which is the method of Embodiment B1 and wherein the polymer has a g’_vis of 0-50 to 0.91.

[0144] This invention also relates to Embodiment B3, which is the method of Embodiment B1 or B2 and wherein the polymer has a d at a G* of 50 kPa of 30° to 60°.

[0145] This invention also relates to Embodiment B4, which is the method of Embodiment B1 or B2 or B3 and wherein the first and second olefin comonomer-derived units are different and each selected from the group consisting of: cyclooctene, 1,5-cyclooctadiene, 1-hydroxy- 4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbomene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbomadiene, cis-5-norbomene-endo-2,3- dicarboxylic anhydride, dimethyl norbomene carboxylate, and norbornene-exo-2,3-carboxylic anhydride.

[0146] This invention also relates to Embodiment B5, which is the method of Embodiment B1 or B2 or B3 or B4 or and wherein the ratio of the first cyclic olefin comonomer-derived unit to the second cyclic olefin comonomer-derived unit is 5:1 to 50:1.

[0147] This invention also relates to Embodiment B6, which is the method of Embodiment B1 or B 2 or B 3 or B 4 or B 5 and wherein the polymer has a weight average molecular weight of 1 kDa to 1,000 kDa.

[0148] This invention also relates to Embodiment B7, which is the method of Embodiment B 1 or B2 or B3 or B4 or B5 or B6 and wherein the polymer has a molecular weight distribution of 1 to 10. [0149] This invention also relates to Embodiment Cl, which a polymer comprising: a mol ratio of a first cyclic olefin comonomer-derived unit to a second cyclic olefin comonomer- derived unit of 3:1 to 100:1 and having (a) a g’_vis of 0-50 to 0.91 and/or a d at a G* of 50 kPa of 30° to 60°.

[0150] This invention also relates to Embodiment C2, which is the method of Embodiment Cl and wherein the first and second olefin comonomer-derived units are different and each selected from the group consisting of: cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4- cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbomene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbomadiene, cis-5-norbomene-endo-2,3- dicarboxylic anhydride, dimethyl norbomene carboxylate, and norbornene-exo-2,3-carboxylic anhydride.

[0151] This invention also relates to Embodiment C3, which is the method of Embodiment C1 or C2 and wherein the polymer has a weight average molecular weight of 1 kDa to 1,000 kDa.

[0152] This invention also relates to Embodiment C4, which is the method of Embodiment Cl or C2 or C3 and wherein the polymer has a molecular weight distribution of 1 to 10.

[0153] To facilitate a better understanding of the embodiments of the present invention, the following examples of preferred or representative embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the invention.

EXAMPLES

[0154] The following abbreviations are used herein: DCPD is dicyclopentadiene; NBE is norbomene; BHT is butylated hydroxy toluene; Me is methyl; cC5 is cyclopentene; and Ph is phenyl.

[0155] Commercial cyclopentene was purified by passing through the column with activated basic alumina. DCPD was dissolved in toluene at a volume ratio of 1:1, and the resulting solution was passed through activated basic alumina column. NBE was purified and used in the same fashion.

