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WO2021113503A1 - Polymères préparés par polymérisation par métathèse par ouverture de cycle - Google Patents

Polymères préparés par polymérisation par métathèse par ouverture de cycle Download PDF

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Publication number
WO2021113503A1
WO2021113503A1 PCT/US2020/063095 US2020063095W WO2021113503A1 WO 2021113503 A1 WO2021113503 A1 WO 2021113503A1 US 2020063095 W US2020063095 W US 2020063095W WO 2021113503 A1 WO2021113503 A1 WO 2021113503A1
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cyclic olefin
olefin comonomer
polymer
kda
reaction mixture
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Inventor
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
Shuhui Kang
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ExxonMobil Chemical Patents Inc
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/122—Copolymers statistical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/13—Morphological aspects
    • C08G2261/132—Morphological aspects branched or hyperbranched
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3321—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from cyclopentene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3324—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from norbornene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/33—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain
    • C08G2261/332—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms
    • C08G2261/3325—Monomer units or repeat units incorporating structural elements in the main chain incorporating non-aromatic structural elements in the main chain containing only carbon atoms derived from other polycyclic systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/76—Post-treatment crosslinking

Definitions

  • the present disclosure relates to ring-opening metathesis polymerization.
  • 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 involves the formation of unsaturated polymers from the ring opening of one, two, or more cyclic olefin comonomers.
  • 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.
  • 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.
  • the properties of the resultant polymer 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.
  • 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.
  • 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.
  • ROMP ring-opening metathesis polymerization
  • 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.
  • 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.
  • This invention also relates to a polymer having (a) a ⁇ at a G* of 50 kPa of 30° to 60° and/or (b) a g’ vis of 0.50 to 0.91.
  • FIGURE 1 is a copolymer with 13 C NMR assignments for determining the DCPD cis/trans ratio.
  • FIGURE 2 (FIG. 2) is a copolymer with 1 H NMR assignments for determining the mol% NBE.
  • FIGURE 3 (FIG. 3) is an in situ catalyst synthesis and polymerization scheme.
  • FIGURE 4 is small amplitude oscillatory (SAOS) data for a linear homopolymer, a long chain branching cyclopentene/dicyclopentadiene copolymer, and a linear cyclopentene/dicyclopentadiene copolymer.
  • SAOS small amplitude oscillatory
  • FIGURE 5 is a van Gurp Palmen plot for a linear homopolymer, a long chain branching cyclopentene/dicyclopentadiene copolymer, and a linear cyclopentene/dicyclopentadiene copolymer.
  • FIGURE 6A is 4-detector gel permeation chromatography (GPC 4D) data for a linear homopolymer.
  • FIGURE 6B is GPC 4D data for a long chain branching cyclopentadiene/dicyclopentadiene copolymer.
  • FIGURE 6C is GPC 4D data for a linear cyclopentadiene/dicyclopentadiene copolymer.
  • 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.
  • 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.
  • the present disclosure also relates to the polymers resulting from the foregoing methods.
  • 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.
  • LCB long chain branching
  • room temperature is 25 °C.
  • DCPD is dicyclopentadiene.
  • an “olefin,” alternatively referred to as “alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond.
  • 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.
  • the term “copolymer(s)” refers to polymers formed by the polymerization of at least two different monomers (i.e., mer units).
  • 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.
  • 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.
  • “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.
  • 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%
  • 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.
  • the mol ratio of first cyclic olefin comonomer-derived units to second cyclic olefin comonomer-derived units is determined using 1 H 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.
  • the ratio of cis to trans in a polymer is determined by 13 C 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.
  • 1-ethyl-3,4-dimethylpyrrolidine-2,5-dione has cis carbon atoms with a 13 C chemical shift of about 12.9 ppm for trans carbons and a 13 C 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.
  • 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 (CDCl 3 ) solvent to prepare a solution with a concentration of 30 mg/mL for 1 H NMR and 67 mg/mL for 13 C NMR.
  • 1 H NMR was recorded using a 30° flip angle RF pulse, 512 transients, with a delay of 5 seconds between pulses.
  • 13 C NMR was recorded using a 90° pulse, inverse gated decoupling, a 60 second delay, and 512 transients.
  • cC5 cis/trans ratio was determined from 13 C 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.
  • M n is the number average molecular weight
  • M w is the weight average molecular weight
  • M z is the z average molecular weight.
  • 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”).
  • LS 18-angle light scattering
