RING-OPENING METATHESIS (ROMP) POLYMERIZATION COMPOSITION, METHOD FOR MANUFACTURING A POLYMER BY ROMP, METHOD FOR MANUFACTURING A POLYMER COMPOSITE BY ROMP AND ARTICLES OF MANUFACTURE COMPRISING SAID COMPOSITION, AS WELL AS MADE BY SAID METHODS

Description

[001] This application claims the benefit of U.S. Provisional Patent Application No. 61 / 842,885, filed July 3, 2013, the contents of which are incorporated herein by reference. TECHNICAL FIELD

[002] The present invention relates to methods and compositions for olefin metathesis. More particularly, the present invention relates to methods and compositions for ring-opening metathesis (ROMP) polymerization reactions and the manufacture of polymer articles and / or polymer composite articles via ROMP. Polymer products produced via the metathesis reactions of the invention can be used in a wide range of materials and composite applications. The invention has utility in the fields of polymer and materials chemistry and manufacturing. FUNDAMENTALS

[003] Thermoset polymer molding is a technologically and commercially important processing technique. In a known version of this technique, a liquid cyclic olefin monomer resin is combined with at least one olefin carbene metal metathesis catalyst to form a ROMP composition, and the ROMP composition is added (e.g., poured, molded, infused, injected, etc.) into a mold. The ROMP composition is subjected to conditions effective for polymerizing the ROMP composition, and in conclusion, the molded article is subjected to any post-curing processing. Petition 870210098125, dated 10 / 25 / 2021, page 21 / 187 2 / 158 optional which may be required. As is known in the art, liquid cyclic olefin monomer resin may optionally contain modifiers, fillers, boosters, flame retardants, added pigments, etc. Examples of such prior art ROMP compositions are disclosed in U.S. Pat. Nos. 5,342,909; 6,310,121; 6,515,084; 6,525,125; 6,759,537; 7,329,758, etc.

[004] Commercially important cyclic olefin monomer resins generally comprise readily available and inexpensive cyclic olefins, such as norbornene monomers, particularly dicyclopentadiene (DCPD). Unfortunately, high-purity DCPD melts at 32°C to 34°C and is then a solid at room temperature (typically 20 to 25°C). Therefore, high-purity DCPD must be heated during its formulation with catalyst(s) and other additives, and transported through coated heat lines to maintain a liquid state for use in many polymer molding techniques, such as RIM (Reaction Injection Molding), RTM (Resin Transfer Molding), and VARTM (Vacuum Assisted Resin Transfer Molding).

[005] It is known in the art that the melting point of DCPD can be degraded by adding an adulterant in the form of higher cyclopentadiene oligomers that are copolymerizable with dicyclopentadiene, such as cyclopentadiene trimer (tricyclopentadiene). In fact, commercially available liquid DCPD monomer resins for use in molding polymer articles typically contain between 10% and 30% by weight of tricyclopentadiene, and smaller amounts of higher cyclopentadiene oligomers, such as cyclopentadiene tetramers and pentamers (e.g., tetracyclopentadiene and pentacyclopentadiene).

[006] Liquid DCPD monomer resins for use in molding polymer articles containing higher amounts of cyclopentadiene trimer have been reported in the literature European Pat. No. EP0271007B2 and US Pat. No. 4,703,098 Petition 870210098125, dated 10 / 25 / 2021, p. 22 / 187 3 / 158 disclosed liquid mixtures containing (a) 52% by weight DCPD, 43.25% by weight tricyclopentadiene, and 4.75% by weight tetracyclopentadiene; and (b) 42% by weight DCPD, 51.5% by weight tricyclopentadiene, and 6.5% by weight tetracyclopentadiene. However, the inventors discovered that below 40 °C, particularly at or below room temperature, solids precipitated from such mixtures. This is particularly problematic as below 40 °C, particularly at or below room temperature, such prior art resin compositions are not suitable for use in the preparation of composite articles, particularly using resin infusion techniques such as VART™, as the solids may clog the infusion ports and / or equipment and may also act to reduce the infusion of the resin into the composite substrate material.Furthermore, these solids can also act to clog or foul the equipment, such as material to supply injection lines and / or ports used in reaction injection molding (RIM) techniques, when molding polymer and / or polymer composite articles.

[007] To successfully mold a polymer and / or polymer composite article using liquid DCPD monomer resins, it is important that the molded article be free or substantially free of defects (e.g., undesirable pores, cavities, bubbles, voids, mesh line and / or internal stress ruptures). This issue is particularly important as molded polymer and / or polymer composite articles that have defects requiring repair or need to be discarded, which in either situation lead to increased manufacturing costs.

[008] In a typical molding operation, the temperature of the pre-catalyzed liquid DCPD monomer resin is typically below 40 °C, and preferably at or below ambient temperature. Heating the pre-catalyzed liquid DCPD monomer resin above ambient temperature, Petition 870210098125, dated 10 / 25 / 2021, page 23 / 187 4 / 158 particularly above 40 °C, in general, reduces the pot life of the ROMP (catalyzed monomer resin) composition, making it difficult to properly fill the mold and / or infuse the substrate materials, particularly when manufacturing large polymer articles and / or large polymer composite articles. Furthermore, heating liquid DCPD monomer resin may require special equipment (e.g., heated tanks and / or lines) which increases the overall cost of molding ROMP polymer articles and / or ROMP polymer composite articles.Methods and additives for controlling the pot life of liquid catalyzed cyclic olefinic monomeric resins (e.g., liquid DCPD monomer resins) are known; however, in general, at temperatures above 40 °C, large amounts of additives may be required to provide adequate pot life, but the use of large amounts of such additives may negatively affect the thermal and mechanical properties of the molded polymer article and / or polymer composite article, thus requiring the need for optional post-curing processing which also increases the overall cost of ROMP molded polymer articles and / or ROMP polymer composite articles.

[009] Typically, following the catalysis of liquid DCPD monomer resin to form a ROMP composition, the polymerization of the monomer resin progresses and the viscosity of the ROMP composition increases, progressing from a liquid state, through a gel state, to the final hard polymer. At some point during the progression, the temperature generally begins to rise rapidly leading to an exothermic form. A general issue with polymer molding articles using liquid DCPD monomer resins is that during the exothermic phase of polymerization, dicyclopentadiene and / or other low-boiling compounds that may be present in the liquid DCPD monomer resin (e.g., cyclopentadiene monomer) may volatilize. Petition 870210098125, dated 10 / 25 / 2021, page 24 / 187 5 / 158 frequently lead to the formation of defects in the interior and / or on the surface of molded polymer articles and / or polymer composite articles. It is known in the art that low molecular weight, low-boiling hydrocarbon compounds (e.g., cyclopentadiene monomer) can be removed from liquid DCPD monomer resin by vacuum extraction and / or inert gas diffusion. However, the inventors have found that the removal of low molecular weight, low-boiling hydrocarbon compounds, such as cyclopentadiene monomer, alone is not sufficient to reduce and / or eliminate defect formation in the interior and / or on the surface of molded ROMP polymer articles and / or ROMP polymer composite articles.

[0010] Although there have been attempts to modulate the exothermic temperature (e.g., through mold temperature manipulation and / or the addition of additives) to control forming defects, it is typically advantageous to allow the ROMP composition to achieve a maximum (high) exothermic temperature in order to optimize the thermal and mechanical properties of the molded polymer article and / or polymer composite article, thereby reducing and / or eliminating the need for additional optional post-curing processing.

[0011] Therefore, it would be useful and commercially important to be able to rapidly heat the ROMP composition in a mold (e.g., at a rate greater than 0.5 °C / min) and / or add the ROMP composition to a preheated mold at a temperature of approximately 60 °C to 200 °C, both of which would allow the ROMP composition to reach a maximum (high) exothermic temperature and additionally take into account a reduction in the overall cycle time. This reduction in cycle time provides an economic advantage, in that more polymer articles and / or polymer composite articles can be made during the same period of time. In other words, it would be preferable to be able to add the ROMP composition to a heated mold and / or start heating. Petition 870210098125, dated 10 / 25 / 2021, p. 25 / 187 6 / 158 of the ROMP composition as quickly as possible once the mold is filled and / or the composite substrate material is infused with the ROMP composition. More particularly, it would be preferable to be able to add a ROMP composition, having an initial temperature below 40 °C, preferably at or below ambient temperature, to a mold heated to 60 °C to 200 °C and / or to start heating the ROMP composition in the mold at a rate greater than 0.5 °C / min as quickly as the mold is filled and / or the composite substrate material is infused with the ROMP composition.

[0012] Generally, however, it has been observed that if liquid DCPD monomer resin compositions containing 10% to 30% cyclopentadiene trimer are used in a ROMP composition to mold polymer articles and / or polymer composite articles, the resulting molded polymer article and / or polymer composite article will typically contain defects, particularly if such a ROMP composition at an initial temperature below 40 °C, preferably at or below ambient temperature, is added to a mold preheated to a temperature of about 60 °C to 200 °C and / or if the mold is rapidly heated at a rate greater than 0.5 °C / min.

[0013] Therefore, despite the advances made in the technique, there is a need for liquid cyclic olefinic monomeric resins, particularly resins that are stable homogeneous liquid storage resins, which can be combined with a catalyst composition comprising at least one olefin carbene metal metathesis catalyst to form a ROMP composition, where the ROMP composition can be added to a preheated mold and / or the mold can be rapidly heated to prepare molded polymer articles and / or polymer composite articles, where the resulting molded polymer articles and / or polymer composite articles are free or substantially free of defects. Petition 870210098125, dated 10 / 25 / 2021, p. 26 / 187 7 / 158

[0014] More particularly, there is a need for liquid DCPD resin compositions that are stable homogeneous liquids between 39 °C and 10 °C, which can be combined with a catalyst composition comprising at least one carbene olefin metal metathesis catalyst to form a ROMP composition, wherein the ROMP composition is below 40 °C, preferably at or below ambient temperature, and the ROMP composition can be added to a mold preheated to 60 °C to 200 °C and / or the mold can be rapidly heated (e.g., at a rate greater than 0.5 °C / min) to prepare molded polymer articles and / or polymer composite articles, wherein the resulting molded polymer articles and / or polymer composite articles are free or substantially free of defects.

[0015] The present invention is directed to address one or more of the problems mentioned above. SUMMARY OF THE INVENTION

[0016] It is an object of the present invention to provide liquid cyclic olefinic monomeric resins, particularly resins that are stable storage homogeneous liquids, methods using such resins, and use of such resins to prepare ROMP compositions for the manufacture of polymer articles and / or polymer composite articles by means of ROMP, wherein the polymer articles and / or polymer composite articles are free or substantially free of defects.

[0017] More particularly, it is an object of the present invention to provide cyclic olefin compositions and / or resin compositions that are stable homogeneous liquids between 39 °C and 10 °C, which can be combined with a catalyst composition comprising at least one olefin carbene metal metathesis catalyst to form a ROMP composition, wherein the ROMP composition is below 40 °C, preferably at or below ambient temperature, and the ROMP composition can be added to a preheated mold between 60 °C Petition 870210098125, dated 10 / 25 / 2021, p. 27 / 187 8 / 158 at 200 °C and / or the mold can be rapidly heated (e.g., at a rate greater than 0.5 °C / min) to prepare molded polymer articles and / or polymer composite articles, where the resulting molded polymer articles and / or polymer composite articles are free or substantially free of defects.

[0018] The inventors have discovered that a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35% to 70% by weight of tricyclopentadiene, when combined with a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, allows the preparation of polymer articles and / or polymer composite articles that are free or substantially free of visual defects, internal defects and / or surface defects (e.g., undesirable pores, cavities, bubbles, voids, mesh line and / or internal stress ruptures). In particular, the present invention mitigates against problems related to defects that are thought to be caused by volatilization of low-boiling compounds present in the cyclic olefin composition or generated during the polymerization cycle (exotherm).Defects thought to be caused by volatilization of low-boiling compounds present in the cyclic olefin composition or generated during polymerization are a particular issue with the olefin metal carbene metathesis catalysts (polymerization catalysts) of the invention, particularly ruthenium-based olefin metal carbene metathesis catalysts of the invention. This is especially the case with ruthenium-based metal carbene metathesis catalysts that are commonly called Second Generation Grubbs catalysts and / or Grubbs-Hoveyda catalysts. Second Generation Grubbs catalysts and / or Grubbs-Hoveyda catalysts generally propagate the polymerization (e.g., ROMP) of cyclic olefins faster than ruthenium-based olefin metal carbene metathesis catalysts that are commonly called First Generation Grubbs catalysts. Without being limited by... Petition 870210098125, dated 10 / 25 / 2021, page 28 / 187 9 / 158 theory, during a ROMP reaction, defects that are thought to be caused by volatilization of low-boiling compounds are exacerbated with faster-propagating catalysts (e.g., Second Generation Grubbs catalysts and / or Grubbs-Hoveyda catalysts) compared to slower-propagating catalysts (e.g., First Generation Grubbs catalysts).

[0019] More particularly, the inventors have found that a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and 64.99% to 26.00% by weight of dicyclopentadiene, when combined with a catalyst composition comprising at least one olefin carbene metal metathesis catalyst, allows the preparation of polymer articles and / or polymer composite articles that are free from visual defects, substantially free from visual defects, or contain fewer visual defects, internal defects and / or surface defects (e.g., undesirable pores, cavities, bubbles, voids, mesh line and / or internal stress ruptures) than the same articles prepared using liquid DCPD monomer resins containing between 10% to 30% by weight of tricyclopentadiene.In particular, the present invention mitigates problems related to defects that are thought to be caused by volatilization of dicyclopentadiene and / or other low-boiling compounds present in the cyclic olefin composition or generated during the polymerization cycle (exotherm). Defects that are thought to be caused by volatilization of dicyclopentadiene and / or other low-boiling compounds present in the cyclic olefin composition or generated during polymerization are a particular issue with the olefin carbene metal metathesis catalysts (polymerization catalysts) of the invention, particularly the ruthenium olefin carbene metal metathesis catalysts of the invention. This is especially the... Petition 870210098125, dated 10 / 25 / 2021, p. 29 / 187 10 / 158 case with ruthenium-carbene metal metathesis catalysts that are commonly called Second Generation Grubbs catalysts and / or Grubbs-Hoveyda catalysts. Second Generation Grubbs catalysts and / or Grubbs-Hoveyda catalysts, in general, propagate the polymerization (e.g., ROMP) of cyclic olefins faster than ruthenium-carbene olefin metal metathesis catalysts that are commonly called First Generation Grubbs catalysts. Without being limited by theory, during a ROMP reaction, defects that are thought to be caused by volatilization of dicyclopentadiene and / or other low-boiling compounds are exacerbated with faster-propagating catalysts (e.g., Second Generation Grubbs catalysts and / or Grubbs-Hoveyda catalysts) compared to slower-propagating catalysts (e.g., First Generation Grubbs catalysts).In other words, during a ROMP reaction, liquid DCPD monomer resins containing 10% to 30% by weight of tricyclopentadiene show a greater tendency to possess volatilization-related defects when catalyzed with faster-propagating catalysts (e.g., Second Generation Grubbs catalysts and / or Grubbs-Hoveyda catalysts) compared to slower-propagating catalysts (e.g., First Generation Grubbs catalysts).

[0020] Generally, liquid cyclic olefin compositions of the invention having a tricyclopentadiene content of 35 percent by weight or above have decreased flammability (e.g., increased flash point) compared to commercially available liquid DCPD monomer resins. Additionally, the inventors have found that the liquid cyclic olefin compositions of the invention may offer an additional benefit in that such cyclic olefin compositions may allow the preparation of liquid resin compositions (e.g., liquid DCPD resin compositions) that may have a lower flash point. Petition 870210098125, dated 10 / 25 / 2021, page 30 / 187 11 / 158 greater than 60.5 °C. Liquid resin compositions that have a flash point greater than 60.5 °C are designated as liquid fuels according to the Globally Harmonized System (GHS) flammable and liquid fuel criteria. Liquid resin compositions that have a flash point less than 60.5 °C are designated as flammable liquids according to the GHS flammable liquid and liquid fuel criteria. Liquid resin compositions that are designated as liquid fuels rather than flammable liquids offer several advantages / benefits including ease of handling, reduced transportation costs, and additional safety features, as well as other advantages / benefits.

[0021] In general, the liquid cyclic olefin compositions of the invention having a tricyclopentadiene content of 35 percent by weight or above have decreased toxicity compared to commercially available liquid DCPD monomer resins. In particular, the inventors have found that the liquid cyclic olefin compositions of the invention may offer an additional benefit in that such cyclic olefin compositions may allow the preparation of liquid resin compositions (e.g., liquid DCPD resin compositions) that may be designated as H331 (toxic if inhaled) instead of H330 (fatal if inhaled) in accordance with Globally Harmonised System (GHS) Criteria. For example, the following cyclic olefin composition should be designated as H331 (toxic if inhaled): DCPD (40% by weight), tricyclopentadiene (57% by weight), tetracyclopentadiene (3% by weight).For example, the following resin composition should be designated as H331 (toxic if inhaled): DCPD (43% by weight), tricyclopentadiene (53% by weight), tetracyclopentadiene (4% by weight), Ethanox 4702 (3 phr), 5-vinyl-2-norbornene (1% by weight), triphenylphosphine (0.6 phr), elastomeric impact modifier (4 phr). For example, the following resin composition should be designated as H331 (toxic if inhaled): DCPD (37% by weight), tricyclopentadiene. Petition 870210098125, dated 10 / 25 / 2021, p. 31 / 187 12 / 158 (60% by weight), tetracyclopentadiene (3% by weight), liquid MDI (4 phr). For example, the following resin composition should be designated as H331 (toxic if inhaled): DCPD (41% by weight), tricyclopentadiene (57% by weight), tetracyclopentadiene (2% by weight), Ethanox 4702 (2 phr), 5-vinyl-2-norbornene (1 phr), triphenylphosphine (0.6 phr), and adhesion promoter composition (A) (4 phr).

[0022] One embodiment of the invention provides a cyclic olefin composition comprising 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and 64.99% to 26.00% by weight of dicyclopentadiene.

[0023] Another embodiment of the invention provides a cyclic olefin composition comprising 40.00% to 65.00% by weight of tricyclopentadiene, 0.01% to 3.50% by weight of tetracyclopentadiene, and 59.99% to 31.50% by weight of dicyclopentadiene.

[0024] Another embodiment of the invention provides a cyclic olefin composition comprising 40.00% to 60.00% by weight of tricyclopentadiene, 0.01% to 3.00% by weight of tetracyclopentadiene, and 59.99% to 37.00% by weight of dicyclopentadiene.

[0025] Another embodiment of the invention provides a cyclic olefin composition comprising 35.00 to 70.0 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and 64.99 to 26.00 percent by weight of dicyclopentadiene, where percent by weight is determined by gas chromatography.

[0026] Another embodiment of the invention provides a cyclic olefin composition comprising 40.00 to 65.00 percent by weight of tricyclopentadiene, 0.01 to 3.50 percent by weight of tetracyclopentadiene, and 59.99 to 31.50 percent by weight of dicyclopentadiene, where percent by weight is determined by gas chromatography. Petition 870210098125, dated 10 / 25 / 2021, page 32 / 187 13 / 158

[0027] Another embodiment of the invention provides a cyclic olefin composition comprising 40.00 to 60.00 percent by weight of tricyclopentadiene, 0.01 to 3.00 percent by weight of tetracyclopentadiene, and 59.99 to 37.00 percent by weight of dicyclopentadiene, where percent by weight is determined by gas chromatography.

[0028] Another embodiment of the invention provides a cyclic olefin composition comprising 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and 64.99% to 26.00% by weight of dicyclopentadiene, wherein the cyclic olefin composition is a stable homogeneous liquid between 39 °C and 10 °C, between 39 °C and 15 °C, 39 °C and 20 °C, between 39 °C and 25 °C, between 39 °C and 30 °C, between 39 °C and 35 °C, between 30 °C and 15 °C, between 35 °C and 20 °C, between 35 °C and 25 °C, between 25 °C and 20 °C, or between 25°C and 10°C.

[0029] Another embodiment of the invention provides a cyclic olefin composition comprising 40.00% to 65.00% by weight of tricyclopentadiene, 0.01% to 3.50% by weight of tetracyclopentadiene, and 59.99% to 31.50% by weight of dicyclopentadiene, wherein the cyclic olefin composition is a stable homogeneous liquid between 39 °C and 10 °C, between 39 °C and 15 °C, 39 °C and 20 °C, between 39 °C and 25 °C, between 39 °C and 30 °C, between 39 °C and 35 °C, between 30 °C and 15 °C, between 35 °C and 20 °C, between 35 °C and 25 °C, between 25 °C and 20 °C, or between 25°C and 10°C.

[0030] Another embodiment of the invention provides a cyclic olefin composition comprising 40.00% to 60.00% by weight of tricyclopentadiene, 0.01% to 3.00% by weight of tetracyclopentadiene, and 59.99% to 37.00% by weight of dicyclopentadiene, wherein the cyclic olefin composition is a stable homogeneous liquid between 39 °C and 10 °C, between 39 °C and 15 °C, 39 °C and 20 °C, between 39 °C and 25 °C, between 39 °C and 30 °C, between 39 °C and 35 °C, between 30 °C and 15 °C, between 35 °C and 20 °C, between 35 °C and 25 °C, between 25 °C and 20 °C, or between 25°C and 10°C.

[0031] Another embodiment of the invention provides a composition Petition 870210098125, dated 10 / 25 / 2021, page 33 / 187 14 / 158 resin comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and 64.99% to 26.00% by weight of dicyclopentadiene.

[0032] Another embodiment of the invention provides a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00% to 65.00% by weight of tricyclopentadiene, 0.01% to 3.50% by weight of tetracyclopentadiene, and 59.99% to 31.50% by weight of dicyclopentadiene.

[0033] Another embodiment of the invention provides a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00% to 60.00% by weight of tricyclopentadiene, 0.01% to 3.00% by weight of tetracyclopentadiene, and 59.99% to 37.00% by weight of dicyclopentadiene.

[0034] Another embodiment of the invention provides a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and 64.99% to 26.00% by weight of dicyclopentadiene, wherein the resin composition is a stable homogeneous liquid between 39 °C and 10 °C, between 39 °C and 15 °C, 39 °C and 20 °C, between 39 °C and 25 °C, between 39 °C and 30 °C, between 39 °C and 35 °C, between 30 °C and 15 °C, between 35 °C and 20 °C, between 35 °C and 25 °C, between 25°C to 20°C, or between 25°C to 10°C.

[0035] Another embodiment of the invention provides a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00% to 65.00% by weight of tricyclopentadiene, 0.01% to 3.50% by weight of tetracyclopentadiene, and 59.99% to 31.50% by weight of dicyclopentadiene, wherein the resin composition is a stable homogeneous liquid. Petition 870210098125, dated 10 / 25 / 2021, page 34 / 187 15 / 158 between 39 °C to 10 °C, between 39 °C to 15 °C, 39 °C to 20 °C, between 39 °C to 25 °C, between 39 °C to 30 °C, between 39 °C to 35 °C, between 30 °C to 15 °C, between 35 °C to 20 °C, between 35 °C to 25 °C, between 25 °C to 20 °C, or between 25 °C to 10 °C.

[0036] Another embodiment of the invention provides a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00% to 60.00% by weight of tricyclopentadiene, 0.01% to 3.00% by weight of tetracyclopentadiene, and 59.99% to 37.00% by weight of dicyclopentadiene, wherein the resin composition is a stable homogeneous liquid between 39 °C and 10 °C, between 39 °C and 15 °C, 39 °C and 20 °C, between 39 °C and 25 °C, between 39 °C and 30 °C, between 39 °C and 35 °C, between 30 °C and 15 °C, between 35 °C and 20 °C, between 35 °C and 25 °C, between 25°C to 20°C, or between 25°C to 10°C.