[0156] Linear homopolymer. A linear homopolymer used as a comparison sample below was produced as follows. The catalyst was formed in situ by adding solid (p-MeC₆H₄O)₂AlCl (0.757 mmol) to a solution of WCl₆ (0.378 mmol) in toluene (20 mL). After stirring for 1 hour, the resulting mixture was added to the solution of cyclopentene (103 g, 1.513 mol) and triethylaluminum (86 mg, 0.757 mmol) in toluene (400 mL) at 20°C. After 3 hours of intense mechanical stirring, a solution of BHT (4.48 mmol) in 100 mL of ethanol/toluene mixture (1:4, v:v, respectively) was added. The obtained mixture was poured into ethanol (1 L). The precipitated polymer was then washed 3 times with ethanol (250 mL each) and dried under the stream of nitrogen over 72 hours to give 16.0 g of the product. [0157] Eight samples of cC5/DCPD copolymers and one sample of cC5/NBE copolymer were prepared as follows according to the in situ catalyst synthesis and polymerization scheme presented in FIG. 3. In situ generated catalysts were (4-MeC₆H₄O)₄W=CHMe or (4-(PhCH₂)C₆H₄O)₄W=CHMe. [0158] Sample 1. The catalyst was formed in situ by adding solid (p-MeC₆H₄O)₂AlCl (2.02 mmol) to a solution of WCl₆ (1.01 mmol) in toluene (20 mL). After stirring for one hour at ambient conditions, the resulting mixture was added to a solution containing cyclopentene (first comonomer) (1.513 mol), triethylaluminum (activator) (2.02 mmol), and toluene (600 mL) at 0°C. A solution of DCPD (second comonomer) (10 mmol) in toluene (100 mL) was added dropwise to the reaction mixture over 20 minutes under intense mechanical stirring. After an additional 5 minutes, a solution of BHT (4.48 mmol) in 100 mL of ethanol/toluene mixture (1:4, v:v, respectively) was added. The obtained mixture was poured into ethanol (1 L). The precipitated polymer was then washed 3 times with ethanol (200 mL each) and dried under the stream of nitrogen over 16 hours to give 19.4 g of the product. [0159] Sample 2. The catalyst was formed in situ by adding solid (p-MeC₆H₄O)₂AlCl (2.02 mmol) to a solution of WCl6 (1.01 mmol) in toluene (20 mL). After stirring for one hour at ambient conditions, the resulting mixture was added to a solution containing cyclopentene (first comonomer) (2.02 mol), triethylaluminum (activator) (2.02 mmol), and toluene (700 mL) at 0°C. A solution of DCPD (second comonomer) (10 mmol) in toluene (100 mL) was added dropwise to the reaction mixture over 50 minutes under intense mechanical stirring. After an additional 5 minutes, a solution of BHT (2.02 mmol) in 100 mL of ethanol/toluene mixture (1:4, v:v, respectively) was added. The obtained mixture was added to ethanol (1 L). The precipitated polymer was washed 3 times with ethanol (200 mL each) and dried under the stream of nitrogen over 16 hours to give 24.0 g of the product. [0160] Sample 3. The catalyst was formed in situ by adding solid (p-MeC₆H₄O)₂AlCl (1.01 mmol) to a solution of WCl₆ (0.505 mmol) in toluene (20 mL). After stirring for one hour at ambient conditions, the resulting mixture was added to a solution containing cyclopentene (first comonomer) (0.757 mol), triethylaluminum (activator) (1.01 mmol), and toluene (500 mL) at 0°C. A solution of DCPD (second comonomer) (0.11 mol) in toluene (15 mL) was added dropwise to the reaction mixture over 15 minutes under intense mechanical stirring. After an additional 5 minutes, a solution of BHT (4.48 mmol) in 100 mL of ethanol/toluene mixture (1:4, v:v, respectively) was added. The obtained mixture was added to ethanol (1 L). The precipitated polymer was washed 3 times with ethanol (500 mL each) and dried under vacuum at 50°C for 4 hours to give 29.44 g of the product.

[0161] Sample 4. The catalyst was formed in situ by adding solid (p-MeC₆H₄O)₂AlCl (2.02 mmol) to a solution of WCl₆ (1.01 mmol) in toluene (20 mL). After stirring for one hour at ambient conditions, the resulting mixture was added to a solution containing cyclopentene (first comonomer) (2.02 mol), triethylaluminum (activator) (2.02 mmol), and toluene (700 mL) at 0°C. A solution of DCPD (second comonomer) (6 mmol) in toluene (15 mL) was added dropwise to the reaction mixture over 50 minutes under intense mechanical stirring. After an additional 5 minutes, a solution of BHT (2.02 mmol) in 100 mL of ethanol/toluene mixture (1:4, v:v, respectively) was added. The obtained mixture was added to ethanol (1 L). The precipitated polymer was washed 3 times with ethanol (500 mL each) and dried under vacuum at 50°C for 4 hours to give 24 g of the product.