  • DRI differential refractive index detector
  • THF tetrahydrofuran
  • BHT butylated hydroxytoluene
  • 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.
  • PS monodispersed polystyrene
  • LS molecular weight, M was determined by analyzing the LS output using the Zimm model for static light scattering and determined using the following equation:
  • ⁇ R( ⁇ ) is the measured excess Rayleigh scattering intensity at scattering angle ⁇
  • c is the polymer concentration determined from the DRI analysis
  • a 2 is the second virial coefficient
  • P( ⁇ ) is the form factor for a mono-disperse random coil
  • the dn/dc is measured as 0.1154 by DRI detector.
  • a four capillaries viscometer with a Wheatstone bridge configuration was used to determine the intrinsic viscosity [ ⁇ ] from the measured specific viscosity ( ⁇ S ) and the concentration “C”.
  • ⁇ s C[ ⁇ ] + 0.3(C[ ⁇ ]) 2 .
  • the average intrinsic viscosity, [ ⁇ ] avg , of the sample was calculated using the following equation: where the summations are over the chromatographic slices, i, between the integration limits.
  • 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 ⁇ and k used for the reference linear polymer are 0.725 and 0.000291, respectively.
  • All the concentration is expressed in g/cm 3
  • molecular weight is expressed in g/mol
  • intrinsic viscosity is expressed in dL/g unless otherwise noted.
  • SAOS small amplitude oscillatory shear
  • An indication of high levels of branched structure is a high value of ⁇ 5 , corresponding to the relaxation time of 100 sec, relative to the zero shear viscosity.
  • the viscosity fraction of the 100 sec relaxation time is ⁇ 5 divided by the zero shear viscosity, ⁇ 0 .
  • Chains with long relaxation times cannot relax during the cycle time of the SAOS experiment and lead to high zero shear viscosities.
  • 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.
  • This ratio is the typical output of the SAOS experiments.
  • a dynamic mechanical spectrometer such as the Advanced Rheometrics Expansion System (ARES).
  • a high degree of shear thinning indicates a polymer is readily processable in high shear fabrication processes, for example, by injection molding.
  • 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 ( ⁇ ), and the complex viscosity ( ⁇ *) were measured as the frequency is varied from 0.001 to 628 rad/s.
  • the phase or loss angle ⁇ is the inverse tangent of the ratio of G′′ (the shear loss modulus) to G′ (the shear storage modulus).
  • G′′ the shear loss modulus
  • G′ the shear storage modulus
  • DST degree of shear thinning
  • the complex modulus (G*) is equal to [(G') 2 + (G'') 2 ] 1/2 .
  • the plot of phase angle ( ⁇ ) 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 ⁇ listed in the various tables of this invention are those at a G* of 50 kPa. The lower this ⁇ , the higher is the melt elasticity or melt strength.
  • compositions and Methods 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
  • k 2 k 1 *(2 or greater)
  • 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.
  • 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.
  • 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).
  • a time period e.g. 1 second to 15 minutes, or 5 seconds to 10 minutes, or 30 seconds to 5 minutes.
  • Addition of the second cyclic olefin comonomer to the reaction mixture can be over time in any suitable method.
  • 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).
  • the second cyclic olefin comonomer can be added to the reaction mixture continuously over time.
  • a combination of the foregoing may be used.
  • 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.
  • 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.
  • 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.
  • time period e.g. 1 minute to 5 hours, or 1 minute to 1 hour, or 1 minute to 30 minutes
  • 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.
  • 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.
  • 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.
  • the temperature of the reaction may be -50°C to 200°C, or -25°C to 100°C, or -10°C to 25°C.
  • 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.
  • 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.
  • 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.
  • 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.
  • Catalysts suitable for use in conjunction with the methods described herein are any catalysts capable of performing ROMP.
  • the catalyst is a tungsten or ruthenium metal complex-based metathesis catalyst.
  • 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 C 1 to C 8 alkyl
  • each R* is independently H or a C 1 to C 7 alkyl
  • each Z is independently halide or a C 1 to C 8 alkyl radical.
  • 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’) 2 X), 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 .
  • R’ is independently a monovalent hydrocarbyl comprising from 1 to 20 atoms selected from Groups 14, 15, and 16 of the periodic table
  • X is halogen .
  • 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) c M 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.
  • 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 u R a X (u-a) ⁇ M u (OR’) a X (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 C 1 to C 8 alkyl.
  • 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-GD 2 ):
  • 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 C 1 -
  • the reaction mixture further comprises a metal alkyl activator (A) according to the formula M u R a X (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.
  • M v is W, Mo, Nb, or Ta.
  • two or more R’O- ligands are connected to form a single bidentate chelating moiety.
  • 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’) m Y (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 C 1 to C 8 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