[0037] Another embodiment of the invention provides a process for preparing a substantially vacuum-free article, comprising combining a resin composition and a catalyst composition to form a ROMP composition, wherein the catalyst composition comprises at least one carbene olefin metal metathesis catalyst and the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.1% to 4.00% by weight of tetracyclopentadiene, and 64.99% to 26.00% by weight of dicyclopentadiene, and subjecting the ROMP composition to conditions effective for promoting an olefin metathesis reaction (e.g., a ring-opening metathesis polymerization reaction).

[0038] Another embodiment of the invention provides a process for preparing a substantially vacuum-free article, comprising combining a resin composition and a catalyst composition to form a ROMP composition, wherein the catalyst composition comprises at least one carbene olefin metal metathesis catalyst and the resin composition Petition 870210098125, dated 10 / 25 / 2021, page 35 / 187 16 / 158 comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00% to 65.00% by weight of tricyclopentadiene, 0.1% to 3.50% by weight of tetracyclopentadiene, and 59.99% to 31.50% by weight of dicyclopentadiene, and subjecting the ROMP composition to conditions effective for promoting an olefin metathesis reaction (e.g., a ring-opening metathesis polymerization reaction).

[0039] Another embodiment of the invention provides a process for preparing a substantially vacuum-free article, comprising combining a resin composition and a catalyst composition to form a ROMP composition, wherein the catalyst composition comprises at least one carbene olefin metal metathesis catalyst and the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00% to 60.00% by weight of tricyclopentadiene, 0.1% to 3.00% by weight of tetracyclopentadiene, and 59.99% to 37.00% by weight of dicyclopentadiene, and subjecting the ROMP composition to conditions effective for promoting an olefin metathesis reaction (e.g., a ring-opening metathesis polymerization reaction).

[0040] Another embodiment of the invention provides a fabrication article comprising a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and 64.99% to 26.00% by weight of dicyclopentadiene.

[0041] Another embodiment of the invention provides a fabrication article comprising a resin composition and a catalyst composition comprising at least one carbene metal metathesis catalyst. Petition 870210098125, dated 10 / 25 / 2021, page 36 / 187 17 / 158 olefin, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00% to 65.00% by weight of tricyclopentadiene, 0.01% to 3.50% by weight of tetracyclopentadiene, and 59.99% to 31.50% by weight of dicyclopentadiene.

[0042] Another embodiment of the invention provides a fabrication article comprising a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00% to 60.00% by weight of tricyclopentadiene, 0.01% to 3.00% by weight of tetracyclopentadiene, and 59.99% to 37.00% by weight of dicyclopentadiene.

[0043] Another embodiment of the invention provides a fabrication article, the fabrication article comprising a ROMP polymer, wherein the ROMP polymer is the reaction product of a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and 64.99% to 26.00% by weight of dicyclopentadiene.

[0044] Another embodiment of the invention provides a fabrication article, the fabrication article comprising a ROMP polymer, wherein the ROMP polymer is the reaction product of a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00% to 65.00% by weight of tricyclopentadiene, 0.01% to 3.50% by weight of tetracyclopentadiene, and 59.99% to 31.50% by weight of dicyclopentadiene. Petition 870210098125, dated 10 / 25 / 2021, page 37 / 187 18 / 158

[0045] Another embodiment of the invention provides a fabrication article, the fabrication article comprising a ROMP polymer, wherein the ROMP polymer is the reaction product of a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00% to 60.00% by weight of tricyclopentadiene, 0.01% to 3.00% by weight of tetracyclopentadiene, and 59.99% to 37.00% by weight of dicyclopentadiene.

[0046] Another embodiment of the invention provides a fabrication article, the fabrication article comprising a ROMP polymer composite, wherein the ROMP polymer composite is the reaction product of a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and 64.99% to 26.00% by weight of dicyclopentadiene.

[0047] Another embodiment of the invention provides a fabrication article, the fabrication article comprising a ROMP polymer composite, wherein the ROMP polymer composite is the reaction product of a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00% to 65.00% by weight of tricyclopentadiene, 0.01% to 3.50% by weight of tetracyclopentadiene, and 59.99% to 31.50% by weight of dicyclopentadiene.

[0048] Another embodiment of the invention provides a fabricated article, the fabricated article comprising a ROMP polymer composite, wherein the ROMP polymer composite is the reaction product of a Petition 870210098125, dated 10 / 25 / 2021, page 38 / 187 19 / 158 resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00% to 60.00% by weight of tricyclopentadiene, 0.01% to 3.00% by weight of tetracyclopentadiene, and 59.99% to 37.00% by weight of dicyclopentadiene.

[0049] Another embodiment of the invention provides a ROMP composition comprising a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; and a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00 to 70.00 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and 64.99 to 26.00 percent by weight of dicyclopentadiene.

[0050] Another embodiment of the invention provides a ROMP composition comprising a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; and a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00 to 65.00 percent by weight of tricyclopentadiene, 0.01 to 3.50 percent by weight of tetracyclopentadiene, and 59.99 to 31.50 percent by weight of dicyclopentadiene.

[0051] Another embodiment of the invention provides a ROMP composition comprising a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; and a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00 to 60.00 percent by weight of tricyclopentadiene, 0.01 to 3.00 percent by weight of tetracyclopentadiene, and 59.99 to 37.00 percent by weight of dicyclopentadiene.

[0052] Another embodiment of the invention provides a method, Petition 870210098125, dated 10 / 25 / 2021, page 39 / 187 20 / 158 comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00 to 70.00 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and 64.99 to 26.00 percent by weight of dicyclopentadiene; combining the catalyst composition and the resin composition to form a ROMP composition; and subjecting the ROMP composition to conditions effective for promoting an olefin metathesis reaction.

[0053] Another embodiment of the invention provides a method for manufacturing a ROMP polymer, comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00 to 70.00 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and 64.99 to 26.00 percent by weight of dicyclopentadiene; combining the catalyst composition and the resin composition to form a ROMP composition; and subjecting the ROMP composition to conditions effective for promoting the polymerization of the ROMP composition.

[0054] Another embodiment of the invention provides a method comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00 to 65.00 percent by weight of tricyclopentadiene, 0.01 to 3.50 percent by weight of tetracyclopentadiene, and 59.99 to 31.50 percent by weight of dicyclopentadiene; combining the catalyst composition and the resin composition to form a ROMP composition; and subjecting it to Petition 870210098125, dated 10 / 25 / 2021, page 40 / 187 21 / 158 ROMP composition under effective conditions to promote an olefin metathesis reaction.

[0055] Another embodiment of the invention provides a method for manufacturing a ROMP polymer, comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00 to 65.00 percent by weight of tricyclopentadiene, 0.01 to 3.50 percent by weight of tetracyclopentadiene, and 59.99 to 31.50 percent by weight of dicyclopentadiene; combining the catalyst composition and the resin composition to form a ROMP composition; and subjecting the ROMP composition to conditions effective for promoting the polymerization of the ROMP composition.

[0056] Another embodiment of the invention provides a method comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00 to 60.00 percent by weight of tricyclopentadiene, 0.01 to 3.00 percent by weight of tetracyclopentadiene, and 59.99 to 37.00 percent by weight of dicyclopentadiene; combining the catalyst composition and the resin composition to form a ROMP composition; and subjecting the ROMP composition to conditions effective for promoting an olefin metathesis reaction.

[0057] Another embodiment of the invention provides a method for manufacturing a ROMP polymer, comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00 to 60.00 by Petition 870210098125, dated 10 / 25 / 2021, page 41 / 187 22 / 158 percent by weight of tricyclopentadiene, 0.01 to 3.00 percent by weight of tetracyclopentadiene, and 59.99 to 37.00 percent by weight of dicyclopentadiene; combine the catalyst composition and the resin composition to form a ROMP composition; and subject the ROMP composition to conditions effective in promoting the polymerization of the ROMP composition.

[0058] Another embodiment of the invention provides a method comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00 to 70.00 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and 64.99 to 26.00 percent by weight of dicyclopentadiene; combining the catalyst composition and the resin composition to form a ROMP composition; contacting the ROMP composition with a substrate material; and subjecting the ROMP composition to conditions effective for promoting an olefin metathesis reaction.

[0059] Another embodiment of the invention provides a method for manufacturing a ROMP polymer composite, comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00 to 70.00 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and 64.99 to 26.00 percent by weight of dicyclopentadiene; combining the catalyst composition and the resin composition to form a ROMP composition; contacting the ROMP composition with a substrate material; and subjecting the ROMP composition to conditions effective for promoting polymerization of the ROMP composition.

[0060] Another embodiment of the invention provides a method, Petition 870210098125, dated 10 / 25 / 2021, page 42 / 187 23 / 158 comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00 to 65.00 percent by weight of tricyclopentadiene, 0.01 to 3.50 percent by weight of tetracyclopentadiene, and 59.99 to 31.50 percent by weight of dicyclopentadiene; combining the catalyst composition and the resin composition to form a ROMP composition; contacting the ROMP composition with a substrate material; and subjecting the ROMP composition to conditions effective for promoting an olefin metathesis reaction.

[0061] Another embodiment of the invention provides a method for manufacturing a ROMP polymer composite, comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00 to 65.00 percent by weight of tricyclopentadiene, 0.01 to 3.50 percent by weight of tetracyclopentadiene, and 59.99 to 31.50 percent by weight of dicyclopentadiene; combining the catalyst composition and the resin composition to form a ROMP composition; contacting the ROMP composition with a substrate material; and subjecting the ROMP composition to conditions effective for promoting polymerization of the ROMP composition.

[0062] Another embodiment of the invention provides a method comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00 to 60.00 percent by weight of tricyclopentadiene, 0.01 to 3.00 percent by weight of tetracyclopentadiene, and 59.99 to 37.00 percent by weight of dicyclopentadiene; combining the catalyst composition Petition 870210098125, dated 10 / 25 / 2021, page 43 / 187 24 / 158 and the resin composition to form a ROMP composition; contact the ROMP composition with a substrate material; and subject the ROMP composition to conditions effective in promoting an olefin metathesis reaction.

[0063] Another embodiment of the invention provides a method for manufacturing a ROMP polymer composite, comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 40.00 to 60.00 percent by weight of tricyclopentadiene, 0.01 to 3.00 percent by weight of tetracyclopentadiene, and 59.99 to 37.00 percent by weight of dicyclopentadiene; combining the catalyst composition and the resin composition to form a ROMP composition; contacting the ROMP composition with a substrate material; and subjecting the ROMP composition to conditions effective for promoting polymerization of the ROMP composition.

[0064] Another embodiment of the invention provides a cyclic olefin composition comprising 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins.

[0065] Another embodiment of the invention provides a cyclic olefin composition comprising 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins, wherein the other cyclic olefins have a melting point below 35 °C.

[0066] Another embodiment of the invention provides a cyclic olefin composition comprising 35.00 to 70.00 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and up to 64.99 percent by weight of one or more other cyclic olefins, wherein the percentage in Petition 870210098125, dated 10 / 25 / 2021, page 44 / 187 25 / 158 weight is determined by gas chromatography.

[0067] Another embodiment of the invention provides a cyclic olefin composition comprising 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins, wherein the cyclic olefin composition is a stable homogeneous liquid between 39 °C and 10 °C, between 39 °C and 15 °C, 39 °C and 20 °C, between 39 °C and 25 °C, between 39 °C and 30 °C, between 39 °C and 35 °C, between 30 °C and 15 °C, between 35 °C and 20 °C, between 35 °C and 25 °C, between 25 °C and 20 °C, or between 25°C and 10°C.

[0068] Another embodiment of the invention provides a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins.

[0069] Another embodiment of the invention provides a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins, wherein the resin composition is a stable homogeneous liquid between 39 °C and 10 °C, between 39 °C and 15 °C, 39 °C and 20 °C, between 39 °C and 25 °C, between 39 °C and 30 °C, between 39 °C and 35 °C, between 30 °C and 15 °C, between 35 °C and 20 °C, between 35 °C and 25 °C, between 25°C to 20°C, or between 25°C to 10°C.

[0070] Another embodiment of the invention provides a ROMP composition comprising a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; and a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other Petition 870210098125, dated 10 / 25 / 2021, page 45 / 187 26 / 158 cyclic olefins.

[0071] Another embodiment of the invention provides a method comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins; combining the catalyst composition and the resin composition to form a ROMP composition; and subjecting the ROMP composition to conditions effective for promoting an olefin metathesis reaction.

[0072] Another embodiment of the invention provides a method for manufacturing a ROMP polymer, comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins; combining the catalyst composition and the resin composition to form a ROMP composition; and subjecting the ROMP composition to conditions effective for promoting polymerization of the ROMP composition.

[0073] Another embodiment of the invention provides a method comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% in Petition 870210098125, dated 10 / 25 / 2021, page 46 / 187 27 / 158 weight of one or more other cyclic olefins; combine the catalyst composition and the resin composition to form a ROMP composition; contact the ROMP composition with a substrate material; and subject the ROMP composition to conditions effective for promoting an olefin metathesis reaction.

[0074] Another embodiment of the invention provides a method for manufacturing a ROMP polymer, comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins; combining the catalyst composition and the resin composition to form a ROMP composition; contacting the ROMP composition with a substrate material; and subjecting the ROMP composition to conditions effective for promoting polymerization of the ROMP composition.

[0075] Another embodiment of the invention provides a process for preparing a substantially vacuum-free article, comprising combining a resin composition and a catalyst composition to form a ROMP composition, wherein the catalyst composition comprises at least one carbene olefin metal metathesis catalyst and the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins, and subjecting the ROMP composition to conditions effective for promoting an olefin metathesis reaction (e.g., a ring-opening metathesis polymerization reaction).

[0076] Another embodiment of the invention provides an article of Petition 870210098125, dated 10 / 25 / 2021, page 47 / 187 28 / 158 manufacturing, comprising a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins.

[0077] Another embodiment of the invention provides a fabrication article, the fabrication article comprising a ROMP polymer, wherein the ROMP polymer is the reaction product of a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins.

[0078] Another embodiment of the invention provides a fabrication article, the fabrication article comprising a ROMP polymer composite, wherein the ROMP polymer composite is the reaction product of a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other cyclic olefins.

[0079] Another embodiment of the invention provides a cyclic olefin composition, wherein the cyclic olefin composition comprises 35 to 70 percent by weight of tricyclopentadiene and less than 4 percent by weight of tetracyclopentadiene. Petition 870210098125, dated 10 / 25 / 2021, page 48 / 187 29 / 158

[0080] Another embodiment of the invention provides a cyclic olefin composition, wherein the cyclic olefin composition comprises 35 to 70 percent by weight of tricyclopentadiene and less than 3.5 percent by weight of tetracyclopentadiene.

[0081] Another embodiment of the invention provides a cyclic olefin composition, wherein the cyclic olefin composition comprises 35 to 70 percent by weight of tricyclopentadiene and less than 3 percent by weight of tetracyclopentadiene.

[0082] Another embodiment of the invention provides a cyclic olefin composition comprising 55% to 58% by weight of tricyclopentadiene, 0% to 3.6% by weight of tetracyclopentadiene, and 38% to 42% by weight of dicyclopentadiene.

[0083] Another embodiment of the invention provides a cyclic olefin composition comprising 55% to 58% by weight of tricyclopentadiene, 0% to 3.6% by weight of tetracyclopentadiene, and 38% to 42% by weight of dicyclopentadiene, wherein the cyclic olefin composition is a stable homogeneous liquid between 39 °C to 10 °C, between 39 °C to 15 °C, 39 °C to 20 °C, between 39 °C to 25 °C, between 39 °C to 30 °C, between 39 °C to 35 °C, between 30 °C to 15 °C, between 35 °C to 20 °C, between 35 °C to 25 °C, between 25 °C to 20 °C, or between 25 °C to 10 °C.

[0084] Another embodiment of the invention provides a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 55% to 58% by weight of tricyclopentadiene, 0% to 3.6% by weight of tetracyclopentadiene, and 38% to 42% by weight of dicyclopentadiene.

[0085] Another embodiment of the invention provides a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 55% to 58% by weight of tricyclopentadiene, 0% to 3.6% by weight of tetracyclopentadiene, and 38% to 42% by weight of dicyclopentadiene, wherein the resin composition is a stable homogeneous liquid between 39 °C and 10 °C, between 39 Petition 870210098125, dated 10 / 25 / 2021, page 49 / 187 30 / 158 °C to 15 °C, 39 °C to 20 °C, between 39 °C to 25 °C, between 39 °C to 30 °C, between 39 °C to 35 °C, between 30 °C to 15 °C, between 35 °C to 20 °C, between 35 °C to 25 °C, between 25 °C to 20 °C, or between 25 °C and 10 °C.

[0086] Another embodiment of the invention provides a process for preparing a substantially vacuum-free article, comprising combining a resin composition and a catalyst composition to form a ROMP composition, wherein the catalyst composition comprises at least one carbene olefin metal metathesis catalyst and the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 55% to 58% by weight of tricyclopentadiene, 0% to 3.6% by weight of tetracyclopentadiene, and 38% to 42% by weight of dicyclopentadiene, and subjecting the ROMP composition to conditions effective for promoting an olefin metathesis reaction (e.g., a ring-opening metathesis polymerization reaction).

[0087] Another embodiment of the invention provides a fabrication article comprising a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 55% to 58% by weight of tricyclopentadiene, 0% to 3.6% by weight of tetracyclopentadiene, and 38% to 42% by weight of dicyclopentadiene.

[0088] Another embodiment of the invention provides a fabrication article, the fabrication article comprising a ROMP polymer, wherein the ROMP polymer is the reaction product of a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 55% to 58% by weight of tricyclopentadiene, 0% to 3.6% by weight of tetracyclopentadiene, and 38% to 42% Petition 870210098125, dated 10 / 25 / 2021, page 50 / 187 31 / 158 by weight of dicyclopentadiene.

[0089] Another embodiment of the invention provides a fabrication article, the fabrication article comprising a ROMP polymer composite, wherein the ROMP polymer composite is the reaction product of a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, wherein the resin composition comprises a cyclic olefin composition, wherein the cyclic olefin composition comprises 55% to 58% by weight of tricyclopentadiene, 0% to 3.6% by weight of tetracyclopentadiene, and 38% to 42% by weight of dicyclopentadiene.

[0090] Another embodiment of the invention provides a ROMP composition comprising a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; and a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 55% to 58% by weight of tricyclopentadiene, 0% to 3.6% by weight of tetracyclopentadiene, and 38% to 42% by weight of dicyclopentadiene.

[0091] Another embodiment of the invention provides a method comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 55% to 58% by weight of tricyclopentadiene, 0% to 3.6% by weight of tetracyclopentadiene, and 38% to 42% by weight of dicyclopentadiene; combining the catalyst composition and the resin composition to form a ROMP composition; and subjecting the ROMP composition to conditions effective for promoting an olefin metathesis reaction.

[0092] Another embodiment of the invention provides a method for manufacturing a ROMP polymer, comprising providing a catalyst composition comprising at least one carbene metal metathesis catalyst. Petition 870210098125, dated 10 / 25 / 2021, page 51 / 187 32 / 158 olefin; provide a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 55% to 58% by weight of tricyclopentadiene, 0% to 3.6% by weight of tetracyclopentadiene, and 38% to 42% by weight of dicyclopentadiene; combine the catalyst composition and the resin composition to form a ROMP composition; and subject the ROMP composition to conditions effective in promoting the polymerization of the ROMP composition.

[0093] Another embodiment of the invention provides a method comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 55% to 58% by weight of tricyclopentadiene, 0% to 3.6% by weight of tetracyclopentadiene, and 38% to 42% by weight of dicyclopentadiene; combining the catalyst composition and the resin composition to form a ROMP composition; contacting the ROMP composition with at least one substrate material; and subjecting the ROMP composition to conditions effective for promoting an olefin metathesis reaction.

[0094] Another embodiment of the invention provides a method for manufacturing a ROMP polymer composite, comprising providing a catalyst composition comprising at least one carbene olefin metal metathesis catalyst; providing a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 55% to 58% by weight of tricyclopentadiene, 0% to 3.6% by weight of tetracyclopentadiene, and 38% to 42% by weight of dicyclopentadiene; combining the catalyst composition and the resin composition to form a ROMP composition; contacting the ROMP composition with at least one substrate material; and subjecting the ROMP composition to conditions effective in promoting the Petition 870210098125, dated 10 / 25 / 2021, page 52 / 187 33 / 158 polymerization of the ROMP composition.

[0095] In another embodiment, the invention provides a ROMP composition comprising a catalyst composition comprising at least one olefin metal carbene metathesis catalyst and a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other olefins, wherein the ROMP composition or the resin composition is 39.9°C to 20°C, 39.9°C to 25°C, 39.9°C to 30°C, 35°C to 20°C, or 35°C to 25°C, and the ROMP composition may be added to a mold preheated to 60°C. 200 °C, 60 °C to 150 °C, 60 °C to 120 °C, 60 °C to 100 °C, 60 °C to 90 °C, or 60 °C to 80 °C, and / or the mold can be rapidly heated (e.g., at a rate greater than 0.5 °C / min) to prepare molded polymer articles and / or polymer composite articles.where the resulting molded polymer articles and / or polymer composite articles are free or substantially free of defects.

[0096] In another embodiment, the invention provides a ROMP composition comprising a catalyst composition comprising at least one olefin metal carbene metathesis catalyst and a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00 to 70.00 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and 64.99 to 26.00 percent by weight of dicyclopentadiene, wherein the ROMP composition or the resin composition is 39.9 °C to 20 °C, 39.9 °C to 25 °C, 39.9 °C to 30 °C, 35 °C to 20 °C, or 35 °C to 25 °C, and the ROMP composition may be added to a preheated mold at 60 °C to 200 °C, 60 °C to 150 °C, 60 °C to 120 °C, 60 °C to 100 °C, 60 °C to 90 °C, or 60 °C to 80 °C, and / or the mold can be rapidly heated (for example, Petition 870210098125, dated 10 / 25 / 2021, p. 53 / 187 34 / 158 at a rate greater than 0.5 °C / min) to prepare molded polymer articles and / or polymer composite articles, wherein the resulting molded polymer articles and / or polymer composite articles are free or substantially free of defects.

[0097] In another embodiment, the invention provides for the use of a cyclic olefin composition comprising 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other olefins to prepare a resin composition.

[0098] In another embodiment, the invention provides for the use of a cyclic olefin composition comprising 35.00 to 70.00 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and 64.99 to 26.00 percent by weight of dicyclopentadiene to prepare a resin composition.

[0099] In another embodiment, the invention provides for the use of a cyclic olefin composition to prepare a resin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other olefins, wherein the cyclic olefin composition is a stable homogeneous liquid between 39 °C and 10 °C, between 39 °C and 15 °C, 39 °C and 20 °C, between 39 °C and 25 °C, between 39 °C and 30 °C, between 39 °C and 35 °C, between 30 °C and 15 °C, between 35 °C and 20 °C, between 35 °C and 25 °C, between 25 °C to 20 °C, or between 25 °C to 10 °C.

[00100] In another embodiment, the invention provides for the use of a cyclic olefin composition to prepare a resin composition, wherein the cyclic olefin composition comprises 35.00 to 70.00 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and 64.99 to 26.00 percent by weight of dicyclopentadiene, wherein the resin composition is a stable homogeneous liquid between 39 °C and 10 °C, between 39 °C and 15 °C, 39 °C and 20 °C, Petition 870210098125, dated 10 / 25 / 2021, page 54 / 187 35 / 158 between 39 °C to 25 °C, between 39 °C to 30 °C, between 39 °C to 35 °C, between 30 °C to 15 °C, between 35 °C to 20 °C, between 35 °C to 25 °C, between 25 °C to 20 °C, or between 25 °C to 10 °C.