[0162] Sample 5. The catalyst was formed in situ by adding solid (4-(PhCH₂)C₆H₄O)₂AlCl (2.02 mmol) to a solution of WCl₆ (1.01 mmol) in toluene (20 mL). After stirring for one hour at ambient conditions, the resulting mixture was added to a solution containing cyclopentene (first comonomer) (4.035 mol), triethylaluminum (activator) (2.02 mmol), and toluene (1,200 mL) at 0°C. A solution of DCPD (second comonomer) (27.3 mmol) in toluene (15 mL) was slowly added to the reaction mixture over 35 minutes under intense mechanical stirring. After an additional 20 minutes, a solution of BHT (9.0 mmol) in 100 mL of ethanol/toluene mixture (1:4, v:v, respectively) was added. The obtained mixture was added to ethanol (1 L). The precipitated polymer was washed 3 times with ethanol (500 mL each) and dried under vacuum at 55°C for 4 hours to give 98 g of the product.

[0163] Sample 6. In contrast to Sample 5, both monomers were combined together before adding the catalyst. The catalyst was formed in situ by adding solid (4-(PhCH₂)C₆H₄O)₂AlCl (2.02 mmol) to a solution of WCl₆ (1.01 mmol) in toluene (20 mL). After stirring for one hour at ambient conditions, the resulting mixture was added to a solution containing cyclopentene (first comonomer) (4.035 mol), DCPD (second comonomer) (27.3 mmol, triethylaluminum (activator) (2.02 mmol), and toluene (1,200 mL) at 0°C. After 1 hour, a solution of BHT (9.0 mmol) in 100 mL of ethanol/toluene mixture (1:4, v:v, respectively) was added. The obtained mixture was added to ethanol (1.5 L). The precipitated polymer was washed 3 times with ethanol (500 mL each) and dried under vacuum at 55°C for 4 hours to give 77 g of the product. [0164] Sample 7. The catalyst was formed in situ by adding solid (4-(PhCH₂)C₆H₄O)₂AlCl (2.02 mmol) to a solution of WCl₆ (1.01 mmol) in toluene (20 mL). After stirring for one hour at ambient conditions, the resulting mixture was added to a solution containing cyclopentene (first comonomer) (4.035 mol), triethylaluminum (activator) (2.02 mmol), and toluene (2,200 mL) at 0°C. A solution of DCPD (second comonomer) (27.3 mmol) in toluene (15 mL) was slowly added to the reaction mixture over 60 minutes under intense mechanical stirring. After an additional 2 hours, a solution of BHT (4.48 mmol) in 100 mL of ethanol/toluene mixture (1:4, v:v, respectively) was added. The obtained mixture was added to methanol (4 L). The precipitated polymer was washed 3 times with methanol (500 mL each) and dried under vacuum at 55°C for 4 hours to give 139 g of the product.

[0165] Sample 8. The catalyst was formed in situ by adding solid (4-(PhCH₂)C₆H₄O)₂AlCl (1.26 mmol) to a solution of WCl₆ (0.63 mmol) in toluene (20 mL). After stirring for one hour at ambient conditions, the resulting mixture was added to a solution containing cyclopentene (first comonomer) (1.26 mol), triethylaluminum (activator) (1.26 mmol), and toluene (1,500 mL) at 0°C. A solution of DCPD (second comonomer) (13 mmol) in toluene (15 mL) was slowly added to the reaction mixture over 60 minutes under intense mechanical stirring. After an additional 16 hours, a solution of BHT (4.48 mmol) in 100 mL of ethanol/toluene mixture (1:4, v:v, respectively) was added. The obtained mixture was added to methanol (4 L). The precipitated polymer was washed 3 times with methanol (500 mL each) and dried under vacuum at 55°C for 4 hours to give 42 g of the product.