  • 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 C 1 to C 8 alkyl; each R* is independently hydrogen or C 1 to C 7 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.
  • the alkyl aluminum compound (II) is a dialkyl aluminum halide (VI)
  • the aluminum precatalyst is a di-halo tetrakis alkoxide aluminum dimer (VII) according to the general formula: ;
  • a molar ratio of M v to M u -R in metal alkyl activator M u R a X (u-a) is from 1 to 2 to 1 to 15.
  • the alkoxy ligand R’O- comprises a C 7 to C 20 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:
  • R 1 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
  • R 2 through R 9 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 R 2 through R 9 join together for form a ring having 40 or less atoms from Groups 14, 15, and/or 16 of the periodic table.
  • 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:
  • 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]
  • 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 R 1 is a direct bond between the two rings or
  • 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:
  • 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:
  • 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 al
  • 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; R 1 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 R 2 through R 14 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 R 2 through R 9 and/or two or more of R 10 through R 14 join together to form a ring comprising 40 atoms or less from Groups 14, 15, and 16 of the periodic table.
  • 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
  • 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- GD 2 ): wherein M u is a Group 1, 2,
  • ethers e.g.,
  • catalysts suitable for use in conjunction with the methods described herein may include, but are not limited to:
  • X and X 1 are, independently, any anionic ligand, preferably a halogen (preferably chlorine), an alkoxide or a triflate, 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 and L 1 are, independently, a neutral two electron donor, preferably a phosphine or a N-heterocyclic carbene, L and L 1 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;
  • L 1 and X 1 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;
  • R 1 and R 2 may be different or the same and may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl; and/or
  • 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 C 1 to C 30 hydrocarbyl or substituted hydrocarbyl, preferably methyl, ethyl, propyl or butyl
  • R * is hydrogen or a C 1 to C 30 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 C 1 to C 30 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 C 1 to C 30 hydrocarbyl or substituted hydrocarbyl, preferably a C 2 to C 6 , hydrocarbyl, preferably ethyl;
  • R 10* , R 11* , R 12* are, independently hydrogen or a C 1 to C 30 hydrocarbyl or substituted hydrocarbyl, preferably hydrogen or methyl; each G, is, independently, hydrogen, halogen or C 1 to C 30 substituted or unsubstituted hydrocarbyl (preferably a C 1 to C 30 substituted or unsubstituted alkyl or a substituted or unsubstituted C 4 to C 30 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):
  • 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 C 1 to C 30 hydrocarbyl, and a C 1 to C 30 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, C 1 to C 12 hydrocarbyl groups, substituted C 1 to C 12 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
  • 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 C 1 to C 30 hydrocarbyl, and a C 1 to C 30 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, C 1 to C 12 hydrocarbyl groups, substituted C 1 to C 12 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).
  • 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.
  • Two or more catalysts may optionally be used including combinations of the foregoing catalysts.
  • an activator can be included with the catalyst.
  • 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.
  • 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.
  • 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 ISOPARTM(synthetic isoparaffins, commercially available from ExxonMobil Chemical Company)); perhalogenated hydrocarbons (e.g., perfluorinated C 4 -C 10 alkanes, chlorobenzene, and aromatic); alkyl substituted aromatic compounds (e.g., benzene, toluene, mesitylene, and
  • 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.
  • quenching compounds that stop the polymerization reaction are antioxidants, which may be dispersed in alcohols (e.g., methanol or ethanol).
  • quenching compounds may include, but are not limited to, butylated hydroxytoluene, IRGANOXTM antioxidants (available from BASF), and the like, and any combination thereof.
  • 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.
  • 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.
  • an inert atmosphere e.g., under a nitrogen or argon environment
  • the ROMP process may be carried out in a continuous reactor or batch reactors.
  • 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.
  • the second cyclic olefin comonomer incorporates to a greater degree than the first cyclic olefin comonomer.
  • first cyclic olefin comonomer 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the long chain branching 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 (
  • a linear polymer is characterized by a monotonic decreasing dependence of the loss angle with
  • Polymers of the present disclosure having a long chain branching structure may have a ⁇ 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 ⁇ at a G* of 50 kPa of 65° to 80°, or 70° to 80°, or 70° to 75°.
  • 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.