[00101] In another embodiment, the invention provides for the use of a cyclic olefin composition to prepare a polymer article that is free or substantially free of defects, wherein the polymer article is formed by a polymerization reaction of a ROMP composition, the ROMP composition comprising a resin composition and a catalyst composition comprising at least one olefin carbene metal metathesis catalyst, the resin composition comprising a cyclic olefin composition comprising 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other olefins.

[00102] In another embodiment, the invention provides for the use of a cyclic olefin composition to prepare a polymer article, wherein the polymer article is formed by a polymerization reaction of a ROMP composition, the ROMP composition comprising a resin composition and a catalyst composition comprising at least one olefin carbene metal metathesis catalyst, the resin composition comprising a cyclic olefin composition comprising 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other olefins.

[00103] In another embodiment, the invention provides for the use of a cyclic olefin composition to prepare a polymeric composite article that is free or substantially free of defects, wherein the polymeric composite article is formed by a polymerization reaction of a ROMP composition in contact with a substrate material, the ROMP composition comprising a resin composition and a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, the resin composition Petition 870210098125, dated 10 / 25 / 2021, page 55 / 187 36 / 158 comprising a cyclic olefin composition comprising 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other olefins.

[00104] In another embodiment, the invention provides for the use of a cyclic olefin composition to prepare a polymeric composite article, wherein the polymeric composite article is formed by a polymerization reaction of a ROMP composition in contact with a substrate material, the ROMP composition comprising a resin composition and a catalyst composition comprising at least one olefin carbene metal metathesis catalyst, the resin composition comprising a cyclic olefin composition comprising 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene, and up to 64.99% by weight of one or more other olefins.

[00105] In another embodiment, the invention provides for the use of a cyclic olefin composition to prepare a polymer article that is free or substantially free of defects, wherein the polymer article is formed by a polymerization reaction of a ROMP composition, the ROMP composition comprising a resin composition and a catalyst composition comprising at least one olefin carbene metal metathesis catalyst, the resin composition comprising a cyclic olefin composition comprising 35.00 to 70.00 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and 64.99 to 26.00 percent by weight of dicyclopentadiene.

[00106] In another embodiment, the invention provides for the use of a cyclic olefin composition to prepare a polymer article, wherein the polymer article is formed by a polymerization reaction of a ROMP composition, the ROMP composition comprising a resin composition and a Petition 870210098125, dated 10 / 25 / 2021, page 56 / 187 37 / 158 catalyst composition comprising at least one carbene olefin metal metathesis catalyst, the resin composition comprising a cyclic olefin composition comprising 35.00 to 70.00 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and 64.99 to 26.00 percent by weight of dicyclopentadiene.

[00107] In another embodiment, the invention provides for the use of a cyclic olefin composition to prepare a polymeric composite article that is free or substantially free of defects, wherein the polymeric composite article is formed by a polymerization reaction of a ROMP composition in contact with a substrate material, the ROMP composition comprising a resin composition and a catalyst composition comprising at least one olefin carbene metal metathesis catalyst, the resin composition comprising a cyclic olefin composition comprising 35.00 to 70.00 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and 64.99 to 26.00 percent by weight of dicyclopentadiene.

[00108] In another embodiment, the invention provides for the use of a cyclic olefin composition to prepare a polymeric composite article, wherein the polymeric composite article is formed by a polymerization reaction of a ROMP composition in contact with a substrate material, the ROMP composition comprising a resin composition and a catalyst composition comprising at least one olefin carbene metal metathesis catalyst, the resin composition comprising a cyclic olefin composition comprising 35.00 to 70.00 percent by weight of tricyclopentadiene, 0.01 to 4.00 percent by weight of tetracyclopentadiene, and 64.99 to 26.00 percent by weight of dicyclopentadiene.

[00109] Forms of embodiment here are not intended to be interpreted in a limiting sense. Various modifications in the form and detail of the embodiments of Petition 870210098125, dated 10 / 25 / 2021, page 57 / 187 38 / 158 invention, as well as other aspects and variations of the invention, will be evident to a skilled technician in light of the detailed description and examples that follow. DETAILED DESCRIPTION OF THE DISCLOSURE Terminology and Definitions

[00110] Unless otherwise indicated, the invention is not limited to specific reagents, substituents, catalysts, cyclic olefins, resin compositions, cyclic olefin compositions, catalyst compositions, reaction conditions, or the like, as such may vary. Also, it is understood that the terminology used herein is for the purpose of describing particular embodiments only and should not be construed as being limiting.

[00111] As used in the descriptive report and appended claims, the singular forms “a / an” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “an α-olefin” includes a single α-olefin as well as a combination or mixture of two or more α-olefins, reference to “a substituent” encompasses a single substituent as well as two or more substituents, and the like.

[00112] As used in the descriptive report and appended claims, the terms “for example”, “such as”, or “including” are intended to introduce examples that further clarify the general subject matter. Unless otherwise specified, these examples are provided only as an aid to understanding the invention and are not intended to be limiting in any way.

[00113] In this descriptive report and in the claims that follow, reference will be made to various terms, which will be defined to have the following meanings:

[00114] The term “alkyl”, as used herein, refers to a linear, branched or cyclic saturated hydrocarbon group, typically, though not necessarily, containing 1 to about 24 carbon atoms, preferably 1 to Petition 870210098125, dated 10 / 25 / 2021, p. 58 / 187 39 / 158 about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl, and the like. Generally, though again not necessarily, alkyl groups here contain from 1 to about 12 carbon atoms. The term “lower alkyl” refers to an alkyl group of 1 to 6 carbon atoms, and the specific term “cycloalkyl” refers to a cyclic alkyl group, typically having 4 to 8, preferably 5 to 7, carbon atoms. The term “substituted alkyl” refers to alkyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkyl” and “heteroalkyl” refer to alkyl in which at least one carbon atom is substituted with a heteroatom.Unless otherwise indicated, the terms "alkyl" and "lower alkyl" include linear, branched, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkyl and lower alkyl, respectively.

[00115] The term “alkylene”, as used herein, refers to a linear, branched or cyclic difunctional alkyl group, where “alkyl” is as defined above.

[00116] The term “alkenyl”, as used herein, refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 24 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like. Preferred alkenyl groups herein contain from 2 to about 12 carbon atoms. The term “lower alkenyl” refers to an alkenyl group of 2 to 6 carbon atoms, and the specific term “cycloalkenyl” refers to a cyclic alkenyl group, preferably having 5 to 8 carbon atoms. The term “substituted alkenyl” refers to alkenyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkenyl” and “heteroalkenyl” refer to alkenyl in which at least one carbon atom is substituted with a heteroatom. Unless otherwise indicated, the terms “alkenyl” and “alkenyl” Petition 870210098125, dated 10 / 25 / 2021, p. 59 / 187 40 / 158 inferior” include linear, branched, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkenyl and inferior alkenyl, respectively.

[00117] The term “alkenylene”, as used herein, refers to a linear, branched or difunctional cyclic alkenyl group, where “alkenyl” is as defined above.

[00118] The term “alkynyl,” as used herein, refers to a linear or branched hydrocarbon group of 2 to about 24 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Preferred alkynyl groups herein contain 2 to about 12 carbon atoms. The term “lower alkynyl” refers to an alkynyl group of 2 to 6 carbon atoms. The term “substituted alkynyl” refers to alkynyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkynyl” and “heteroalkynyl” refer to alkynyl in which at least one carbon atom is substituted with a heteroatom. Unless otherwise indicated, the terms “alkynyl” and “lower alkynyl” include linear, branched, unsubstituted, substituted, and / or heteroatom-containing alkynyl and lower alkynyl, respectively.

[00119] The term “alkoxy”, as used herein, refers to an alkyl group linked via a single, terminal ether bond; that is, an “alkoxy” group may be represented as -O-alkyl where alkyl is as defined above. A “lower alkoxy” group refers to an alkoxy group containing from 1 to 6 carbon atoms. Analogously, “alkenyloxy” and “lower alkenyloxy” respectively refer to an alkenyl and lower alkynyl group linked via a single, terminal ether bond, and “alkynyloxy” and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group linked via a single, terminal ether bond.

[00120] The term “aryl”, as used herein, and unless otherwise specified, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or Petition 870210098125, dated 10 / 25 / 2021, p. 60 / 187 41 / 158 indirectly linked (such that different aromatic rings are linked to a common group such as a methylene or ethylene moiety). Preferred aryl groups contain from 5 to 24 carbon atoms, and particularly preferred aryl groups contain from 5 to 14 carbon atoms. Exemplary aryl groups contain one or two fused or linked aromatic rings, for example, penyl, naphthyl, bipenyl, diphenyl ether, diphenylamine, benzophenone, and the like. “Substituted aryl” refers to an aryl moiety substituted with one or more substituent groups, and the terms “heteroatom-containing aryl” and “heteroaryl” refer to aryl substituents in which at least one carbon atom is substituted with a heteroatom, as will be described in detail below.

[00121] The term “aryloxy”, as used herein, refers to an aryl group connected via a single, terminal ether bond, wherein “aryl” is as defined above. An “aryloxy” group may be represented as -O-aryl where aryl is as defined above. Preferred aryloxy groups contain from 5 to 24 carbon atoms, and particularly preferred aryloxy groups contain from 5 to 14 carbon atoms. Examples of aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxyphenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.

[00122] The term “alquaryl” refers to an aryl group with an alkyl substituent, and the term “aralkyl” refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined above. Preferred alquaryl and aralkyl groups contain from 6 to 24 carbon atoms, and particularly preferred alquaryl and aralkyl groups contain from 6 to 16 carbon atoms. Alkyl groups include, without limitation, p-methylpenyl, 2,4-dimethylpenyl, p-cyclohexylpenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethylcyclopenta-1,4-diene, and the like. Examples of aralkyl groups include, without limitation, benzyl, 2-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclo Petition 870210098125, dated 10 / 25 / 2021, p. 61 / 187 42 / 158 hexylmethyl, and the like. The terms “alquaryloxy” and “aralkyloxy” refer to substituents of the formula -OR where R is alkyl or aralkyl, respectively, as exactly defined.

[00123] The term “acyl” refers to substituents having the formula -(CO)-alkyl, -(CO)-aryl, -(CO)-aralkyl, -(CO)-alquaryl, -(CO)-alkenyl, or -(CO)-alkynyl, and the term “acyloxy” refers to substituents having the formula -O(CO)-alkyl, -O(CO)-aryl, -O(CO)-aralkyl, -O(CO)-alquaryl, -O(CO)-alkenyl, -O(CO)-alkynyl wherein “alkyl”, “aryl”, “aralkyl”, alquaryl, alkenyl, and alkynyl are as defined above.

[00124] The terms “cyclic” and “ring” refer to alicyclic or aromatic groups that may or may not be substituted and / or contain a heteroatom, and which may be monocyclic, bicyclic, or polycyclic. The term “alicyclic” is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic, or polycyclic.

[00125] The terms “halo” and “halogen” are used in the conventional sense to refer to a substituent for chlorine, bromine, fluorine, or iodine.

[00126] “Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species, such as alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and the like. The term “lower hydrocarbyl” refers to a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the term “hydrocarbylene” refers to a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species. The term "lower hydrocarbylene" refers to a hydrocarbylene group with 1 to 6 carbon atoms."Substituted hydrocarbyl" refers to a substituted hydrocarbyl with one or more substituent groups. Petition 870210098125, dated 10 / 25 / 2021, p. 62 / 187 43 / 158 and the terms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom. Similarly, “substituted hydrocarbylene” refers to hydrocarbylene substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbylene” and “heterohydrocarbylene” refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom. Unless otherwise indicated, the term “hydrocarbyl” and “hydrocarbylene” should be interpreted as including substituted and / or heteroatom-containing hydrocarbyl and heteroatom-containing hydrocarbylene moieties, respectively.

[00127] The term “heteroatom-containing” as in a “heteroatom-containing hydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms are replaced with an atom other than carbon, for example, nitrogen, oxygen, sulfur, phosphorus, or silicon, typically nitrogen, oxygen, or sulfur. Similarly, the term “heteroalkyl” refers to an alkyl substituent that is heteroatom-containing, the term “heterocyclic” refers to a cyclic substituent that is heteroatom-containing, the terms “heteroaryl” and “heteroaromatic” respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like. It should be noted that a “heterocyclic” group or compound may or may not be aromatic, and furthermore that “heterocycles” can be monocyclic, bicyclic, or polycyclic as described above with respect to the term “aryl”.Examples of heteroalkyl groups include, without limitation, alkoxyaryl, substituted alkylsulfanyl-alkyl, N-alkylated aminoalkyl, and the like. Examples of heteroaryl substituents include, without limitation, pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc., and examples of alicyclic groups containing heteroatoms include, without limitation, pyrrolidine, morpholino, piperazine, piperidine, etc.

[00128] For “substituted” as in “substituted hydrocarbyl”, “alkyl Petition 870210098125, dated 10 / 25 / 2021, page 63 / 187 44 / 158 substituted”, “substituted aryl” and the like, as alluded to in some of the definitions previously mentioned, means that in the hydrocarbyl, alkyl, aryl or other moiety, at least one hydrogen atom bonded to a carbon atom (or other) is substituted with one or more non-hydrogen substituents. Examples of such substituents include, without limitation: functional groups referred to herein as “Fn”, such as halo, hydroxyl, sulfhydryl, C1-C24 alkoxy, C2-C24 alkenyloxy, C2-C24 alkynyloxy, C5-C24 aryloxy, C6-C24 aralkyloxy, C6-C24 alquaryloxy, acyl (including C2-C24 alkylcarbonyl (-CO-alkyl) and C6-C24 arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl, including C2-C24 alkylcarbonyloxy) (-O-CO-alquila) e arilcarbonilóxi C6-C24 (-O-COarila)), alcoxicarbonila C2-C24 (-(CO)-O-alquila), ariloxicarbonila C6-C24 (-(CO)-Oarila), halocarbonila (-CO)-X onde X é halo), alquilcarbonato C2-C24 (-O-(CO)-Oalquila), arilcarbonato C6-C24 (-O-(CO)-O-arila), carbóxi (-CO-OH),carboxylate (-COO), carbamoyl (-(CO)-NH2), mono-(C1-C24 alkyl)-substituted carbamoyl (-(CO)NH(C1-C24 alkyl)), di-(C1-C24 alkyl)-substituted carbamoyl (-(CO)-N(C1C24 alkyl)2), mono-(C1-C24 haloalkyl)-substituted carbamoyl (-(CO)-NH(haloalkyl C1C24)), di-(haloalkyl C1-C24)-substituted carbamoyl (-(CO)-N(haloalkyl C1C24)2), mono-(aryl C5-C24)-substituted carbamoyl (-(CO)-NH-aryl), di-(aryl C5-C24)carbamoyl substituted (-(CO)-N(aryl C5-C24)2), di-N-(alkyl C1-C24), N-(C5-C24 aryl)substituted carbamoyl (-(CO)-N(C1-C24 alkyl)(C5-C24 aryl), thiocarbamoyl (-(CS)NH2), mono-(C1-C24 alkyl)-substituted thiocarbamoyl (-(CS)-NH(C1-C24 alkyl)), di(C1-C24 alkyl)-substituted thiocarbamoyl (-(CS)-N(alkyl C1-C24)2), mono-(aryl C5C24)-substituted thiocarbamoyl (-(CS)-NH-aryl), di-(aryl C5-C24)-substituted thiocarbamoyl (-(CS)-N(aryl C5-C24)2), di-N-(alkyl C1-C24), substituted N-(aryl C5-C24)thiocarbamoyl (-(CS)-N(alkyl C1-C24)(aryl C5-C24),carbamide (-NH-(CO)NH2), cyano (-C^N), cyanate (-Ο^ξΝ), thiocyanate (-SC^N), isocyanate (-N=C=O), thioisocyanate (-N=C=S), formyl (-(CO)-H), thioformyl (-(CS)-H), amino (-NH2), mono(alkyl C1-C24)-substituted amino (-NH(C1-C24 alkyl), di-(C1-C24 alkyl)-amino, Petition 870210098125, dated 10 / 25 / 2021, page 64 / 187 45 / 158 substituted (-N(alkyl 61-624)2), substituted mono-(aryl C5-C24)-amino (-NH(aryl C5C24), substituted di-(aryl C5-C24)-amino (-N(aryl 65-624)2), C2-C24 alkylamido (-NH(CO)-alkyl), C6-C24 arylamido (-NH-(CO)-aryl), imino (-CR=NH where R includes without limitation hydrogen, C1-C24 alkyl, C5-C24 aryl, C6-C24 alkyl, C6-C24 aralkyl, etc.), C2-C20 alkylimino (-CR=N(alkyl), where R includes without limitation hydrogen, C1-C24 alkyl, C5-C24 aryl, C6-C24 alkyl, C6-C24 aralkyl, etc.), arylimino (CR=N(aryl), where R includes without limitation hydrogen, C1-C20 alkyl, C5-C24 aryl, C6-C24 alquaryl, C6-C24 aralkyl, etc.), nitro (-NO2), nitroso (-NO), sulfo (-SO2-OH), sulfonate (-SO2-O), C1-C24 alkylsulfanyl (-S-alkyl; also called “alkylthio”), C5-C24 arylsulfanyl (-S-aryl;also called “arylthio”), C1-C24 alkylsulfinyl ((SO)-alkyl), C5-C24 arylsulfinyl (-(SO)-aryl), C1-C24 alkylsulfonyl (-SO2-alkyl), C1-C24 monoalkylaminosulfonyl (-SO2-N(H) alkyl), C1-C24 dialkylaminosulfonyl (-SO2-N(alkyl)2), C5-C24 arylsulfonyl (-SO2-aryl), boryl (-BH2), boron (-B(OH)2), boronate (-B(OR)2 where R includes without limitation alkyl or other hydrocarbyl), phosphono (-P(O)(OH)2), phosphonate (-R(O)(O)2), phosphinate (-P(O)(O-)), phospho (-PO2), and phosphine (PH2); and the C1-C24 alkyl hydrocarbyl moieties (preferably C1-C12 alkyl, more preferably C1-C6 alkyl), C2-C24 alkenyl moieties (preferably C2-C12 alkenyl, more preferably C2-C6 alkenyl), C2-C24 alkynyl moieties (preferably C2-C12 alkynyl, more preferably C2-C6 alkynyl), C5-C24 aryl moieties (preferably C5-C14 aryl moieties), C6-C24 alquaryl moieties (preferably C6-C16 alquaryl moieties), and C6-C24 aralkyl moieties (preferably C6-C16 aralkyl moieties).

[00129] By “functionalized” as in “functionalized hydrocarbyl”, “functionalized alkyl”, “functionalized olefin”, “functionalized cyclic olefin” and the like, it is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bonded to a carbon atom (or other) is replaced with one or more functional groups such as those described above. The term “functional group” is meant to include any functional species that Petition 870210098125, dated 10 / 25 / 2021, page 65 / 187 46 / 158 is suitable for the use described herein. In particular, as used herein, a functional group would necessarily possess the ability to react with or bind to corresponding functional groups on a substrate surface.

[00130] Furthermore, the aforementioned functional groups may, if a particular group permits, be further replaced with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically mentioned above. Similarly, the aforementioned hydrocarbyl moieties may be further replaced with one or more additional functional groups or hydrocarbyl moieties as noted above.

[00131] “Optional” or “optionally” means that the circumstance subsequently described may or may not occur, so the description includes instances where the circumstance occurs and instances where it does not occur. For example, the phrase “optionally substituted” means that a non-hydrogen substituent may or may not be present on a given atom, and thus the description includes structures in which a non-hydrogen substituent is present and structures in which a non-hydrogen substituent is not present.

[00132] The term “substrate material,” as used herein, is intended to generally mean any material that the resin compositions of the invention may be contacted with, applied to, or have the substrate material incorporated into the resin. Without limitation, such materials include reinforcing materials such as filaments, fibers, slivers, mats, weaves, fabrics, mesh material, cloth or other known structures, glass fibers and fabrics, carbon fibers and fabrics, aramid fibers and fabrics, and polyolefin or other polymer fibers or fabrics. Other suitable substrate materials include metallic density modulators, microparticulate density modulators such as microspheres, glass microspheres, ceramic microspheres, microballoons, cenospheres, and macroparticulate density modulators such as glass or ceramic beads. A polymer composite Petition 870210098125, dated 10 / 25 / 2021, page 66 / 187 47 / 158 of ROMP can be understood as a substrate material or a mixture of different substrate materials.

[00133] The expressions “substantially defect-free” and “substantially defect-free” mean that there is less than one visible defect per square inch of polymer, as observed with the naked eye. A defect includes, for example, undesirable pores, cavities, bubbles, voids, mesh line and / or internal stress structures. In particular, the present invention mitigates against problems related to defects that are thought to be caused by volatilization of low-boiling compounds present in cyclic olefin compositions or generated during the polymerization cycle (exotherm) as discussed herein. A volatilization-related defect may be visually present on the surface of the ROMP polymer article and / or ROMP polymer composite article. A volatilization-related defect may also be visually present within the ROMP polymer article and / or ROMP polymer composite article when the article is cut into sections.Other examples of defects that may also be present can be related to poor mixing, such as trapped air bubbles and / or surface defects related to imperfect mold surfaces.

[00134] As is known in the art, weight percent (% by weight) can be represented by area percent (% by area) of gas chromatography (GC). Consequently, GC area percent obtained from GC was reported as % by weight. Weight percent (% by weight) and % by weight are used interchangeably herein. Membership Promoter

[00135] The adhesion promoters that can be used in the present invention disclosed herein are, in general, compounds containing at least two isocyanate groups (such as, for example, methylene diphenyl diisocyanate and diisocyanate of Petition 870210098125, dated 10 / 25 / 2021, page 67 / 187 48 / 158 hexamethylene). The adhesion promoter may be a diisocyanate, triisocyanate, or polyisocyanate (i.e., containing four or more isocyanate groups). The adhesion promoter may be a mixture of at least one diisocyanate, triisocyanate, or polyisocyanate. In a more particular aspect of the invention, the adhesion promoter comprises, or is limited to, a diisocyanate compound, or mixtures of diisocyanate compounds. Such adhesion promoters and their use are described in International Publication PCT Number WO 2012 / 174502.

[00136] In general, adhesion promoters that can be used in the present invention can be any compound having at least two isocyanate groups. Suitable adhesion promoters include, without limitation, isocyanate compounds comprising at least two isocyanate groups, and wherein the compounds are selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functionalized hydrocarbyl compounds. As described above, suitable hydrocarbyl adhesion promoter compounds generally include alkyl, cycloalkyl, alkylene, alkenyl, alkynyl, aryl, cycloalkyl, alquaryl, and aralkyl compounds. Substituted heteroatom-containing and functionalized hydrocarbyl adhesion promoter compounds include the aforementioned hydrocarbyl compounds, as well as variations thereof observed above.