[0166] Sample 9. The catalyst was formed in situ by adding solid (4-(PhCH₂)C₆H₄O)₂AlCl (1.26 mmol) to a solution of WCl₆ (0.63 mmol) in toluene (20 mL). After stirring for one hour at ambient conditions, the resulting mixture was added to a solution containing cyclopentene (first comonomer) (1.261 mol), triethylaluminum (activator) (1.261 mmol), and toluene (900 mL) at 0°C. A solution of NBE (second comonomer) (7.22 mmol) in toluene (15 mL) was slowly added to the reaction mixture over 20 minutes under intense mechanical stirring. After an additional 2 hours, a solution of BHT (4.48 mmol) in 100 mL of ethanol/toluene mixture (1:4, v:v, respectively) was added. The obtained mixture was added to methanol (3 L). The precipitated polymer was washed 3 times with methanol (200 mL each) and dried under vacuum at 50°C for 4 hours to give 36.1 g of the product.

[0167] The foregoing reactions and results of the foregoing reactions are summarized in Table 1. The properties of said example as compared to the linear cyclopentene homopolymer are provided in Table 2. The ratio of the cyclopentene-derived unit and the DCPD-derived unit as well as the ratio of cis to trans were determined by ¹³C NMR. The molecular weight characteristics were determined by GPC.

Table 1

Table 2

[0168] Long chain branching can be qualitatively determined by the rheological response of the samples. FIG. 4 shows small amplitude oscillatory (SAOS) data for the linear cyclopentene homopolymer, a LCB cC5/DCPD copolymer (Sample 7), and a linear cC5/DCPD copolymer (Sample 9). The difference in rheological response is due to a difference in chain topology. Specifically, the branched sample shows improved shear thinning and higher melt strength, compared to the two linear polymers.

[0169] FIG. 5 is the van Gurp Palmen plots for the linear homopolymer, a LCB cC5/DCPD copolymer (Sample 7), and a linear cC5/DCPD copolymer (Sample 9). Sample 7 shows the typical depression of the phase angle (delta) characteristic of LCB polymers, whereas the linear cyclopentene homopolymer and Sample 9 show the typical monotonic dependence of the complex modulus with phase angle.

[0170] Additionally, LCB is confirmed by the low temperature GPC 4D data shown in FIGS. 4A-4C. The typical depression of the g’ value in the high molecular fractions indicates the presence of LCB in Sample 7 (FIG. 6B), whereas the nearly constant g’ value of ~1 is indicative of the absence of LCB, the linear cyclopentene homopolymer (FIG. 6A) and Sample 9 (FIG. 6C). Table 3. LCB quantification

[0171] The slower addition rate of DCPD (the more reactive comonomer) yields a lower concentration of DCPD in the resultant polymer. Slower addition and higher cC5 :DCPD ratios yield higher concentrations of cC5 in the resultant polymer as seen in samples 1 and 2 with 97 mol% cC5. Given that cC5 has a reactivity under these conditions and catalyst of at least 10 times slower, illustrates that the methods described herein provide a straightforward and robust ROMP synthesis for tailoring polymer compositions including high incorporation of the less reactive comonomer. [0172] Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered, combined, or modified and all such variations are considered within the scope and spirit of the present invention. The invention illustratively disclosed herein suitably may be practiced in the absence of any element that is not specifically disclosed herein and/or any optional element disclosed herein. While compositions and methods are described in terms of “comprising,” “containing,” "having," or “including” various components or steps, the compositions and methods can also “consist essentially of’ or “consist of’ the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. Moreover, the indefinite articles “a” or “an,” as used in the claims, are defined herein to mean one or more than one of the element that it introduces.

Claims

CLAIMS The invention claimed is:

1. A method comprising: contacting a first cyclic olefin comonomer with a metathesis catalyst to produce a reaction mixture; and adding a second cyclic olefin comonomer to the reaction mixture over time at a rate of 0.01 mol% per minute to 25 mol% per minute based on a total amount of the second cyclic olefin comonomer added to the reaction mixture to produce a polymer, wherein a final mol to mol ratio of first cyclic olefin comonomer to second cyclic olefin comonomer added to the reaction mixture is 1:1 to 500:1; and wherein the second cyclic olefin comonomer has a higher reactivity with the metathesis catalyst than the first cyclic olefin comonomer.