  • the polymers of the present disclosure having a long chain branching structure may have (a) a ⁇ 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:
  • the polymers of the present disclosure having a linear structure may have (a) a ⁇ 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
  • 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.
  • 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.
  • 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 ⁇ 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 ⁇ 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
  • 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.
  • 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.
  • 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.
  • 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 ⁇ 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.
  • 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.
  • 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 ⁇ 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
  • 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 ⁇ 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 k
  • This invention also relates to a polymer having (a) a ⁇ 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:
  • This invention also relates to a polymer having (a) a ⁇ 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
  • 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
  • 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 there
  • 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)
  • 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 there
  • 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 there
  • Embodiment A1 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.
  • 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).
  • 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°).
  • Embodiment A4 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).
  • Embodiment A5 which is the method of Embodiment A1 or A4 and wherein the polymer has a ⁇ at a G* of 65° to 80° (or 70° to 80°, or 70° to 75°).
  • 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.
  • 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.
  • Embodiment A8 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.
  • Embodiment A9 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • Embodiment B2 which is the method of Embodiment B1 and wherein the polymer has a g’ vis of 0-50 to 0.91.
  • Embodiment B3 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°.
  • Embodiment B4 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-
  • Embodiment B5 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.
  • Embodiment B6 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.
  • 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.
  • 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°.
  • 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 anhydr
  • 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.
  • Embodiment C4 is the method of Embodiment Cl or C2 or C3 and wherein the polymer has a molecular weight distribution of 1 to 10.
  • DCPD dicyclopentadiene
  • NBE norbomene
  • BHT butylated hydroxy toluene
  • Me is methyl
  • cC5 is cyclopentene
  • Ph is phenyl.
  • 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-MeC 6 H 4 O) 2 AlCl (0.757 mmol) to a solution of WCl 6 (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.
  • cyclopentene 103 g, 1.513 mol
  • triethylaluminum 86 mg, 0.757 mmol
  • the catalyst was formed in situ by adding solid (p-MeC 6 H 4 O) 2 AlCl (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.
  • Sample 4 The catalyst was formed in situ by adding solid (p-MeC 6 H 4 O) 2 AlCl (2.02 mmol) to a solution of WCl 6 (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.
  • Sample 5 The catalyst was formed in situ by adding solid (4-(PhCH 2 )C 6 H 4 O) 2 AlCl (2.02 mmol) to a solution of WCl 6 (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.
  • 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-(PhCH 2 )C 6 H 4 O) 2 AlCl (2.02 mmol) to a solution of WCl 6 (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.
  • Sample 8 The catalyst was formed in situ by adding solid (4-(PhCH 2 )C 6 H 4 O) 2 AlCl (1.26 mmol) to a solution of WCl 6 (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.
  • Sample 9 The catalyst was formed in situ by adding solid (4-(PhCH 2 )C 6 H 4 O) 2 AlCl (1.26 mmol) to a solution of WCl 6 (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.
  • first comonomer 1.261 mol
  • triethylaluminum (activator) 1.261 mmol
  • toluene 900 mL
  • 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).
  • SAOS small amplitude oscillatory
  • 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.
  • 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
  • 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.

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Abstract

L'invention concerne un procédé de polymérisation par métathèse par ouverture de cycle (ROMP) qui peut consister à mettre en contact dans la durée un premier comonomère oléfinique cyclique avec le mélange réactionnel à une vitesse de 0,01 % en moles par minute à 25 % en moles par minute en fonction de la quantité totale de second comonomère oléfinique cyclique ajoutée au mélange réactionnel pour produire un polymère, un rapport final mole pour mole entre le premier comonomère oléfinique cyclique et le second comonomère oléfinique cyclique ajouté au mélange réactionnel variant de 1/1 à 500/1 ; et le second comonomère oléfinique cyclique présentant une réactivité plus grande à l'égard du catalyseur de métathèse que le premier comonomère oléfinique cyclique.
PCT/US2020/063095 2019-12-04 2020-12-03 Polymères préparés par polymérisation par métathèse par ouverture de cycle Ceased WO2021113503A1 (fr)

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