[00137] The adhesion promoters that can be used in the present invention may be an alkyl diisocyanate. An alkyl diisocyanate refers to a linear, branched, saturated or unsaturated cyclic hydrocarbon group, typically, though not necessarily, containing 1 to about 24 carbon atoms, preferably a diisocyanate containing 2 to about 12 carbon atoms, and more preferably a diisocyanate containing 6 to 12 carbon atoms, such as hexamethylene diisocyanate (HDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like. Cyclodialkyl isocyanates contain Petition 870210098125, dated 10 / 25 / 2021, page 68 / 187 49 / 158 cyclic alkyl group, typically having 4 to 16 carbon atoms. A preferred cyclodialkyl isocyanate containing 6 to about 12 carbon atoms are cyclohexyl, cyclooctyl, cyclodecyl, and the like. A more preferred cyclodialkyl isocyanate originates as a condensation product of acetone called 5-isocyanato-1(isocyanatomethyl)-1,3,3-trimethylcyclohexane, commonly known as isophorone diisocyanate (IPDI) and the isomers isocyanato-[(isocyanatocyclohexyl)methyl]cyclohexane (H12MDI). H12MDI is derived from the hydrogenated form of methylene diphenyl diisocyanate (MDI) of aryl diisocyanate.

[00138] The adhesion promoters that can be used in the present invention may be an aryl diisocyanate. Aryl diisocyanates refer to aromatic diisocyanates containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are linked to a common group such as a methylene or ethylene moiety). Preferred aryl diisocyanates contain from 5 to 24 carbon atoms, and particularly preferred aryl diisocyanates contain from 5 to 14 carbon atoms. Exemplary aryl diisocyanates contain one or two fused or linked aromatic rings, for example, penyl, tolyl, xylyl, naphthyl, bipenyl, diphenyl ether, benzophenone, and the like.Preferred aromatic diisocyanates include toluene diisocyanates, tetramethylxylene diisocyanate (TMXDI), and methylene diphenyl diisocyanate (MDI), which may comprise any mixture of their three isomers, 2,2'-MDI, 2,4'-MDI, and 4,4'-MDI.

[00139] The adhesion promoters that can be used in the present invention may be an isocyanate-containing polymer, such as, for example, diisocyanates. Isocyanate-containing polymer refers to a polymer containing two or more terminal and / or pendant alkyl or aryl isocyanate groups. Isocyanate-containing polymers generally have minimal solubility in the resin to provide improved mechanical properties. Preferred isocyanate-containing polymers Petition 870210098125, dated 10 / 25 / 2021, page 69 / 187 50 / 158 includes, but is not limited to, PM200 (poly MDI), Lupranate® (BASF poly MDI), Krasol® isocyanate-terminated polybutadiene prepolymers, such as, for example, Krasol® LBD2000 (TDI-based), Krasol® LBD3000 (TDI-based), Krasol® NN-22 (MDI-based), Krasol® NN-23 (MDI-based), Krasol® NN-25 (MDI-based), and the like. Krasol® isocyanate-terminated polybutadiene prepolymers are available from Cray Valley.

[00140] The adhesion promoters that can be used in the present invention can be a trimer of alkyl diisocyanates and aryl diisocyanates. In its simplest form, any combination of polyisocyanate compounds can be trimerized to form an isocyanurate ring containing functional isocyanate groups. Trimers of alkyl diisocyanate and aryl diisocyanates may also be referred to as alkyl diisocyanate isocyanurates or aryl diisocyanates. Preferred alkyl diisocyanate and aryl diisocyanate trimers include, but are not limited to, hexamethylene diisocyanate (HDIt) trimer, isophorone diisocyanate trimer, toluene diisocyanate trimer, tetramethylxylene diisocyanate trimer, methylene diphenyl diisocyanate trimers, and the like.The most preferred adhesion promoters are toluene diisocyanates, tetramethylxylene diisocyanate (TMXDI), and methylene diphenyl diisocyanate (MDI) including any mixture of its three isomers 2,2'-MDI, 2,4'-MDI and 4,4'-MDI; liquid MDI; solid MDI; hexamethylenediisocyanate trimer (HDIt); hexamethylenediisocyanate (HDI); isophorone diisocyanate (IPDI); 4,4'-methylene bis(cyclohexyl isocyanate) (H12MDI); polymeric MDI (PM200); MDI prepolymer (Lupranate® 5080); liquid carbodiimide-modified 4,4'-MDI (Lupranate®MM103); liquid MDI (Lupranate®MI); liquid MDI (Mondur®ML); and liquid MDI (Mondur®MLQ). Even more preferred adhesion promoters are methylene diphenyl diisocyanate (MDI), including any mixture of its three isomers 2,2'-MDI, 2,4'-MDI and 4,4'-MDI; liquid MDI; solid MDI; hexamethylene diisocyanate trimer (HDIt); diisocyanate. Petition 870210098125, dated 10 / 25 / 2021, page 70 / 187 51 / 158 hexamethylene (HDI); isophorone diisocyanate (IPDI); 4,4'-methylene bis(cyclohexyl isocyanate) (H12MDI); polymeric MDI (PM200); MDI prepolymer (Lupranate® 5080); liquid carbodiimide-modified 4,4'-MDI (Lupranate® MM103); liquid MDI (Lupranate® MI); liquid MDI (Mondur® ML); liquid MDI (Mondur® MLQ).

[00141] Any concentration of adhesion promoter that improves the mechanical properties of the olefin composite (e.g., ROMP polymer composite) is sufficient for the invention. In general, suitable amounts of adhesion promoter range from 0.001 to 50 phr, particularly 0.05 to 10 phr, more particularly 0.1 to 10 phr, or even more particularly 0.5 to 4.0 phr. One or more adhesion promoters may be used in the present invention.

[00142] Additional adhesion promoters suitable for use in the present invention comprise functionalized silanes of the formula Fn-(A)n-Si(Y*)3, wherein Y* is selected from halide (preferably chloride) or OR; Fn is a functional group selected from acrylate, methacrylate, allyl, vinyl, alkene, cycloalkene, or norbornene; A is a divalent linking group selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or heteroatom-containing substituted hydrocarbylene; n is 0 or 1; and R is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl, preferably lower alkyl, more preferably methyl, ethyl, or isopropyl; and a peroxide selected from dialkyl and diaryl peroxides.

[00143] Additional adhesion promoters for use in the present invention and methods for their use include those disclosed in International Patent Application No. PCT / US00 / 03002, the contents of which are incorporated herein by reference. Compounds Comprising a Functional Group Containing a Heteroatom and an Active Olefin Metathesis

[00144] The compound comprising a heteroatom-containing functional group and an active olefin metathesis typically contains between 2 and 20 Petition 870210098125, dated 10 / 25 / 2021, page 71 / 187 52 / 158 carbons with hydroxyl, amine, thiol, phosphorus, or silane functional groups. Compounds comprising a heteroatom-containing functional group and an active olefin metathesis that can be used in the present invention disclosed herein are, in general, compounds containing at least one heteroatom-containing functional group and at least one active olefin metathesis and are of the following general structure: (OM)-(Q*)n-(X*)-H where OM, Q*, and X* are as follows: OM is an active olefin metathesis fragment selected from cyclic olefins and acyclic olefins, where the carbon-carbon double bond is typically not tetra-substituted (e.g., at least one substituent is a hydrogen); Q* is an optional linking group (e.g., n = 0 or 1) such as, for example, a hydrocarbylene (including, for example, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and heteroatom-containing substituted hydrocarbylene, such as substituted and / or heteroatom-containing alkylene) or a (CO)- group; and X* is oxygen, sulfur, or a heteroatom-containing fragment such as N(RX), P(RX), OP(RX), OP(RX)O, OP(ORX)O, P(=O)(RX), OP(=O)(RX), OP(=O)(RX)O, OP(=O)(ORX)O, Si(RX)2, Si(RX)2O, Si(ORX)2O, or Si(RX)(ORX)O, wherein each RX is, independently of the others, a hydrogen or a hydrocarbyl group optionally comprising other functional groups. Each RX is, independently of the others, most commonly a hydrogen, aryl, or lower alkyl group.

[00145] Active olefin metatheses include cyclic olefins as described herein, where such cyclic olefins may be optionally substituted, C5 to C24 hydrocarbons optionally containing heteroatoms, mono-unsaturated, di-unsaturated, or poly-unsaturated which may be mono-, di-, or polycyclic. The cyclic olefin may, in general, be any strained or non-strained cyclic olefin, Petition 870210098125, dated 10 / 25 / 2021, page 72 / 187 53 / 158 provided that the cyclic olefin is capable of participating in a ROMP reaction individually or as part of a cyclic ROMP olefin composition. Active olefin metasesis also includes acyclic olefins, where such acyclic olefins may be optionally substituted, optionally containing heteroatoms, C2 to C30 monounsaturated, diunsaturated or polyunsaturated hydrocarbons, typically C2 to C20 hydrocarbons, or more typically C2 to C12 hydrocarbons. Acyclic olefins may contain one or more terminal olefins and / or one or more internal olefins, and / or any combination of terminal olefins and / or internal olefins.

[00146] In the heteroatom-containing functional group, X* is commonly oxygen, sulfur, or NRXe is most commonly oxygen, i.e., a substituted hydroxyolefin. Preferred compounds comprising a heteroatom-containing functional group and an active olefin metathesis include, but are not limited to, 5-norbornene-2-methanol (NB-MeOH); 2-hydroxyethyl bicyclo[2,2,1]hept-2-enecarboxylate (HENB); 2-hydroxyethyl acrylate (HEA); allyl alcohol; oleyl alcohol; 9-decen-1-ol; vinyl alcohol, allyl alcohol, cis-13-dodecenol, and trans-9-octadecenol, and other unsaturated alcohols, norbornyl alcohol, 2-cycloocten-1-ol, 2-cyclooctadiene-1-ol, and p-vinylphenol, and other alcohols having an alicyclic structure; 2-hydroxyethyl methacrylate;2-hydroxy-methacrylate of 3-acryloxypropyl, ethoxylated hydroxyethyl acrylate, ethoxylated hydroxyethyl methacrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate, phenol acrylate, phenol methacrylate, bisphenol A type epoxy acrylate, novolac type epoxy acrylate, and brominated bisphenol A type epoxy acrylate, and other methacrylates or acrylics having one or more methacrylate or acrylate groups and hydroxyl groups, etc.;

[00147] The compound comprising a heteroatom-containing functional group and an active olefin metathesis is combined with a compound containing at least two isocyanate groups and pre-reacted to provide a Petition 870210098125, dated 10 / 25 / 2021, page 73 / 187 54 / 158 adhesion-promoting composition having storage stability in resin and providing an olefin metathesis composite with improved mechanical properties. Any concentration of a compound comprising a heteroatom-containing functional group and an active olefin metathesis is sufficient for use in the preparation of adhesion-promoting compositions of the invention, wherein the mol% or mol equivalents of a compound comprising a heteroatom-containing functional group and an active olefin metathesis used to form the pre-reacted mixture is less than the mol% or mol equivalents of a compound containing at least two isocyanate groups used to form the pre-reacted mixture. Mole ratios of a compound comprising a heteroatom-containing functional group and an active olefin metathesis relative to a compound containing at least two isocyanate groups range from 0.001:1 to 0.90:1.Preferred mole ratios of a compound comprising a heteroatom-containing functional group and an active olefin metathesis relative to a compound containing at least two isocyanate groups range from 0.01:1 to 0.75:1, particularly 0.01:1 to 0.5:1, more particularly 0.02:1 to 0.25:1. One skilled in the art will recognize that the optimum ratio of a compound comprising a heteroatom-containing functional group and an active olefin metathesis to a compound containing at least two isocyanate groups may need to be adjusted as a function of the amount of adhesion-promoting composition added to the resin composition.

[00148] In another embodiment, a compound comprising a heteroatom-containing functional group and an active olefin metathesis can be combined with a resin composition comprising a cyclic olefin composition, providing an olefin metathesis composite with improved mechanical properties. A compound comprising a heteroatom-containing functional group and an active olefin metathesis can be combined with a resin composition comprising a cyclic olefin composition and a Petition 870210098125, dated 10 / 25 / 2021, page 74 / 187 55 / 158 adhesion promoter providing an olefin metathesis composite with improved mechanical properties. Any concentration of a compound comprising a heteroatom-containing functional group and an active olefin metathesis that improves the mechanical properties of the olefin composite is sufficient for the invention. In general, suitable amounts of a compound comprising a heteroatom-containing functional group and an active olefin metathesis range from 0.001 to 50 phr, particularly 0.05 to 10 phr, more particularly 0.1 to 10 phr, or even more particularly 0.5 to 4.0 phr. One or more compounds comprising a heteroatom-containing functional group and an active olefin metathesis may be used in the present invention. Compositions Promoting Adherence

[00149] Adhesion-promoting compositions that can be used in the present invention disclosed herein are, in general, compositions comprising at least one adhesion promoter, discussed above (i.e., at least one compound containing at least two isocyanate groups (e.g., methylene diphenyl diisocyanate, hexamethylene diisocyanate)) and at least one compound comprising a heteroatom-containing functional group and an active olefin metathesis, discussed above (e.g., 2-hydroxyethyl bicyclo[2,2,1]hept-2-ene-5-carboxylate (HENB), 2-hydroxyethyl acrylate (HEA), oleyl alcohol, 9-decen-1-ol), wherein the compounds can be combined in various ratios to form a pre-reacted mixture, wherein the pre-reacted mixture is then subsequently added to a resin composition, and wherein the adhesion-promoting composition possesses in-resin storage stability.

[00150] Compounds containing at least two isocyanate groups and compounds comprising a heteroatom-containing functional group and an active olefin metathesis useful for preparing adhesion-promoting compositions of the invention are disclosed herein. Petition 870210098125, dated 10 / 25 / 2021, p. 75 / 187 56 / 158

[00151] Preferred adhesion-promoting compositions include, but are not limited to, pre-reacted mixtures of liquid MDI (Mondur® MLQ) and 2-hydroxyethyl bicyclo[2,2,1]hept2-ene-carboxylate (HENB); pre-reacted mixtures of liquid MDI (Mondur®MLQ) and 2-hydroxyethyl acrylate (HEA); pre-reacted mixtures of liquid MDI (Mondur®MLQ) and oleyl alcohol; and pre-reacted mixtures of liquid MDI (Mondur® MLQ) and 9-decen-1-ol.

[00152] Any concentration of adhesion-promoting composition that improves the mechanical properties of the olefin composite is sufficient for the invention. In general, suitable amounts of adhesion-promoting composition range from 0.001 to 50 phr, particularly 0.05 to 10 phr, more particularly 0.1 to 10 phr, or even more particularly 0.5 to 4.0 phr. Substrate Surfaces

[00153] The present invention is generally suitable for use with any substrate material wherein the addition of an adhesion promoter or adhesion-promoting composition provides beneficial improvements in the adhesion of a resin composition (e.g., ROMP) to the substrate material as compared to a resin composition that is the same except that the adhesion promoter or adhesion-promoting composition is not included. Furthermore, the present invention is generally suitable for use with any substrate material wherein the addition of an adhesion promoter or adhesion-promoting composition provides beneficial improvements in the adhesion of a polymer matrix (e.g., ROMP polymer matrix) to a substrate material as compared to a polymer matrix that is the same except that the adhesion promoter or adhesion-promoting composition is not included.The present invention is particularly beneficial for use with glass and carbon material surfaces suitable for use with epoxy and methacrylate resins, including those containing finishes or dimensions, in which case the finishes or dimensions do not. Petition 870210098125, dated 10 / 25 / 2021, page 76 / 187 57 / 158 need to be removed (e.g., by washing or hot cleaning) for the adhesion promoter or adhesion-promoting composition to be effective. The present invention is also suitable for use with wood and aluminum materials. Suitable substrate materials may also be selected from fibrous, woven, microparticulate, ceramic, metallic, polymeric, and semiconductor materials. A polymer-matrix composite (e.g., ROMP-matrix polymer composite) may comprise a single substrate material or a mixture of different substrate materials. Cyclic Olefins

[00154] Resin compositions and / or cyclic olefin compositions that can be used with the present invention disclosed herein comprise one or more cyclic olefins. In general, any cyclic olefin suitable for the metathesis reactions disclosed herein can be used. Such cyclic olefins may optionally be substituted, optionally containing heteroatoms, C5 to C24 mono-unsaturated, di-unsaturated or poly-unsaturated hydrocarbons that may be mono-, di-, or polycyclic. The cyclic olefin may, in general, be any strained or un-strained cyclic olefin, provided that the cyclic olefin is capable of participating in a ROMP reaction individually or as part of a cyclic olefin composition or as part of a resin composition.Although certain strainless cyclic olefins such as cyclohexene are generally understood not to undergo ROMP reactions on their own, under appropriate circumstances, such strainless cyclic olefins may nevertheless be ROMP-active. For example, when present as a co-monomer in a ROMP composition, strainless cyclic olefins may be ROMP-active. Consequently, as used herein, and as would be assessed by a qualified technician, the term “strainless cyclic olefin” is intended to refer to those strainless cyclic olefins that may undergo a ROMP reaction under any conditions, or in any ROMP composition, provided that the olefin... Petition 870210098125, dated 10 / 25 / 2021, page 77 / 187 58 / 158 cyclic without tension is activated by ROMP.

[00155] In general, the cyclic olefin can be represented by the structure of formula (A) (A) RA1RA2 where J, RA1, and RA2 are as follows: RA1 and RA2 are independently selected from the group consisting of hydrogen, hydrocarbyl (e.g., C1-C20 alkyl, C5-C20 aryl, C5-C30 aralkyl, or C5-C30 alquaryl), substituted hydrocarbyl (e.g., substituted C1-C20 alkyl, C5-C20 aryl, C5-C30 aralkyl, or C5-C30 alquaryl), heteroatom-containing hydrocarbyl (e.g., C1-C20 heteroalkyl, C5-C20 heteroaryl, C5-C30 heteroatom-containing aralkyl, or C5-C30 heteroatom-containing alquaryl), and substituted heteroatom-containing hydrocarbyl (e.g., substituted C1-C20 heteroalkyl, C5-C20 heteroaryl, C5-C30 heteroatom-containing aralkyl, or C5-C30 alquaryl). heteroatom) and, if substituted hydrocarbyl or hydrocarbyl containing a substituted heteroatom, wherein the substituents may be functional groups (“Fn”) such as phosphonate, phosphoryl, phosfanyl, phosphine, sulfonate, C1-C20 alkylsulfanyl, C5-C20 arylsulfanyl, C1-C20 alkylsulfonyl, C5-C20 arylsulfonyl, C1-C20 alkylsulfinyl,C5-C20 arylsulfinyl, sulfonamide, amino, amido, imino, nitro, nitroso, hydroxyl, C1-C20 alkoxy, C5-C20 aryloxy, C2-C20 alkoxycarbonyl, C5-C20 aryloxycarbonyl, carboxyl, carboxylate, mercapto, formyl, C1-C20 thioester, cyano, cyanate, thiocyanate, isocyanate, thioisocyanate, carbamoyl, epoxy, styrenyl, silyl, silyloxyl, silanyl, siloxazanyl, boronate, boryl, or halogen, or a metal-containing or metalloid-containing group (wherein the metal may be, for example, Sn or Ge). RA1 and RA2 may themselves be one of the aforementioned groups, such that the Fn moiety is directly bonded to the olefinic carbon atom indicated in the structure. In the latter case, however, the functional group will not, in general, be directly linked to the olefinic carbon through one or more, Petition 870210098125, dated 10 / 25 / 2021, page 78 / 187 59 / 158 lone pairs containing an electron heteroatom, for example, an oxygen, sulfur, nitrogen or phosphorus atom, or through an electron-rich metal or metalloid such as Ge, Sn, As, Sb, Se, Te, etc. With such functional groups, there will normally be an intervening Z* linkage, such as RA1e / or RA2 when they were the structure -(Z*)n-Fn where n is 1, Fn is the functional group, and Z* is a hydrocarbylene linkage group such as an alkylene, substituted alkylene, heteroalkylene, substituted heteroalkene, arylene, substituted arylene, heteroarylene, or substituted heteroarylene linkage. J is a saturated or unsaturated hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or heteroatom-containing substituted hydrocarbylene linkage, wherein when J is substituted hydrocarbylene or heteroatom-containing substituted hydrocarbylene, the substituents may include one or more -(Z*)n-Fn groups, wherein n is zero or 1, and Fn and Z* are as previously defined. Additionally, two or more substituents attached to the carbon atom in the ring (or others) within J may be linked to form a bicyclic or cyclic polyolefin. J will generally contain in the range of approximately 5 to 14 ring atoms, typically 5 to 8 ring atoms for a cyclic monoolefin, and for bicyclic and cyclic polyolefins, each ring will generally contain 4 to 8, typically 5 to 7, ring atoms.

[00156] Cyclic monounsaturated olefins encompassed by structure (A) can be represented by structure (B) (B) ra1 where b is an integer, generally, though not necessarily, in the range of 1 to 10, typically 1 to 5, RA1 and RA2 are as defined above for structure (A), and RB1, RB2, RB3, RB4, Petition 870210098125, dated 10 / 25 / 2021, page 79 / 187 60 / 158 RB5 and RB6 are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and -(Z*)n-Fn where n, Z*, and Fn are as previously defined, and wherein if any of the RB1 to RB6 moieties is substituted hydrocarbyl or substituted heteroatom-containing hydrocarbyl, the substituents may include one or more -(Z*)n-Fn groups. Consequently, RB1, RB2, RB3, RB4, RB5, and RB6 may be, for example, hydrogen, hydroxyl, C1-C20 alkyl, C5-C20 aryl, C1-C20 alkoxy, C5-C20 aryloxy, C2-C20 alkoxycarbonyl, C5-C20 aryloxycarbonyl, amino, amido, nitro, etc. Furthermore, any of the RB1, RB2, RB3, RB4, RB5, and RB6 portions may be linked to any of the other RB1, RB2, RB3, RB4, RB5, and RB6 portions to provide a substituted or unsubstituted alicyclic group containing 4 to 30 atoms in the carbon ring or a substituted or unsubstituted aryl group containing 6 to 18 atoms in the carbon ring or combinations thereof, and the linkage may include heteroatoms or functional groups, for example, the linkage may include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride portion. The alicyclic group may be monocyclic, bicyclic, or polycyclic. When unsaturated, the cyclic group may contain monounsaturation or multiunsaturation, with monounsaturated cyclic groups being preferred.When substituted, the rings contain mono-substitution or multi-substitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z*)n-Fn where n is zero or 1, Z* and Fn are as defined above, and functional groups (Fn) given above.

[00157] Examples of monounsaturated, cyclic monoolefins encompassed by structure (B) include, without limitation, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, and cycloeicosene, and substituted versions of Petition 870210098125, dated 10 / 25 / 2021, p. 80 / 187 61 / 158 same as 1-methylcyclopentene, 1-ethylcyclopentene, 1-isopropylcyclohexene, 1-chloropentene, 1-fluorocyclopentene, 4-methylcyclopentene, 4-methoxycyclopentene, 4-ethoxycyclopentene, cyclopent-3-enethiol, cyclopent-3-ene, 4-methylsulfanylcyclopentene, 3-methylcyclohexene, 1-methylcyclooctene, 1,5-dimethylcyclooctene, etc.

[00158] Monocyclic diene reagents encompassed by structure (A) can generally be represented by structure (C) (C) where ced are independently integers in the range of 1 to about 8, typically 2 to 4, preferably 2 (such that the reagent is a cyclooctadiene), RA1 and RA2 are as defined above for structure (A), and RC1, RC2, RC3, RC4, RC5, and RC6 are defined as for RB1 to RB6. In this case, it is preferred that RC3 and RC4 are not hydrogen substituents, in which case the second olefinic moiety is tetrasubstituted. Examples of monocyclic diene reagents include, without limitation, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, and substituted analogues thereof. Triene reagents are analogous to the diene (C) structure and will generally contain at least one methylene linkage between any two olefinic segments.