2. The method of claim 1, wherein the polymer has a g’_vis of 0-50 to 0.91.

3. The method of any preceding claim, wherein the polymer has a d at a G* of 50 kPa of 30° to 60°.

4. The method of any preceding claim, wherein contacting the first cyclic olefin comonomer with the metathesis catalyst is in the presence of an activator.

5. The method of any preceding claim, wherein the reaction mixture further comprises a diluent at 60 vol% or less based on a total volume of the reaction mixture.

6. The method of any preceding claim further comprising: reacting the first cyclic olefin comonomer with the metathesis catalyst in the reaction mixture for 1 second to 15 minutes before adding the second cyclic olefin comonomer.

7. The method of any preceding claim, wherein adding the second cyclic olefin comonomer to the reaction mixture over time is in batches over time.

8. The method of one of claims 1-4, wherein adding the second cyclic olefin comonomer to the reaction mixture over time is continuous over time.

9. The method of any preceding claim further comprising: quenching the reaction mixture after adding the total amount of the second cyclic olefin comonomer to the reaction mixture.

10. The method of claim 9, wherein quenching is 1 minute to 5 hours after adding the total amount of the second cyclic olefin comonomer to the reaction mixture.

11. The method of any preceding claim, wherein the polymer has a mol ratio of first cyclic olefin comonomer-derived units to second cyclic olefin comonomer-derived units of 3:1 to 100:1.

12. The method of any preceding claim, wherein the polymer has a ratio of cis to (runs of 50:50 to 5:95.

13. The method of any preceding claim, wherein the polymer has a weight average molecular weight of 1 kDa to 1,000 kDa.

14. The method of any preceding claim, wherein the polymer has a molecular weight distribution of 1 to 10.

15. A polymer comprising: a mol ratio of a first cyclic olefin comonomer-derived unit to a second cyclic olefin comonomer-derived unit of 3:1 to 100:1 and having a ratio of cis to trans of 50:50 to 5:95.

16. The polymer of claim 15, wherein the polymer has a g’_vis of 0-50 to 0.91.

17. The polymer of any one of claims 15-16, wherein the polymer has a d at a G* of 50 kPa of 30° to 60°.

18. The polymer of any one of claims 15-17, wherein the first and second olefin comonomer-derived units are different and each selected from the group consisting of: cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbomene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, cis-5-norbornene-endo-2,3-dicarboxylic anhydride, dimethyl norbomene carboxylate, and norbornene-exo-2,3-carboxylic anhydride.

19. The polymer of any one of claims 15-18, wherein the ratio of the first cyclic olefin comonomer-derived unit to the second cyclic olefin comonomer-derived unit is 5:1 to 50:1.

20. The polymer of any one of claims 15-19, wherein the ratio of the ratio of cis to (runs is 20:80 to 5:95.

21. The polymer of any one of claims 15-20, wherein the polymer has a weight average molecular weight of 1 kDa to 1,000 kDa.

22. The polymer of any one of claims 15-21, wherein the polymer has a molecular weight distribution of 1 to 10.

23. A polymer comprising: a mol ratio of a first cyclic olefin comonomer-derived unit to a second cyclic olefin comonomer-derived unit of 3:1 to 100:1 and having (a) a g’_vis of 0-50 to 0.91 and/or a δ at a G* of 50 kPa of 30° to 60°.

24. The polymer of claim 23, wherein the first and second olefin comonomer-derived units are different and each selected from the group consisting of: cyclooctene, 1,5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, dicyclopentadiene (DCPD), cyclopentene (cC5), norbomene, norbornadiene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbomadiene, cis-5-norbomene- endo-2,3-dicarboxylic anhydride, dimethyl norbomene carboxylate, and norbornene-exo-2,3- carboxylic anhydride.

25. The polymer of any one of claims 23-24, wherein the polymer has a weight average molecular weight of 1 kDa to 1,000 kDa.

26. The polymer of any one of claims 23-25, wherein the polymer has a molecular weight distribution of 1 to 10.