[00159] Bicyclic and cyclic polyolefins encompassed by structure (A) can generally be represented by structure (D) (D) Petition 870210098125, dated 10 / 25 / 2021, p. 81 / 187 62 / 158 wherein RA1 and RA2 are as defined above for structure (A), RD1, RD2, RD3, and RD4 are as defined for RB1 to RB6, and is an integer in the range of 1 to 8 (typically 2 to 4) f is generally 1 or 2; T is lower alkylene or alkenylene (generally substituted or unsubstituted methyl or ethyl), CHRG1, C(RG1)2, ​​O, S, N-RG1, PRG1, O=P-RG1, Si(RG1)2, ​​B-RG1, or As-RG1 wherein RG1 is alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, alquaryl, aralkyl, or alkoxy.Furthermore, any of the RD1, RD2, RD3, and RD4 portions can be linked to any of the other RD1, RD2, RD3, and RD4 portions to provide a substituted or unsubstituted alicyclic group containing 4 to 30 atoms in the carbon ring or a substituted or unsubstituted aryl group containing 6 to 18 atoms in the carbon ring or combinations thereof, and the linkage may include heteroatoms or functional groups, for example, the linkage may include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride portion. The cyclic group may be monocyclic, bicyclic, or polycyclic. When unsaturated, the cyclic group may contain mono-unsaturation or multi-unsaturation, with mono-unsaturated cyclic groups being preferred.When substituted, the rings contain mono-substitution or multi-substitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, (Z*)n-Fn where n is zero or 1, Z* and Fn are as defined above, and functional groups (Fn) are given above.

[00160] Cyclic olefins covered by structure (D) are in the norbornene family, as used herein, norbornene meaning any compound that includes at least one norbornene or substituted norbornene moiety, including without limitation norbornene, substituted norbornene(s), norbornadiene, substituted norbornadiene(s), polycyclic norbornenes, and substituted polycyclic norbornene(s). Norbornenes within this group can, in general, be represented by structure (E) Petition 870210098125, dated 10 / 25 / 2021, p. 82 / 187 63 / 158 RE1rE4rE5 (E) RE2RE3 where RA1 and RA2 are as defined above for structure (A), T is as defined above for structure (D), RE1, RE2, RE3, RE4, RE5, RE6, RE7, and RE8 are as defined for RB1 to RB6, and “a” represents a single bond or a double bond, f is generally 1 or 2, “g” is an integer from 0 to 5, and when “a” is a double bond, one of RE5, RE6 and one of RE7, RE8 is not present.

[00161] Furthermore, any of the RE5, RE6, RE7, and RE8 portions may be linked to any of the other RE5, RE6, RE7, and RE8 portions to provide a substituted or unsubstituted alicyclic group containing 4 to 30 atoms in the carbon ring or a substituted or unsubstituted aryl group containing 6 to 18 atoms in the carbon ring or combinations thereof, and the linkage may include heteroatoms or functional groups, for example, the linkage may include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride portion. The cyclic group may be monocyclic, bicyclic, or polycyclic. When unsaturated, the cyclic group may contain mono-unsaturation or multi-unsaturation, with mono-unsaturated cyclic groups being preferred.When substituted, the rings contain mono-substitution or multi-substitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z*)n-Fn where n is zero or 1, Z* and Fn are as defined above, and functional groups (Fn) given above.

[00162] More preferred cyclic olefins having at least one norbornene moiety have the structure (F): Petition 870210098125, dated 10 / 25 / 2021, p. 83 / 187 64 / 158 (F) where RF1, RF2, RF3, and RF4 are as defined for RB1 to RB6, and “a” represents a single bond or a double bond, “g” is an integer from 0 to 5, and when “a” is a double bond, one of RF1, RF2, and one of RF3, RF4 is not present.

[00163] Furthermore, any of the RF1, RF2, RF3, and RF4 moieties may be linked to any of the other RF1, RF2, RF3, and RF4 moieties to provide a substituted or unsubstituted alicyclic group containing 4 to 30 atoms in the carbon ring or a substituted or unsubstituted aryl group containing 6 to 18 atoms in the carbon ring or combinations thereof, and the linkage may include heteroatoms or functional groups, for example, the linkage may include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety. The alicyclic group may be monocyclic, bicyclic, or polycyclic. When unsaturated, the cyclic group may contain mono-unsaturation or multi-unsaturation, with mono-unsaturated cyclic groups being preferred.When substituted, the rings contain mono-substitution or multi-substitution wherein the substituents are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z*)n-Fn where n is zero or 1, Z* and Fn are as defined above, and functional groups (Fn) given above.

[00164] One route for the preparation of substituted hydrocarbyls and functionally substituted norbornenes employs the Diels-Alder cycloaddition reaction in which cyclopentadiene or substituted cyclopentadiene is reacted with a suitable dienophile at elevated temperatures to form the substituted norbornene adduct, generally shown by the following reaction Scheme 1: SCHEME 1 Petition 870210098125, dated 10 / 25 / 2021, p. 84 / 187 65 / 158 where RF1a and RF4 are as previously defined for structure (F).

[00165] Other norbornene adducts can be prepared by the thermal pyrolysis of dicyclopentadiene in the presence of a suitable dienophile. The reaction proceeds by initial pyrolysis of dicyclopentadiene to cyclopentadiene followed by Diels-Alder cycloaddition of cyclopentadiene and dienophile to obtain the adduct shown below in Scheme 2: SCHEME 2 where “g” is an integer from 0 to 5, and RF1 to RF4 are as previously defined for structure (F).

[00166] Norbornadiene and higher Diels-Alder adducts thereof can similarly be prepared by the thermal reaction of cyclopentadiene and dicyclopentadiene in the presence of an acetylenic reagent as shown below in Scheme 3: SCHEME 3 Petition 870210098125, dated 10 / 25 / 2021, p. 85 / 187 66 / 158 where “g” is an integer from 0 to 5, RF1 and RF4 are as previously defined for structure (F)

[00167] Examples of bicyclic and cyclic polyolefins include, without limitation, dicyclopentadiene (DCPD); trimer and other higher-order oligomers of cyclopentadiene including, without limitation, tricyclopentadiene (cyclopentadiene trimer), cyclopentadiene tetramer (tetracyclopentadiene), and cyclopentadiene pentamer (pentacyclopentadiene); ethylidenonorbornene; dicyclohexadiene; norbornene; 5-methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5-benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethyloxycarbonyl-1-norbornene; 5-methyl-5-methoxycarbonylnorbornene; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbornene; cyclohexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo, endo-5,6dimethoxynorbornene; endo, exo-5,6-dimethoxycarbonylnorbornene; endo, endo-5,6dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyltetracyclododecene; 8-ethyltetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclododecene; 8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene; and the like, and their structural isomers, stereoisomers, and mixtures thereof. Examples of additional bicyclic and cyclic polyolefins include, without limitation, C2-C12 substituted hydrocarbyl norbornenes such as 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5-vinyl-2-norbornene, 5-ethyllidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, and 5-butenyl-2-norbornene, and the like. It is well understood by a person in the art that bicyclic and cyclic polyolefins Petition 870210098125, dated 10 / 25 / 2021, page 86 / 187 67 / 158 as disclosed herein may consist of a variety of structural isomers and / or stereoisomers, any and all of which are suitable for use in the present invention. Any reference herein to such bicyclic and cyclic polyolefins unless specifically stated includes mixtures of any and all such structural isomers and / or stereoisomers.

[00168] Preferred cyclic olefins include C5 to C24 unsaturated hydrocarbons. Also preferred are C5 to C24 cyclic hydrocarbons containing one or more (typically 2 to 12) heteroatoms such as O, N, S, or P. For example, crown ether cyclic olefins may include numerous O heteroatoms along the ring, and these are within the scope of the invention. Furthermore, preferred cyclic olefins are C5 to C24 hydrocarbons containing one or more (typically 2 or 3) olefins. For example, the cyclic olefin may be mono-, di-, or tri-unsaturated. Examples of cyclic olefins include, without limitation, cyclooctene, cyclododecene, and (c,t,t)-1,5,9-cyclododecatriene.

[00169] Cyclic olefins may also comprise multiple rings (typically 2 or 3). For example, a cyclic olefin may be mono-, di-, or tri-cyclic. When a cyclic olefin comprises more than one ring, the rings may or may not be fused. Preferred examples of cyclic olefins comprising multiple rings include norbornene, dicyclopentadiene, tricyclopentadiene, and 5-ethyllidene-2-norbornene.

[00170] Cyclic olefins can also be substituted, for example, a C5 to C24 cyclic hydrocarbon in which one or more (typically 2, 3, 4, or 5) of the hydrogens are substituted without non-hydrogen substituents. Suitable non-hydrogen substituents can be chosen from the substituents described above. For example, functionalized cyclic olefins, i.e., C5 to C24 cyclic hydrocarbons in which one or more (typically 2, 3, 4, or 5) of the hydrogens are substituted with functional groups, are within the scope of the invention. Groups Petition 870210098125, dated 10 / 25 / 2021, page 87 / 187 Suitable functionals can be chosen from the functional groups described above. For example, a cyclic olefin functionalized with an alcohol group can be used to prepare a telechellic polymer comprising pendant alcohol groups. Functional groups in the cyclic olefin can be protected in cases where the functional group interferes with the metathesis catalyst, and any of the protecting groups commonly used in the art can be employed. Acceptable protecting groups can be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd ed. (New York: Wiley, 1999). Examples of functionalized cyclic olefins include, without limitation, 2-hydroxymethyl-5-norbornene, 2-[(2-hydroxyethyl)carboxylate]-5-norbornene, cidecanol, 5-n-hexyl-2-norbornene, 5-n-butyl-2-norbornene.

[00171] Cyclic olefins incorporating any combination of the above-mentioned features (i.e., heteroatoms, substituents, multiple olefins, multiple rings) are suitable for the methods disclosed herein. Additionally, cyclic olefins incorporating any combination of the above-mentioned features (i.e., heteroatoms, substituents, multiple olefins, multiple rings) are suitable for the invention disclosed herein.

[00172] The cyclic olefins useful in the methods disclosed herein may be strained or unstrained. It will be assessed that the amount of ring strain varies for each cyclic olefin compound, and depends on several factors including ring size, the presence and identity of substituents, and the presence of multiple rings. Ring strain is a factor in determining the reactivity of a molecule to ring-opening olefin metathesis reactions. Highly strained cyclic olefins, such as certain bicyclic compounds, readily undergo ring-opening reactions with olefin metathesis catalysts. Less strained cyclic olefins, such as certain unsubstituted hydrocarbon monocyclic olefins, are generally less reactive. In some cases, ring-opening reactions Petition 870210098125, dated 10 / 25 / 2021, pp. 88 / 187 69 / 158 of relatively strain-free (and therefore relatively non-reactive) cyclic olefin rings can become possible when carried out in the presence of the olefinic compounds disclosed herein. Additionally, cyclic olefins useful in the invention disclosed herein can be strained or strain-free.

[00173] The resin compositions and / or cyclic olefin compositions of the present invention may comprise a plurality of cyclic olefins. A plurality of cyclic olefins may be used to prepare metathesis polymers from the olefinic compound. For example, two cyclic olefins selected from the cyclic olefins described above may be used to form metathesis products incorporating both cyclic olefins. Where two or more cyclic olefins are used, an example of a second cyclic olefin is a cyclic alkenol, i.e., a C5-C24 cyclic hydrocarbon in which at least one of the hydrogen substituents is substituted with an alcohol or protected alcohol moiety to obtain a functionalized cyclic olefin.

[00174] The use of a plurality of cyclic olefins, and in particular when at least one of the cyclic olefins is functionalized, allows additional control over the positioning of functional groups within the products. For example, the density of crosslinking points can be controlled in polymers and macromonomers prepared using the methods disclosed herein. Control over the quantity and density of substituents and functional groups also allows control over the physical properties (e.g., melting point, tensile strength, glass transition temperature, etc.) of the products. Control over these and other properties is possible for reactions using only a single cyclic olefin, but it will be evaluated that the use of a plurality of cyclic olefins further improves the range of possible metathesis products and polymers formed.

[00175] Examples of cyclic olefins include dicyclopentadiene; tricyclopentadiene; dicyclohexadiene; norbornene; 5-methyl-2-norbornene; 5-ethyl-2 Petition 870210098125, dated 10 / 25 / 2021, p. 89 / 187 70 / 158 norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2-norbornene; 5-phenylnorbornene; 5benzylnorbornene; 5-acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethoxycarbonyl-1norbornene; 5-methyl-5-methoxycarbonylnorbornene; 5-cyanonorbornene; 5,5,6-trimethyl2-norbornene; cyclohexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene; endo, exo-5,6-dimethoxycarbonylnorbornene; endo, endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbornene; norbornadiene; tricycloundecene; tetracyclododecene; 8-methyltetracyclododecene; 8-ethyltetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclododecene; 8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene; higher-order oligomers of cyclopentadiene such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the like; and C2-C12 substituted hydrocarbyl norbornenes such as 5-butyl-2-norbornene; 5-hexyl-2-norbornene; 5-octyl-2-norbornene; 5-decyl-2-norbornene;5-dodecyl-2-norbornene; 5-vinyl-2-norbornene; 5-ethyllidene-2-norbornene; 5-isopropenyl-2-norbornene; 5-propenyl-2-norbornene; and 5-butenyl-2-norbornene, and the like. Examples of cyclic olefins include dicyclopentadiene, tricyclopentadiene, and higher-order oligomers of cyclopentadiene, such as cyclopentadiene tetramer, cyclopentadiene pentamer and similar tetracyclododecene, norbornene, and C2-C12 substituted hydrocarbyl norbornenes, such as 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, 5-dodecyl-2-norbornene, 5-vinyl-2-norbornene, 5-ethyllidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, 5-butenyl-2-norbornene, and the like.

[00176] Examples of cyclic olefins include dicyclopentadiene, tricyclopentadiene, and higher-order oligomers of cyclopentadiene, such as cyclopentadiene tetramer, cyclopentadiene pentamer, and the like, including structural isomers and / or stereoisomers, any and all of which are suitable for use in the present invention. Examples of cyclic olefins include Petition 870210098125, dated 10 / 25 / 2021, p. 90 / 187 71 / 158 dicyclopentadiene, tricyclopentadiene, and tetracyclopentadiene, including structural isomers and / or stereoisomers, any and all of which are suitable for use in the present invention. Examples of cyclic olefins include dicyclopentadiene and tricyclopentadiene, including structural isomers and / or stereoisomers, any and all of which are suitable for use in the present invention. Metal-Carbeno Olefin Metathesis Catalysts

[00177] Catalyst compositions that can be used with the present invention disclosed herein comprise one or more carbene olefin metal metathesis catalysts. Carbeno olefin metal metathesis catalysts that can be used in the invention disclosed herein are preferably a Group 8 transition metal complex having the structure of formula (I) (I) wherein: M is a Group 8 transition metal; L1, L2, and L3 are neutral electron-donating ligands; n is 0 or 1, such that L3 may or may not be present; m is 0, 1, or 2; k is 0 or 1; X1 and X2 are anionic ligands; and R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein any two or more of X1, X2, L1, L2, L3, R1, and R2 may be taken together to form one or more cyclic groups, and wherein any one or more of X1, X2, L1, L2, L3, R1, and R2 may be connected to a support. Petition 870210098125, dated 10 / 25 / 2021, p. 91 / 187 72 / 158

[00178] Additionally, in formula (I), one or both of R1 and R2 may have the structure -(W)n-U+V', wherein W is selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or heteroatom-containing substituted hydrocarbylene; U is a positively charged Group 15 or Group 16 element substituted with hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; V is a negatively charged counter-ion; en is zero or 1. Furthermore, R1 and R2 may be taken together to form an indenylidene moiety.

[00179] Preferred catalysts contain Ru or Os as the Group 8 transition metal, with Ru being particularly preferred.

[00180] Numerous embodiments of the catalysts useful in the reactions disclosed herein are described in more detail below. For convenience, the catalysts are described in groups, but it should be emphasized that these groups are not meant to be limiting in any way. That is, any of the catalysts useful in the invention may fit the description of more than one of the groups described herein.

[00181] A first group of catalysts, then, are commonly referred to as First Generation Grubbs-type catalysts, and have the structure of formula (I). For the first group of catalysts, M is a Group 8 transition metal, m is 0, 1, or 2, en, X1, X2, L1, L2, L3, R1, and R2 are described as follows.

[00182] For the first group of catalysts, n is 0, and L1 and L2 are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibnite, ether (including cyclic ethers), amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, substituted pyrazine, and thioether. Exemplary ligands are trisubstituted phosphines. Preferred trisubstituted phosphines are of the formula PRH1RH2RH3, where RH1, RH2, and RH3 are each independently substituted or unsubstituted aryl. Petition 870210098125, dated 10 / 25 / 2021, page 92 / 187 73 / 158 or C1-C10 alkyl, particularly primary alkyl, secondary alkyl, or cycloalkyl. In the most preferred group, L1 and L2 are independently selected from the group consisting of trimethylphosphine (PMe3), triethylphosphine (PEt3), tri-n-butylphosphine (PBu3), tri(orthotolyl)phosphine (Po-tolyl3), tri-tert-butylphosphine (P-tert-Bu3), tricyclopentylphosphine (PCyclopentyl3), tricyclohexylphosphine (PCy3), tri-isopropylphosphine (Pi-Pr3), trioctylphosphine (POcts), tri-isobutylphosphine (Pi-Bu3), triphenylphosphine (PPh3), tri(pentafluorophenyl)phosphine (P(C6F5)3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph). Alternatively, L1 and L2 can be independently selected from phosphabicycloalkanes (e.g., monosubstituted 9-phosphabicyclo[3,3,1]nonane, or monosubstituted 9-phosphabicyclo[4,2,1]nonane such as cyclohexylfoban, isopropylfoban, ethylfoban, methylfoban, butylfoban, pentylfoban and the like).

[00183] X1 and X2 are anionic ligands, and may be the same or different, or are linked together to form a cyclic group, typically, though not necessarily, a five- to eight-membered ring. In preferred embodiments, X1 and X2 are each independently hydrogen, halide, or one of the following groups: C1-C20 alkyl, C5-C24 aryl, C1-C20 alkoxy, C5-C24 aryloxy, C2-C20 alkoxycarbonyl, C6-C24 aryloxycarbonyl, C2-C24 acyl, C2-C24 acyloxy, C1-C20 alkylsulfonate, C5-C24 arylsulfonate, C1-C20 alkylsulfanyl, C5-C24 arylsulfanyl, C1-C20 alkylsulfinyl, NO3, -N=C=O, -N=C=S, or C5-C24 arylsulfinyl. Optionally, X1 and X2 may be replaced with one or more selected moieties of C1-C12 alkyl, C1-C12 alkoxy, C5-C24 aryl, and halide, which may, in turn, with the exception of halide, be further replaced with one or more selected halide, C1-C6 alkyl, C1-C6 alkoxy, and phenyl groups.In more preferred embodiments, X1 and X2 are halide, benzoate, C2-C6 acyl, C2-C6 alkoxycarbonyl, C1-C6 alkyl, phenoxy, C1-C6 alkoxy, C1-C6 alkylsulfanyl, aryl, or C1-C6 alkylsulfonyl. In still more preferred embodiments, X1 and X2 are each a halide, CF3CO2, CH3CO2, CFH2CO2. Petition 870210098125, dated 10 / 25 / 2021, page 93 / 187 74 / 158 (CH3)3CO, (CF3)2(CH3)CO, (CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate. In more preferred embodiments, X1 and X2 are each a chloride.

[00184] R1 and R2 are independently selected from hydrogen, hydrocarbyl (e.g., C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5C24 aryl, C6-C24 alkyl, C6-C24 aralkyl, etc.), substituted hydrocarbyl (e.g., substituted C1-C20 alkyl, alkenyl C2-C20, C2-C20 alkynyl, C5-C24 aryl, C6C24 alkyryl, C6-C24 aralkyl, etc.), heteroatom-containing hydrocarbyl (e.g., heteroatom-containing C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, alquaryl C6-C24, aralkyl C6-C24, etc.), and Hydrocarbyl containing a substituted heteroatom (e.g., C1-C20 alkyl containing a substituted heteroatom, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alquaryl, C6-C24 aralkyl, etc.), and functional groups. R1 and R2 may also be linked to form a cyclic group, which may be aliphatic or aromatic, and may contain substituents and / or heteroatoms. Generally, such a cyclic group will contain 4 to 12, preferably 5, 6, 7, or 8 atoms in the ring.

[00185] In preferred catalysts, R1 is hydrogen and R2 is selected from C1-C20 alkyl, C2-C20 alkenyl, and C5-C24 aryl, more preferably C1-C6 alkyl, C2-C6a alkenyl, and C5-C14 aryl. Even more preferably, R2 is penyl, vinyl, methyl, isopropyl, or t-butyl, optionally substituted with one or more selected moieties of C1-C6 alkyl, C1-C6 alkoxy, penyl, and an Fn functional group as defined above. Most preferably, R2 is phenyl or vinyl substituted with one or more selected moieties of methyl, ethyl, chlorine, bromine, iodine, fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl. Optimally, R2 is phenyl or -CH=C(CH3)2.

[00186] Any two or more (typically two, three, or four) of X1, X2, L1, L2, L3, R1, and R2 may be taken together to form a cyclic group, including bidentate or multidentate linkers, as disclosed, for example, in U.S. Patent No. 5,312,940, the disclosure of which is incorporated herein as Petition 870210098125, dated 10 / 25 / 2021, p. 94 / 187 75 / 158 reference. When any of X1, X2, L1, L2, L3, R1, and R2 are linked to form cyclic groups, those cyclic groups may contain 4 to 12, preferably 4, 5, 6, 7, or 8 atoms, or may comprise two or three such rings, which may be fused or linked. The cyclic groups may be aliphatic or aromatic, and may be heteroatom-containing and / or substituted. The cyclic group may, in some cases, form a bidentate ligand or a tridentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates.

[00187] A second group of carbene olefin metal metathesis catalysts, commonly referred to as Second Generation Grubbs-type catalysts, have the structure of formula (I), wherein L1 is a carbene ligand having the structure of formula (II) (II) (III) such that the complex can have the structure of formula (III) where M, m, n, X1, X2, L2, L3, R1, and R2 are as defined for the first group of catalysts, and the remaining substituents are as follows; X and Y are heteroatoms typically selected from N, O, S, and P. Since O and S are divalent, p is necessarily zero when X is O or S, q is necessarily zero when Y is O or S, and k is zero or 1. However, when X is N Petition 870210098125, dated 10 / 25 / 2021, p. 95 / 187 76 / 158 or P, then p is 1, and when Y is N or P, then q is 1. In a preferred embodiment, both X and Y are N; Q1, Q2, Q3, and Q4 are ligands, for example, hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and heteroatom-containing substituted hydrocarbylene, such as substituted and / or heteroatom-containing alkylene) or -(CO)-, ew, x, y, and ez are independently zero or 1, meaning that each ligand is optional. Preferably, w, x, y, and ez are all zero. Furthermore, two or more substituents on adjacent atoms within Q1, Q2, Q3, and Q4 may be attached to form an additional cyclic group; and R3, R3A, R4, and R4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl. Furthermore, X and Y can be independently selected from carbon, and one of the aforementioned heteroatoms, preferably no more than one of X or Y, is carbon. Also, L2 and L3 can be taken together to form a single bindentate electron-donating heterocyclic ligand. Additionally, R1 and R2 can be taken together to form an indenylidene moiety. Furthermore, X1, X2, L2, L3, X, and Y can be further coordinated to boron or a carboxylate.

[00188] Furthermore, any two or more of X1, X2, L1, L2, L3, R1, R2, R3, R3A, R4, R4A, Q1, Q2, Q3, and Q4 can be taken together to form a cyclic group, and any one or more of X1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R2, R3, R3A, R4, and R4A can be connected to a support. Any two or more of X1, X2, L1, L2, L3, R1, R2, R3, R3A, R4, and R4A may also be considered as being -A-Fn, wherein “A” is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, wherein the alkyl moiety of the alkylene and arylalkylene groups may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl moiety of the arylalkylene may be substituted or not. Petition 870210098125, dated 10 / 25 / 2021, p. 96 / 187 77 / 158 substituted, and in which heteroatoms and / or functional groups may be present in the aryl or alkyl portions of the alkylene and arylalkylene groups, and Fn is a functional group, or together to form a cyclic group, and any one or more of X1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R2, R3, R3A, R4, and R4A may be attached to a support.

[00189] A particular class of carbene ligands having the structure of formula (II), where R3A and R4A are linked to form a cyclic group and at least one of X or Y is a nitrogen, or at least one of Q3 or Q4 is a heteroatom-containing hydrocarbylene or heteroatom-containing substituted hydrocarbylene where at least one heteroatom is a nitrogen, are commonly referred to as N-heterocyclic carbene ligands (NHC).

[00190] Preferably, R3A and R4A are linked to form a cyclic group so that the carbene ligand has the structure of formula (IV) R3----N N---R4 (IV) wherein R3 and R4 are as defined for the second group of catalysts above, with preferably at least one of R3 and R4, and more preferably both R3 and R4, being alicyclic or aromatic of one to about five rings, and optionally containing one or more heteroatoms and / or substituents. Q is a ligand, typically a hydrocarbylene ligand, including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and heteroatom-containing substituted hydrocarbylene ligands, wherein two or more substituents on adjacent atoms within Q may also be attached to form an additional cyclic structure, which may be similarly substituted to provide a fused polycyclic structure of two to about five cyclic groups. Q is frequently, though not necessarily, a two-atom bond or a three-atom bond.

[00191] Examples of suitable N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands such as L1 include, but are not limited to, Petition 870210098125, dated 10 / 25 / 2021, p. 97 / 187 78 / 158 the following where DIPP or DiPP is diisopropylphenyl and Mes is 2,4,6-trimethylphenyl: DIPP DIPP Month Month

[00192] Additional examples of suitable N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands such as L1 include, but are not limited to, the following: Petition 870210098125, dated 10 / 25 / 2021, p. 98 / 187 79 / 158 wherein RW1, RW2, RW3, RW4 are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatom-containing hydrocarbyl, and wherein one or both of RW3 and RW4 may be independently selected from halogen, nitro, amido, carboxyl, alkoxy, aryloxy, sulfonyl, carbonyl, thio, or nitroso groups.

[00193] Additional examples of suitable N-heterocyclic carbene (NHC) ligands as L1 are further described in U.S. Pat. Nos. 7,378,528; 7,652,145; 7,294,717; 6,787,620; 6,635,768; and 6,552,139, the contents of each are incorporated herein by reference.

[00194] Additionally, thermally activated N-Heterocyclic Carbene Precursors as disclosed in US Pat. No. 6,838,489, the contents of which are incorporated herein by reference, may also be used with the present invention.

[00195] When M is ruthenium, then the preferred complexes have the structure of formula (V) Petition 870210098125, dated 10 / 25 / 2021, p. 99 / 187 80 / 158 (V)

[00196] In a more preferred embodiment, Q is a two-atom bond having the structure -CR11R12-CR13R14- or -CR11=CR13-, preferably CR11R12-CR13R14-, wherein R11, R12, R13, and R14 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. Examples of functional groups herein include, without limitation, carboxyl, C1-C20 alkoxy, C5-C24 aryloxy, C2-C20 alkoxycarbonyl, C5-C24 alkoxycarbonyl, C2-C24 acyloxy, C1-C20 alkylthio, C5-C24 arylthio, C1-C20 alkylsulfonyl, and C1-C20 alkylsulfinyl, optionally substituted with one or more moieties selected from C1-C12 alkyl, C1-C12 alkoxy, C5-C14 aryl, hydroxyl, sulfhydryl, formyl, and halide. R11, R12, R13, and R14 are preferably independently selected from hydrogen, C1-C12 alkyl, substituted C1-C12 alkyl, C1-C12 heteroalkyl, substituted C1-C12 heteroalkyl, phenyl, and substituted phenyl.Alternatively, any two of R11, R12, R13, and R14 may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure, for example, a C4-C12 alicyclic group or a C5 or C6 aryl group, which may themselves be substituted, for example, with linked or fused alicyclic or aromatic groups, or with other substituents. In another aspect, any one or more of R11, R12, R13, and R14 comprises one or more of the linkers. Additionally, R3 and R4 may be unsubstituted phenyl or phenyl substituted with one or more substituents selected from C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, C5-C24 aryl. Petition 870210098125, dated 10 / 25 / 2021, pp. 100 / 187 81 / 158 substituted C5-C24 aryl, C5-C24 heteroaryl, C6-C24 aralkyl, C6-C24 alquaryl, or halide. In addition, X1 and X2 may be halogens.

[00197] When R3 and R4 are aromatic, they are typically, though not necessarily, compounds of one or two aromatic rings, which may or may not be substituted, for example, R3 and R4 may be penyl, substituted penyl, bipenyl, substituted bipenyl, or the like. In a preferred embodiment, R3 and R4 are the same and are each either unsubstituted phenyl or substituted phenyl with up to three substituents selected from C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, C5-C24 aryl, substituted C5-C24 aryl, C5-C24 heteroaryl, C6-C24 aralkyl, C6-C24 alquaryl, or halide. Preferably, any substituents present are hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C5-C14 aryl, substituted C5-C14 aryl, or halide. As an example, R3 and R4 are mesityl (i.e., Mes as defined here).

[00198] In a third group of carbene olefin metal metathesis catalysts having the structure of formula (I), M, m, n, X1, X2, R1, and R2 are as defined for the first group of catalysts, L1 is a strongly coordinated neutral electron donor ligand such as any of those described for the first and second groups of catalysts, and L2 and L3 are weakly coordinated neutral electron donor ligands in the form of optionally substituted heterocyclic groups. Again, n is zero or 1, such that L3 may or may not be present. Generally, in the third group of catalysts, L2 and L3 are optionally substituted five- or six-membered monocyclic groups containing 1 to 4, preferably 1 to 3, most preferably 1 to 2 heteroatoms, or are optionally substituted bicyclic or polycyclic structures composed of 2 to 5 such five- or six-membered monocyclic groups.If the heterocyclic group is substituted, it must not be substituted on a coordinated heteroatom, and any cyclic portion within a heterocyclic group will generally not be substituted with more than 3 atoms. Petition 870210098125, dated 10 / 25 / 2021, p. 101 / 187 82 / 158 substitutes.

[00199] For the third group of carbene olefin metal metathesis catalysts, examples of L2 and L3 include, without limitation, heterocycles containing nitrogen, sulfur, oxygen, or a mixture thereof.

[00200] Examples of nitrogen-containing heterocycles suitable for L2 and L3 include pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indol, 1H-isoindol, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinoline, quinazoline, naftiridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolilimine, purine, benzimidazole, bisimidazole, phenazine, acridine and carbazole. Additionally, nitrogen-containing heterocycles can optionally be substituted at a non-coordinated heteroatom with a non-hydrogen substituent.

[00201] Examples of sulfur-containing heterocycles suitable for L2 and L3 include thiophene, 1,2-dithiol, 1,3-dithiol, tiepine, benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene, 2H-thiopyran, 4H-thiopyran, and thioanthrene.

[00202] Examples of oxygen-containing heterocycles suitable for L2 and L3 include 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin, oxepin, furan, 2H-1-benzopyran, coumarin, coumarone, chromene, chroman-4-one, isochromen-1-one, isochromen-3-one, xanthene, tetrahydrofuran, 1,4-dioxane, and dibenzofuran.

[00203] Examples of suitable mixed heterocycles for L2 and L3 include isoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxathiol, 1,3-oxathiol, 4H-1,2-oxazine, 2H-1,3-oxazine, 1,4-oxazine, 1,2,5-oxathiazine, o-iso-oxazine, phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, and morpholine. Petition 870210098125, dated 10 / 25 / 2021, page 102 / 187 83 / 158

[00204] Preferred L2 and L3 ligands are aromatic nitrogen-containing and oxygen-containing heterocycles, and particularly preferred L2 and L3 ligands are monocyclic N-heteroaryl ligands that are optionally substituted with 1 to 3, preferably 1 or 2, substituents. Specific examples of particularly preferred L2 and L3 ligands are pyridine and substituted pyridines, such as 3-bromopyridine, 4-bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine, 3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine, 2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine, 3,5-di-iodopyridine, 3,5-dibromo-4-methylpyridine, 3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine, 3,5-dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine, 2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine, 4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine, 3,5-dichloro-4-phenylpyridine, and the like.

[00205] In general, any substituents present in L2 and / or L3 are selected from halo, C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, C5-C24 aryl, substituted C5-C24 aryl, C5-C24 heteroaryl, substituted C5-C24 heteroaryl, C6-C24 alkoryl, substituted C6-C24 alkoryl, C6-C24 heteroalkoryl, substituted C6-C24 heteroalkoryl, C6-C24 aralkyl, substituted C6-C24 aralkyl, C6-C24 heteroaralkyl, substituted C6-C24 heteroaralkyl, and functional groups, with suitable functional groups including, without limitation, C1-C20 alkoxy, C5-C24 aryloxy, C2-C20 alkylcarbonyl, C6-C24 arylcarbonyl, C2-C20 alkylcarbonyloxy, C6-C24 arylcarbonyloxy, C2-C20 alkoxycarbonyl, C6-C24 aryloxycarbonyl, halocarbonyl, C2-C20 alkylcarbonate, C6-C24 arylcarbonate, carboxy, carboxylate, carbamoyl, substituted mono(C1-C20 alkyl)-carbamoyl, di-(C1-C20 alkyl)-substituted carbamoyl, diN-(C1-C20 alkyl), N-(C5-C24 aryl)-substituted carbamoyl,substituted mono-(C5-C24 aryl)carbamoyl, substituted di-(C6-C24 aryl)-carbamoyl, thiocarbamoyl, substituted mono(C1-C20 alkyl)-thiocarbamoyl, substituted di-(C1-C20 alkyl)-thiocarbamoyl, di-N-(C1-C20 alkyl)-N-(aryl C6-C24)-substituted thiocarbamoyl, mono, Petition 870210098125, dated 10 / 25 / 2021, page 103 / 187 84 / 158 (C6-C24 aryl)-substituted thiocarbamoyl, di-(C6-C24 aryl)-substituted thiocarbamoyl, carbamido, formyl, thioformyl, amino, mono-(C1-C20 alkyl)-substituted amino, di(C1-C20 alkyl)-substituted amino, mono-(C5-C24 aryl)-substituted amino, di-(aryl C5C24)-substituted amino, di-N-(C1-C20 alkyl), N-(C5-C24 aryl)-substituted amino, C2-C20 alkylamido, C6-C24 arylamido, imino, C1-C20 alkylimino, C5-C24 arylimino, nitro, and nitroso. Furthermore, two adjacent substituents can be taken together to form a ring, generally a five- or six-membered alicyclic or aryl ring, optionally containing 1 to 3 heteroatoms and 1 to 3 substituents as above.

[00206] Preferred substituents in L2 and L3 include, without limitation, halo, C1-C12 alkyl, substituted C1-C12 alkyl, C1-C12 heteroalkyl, substituted C1-C12 heteroalkyl, C5-C14 aryl, substituted C5-C14 aryl, C5-C14 heteroaryl, substituted C5-C14 heteroaryl, C6-C16 alkyl, substituted C6-C16 alkyl, C6-C16 heteroalkyl, substituted C6-C16 heteroalkyl, C6-C16 aralkyl, substituted C6-C16 aralkyl, C6-C16 heteroaralkyl, substituted C6-C16 heteroaralkyl, C1-C12 alkoxy, C5-C14 aryloxy, C2-C12 alkylcarbonyl, C6-C14 arylcarbonyl, C2-C12 alkylcarbonyloxy, C6C14 arylcarbonyloxy, C2-C12 alkoxycarbonyl, C6-C14 aryloxycarbonyl, halocarbonyl, formyl, amino, mono-(C1-C12 alkyl)-substituted amino, di-(C1-C12 alkyl)-substituted amino, mono(C5-C14 aryl)-substituted amino, di-(aryl C5-C14)-substituted amino, and nitro.

[00207] From the foregoing, the most preferred substituents are halo, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, penyl, substituted penyl, formyl, N,N-di(C1C6 alkyl)amino, nitro, and nitrogen heterocycles as described above (including, for example, pyrrolidine, piperidine, piperazine, pyrazine, pyrimidine, pyridine, pyridazine, etc.).

[00208] In certain embodiments, L2 and L3 can also be taken together to form a bidentate or multidentate ligand containing two or more, generally two, coordinated heteroatoms such as N, O, S, or P, with preferred such ligands being Brookhart-type diimine ligands. A bidentate ligand Petition 870210098125, dated 10 / 25 / 2021, p. 104 / 187 85 / 158 representative have the structure of formula (VI) (VI) wherein R15, R16, R17, and R18 hydrocarbyl (for example, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alquaryl, or C6-C24 aralkyl), substituted hydrocarbyl (for example, substituted C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alquaryl, or C6-C24 aralkyl), heteroatom-containing hydrocarbyl (for example, C1-C20 heteroalkyl, C5-C24 heteroaryl, C6-C24 aralkyl containing a heteroatom, or C6-C24 alquaryl containing a heteroatom), or substituted heteroatom-containing hydrocarbyl (for example, Substituted C1-C20 heteroalkyl, C5-C24 heteroaryl, C6-C24 aralkyl containing a heteroatom, or C6-C24 alquaryl containing a heteroatom), or (1) R15 and R16, (2) R17 and R18, (3) R16 and R17, or (4) both R15 and R16, and R17 and R18, may be taken together to form a ring, i.e., a Nheterocycle. Preferred cyclic groups in such a case are five- and six-membered rings, typically aromatic rings.

[00209] In a fourth group of carbene olefin metal metathesis catalysts having the structure of formula (I), two of the substituents are taken together to form a bidentate ligand or a tridentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates. Specific examples include P(Ph)2CH2CH2P(Ph)2-, -As(Ph)2CH2CH2As(Ph2)-, -P(Ph)2CH2CH2C(CF3)2O-, binaphtholate dianions, pinacolalate dianions, -P(CH3)2(CH2)2P(CH3)2-, and OC(CH3)2(CH3)2CO-. Preferred bidentate ligands are -P(Ph)2CH2CH2P(Ph)2- and P(CH3)2(CH2)2P(CH3)2-. Tridentate ligands include, but are not limited to, (CH3)2NCH2CH2P(Ph)CH2CH2N(CH3)2. Other preferred tridentate ligands are those in which any three of X1, X2, L1, L2, L3, R1, and R2 (e.g., X1, L1, and L2) are taken together to be cyclopentadienyl, indenyl, or fluorenyl, each Petition 870210098125, dated 10 / 25 / 2021, p. 105 / 187 86 / 158 optionally substituted with C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, C5-C20 aryl, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, C5-C20 aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl, or C1-C20 alkylsulfinyl, each of which may be further substituted with C1-C6 alkyl, halide, C1-C6 alkoxy or with a phenyl group optionally substituted with halide, C1-C6 alkyl, or C1-C6 alkoxy. More preferably, in compounds of this type, X, L1, and L2 are taken together to be cyclopentadienyl or indenyl, each optionally substituted with vinyl, C1-C10 alkyl, C5-C20 aryl, C1-C10 carboxylate, C2-C10 alkoxycarbonyl, C1-C10 alkoxy, or C5-C20 aryloxy, each optionally substituted with C1-C6 alkyl, halide, C1-C6 alkoxy, or with a phenyl group optionally substituted with a halide, C1-C6 alkyl, or C1-C6 alkoxy.Most preferably, X, L1 and L2 can be taken together to be cyclopentadienyl, optionally substituted with vinyl, hydrogen, methyl, or phenyl. Tetradentate ligands include, but are not limited to, O2C(CH2)2P(Ph)(CH2)2P(Ph)(CH2)2CO2, phthalocyanines, and porphyrins.

[00210] Complexes in which Y is coordinated to the metal are examples of a fifth group of metal carbene olefin metathesis catalysts, and are commonly called “Grubbs-Hoveyda” catalysts. Grubbs-Hoveyda-active metal carbene metathesis complexes can be described by formula (VII) (VII) in which, M is a Group 8 transition metal, particularly Ru or Os, or, more particularly, Ru; Petition 870210098125, dated 10 / 25 / 2021, pp. 106 / 187 87 / 158 X1, X2, and L1 are as previously defined here for the first and second groups of catalysts; Y is a heteroatom selected from N, O, S, and P; preferably Y is O or N; R5, R6, R7, and R8 are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, substituted halogen amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, where “A” and Fn were defined above; and any combination of Y, Z, R5, R6, R7, and R8 can be linked to form one or more cyclic groups; n is 0, 1, or 2, such that n is 1 for divalent heteroatoms O or S, en is 2 for trivalent heteroatoms N or P; and Z is a selected group of hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl wherein the functional group(s) may independently be one or more of the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl, and trimethylsilyl; and wherein any combination or combinations of X1, X2, L1, Y, Z, R5, R6, R7, and R8 may be attached to a support. Additionally, R5, R6, R7, R8, and Z can independently be thioisocyanate, cyanate, or thiocyanate.

[00211] Examples of complexes comprising Grubbs-Hoveyda ligands suitable in the invention include: Petition 870210098125, dated 10 / 25 / 2021, pp. 107 / 187 88 / 158 where L1, X1, X2, and M are as described for any of the other groups of catalysts. Suitable carbene chelating and carbene precursors are further described by Pederson et al. (U.S. Pat. Nos. 7,026,495 and 6,620,955, disclosures of both of which are incorporated herein by reference) and Hoveyda et al. (U.S. Pat. Nos. 6,921,735 and WO0214376, disclosures of both of which are incorporated herein by reference).

[00212] Other useful complexes include structures in which L2 and R2 according to formulas (I), (III), or (V) are linked, such as styrenic compounds that also include a functional group for attachment to a support. Examples in which the functional group is a functionalized trialkoxysyl moiety include, but are not limited to, the following: Petition 870210098125, dated 10 / 25 / 2021, pp. 108 / 187 89 / 158 R S—Nk'^Si(OR).. R THE THE R R II N—S· THE Si(OR)3 and Si(OR)3 and SÍ(OR)3

[00213] Other examples of complexes having ligands include those having linkages between a neutral NHC ligand and an anionic ligand, a neutral NHC ligand and an alkylidine ligand, a neutral NHC ligand and an L2 ligand, a neutral NHC ligand and an L3 ligand, an anionic ligand and an alkylidine ligand, and any combination thereof. Although the possible structures are too numerous to list here, some suitable structures based on formula (III) include: Petition 870210098125, dated 10 / 25 / 2021, p. 109 / 187 90 / 158 The structure of formula (I), as described above, other transition carbene metal complexes include, but are not limited to: Neutral ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 16, are penta-coordinated, and are of general formula (IX); Petition 870210098125, dated 10 / 25 / 2021, page 110 / 187 91 / 158 neutral ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 18, are hexa-coordinated, and are of the general formula (X); Cationic ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 14, are tetra-coordinated, and are of general formula (XI); and cationic ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 14 or 16, are tetra-coordinated or penta-coordinated, respectively, and are of general formula (XII) (IX) (X) (XI) L (XII) L where: M, X1, X2, L1, L2, L3, R1, and R2 are as defined for any of the four previously defined catalyst groups; Petition 870210098125, dated 10 / 25 / 2021, p. 111 / 187 92 / 158 results are independently zero or 1; t is an integer in the range of zero to 5; k is an integer in the range of zero to 1; Y is any uncoordinated anion (for example, a halide ion, BF4-, etc.); Z1 and Z2 are selected independently from -O-, -S-, -NR2-, -PR2-, P(=O)R2-, -P(OR2)-, -P(=O)(OR2)-, -C(=O)-, -C(=O)O-, -OC(=O)-, -OC(=O)O-, -S(=O), -S(=O)2-, -, and an optionally substituted and / or optionally heteroatom-containing C1-C20 hydrocarbylene bond; Z3 is any cationic moiety such as -P(R2)3+ or -N(R2)3+; and any two or more of X1, X2, L1, L2, L3, Z1, Z2, Z3, R1, and R2 may be taken together to form a cyclic group, for example, a multidentate ligand, and in which any one or more of X1, X2, L1, L2, L3, Z1, Z2, Z3, R1, and R2 may be attached to a support.

[00215] Additionally, another group of carbene olefin metal metathesis catalysts that can be used in the invention disclosed herein is a Group 8 transition metal complex having the structure of formula (XIII): (XIII) where M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly ruthenium; X1, X2, L1 and L2 are as defined for the first and second groups of catalysts defined above; and RG1, RG2, RG3, RG4, RG5, and RG6 are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, Petition 870210098125, dated 10 / 25 / 2021, page 112 / 187 93 / 158 heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanate, thiocyanate, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, substituted halogen amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or A-Fn, wherein “A” is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, wherein the alkyl portion of the alkylene and arylalkylene groups may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene may be substituted or unsubstituted,and wherein heteroatoms and / or functional groups may be present in the aryl or alkyl portions of alkylene and arylalkylene groups, and Fn is a functional group, or any one or more of RG1, RG2, RG3, RG4, RG5, and RG6 may be linked together to form a cyclic group, or any one or more of RG1, RG2, RG3, RG4, RG5, and RG6 may be linked to a support.

[00216] Additionally, a preferred embodiment of the Group 8 transition metal complex of formula XIII is a Group 8 transition metal complex of formula (XIV): (XIV) Petition 870210098125, dated 10 / 25 / 2021, pp. 113 / 187 94 / 158 where M, X1, X2, L1, L2, are as defined above for the Group 8 transition metal complex of formula XIII; and RG7, RG8, RG9, RG10, RG11, RG12, RG13, RG14, RG15 and RG16 are as defined above for RG1, RG2, RG3, RG4, RG5, and RG6 for the Group 8 transition metal complex of formula XIII or any one or more of RG7, RG8, RG9, RG10, RG11, RG12, RG13, RG14, RG15 and RG16 may be linked together to form a cyclic group, or any one or more of RG7, RG8, RG9, RG10, RG11, RG12, RG13, RG14, RG15 and RG16 may be linked to a support.

[00217] Additionally, another preferred embodiment of the Group 8 transition metal complex of formula XIII is a Group 8 transition metal complex of formula (XV): (XV) where M, X1, X2, L1, L2, are as defined above for the Group 8 transition metal complex of formula XIII.

[00218] Additionally, another group of olefin metathesis catalysts that can be used in the invention disclosed herein is a Group 8 transition metal complex comprising a Schiff-based ligand having the structure of formula (XVI): Petition 870210098125, dated 10 / 25 / 2021, pp. 114 / 187 95 / 158 (XVI) where M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly ruthenium; X1 and L1 are as defined for the first and second groups of catalysts defined above; Z is selected from the group consisting of oxygen, sulfur, selenium, NRJ11, PRJ11, AsRJ11, and SbRJ11; and RJ1, RJ2, RJ3, RJ4, RJ5, RJ6, RJ7, RJ8, RJ9, RJ10, and RJ11 are each independently selected from the group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanate, thiocyanate, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen-amide substituted, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, wherein “A” is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, wherein the alkyl moiety of the alkylene and arylalkylene groups may be linear or branched,saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl moiety of the arylalkylene may be substituted or unsubstituted, and wherein heteroatoms and / or functional groups may be present in the aryl moieties or, Petition 870210098125, dated 10 / 25 / 2021, pp. 115 / 187 96 / 158 alkyl of alkylene and arylalkylene groups, and Fn is a functional group, or any one or more of RJ1, RJ2, RJ3, RJ4, RJ5, RJ6, RJ7, RJ8, RJ9, RJ10, and RJ11 can be linked together to form a cyclic group, or any one or more of RJ1, RJ2, RJ3, RJ4, RJ5, RJ6, RJ7, RJ8, RJ9, RJ10, and RJ11 can be connected to a holder.

[00219] Additionally, a preferred embodiment of the Group 8 transition metal complex of formula (XVI) is a Group 8 transition metal complex comprising a Schiff-based ligand having the structure of formula (XVII): (XVII) Rj13 where M, X1, L1, Z, RJ7, RJ8, RJ9, RJ10, and RJ11 are as defined above for Group 8 transition metal complex of formula XVI; and RJ12, RJ13, RJ14, RJ15, RJ16, RJ17, RJ18, RJ19, RJ20, and RJ21 are as defined above for RJ1, RJ2, RJ3, RJ4, RJ5, and RJ6 for the Group 8 transition metal complex of formula XVI, or any one or more of RJ7, RJ8, RJ9, RJ10, RJ11, RJ12, RJ13, RJ14, RJ15, RJ16, RJ17, RJ18, RJ19, RJ20, and RJ21 may be linked together to form a cyclic group, or any one or more of RJ7, RJ8, RJ9, RJ10, RJ11, RJ12, RJ13, RJ14, RJ15, RJ16, RJ17, RJ18, RJ19, RJ20, and RJ21 may be linked to a support.

[00220] Additionally, another preferred embodiment of the Group 8 transition metal complex of formula (XVI) is a Group 8 transition metal complex comprising a Schiff-based ligand having the structure Petition 870210098125, dated 10 / 25 / 2021, pp. 116 / 187 97 / 158 of formula (XVIII): (XVIII) wherein M, X1, L1, Z, RJ7, RJ8, RJ9, RJ10, and RJ11, are as defined above for the Group 8 transition metal complex of formula (XVI).

[00221] Additionally, another group of olefin metathesis catalysts that can be used in the invention disclosed herein is a Group 8 transition metal complex comprising a Schiff-based ligand having the structure of formula (XIX): (19) where M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly ruthenium; X1, L1, R1, and R2 are as defined for the first and second groups of catalysts defined above; Z is selected from the group consisting of oxygen, sulfur, selenium, NRK5, PRK5, AsRK5, and SbRK5; m is 0, 1, or 2; and RK1, RK2, RK3, RK4, and RK5 are each independently selected from Petition 870210098125, dated 10 / 25 / 2021, pp. 117 / 187 98 / 158 group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanate, thiocyanate, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, substituted halogen-amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or A-Fn, wherein “A” is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, wherein the alkyl moiety of the alkylene and arylalkylene groups may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted,wherein the aryl portion of the arylalkylene may be substituted or unsubstituted, and wherein heteroatoms and / or functional groups may be present in the aryl or alkyl portions of the alkylene and arylalkylene groups, and Fn is a functional group, or any one or more of RK1, RK2, RK3, RK4, and RK5 may be linked together to form a cyclic group, or any one or more of RK1, RK2, RK3, RK4, and RK5 may be connected to a support.

[00222] Furthermore, the catalysts of formulas (XVI) to (XIX) may optionally be contacted with an activating compound, wherein at least partial cleavage of a bond between the Group 8 transition metal and at least one Schiff-based ligand occurs, wherein the activating compound is a metal or silicon compound selected from the group consisting of copper(I) halides; zinc compounds of formula Zn(RY1)2, wherein RY1 is halogen, C1-C7 alkyl or aryl; tin compounds represented by formula SnRY2RY3RY4RY5 wherein each of RY2, RY3, RY4 and RY5 is independently selected from the group consisting of halogen, C1-C20 alkyl, C3-C10 cycloalkyl, aryl, benzyl and C2-C7 alkenyl; and silicon compounds represented by the formula SiRY6RY7RY8RY9 where each of RY6, RY7, RY8, Petition 870210098125, dated 10 / 25 / 2021, pp. 118 / 187 99 / 158 RY9 is independently selected from the group consisting of hydrogen, halogen, C1-C20 alkyl, halo, C1-C7 alkyl, aryl, heteroaryl, and vinyl. In addition, catalysts of formulas (XVI) to (XIX) may optionally be contacted with an activating compound wherein at least partial cleavage of a bond between the Group 8 transition metal and at least one Schiff-based ligand occurs, wherein the activating compound is an inorganic acid such as hydrogen iodide, hydrogen bromide, hydrogen chloride, hydrogen fluoride, sulfuric acid, nitric acid, iodic acid, periodic acid, perchloric acid, HOClO, HOClO2, and HOIO3. Furthermore, the catalysts of formulas (XVI) to (XIX) may optionally be contacted with an activating compound wherein at least partial cleavage of a bond between the Group 8 transition metal and at least one Schiff-based ligand occurs, wherein the activating compound is an organic acid such as sulfonic acids including,but not limited to, methanesulfonic acid, aminobenzenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, sulfanilic acid and trifluoromethanesulfonic acid; monocarboxylic acids including but not limited to acetoacetic acid, barbituric acid, bromoacetic acid, bromobenzoic acid, chloroacetic acid, chlorobenzoic acid, chlorophenoxyacetic acid, chloropropionic acid, cis-cinnamic acid, cyanoacetic acid, cyanobutyric acid, cyanophenoxyacetic acid, cyanopropionic acid, dichloroacetic acid, dichloroacetylacetic acid, acid dihydroxybenzoic acid, dihydroxymalic acid, dihydroxytartaric acid, dinicotinic acid, diphenylacetic acid, fluorobenzoic acid, formic acid, furancarboxylic acid, furoic acid, glycolic acid, hippuric acid, iodoacetic acid, iodobenzoic acid, lactic acid, lutidinic acid, mandelic acid, α-naphthoic acid, nitrobenzoic acid, acid nitrophenylacetic acid, o-phenylbenzoic acid, thioacetic acid,Thiophenecarboxylic acid, trichloroacetic acid, and trihydroxybenzoic acid; and other acidic substances such as, but not limited to, picric acid and uric acid.

[00223] In addition, other examples of catalysts that can be used Petition 870210098125, dated 10 / 25 / 2021, pp. 119 / 187 100 / 158 with respect to the present invention are located in the following disclosures, each of which is incorporated herein by reference, U.S. Pat. Nos. 7,687,635; 7,671,224; 6,284,852; 6,486,279; and 5,977,393; International Publication Number WO2010 / 037550; and U.S. Pat. Application Nos. 12 / 303,615; 10 / 590,380; 11 / 465,651 (Publication No: U.S. 2007 / 0043188); and 11 / 465,651 (Publication No: Corrected Publication U.S. 2008 / 0293905); and European Pat. Nos. EP1757613B1 and EP1577282B1.

[00224] Non-limiting examples of carbene olefin metal metathesis catalysts that can be used to prepare sustained complexes and in the reactions disclosed herein include the following, some of which for convenience are identified throughout this disclosure by reference to their molecular weight: Petition 870210098125, dated 10 / 25 / 2021, pp. 120 / 187 101 / 158 C727 Petition 870210098125, dated 10 / 25 / 2021, pp. 121 / 187 102 / 158 Mes—N N—Mes C859 Mes---N. ,N—Mes .Cl P+Cy3 BF4 Ru=C— CI< I PCy3 C841-n C916 PCy3 UC Cl^ py C701 C577 C646 i-Pr i-Pr i-Pr. i-Pr' Py Py----Ru Cl pH C801 C811 Petition 870210098125, dated 10 / 25 / 2021, pp. 122 / 187 103 / 158 C933 C712 pH PCy3 C838 Cl i-Pr Ru cT I THE Cl i-Pr' C824 C785 (X = Br) C879 (X = I) Petition 870210098125, dated 10 / 25 / 2021, pp. 123 / 187 104 / 158 i-Pr· N N--i-Pr JsCl i-Pr' Ru= ci< IO i-Pr N(CH3)2 S^oo DIP DIP II Month Month Month Month CH3—NN—CH3 T <ci RU-=\ cr I \ I Ph Mes—NN—Mes CH3—NN—CH3| <ci Ru-=\ Cl< I \ I Ph Mes—NN—Mes Clr CH3—NN—CH3 I .ci DIP DIP CH3—NN—CH3 I <pl RU=\ CT I \ I Ph Mes—NN—Mes Month Month CH3—NN—CH3 T <ci Ru-=\ ClrI \ I Ph Mes—NN—Mes Petition 870210098125, of 25 / 10 / 2021, page. 124 / 187 105 / 158

[00225] In the molecular structures and formulas shown above, Ph represents penyl, Cy represents cyclohexyl, Cp represents cyclopentyl, Me represents methyl, Bu represents n-butyl, t-Bu represents tert-butyl, i-Pr represents isopropyl, py represents pyridine (coordinated through the N atom), Mes represents mesityl (i.e., 2,4,6-trimethylphenyl), DiPP and DIPP represent 2,6-di-isopropylpenyl, and MiPP represents 2-isopropylphenyl.

[00226] Other examples of olefin carbene metal metathesis catalysts useful for preparing sustained complexes and in the reactions disclosed herein include the following: ruthenium(II) dichloro(3-methyl-2-butenylidene) bis(tricyclopentylphosphine) (C716); ruthenium(II) dichloro(3-methyl-2-butenylidene) bis(tricyclohexylphosphine) (C801); ruthenium(II) dichloro(phenylmethylene) bis(tricyclohexylphosphine) (C823); ruthenium(II) (1,3bis-(2,4,6-trimethylphenyl)-2-imidazolidinilidene) dichloro(phenylmethylene)(triphenylphosphine) (C830); ruthenium(II) dichloro(phenylvinylidene)bis(tricyclohexylphosphine) (C835a); ruthenium (II) dichloro (tricyclohexylphosphine) (o-isopropoxyphenylmethylene) (C601); Ruthenium (II) (1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene) ruthenium (II) dichloro (phenylmethylene) bis (3bromopyridine) (C884); [1,3-bis-(2,4,6-trimethylphenyl)-2imidazolidynylidene]dichloro(o-isopropoxyphenylmethylene)ruthenium(II) (C627); [1,3-bis-(2,4,6Petition 870210098125, of 10 / 25 / 2021, page 125 / 187 106 / 158 trimethylphenyl)-2-imidazolidinylidene] dichloro (benzylidene) (triphenylphosphine) ruthenium(II) (C831); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro (benzylidene)(methyldiphenylphosphine) ruthenium( 11) (C769); [1,3-bis-(2,4,6-trimethylphenyl)-2imidazolidinylidene] dichloro (benzylidene)(tricyclohexylphosphine) ruthenium(II) (C848); [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro (benzylidene) (diethylphenylphosphine) ruthenium(II) (C735); [1,3-bis-(2,4,6-trimethylphenyl)-2imidazolidinylidene]dichloro(benzylidene)(tri-n-butylphosphine)ruthenium(II) (C771); [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(triphenylphosphine)ruthenium(II) (C809); [1,3-bis-(2,4,6-trimethylphenyl)-2imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(methyldiphenylphosphine)ruthenium(II) (C747); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene) (tricyclohexylphosphine)ruthenium(II) (C827);[1,3-bis-(2,4,6-trimethylphenyl)-2imidazolidinylidene] dichloro(3-methyl-2-butenylidene)(diethylphenylphosphine)ruthenium(II) (C713); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro(3-methyl-2-butenylidene) (tri-nbutylphosphine)ruthenium(II) (C749); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro(phenylindenylidene)(triphenylphosphine)ruthenium(II) (C931); [1,3-bis-(2,4,6-trimethylphenyl)2-imidazolidinylidene] dichloro(phenylindenylidene) (methylphenylphosphine)ruthenium(II) (C869); [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro (phenylindenylidene) (tricyclohexylphosphine) ruthenium(II) (C949); [1,3-bis-(2,4,6-trimethylphenyl)-2imidazolidinylidene] dichloro (phenylindenylidene)(diethylphenylphosphine) ruthenium(II) (C835); and [1,3bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro (phenylindenylidene)(tri-nbutylphosphine) ruthenium(II) (C871).;

[00227] Still other carbene olefin metal metathesis catalysts useful in ROMP reactions, and / or in other metathesis reactions, such as ring-closing metathesis, cross-metathesis, ring-opening cross-metathesis, autometathesis, ethenolysis, alkenolysis, acyclic diene metathesis polymerization, and combinations thereof, include the following structures: Petition 870210098125, dated 10 / 25 / 2021, pp. 126 / 187 107 / 158 Petition 870210098125, dated 10 / 25 / 2021, pp. 127 / 187 108 / 158

[00228] In general, the transition metal complexes used as catalysts herein can be prepared by several different methods, such as those described by Schwab et al. (1996) J. Am. Chem. Soc. 118:100-110, Scholl et al. (1999) Org. Lett. 6:953-956, Sanford et al. (2001) J. Am. Chem. Soc. 123:749-750, Pat. US No. 5,312,940, and Pat. US No. 5,342,909, the disclosures of each of which are incorporated herein by reference. Also, see Pub. of Pat. US No. 2003 / 0055262 by Grubbs et al., WO 02 / 079208, and Pat. US No. 6,613,910 by Grubbs et al., disclosures of each of which are incorporated herein by reference. Preferred synthetic methods are described in WO 03 / 11455A1 by Grubbs. Petition 870210098125, dated 10 / 25 / 2021, pp. 128 / 187 109 / 158 et al., the publication of which is incorporated herein by reference.

[00229] Examples of carbene olefin metal metathesis catalysts are Group 8 transition metal complexes having the structure of formula (I) commonly called “First Generation Grubbs” catalysts, formula (III) commonly called “Second Generation Grubbs” catalysts, or formula (VII) commonly called “Hoveyda Grubbs” catalysts.

[00230] Examples of carbene olefin metal metathesis catalysts have the structure of formula (I) (I) where: M is a Group 8 transition metal; L1, L2, and L3 are neutral electron-donating ligands; n is 0 or 1; m is 0.1 or 2; k is 0 or 1; X1 and X2 are anionic ligands; R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein any two or more of X1, X2, L1, L2, L3, R1, and R2 may be taken together to form one or more cyclic groups, and wherein any one or more of X1, X2, L1, L2, L3, R1, and R2 may be attached to a support; and formula (VII) Petition 870210098125, dated 10 / 25 / 2021, pp. 129 / 187 110 / 158 (VII) in which, M is a Group 8 transition metal; L1 is a neutral electron-donating ligand; X1 and X2 are anionic ligands; Y is a heteroatom selected from O or N; R5, R6, R7, and R8 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups; n is 0, 1, or 2; and Z is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein any combination of Y, Z, R5, R6, R7, and R8 can be linked to form one or more cyclic groups, and wherein any combination of X1, X2, L1, Y, Z, R5, R6, R7, and R8 can be linked to a support.

[00231] Examples of carbene olefin metal metathesis catalysts have the structure of formula (I) (I) in which: Petition 870210098125, dated 10 / 25 / 2021, pp. 130 / 187 111 / 158 M is ruthenium; n is 0; m is 0; k is 1; L1 and L2 are trisubstituted phosphines independently selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), tri-isopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1 is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinilidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinilidene, and 1,3-bis(2,6-diisopropylphenyl)imidazol2-ylidene and L2 is a tri-substituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); X1 and X2 are chlorides; R1 is hydrogen and R2 is phenyl or -CH=C(CH3)2 or thienyl; or R1 and R2 are taken together to form 3-phenyl-1H-indene; and formula (VII) (VII) where, M is ruthenium; Petition 870210098125, dated 10 / 25 / 2021, pp. 131 / 187 112 / 158 L1 is a tri-substituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1 is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinilidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinilidene, and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; X1 and X2 are chlorides; Y is oxygen; R5, R6, R7, and R8 are each hydrogen; n is 1; and Z stands for isopropyl.

[00232] Examples of carbene olefin metal metathesis catalysts have the structure of the formula (I)L1(L3)n R1 / / ^M=(C)m=C x2\ ir2(I) (L2)k where: M is ruthenium; n is 0; m is 0; k is 1; L1 is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinilidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinilidene, and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; L2 is a tri-substituted phosphine selected from the group consisting of tri-n Petition 870210098125, dated 10 / 25 / 2021, pp. 132 / 187 113 / 158 butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); X1 and X2 are chlorides; R1 is hydrogen and R2 is phenyl or -CH=C(CH3)2 or thienyl; or R1 and R2 are taken together to form 3-phenyl-1H-indene; and formula (VII) (VII) in which, M is ruthenium; L1 is a tri-substituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1 is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinilidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinilidene, and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; X1 and X2 are chlorides; Y is oxygen; R5, R6, R7, and R8 are each hydrogen; n is 1; and Z stands for isopropyl. Petition 870210098125, dated 10 / 25 / 2021, pp. 133 / 187 114 / 158

[00233] Examples of carbene olefin metal metathesis catalysts have the structure of formula (I) (I) in which: M is ruthenium; n is 0; m is 0; k is 1; L1 is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinilidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinilidene, and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; L2 is a tri-substituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); X1 and X2 are chlorides; R1 is hydrogen and R2 is phenyl or -CH=C(CH3)2 or thienyl; or R1 and R2 are taken together to form 3-phenyl-1H-indene; and formula (VII) Petition 870210098125, dated 10 / 25 / 2021, pp. 134 / 187 115 / 158 (VII) in which, M is ruthenium; L1 is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinilidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinilidene, and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; X1 and X2 are chlorides; Y is oxygen; R5, R6, R7, and R8 are each hydrogen; n is 1; and Z stands for isopropyl.

[00234] Examples of carbene olefin metal metathesis catalysts have the structure of formula (I) |1(L3)n R1 I / / J^M=(C)m=c' x2\ ।R (I)(L where: M is ruthenium; n is 0; m is 0; k is 1; Petition 870210098125, dated 10 / 25 / 2021, pp. 135 / 187 116 / 158 L1 is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinilidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinilidene, and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; L2 is a tri-substituted phosphine selected from the group consisting of tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (Pi-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); X1 and X2 are chloride; and R1 is hydrogen and R2 is phenyl or -CH=C(CH3)2 or thienyl; or R1 and R2 are taken together to form 3-phenyl-1H-indene.

[00235] Suitable supports for any of the catalysts described herein may be synthetic, semi-synthetic, or naturally occurring materials, which may be organic or inorganic, for example, polymeric, ceramic, or metallic. Attachment to the support will generally, though not necessarily, be covalent, and the covalent bond may be direct or indirect. Indirect covalent bonds are typically, though not necessarily, through a functional group on a support surface. Ionic attachments are also suitable, including combinations of one or more anionic groups in metal complexes coupled with supports containing cationic groups, or combinations of one or more cationic groups in metal complexes coupled with supports containing anionic groups.

[00236] When used, suitable supports may be selected from silicas, silicates, aluminas, aluminum oxides, silica-aluminas, aluminosilicates, zeolites, titanias, titanium dioxide, magnetite, magnesium oxides, boron oxides, clays, zirconias, zirconium dioxide, carbon, polymers, cellulose, amylose cellulosic polymers, amylosic polymers, or a combination thereof. The support Petition 870210098125, dated 10 / 25 / 2021, pp. 136 / 187 117 / 158 preferably comprises silica, a silicate, or a combination thereof.

[00237] In certain embodiments, it is also possible to use a support that has been treated to include functional groups, inert moieties, and / or excess binders. Any of the functional groups described herein is suitable for incorporation into the support, and can generally be achieved through techniques known in the field. Inert moieties can also be incorporated into the support, generally to reduce the available attachment sites on the support, for example, in order to control the location, or quantity, of a complex attached to the support.

[00238] The metathesis catalysts described below can be used in olefin metathesis reactions according to techniques known in the field. The catalyst is typically added to the resin composition as a solid, a solution, or as a suspension. When the catalyst is added to the resin composition as a suspension, the catalyst is suspended in a dispersing carrier such as mineral oil, paraffin oil, soybean oil, triisopropylbenzene, or any hydrophobic liquid that has a sufficiently high viscosity to allow effective dispersion of the catalyst, and that is sufficiently inert and has a sufficiently high boiling point so that it does not act as a low-boiling impurity in the olefin metathesis reaction.It will be assessed that the amount of catalyst used (i.e., the “catalyst loading”) in the reaction is dependent on a variety of factors such as the identity of the reactants and the reaction conditions used. It is understood, therefore, that the catalyst loading can be optimally and independently chosen for each reaction. In general, however, the catalyst will be present in an amount ranging from a minimum of about 0.1 ppm, 1 ppm, or 5 ppm, to a maximum of about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000 ppm relative to the amount of an olefinic substrate.

[00239] The catalyst will generally be present in a quantity that varies Petition 870210098125, dated 10 / 25 / 2021, pp. 137 / 187 118 / 158 from a minimum of about 0.00001 mol%, 0.0001 mol%, or 0.0005 mol%, to a maximum of about 0.001 mol%, 0.0015 mol%, 0.0025 mol%, 0.005 mol%, 0.01 mol%, 0.02 mol%, 0.05 mol%, or 0.1 mol% relative to the olefinic substrate.

[00240] When expressed as the molar ratio of monomer to catalyst, the catalyst (the “monomer to catalyst ratio”), the charge will generally be present in an amount ranging from a minimum of about 10,000,000:1, 1,000,000:1, or 200,000:1, to a maximum of about 100,000:1, 66,667:1, 40,000:1, 20,000:1, 10,000:1, 5,000:1, or 1,000:1.

[00241] Catalyst compositions of the invention comprise at least one carbene olefin metal metathesis catalyst. However, catalyst compositions of the invention may also comprise two or more carbene olefin metal metathesis catalysts.

[00242] Furthermore, any prior art metathesis catalyst (or two-component metathesis catalyst system) based on molybdenum or tungsten can also be used with the present invention. Resin Compositions and Articles

[00243] The resin compositions according to the invention generally comprise at least one cyclic olefin composition. Additionally, the resin compositions of the invention may comprise at least one cyclic olefin composition, wherein the resin composition is combined with a catalyst composition comprising at least one carbene olefin metal metathesis catalyst to form a ROMP composition. Additionally, the resin compositions according to the invention may comprise at least one cyclic olefin composition and at least one adhesion promoter. Additionally, the resin compositions according to the invention may comprise at least one cyclic olefin composition and at least one Petition 870210098125, dated 10 / 25 / 2021, pp. 138 / 187 119 / 158 composition of an adhesion promoter. Additionally, the resin compositions of the invention may also comprise at least one cyclic olefin composition and at least one substrate material. Additionally, the resin compositions of the invention may also comprise at least one cyclic olefin composition, at least one adhesion promoter, and at least one substrate material. Additionally, the resin compositions according to the invention may also comprise at least one cyclic olefin composition and at least one adhesion promoter, wherein the resin composition is combined with a catalyst composition comprising at least one carbene olefin metal metathesis catalyst to form a ROMP composition, and the resulting ROMP composition is applied to at least one substrate material.Additionally, the resin compositions according to the invention may also comprise at least one cyclic olefin composition and at least one adhesion promoter comprising at least one compound containing at least two isocyanate groups, wherein the resin composition is combined with a catalyst composition comprising at least one carbene olefin metal metathesis catalyst to form a ROMP composition, and the resulting ROMP composition is applied to at least one substrate material, wherein the substrate material may be a functionalized substrate material, such as, for example, a heteroatom-functionalized substrate, such as, for example, an amino-functionalized substrate.Additionally, the resin compositions according to the invention may also comprise at least one cyclic olefin composition and at least one adhesion promoter comprising at least one compound containing at least two isocyanate groups, wherein the resin composition is combined with a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, and the resulting resin composition is applied to at least one substrate material, such as, for example, a... Petition 870210098125, dated 10 / 25 / 2021, pp. 139 / 187 120 / 158 glass substrate material or carbon substrate material. In another embodiment, cyclic olefin resin, particularly ROMP, the compositions according to the invention comprise at least one cyclic olefin composition, a catalyst composition comprising at least one carbene olefin metal metathesis catalyst, at least one adhesion promoter comprising at least one compound containing at least two isocyanate groups, and at least one heteroatom-functionalized substrate material.

[00244] In another embodiment, the resin compositions according to the invention may additionally comprise an adhesion promoter. The adhesion promoters for use in the present invention are disclosed in International Patent Application No. PCT / US2012 / 042850, the contents of which are also incorporated herein by reference. The amounts of the adhesion promoter in the resin composition may vary within a wide range and may vary depending on the manufacturing operation or the particular end-use application. Generally, any level of the adhesion promoter that produces a desired increase in mechanical properties is of particular interest. When formulated or combined with a resin composition, the concentration of the adhesion promoter typically ranges from 0.001 to 50 phr, particularly 0.05 to 10 phr, more particularly 0.1 to 10 phr, or even more particularly 0.5 to 4.0 phr.

[00245] In another embodiment, the resin compositions according to the invention may additionally comprise an exogenous inhibitor. The exogenous inhibitors or “gel modification additives” for use in the present invention are disclosed in U.S. Pat. No. 5,939,504, the contents of which are also incorporated herein by reference. Non-limiting examples of exogenous inhibitors or “gel modification additives” include water, tetrahydrofuran (THF), 2-methyltetrahydrofuran (2-Me-THF), diethyl ether ((C2H5)2O), methyl tert-butyl ether (CH3OC(CH3)3), dimethoxyethane (CH3OCH2CH2OCH3), diglyme (CH3OCH2OCH2OCH3), Petition 870210098125, dated 10 / 25 / 2021, pp. 140 / 187 121 / 158 trimethylphosphine (PMes), triethylphosphine (PEts), tributylphosphine (PBus), tri(ortho-tolyl)phosphine (Po-tolyls), tri-tert-butylphosphine (P-tert-Bus), tricyclopentylphosphine (PCilopentils), tricyclohexylphosphine (PCys), triisopropylphosphine (Pi-Prs), trioctylphosphine (POcts), triisobutylphosphine (Pi-Bus), triphenylphosphine (PPhs), tri(pentafluorophenyl)phosphine (P(CeF5)s), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), diethylphenylphosphine (PEt2Ph), trimethylphosphine (P(OMe)s), triethylphosphite (P(OEt)s), Triisopropylphosphite (P(Oi-Pr)s), ethyl diphenylphosphinite (P(OEt)Ph2), tributylphosphite (P(OBu)s), triphenylphosphite (P(OPh)s), diethylphenylphosphonite (P(OEt)2Ph), and tribenzylphosphine (P(CH2Ph)s), 2-cyclohexenone, and triphenylphosphine oxide. Preferred exogenous inhibitors include triphenylphosphine, tricyclohexylphosphine, and tributylphosphine.When formulated or combined with a resin composition, the concentration of the exogenous inhibitor typically ranges from 0.001 to 10 phr, particularly 0.01 to 5 phr, and more particularly 0.05 phr. Exogenous inhibitors can be added to the resin composition in the absence of solvent, or as organic solutions. A single exogenous inhibitor may be used, or a combination of two or more different exogenous inhibitors may be used.

[00246] In another embodiment, the resin compositions according to the invention may additionally comprise a hydroperoxide gel modifier. The hydroperoxide gel modifiers for use in the present invention are disclosed in International Patent Application No. PCT / US2012 / 042850, the contents of which are also incorporated herein by reference. Non-limiting examples of hydroperoxide gel modifiers include tert-butyl hydroperoxide, tert-amyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, (2,5-dihydroperoxy)-2,5-dimethylhexane, cyclohexyl hydroperoxide, triphenylmethyl hydroperoxide, pinane hydroperoxide (e.g., Glidox® 500; LyondellBasell), and paramentane hydroperoxide (e.g., Glidox® s00; LyondellBasell). More preferably, hydroperoxides suitable for use include tert-butyl Petition 870210098125, dated 10 / 25 / 2021, pp. 141 / 187 122 / 158 hydroperoxide and cumene hydroperoxide. Hydroperoxide gel-modifying additives can be added to the reaction mixture in the absence of solvent, or as organic or aqueous solutions. A single hydroperoxide compound can be used as the gel-modifying additive, or a combination of two or more different hydroperoxide compounds can be used. All hydroperoxide concentrations that retard the onset of the gel state of a particular metathesis polymerization. Advantageously, the use of hydroperoxide gel modifiers has been found to substantially maintain the properties of the cured polymer, including exothermic peak temperature and mechanical properties. Although not necessarily limited, the hydroperoxide concentration is advantageously between 0.01 and 1000 equivalents with respect to the catalyst. In other embodiments, the hydroperoxide concentration can be between 0.1 and 20 equivalents with respect to the catalyst.Generally, higher hydroperoxide concentrations will lead to a longer pot life. Additionally, in other embodiments, the hydroperoxide concentration may be between 0.05 and 100 equivalents with respect to the catalyst. Furthermore, in other embodiments, the hydroperoxide concentration may be between 0.1 and 50 equivalents with respect to the catalyst.

[00247] In another embodiment, the resin compositions of the invention may additionally comprise at least one 5-alkenyl-2-norbornene as a pot duration adjusting agent. 5-alkenyl-2-norbornenes for use in the present invention are disclosed in Pat. US 5,204,427 and non-limiting examples include 5-vinylbicyclo[2,2,1]hepto-2-ene (5-vinyl-2-norbornene); 5-isopropenylbicyclo[2,2,1]hepto-2-ene (5-isopropenyl-2-norbornene); 5-vinyl-4-vinyl-2-norbornene; 5-propenylbicyclo[2,2,1]hepto-2-ene (5-propenyl-2-norbornene); 5-butenyl-bicyclo[2,2,1]hepto-2ene (5-butenyl-2-norbornene; 5-pentenyl-bicyclo[2,2,1]hepto-2-ene (5-pentenyl-2 Petition 870210098125, dated 10 / 25 / 2021, pp. 142 / 187 123 / 158 norbornene); and its monomethyl, monochlorine, and dichlorine substituents, including the endo and exo isomers, and mixtures thereof. More preferred 5-alkenyl-2-norbornene(s) include 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, and 5-butenyl-2-norbornene, including the endo and exo isomers, and mixtures thereof. The most preferred 5-alkenyl-2-norbornene pot duration adjusting agent is 5-vinyl-2-norbornene, including the endo and exo isomers, and mixtures thereof. 5-Alkenyl-2-Norbornene pot duration adjusting agents are normally used in resin compositions at levels of about 0.01 phr to 10 phr, more preferably at levels of about 0.1 phr to 5 phr, and even more preferably at levels of about 0.1 phr to 3 phr. The 5-Alkenyl-2-Norbornene pot duration adjusting agent can be added to the resin composition in the absence of solvent, or as organic solutions.A single 5-alkenyl-2-norbornene pot duration adjusting agent can be used, or a combination of two or more different 5-alkenyl-2-norbornene pot duration adjusting agents can be used.

[00248] The resin compositions of the invention may optionally be formulated with additives. Suitable additives include, but are not limited to, gel modifiers, hardness modulators, impact modifiers, elastomers, antioxidants, antiozonants, stabilizers, crosslinkers, fillers, binders, coupling agents, thixotropes, wetting agents, biocides, plasticizers, pigments, flame retardants, dyes, fibers and reinforcing materials, including size enhancers and substrates, such as those treated with finishes, coatings, coupling agents, film formers and / or lubricants. Furthermore, the amount of additives present in the resin compositions may vary depending on the particular type of additive used. The concentration of additives in the resin compositions typically ranges from, for example, 0.001 to 85 percent by weight, particularly from 0.1 to 75 percent by weight. Petition 870210098125, dated 10 / 25 / 2021, pp. 143 / 187 124 / 158 percent by weight, or even more specifically, from 2 to 60 percent by weight.

[00249] The resin compositions of the invention may optionally be formulated with or without a crosslinker, for example, a crosslinker selected from dialkyl peroxides, diacyl peroxides, and peroxyacids.

[00250] Suitable impact modifiers or elastomers include, without limitation, natural rubber, butyl rubber, polyisoprene, polybutadiene, polyisobutylene, ethylene-propylene copolymer, styrene-butadiene-styrene triblock rubber, random styrene-butadiene rubber, styrene-isoprene-styrene triblock rubber, styrene-ethylene / butylene-styrene copolymer, styrene-ethylene / propylene-styrene copolymer, ethylene-propylene-diene terpolymers, ethylene-vinyl acetate, and nitrile rubbers.Preferred impact modifiers or elastomers are polybutadiene Diene 55AC10 (Firestone), polybutadiene Diene 55AM5 (Firestone), EPDM Royalene 301T, EPDM Buna T9650 (Bayer), styrene-ethylene / butylene-styrene copolymer Kraton G1651H, Polysar Butyl 301 (Bayer), polybutadiene Taktene 710 (Bayer), styrene-ethylene / butylene-styrene Kraton G1726M, EthyleneOctene Engage 8150 (DuPont-Dow), styrene-butadiene Kraton D1184, EPDM Nordel 1070 (DuPont-Dow), and polyisobutylene Vistanex MML-140 (Exxon). These materials are typically used in resin compositions at levels of about 0.10 phr to 10 phr, but more preferably at levels of about 0.1 phr to 5 phr. Various impact modifiers or polar elastomers may also be used.

[00251] Antioxidants and antiozonants include any antioxidant or antiozonant used in the rubber or plastics industry. An “Index of Commercial Antioxidants and Antiozonants, Fourth Edition” is available from Goodyear Chemicals, The Goodyear Tire and Rubber Company, Akron, Ohio 44316. Suitable stabilizers (i.e., antioxidants or antiozonants) include, without limitation: 2,6-di-tert-butyl-4-methylphenol (BHT); styrenated phenol, such as Wingstay® S (Goodyear); 2- and 3-tert-butyl-4-methoxyphenol; alkylated hindered phenols, such as Petition 870210098125, dated 10 / 25 / 2021, pp. 144 / 187 125 / 158 Wingstay C (Goodyear); 4-hydroxymethyl-2,6-di-tert-butylphenol; 2,6-di-tert-butyl-4-sec-butylphenol; 2,2'-methylenebis(4-methyl-6-tert-butylphenol); 2,2'-methylenebis(4-ethyl-6-tert-butylphenol); 4,4'-methylenebis(2,6-di-tert-butylphenol); various bisphenols, such as Cyanox® 53 (Cytec Industries Inc.) and Permanax WSO; 2,2'-ethylidenebis(4,6-di-tert-butylphenol); 2,2'-methylenebis(4-methyl-6-(1-methylcyclohexyl)phenol); 4,4'-butylidenebis(6-tert-butyl-3-methylphenol); Polybutylated Bisphenol A; 4,4'-thiobis(6-tert-butyl-3-methylphenol); 4,4'-methylenebis(2,6-dimethylphenol); 1,1'-thiobis(2-naphthol); bridged polyalkylphenol methylene, such as ethyl antioxidant 738; 2,2'-thiobis(4-methyl-6-tert-butylphenol); 2,2'-isobutylidenebis(4,6-dimethylphenol); 2,2'-methylenebis(4-methyl-6-cyclohexylphenol); butylated reaction product of p-cresol and dicylopentadiene, such as Wingstay L; tetracis(methylene-3,5-di-tert-butyl-4-hydroxyhydrocinnamate)methane, i.e., Irganox® 1010 (BASF);1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, for example, Ethanox® 330 (Albemarle Corporation); 4,4'-methylenebis(2,6-di-tert-butylphenol), for example, Ethanox 4702 or Ethanox 4710; 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, i.e., Good-rite®3114 (Emerald Performance Materials), 2,5-di-tert-amylhydroquinone, tert-butylhydroquinone, tris(nonylphenylphosphite), bis(2,4-di-tert-butyl)pentaerythritol)diphosphite, distearyl pentaerythritol diphosphite, phenols and bisphenol phosphites, such as Naugard® 492 (Chemtura Corporation), phosphite / phenolic antioxidant combinations, such as Irganox B215; di-n-octadecyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate, such as Irganox 1093;1,6-hexamethylene bis(3-(3,5-di-tert-butyl-4-hydroxyphenylpropionate), such as Irganox 259, and octadecyl-3,5-di-tert-butyl-4-hydroxyhydrocinnamate, namely Irganox 1076, tetracis(2,4-di-tert-butylphenyl)4,4'-biphenylylenediphosphonite, diphenylamine, and 4,4'-diemthoxydiphenylamine. Such materials are normally used in the resin composition at levels of about 0.10 phr to 10 phr, but more preferably at levels of about 0.1 phr to 5 phr.

[00252] Suitable reinforcing materials include those that increase the strength or stiffness of a polymer composite when incorporated with the polymer. Petition 870210098125, dated 10 / 25 / 2021, pp. 145 / 187 126 / 158 Reinforcing materials may be in the form of filaments, fibers, slivers, mats, weaves, fabrics, knitted material, woven fabric, or other known structures. Suitable reinforcing materials include glass fibers and fabrics, carbon fibers and fabrics, aramid fibers and fabrics, polyolefin fibers or fabrics (including ultra-high molecular weight polyethylene fabrics, such as those produced by Honeywell under the trade name Spectra®), and polyoxazole fibers or fabrics (such as those produced by Toyobo Corporation under the trade name Zylon®).Reinforcing materials containing surface finishes, adhesives, or coatings are particularly suitable for the invention described, including Ahlstrom glass roving (R338-2400), Johns Manville glass roving (Star ROV®-086), Owens Corning wicks (OCV 366-AG-207, R25H-X14-2400, SE1200-207, SE1500-2400, SE2350-250), PPG glass wicks (Hybon® 2002, Hybon® 2026), Toho Tenax® towing carbon fiber (HTR-40), and Zoltek towing carbon fiber (Panex® 35). Furthermore, any fabrics prepared using reinforcing materials containing surface finishes, adhesives, or coatings are suitable for the invention. Advantageously, the invention does not require the costly process of removing surface finishes, adhesives, or coatings from the reinforcing materials. Additionally, glass fibers or fabric may include, without limitation, A-glass, E-glass or S-glass, S-2 glass, C-glass, R-glass, ECR-glass, M-glass, D-glass, and quartz, and silica / quartz.Preferred fiberglass reinforcements are those with finishes formulated for use with epoxy, vinyl ester, and / or polyurethane resins. When formulated for use with a combination of these resin types, the reinforcements are sometimes described as “multi-compatible.” Such reinforcements are generally treated during their manufacture with organosilane coupling agents comprising vinyl, amino, glycidoxy, or methacryloxy functional groups (or various combinations thereof) and are coated with a finish to protect the fiber surface and facilitate handling and processing (e.g., winding and...). Petition 870210098125, dated 10 / 25 / 2021, pp. 146 / 187 127 / 158 weaving). Finishes typically comprise a mixture of chemical and polymeric compounds, such as film formers, surfactants, and lubricants. Particularly preferred glass reinforcements are those containing some amount of amino-functionalized silane coupling agent. Particularly preferred finishes are those comprising epoxy-based and / or polyurethane-based film formers. Examples of preferred glass fiber reinforcements are those based on multi-compatible strand Hybon® 2026, 2002, and 2001 (PPG) strand; Ahlstrom R338 epoxysilane size strand; StarRov®086 soft silane size multi-compatible strand (Johns Manville); OCV™ 366, SE 1200, and R25H multi-compatible strand (Owens Corning); Compatible epoxy wicks OCV™ SE 1500 and 2350 (Owens Corning); and Jushi Group multi-compatible glass wicks (type 752, type 396, type 312, type 386).Additional suitable polymer fibers and fabrics may include, without limitation, one or more of polyester, polyamide (e.g., Nylon polyamide available from EI DuPont), aromatic polyamide (such as Kevlar aromatic polyamide available from EI DuPont, or P84 aromatic polyamide available from Lenzing Aktiengesellschaft), polyimide (e.g., Kapton polyimide available from EI DuPont), polyethylene (e.g., Dyneema polyethylene from Toyobo Co., Ltd.). Additional suitable carbon fibers may include, without limitation, AS2C, AS4, AS4C, AS4D, AS7, IM6, IM7, IM9, and PV42 / 850 from Hexcel Corporation; T800S, T1000G, M35J, M40J, M46J, M50J, M55J, M60J, M30S, M30G, and M40 from Toray Industries. Inc.; 12K, G30 - 7000 24K F402, G40 to 800 24K, STS 24K, HTR 40 F22 24K 1550tex from Toho Tenax, Inc.; 34 to 700, 34 to 700WD, 34 to 600, 34 to 600WD, and 34 to 600 unsized from Grafil Inc.; T-300, T-650 / 35, T-300C, and T-650 / 35C from Cytec Industries. Additional suitable carbon fibers may include without limitation AKSACA (A42 / D011), AKSACA (A42 / D012), Blue Star Starafil (10253512). Petition 870210098125, dated 10 / 25 / 2021, pp. 147 / 187 128 / 158 90), Blue Star Starafil (10254061 - 130), SGL Carbon (C30 T050 1.80), SGL Carbon (C50 T024 1.82), Grafil (347R1200U), Grafil (THR 6014A), Grafil (THR 6014K), Hexcel Carbon (AS4C / EXP 12K), Mitsubishi (Pyrofil TR 50S 12L AF), Mitsubishi (Pyrofil TR 50S 12L AF), Toho Tenax (T700SC 12000 - 50C), Toray (T700SC 12000 - 90C), Zoltek (Panex 35 50K, size 11), Zoltek (Panex 35 50K, size 13). Additional suitable carbon fabrics may include, without limitation, carbon fabrics by Vectorply (CL 1800) and Zoltek (Panex 35 UD Fabic-PX35UD0500 - 1220). Additional suitable glass fabrics may include, without limitation, glass fabrics as supplied by Vectorply (E-LT 3500 - 10) based on PPG Hybon® 2026; Saertex (U14EU970 - 01190-T2525 - 125000) based on PPG Hybon® 2002; Chongqing Policomp International Corp. (CPIC® Fiberglass) (EKU 1150(0) / 50 - 600); and Owens Corning (L1020 / 07A06 Xweft 200tex).

[00253] Other suitable fillers include, for example, metallic density modulators, microparticle density modulators, such as, for example, microspheres, and macroparticle density modulators, such as, for example, glass or ceramic beads. Metallic density modulators include, but are not limited to, powdered, agglomerated, shaved, flake, filed, particulate, or granulated metals, metal oxides, metal nitrides, and / or metal carbides, and the like. Preferred metallic density modulators include, among others, tungsten, tungsten carbide, aluminum, titanium, iron, lead, silicon oxide, aluminum oxide, boron carbide, and silicon carbide. Microparticle density modulators include, but are not limited to, glass, metal, thermoplastic (expandable or pre-expanded) or thermosetting, ceramic and / or silicate microspheres.Macroparticle density modulators include, but are not limited to, glass, plastic, or ceramic beads; metal rods, pieces, parts, or grains; hollow glass, ceramic, plastic, or metal spheres, balls, or tubes; and the like. Petition 870210098125, dated 10 / 25 / 2021, pp. 148 / 187 129 / 158

[00254] The invention is also directed to articles manufactured from a resin composition comprising at least one cyclic olefin composition, and a catalyst composition comprising at least one metal carbene olefin metathesis catalyst. Additionally, the invention is directed to articles manufactured from a resin composition comprising at least one cyclic olefin composition, a catalyst composition comprising at least one metal carbene olefin metathesis catalyst, and a substrate material. Additionally, the invention is directed to articles manufactured from a resin composition comprising at least one cyclic olefin composition, at least one adhesion promoter, a catalyst composition comprising at least one metal carbene olefin metathesis catalyst, and a substrate material.

[00255] Additionally, the invention is directed to articles manufactured from a resin composition comprising at least one cyclic olefin composition, at least one adhesion promoter comprising at least one compound containing at least two isocyanate groups, wherein the resin composition is combined with a catalyst composition comprising at least one carbene olefin metal metathesis catalyst to form a ROMP composition, and the resulting ROMP composition is applied to at least one substrate, which may be, for example, a functionalized substrate, such as, for example, a heteroatom-functionalized substrate, such as, for example, an amino-functionalized substrate.

[00256] The articles may include, but are not limited to, those formed by standard manufacturing techniques including casting, centrifugal casting, pultrusion, molding, rotational molding, open molding, reaction injection molding (RIM), resin transfer molding (RTM), decantation, vacuum impregnation, surface coating, filament winding and other methods. Petition 870210098125, dated 10 / 25 / 2021, pp. 149 / 187 130 / 158 known to be useful for the production of polymer articles and / or polymer composite articles. Furthermore, the compositions and articles of manufacture of the invention are not limited to a single polymer interface surface, but also include multilayers and laminates containing multiple polymer interface surfaces. The invention is also suitable for manufacturing articles by infusing resin into a porous material. Such porous materials include, but are not limited to, wood, cement, concrete, open-cell and cross-linked foams and sponges, papers, cardboard, felts, ropes or braids of natural or synthetic fibers, and various agglomerated materials.Additionally, other manufacturing techniques include, but are not limited to, cell casting, dip casting, continuous casting, embedding, filling, encapsulation, film casting or solvent casting, activated casting, mold casting, slurry casting, extrusion, mechanical foaming, chemical foaming, physical foaming, compression molding or combined molding, sterilization, spraying, Vacuum Transfer Resin Assisted Molding (VARTM), Seeman Resin Composite Infusion Molding Process (SCRIMP), blow molding, in-mold coating, in-mold painting or injection molding, vacuum molding, Enhanced Reaction Injection Molding (RRIM), Structural Reaction Injection Molding (SRIM), thermal expansion transfer molding (TERMO), recirculating resin injection molding (RICM), controlled atmospheric pressure resin infusion (CAPRI), hand-layup.To manufacture techniques that require the use of a RIM or mixed direction style shock, including without limitation RIM, SRIM, and RRIM, manufactured articles can be molded using a single mixed direction or a plurality of mixed directions, as well as a plurality of material injection streams (e.g., two resin streams and one catalyst stream). As the invention allows increasingly faster cycle times and increasingly higher mold temperatures using any of the manufacturing techniques. Petition 870210098125, dated 10 / 25 / 2021, pp. 150 / 187 131 / 158 previously mentioned, in particular, mold temperatures above 90oC, may become necessary to mold ROMP compositions of the invention under high pressures or under vacuum to prevent defects caused by mixture problems and / or trapped gases.

[00257] Furthermore, the present invention also allows for the manufacture of fabricated articles of any configuration, weight, size, thickness, or geometric shape. Examples of fabricated articles include without limitation any article molded or formed for use as an aerospace component, a marine component, an automotive component, a sporting goods component, an electrical component, and an industrial component, medical component, dental component, or military component. In one embodiment, an article may be a turbine component used in aircraft or general power generation. In one embodiment, turbine components may include without limitation one or more of an inlet, tower, cowling tower, an acoustic panel, a reverse thrust panel, a fan blade, a fan containment case, a duct bypass, an aerodynamic cowl, or an airfoil component.In one embodiment, an article may be a turbine blade component or may be a turbine blade itself. In another embodiment, an article may be a wind rotor blade, tower, mast cover, or nacelle for wind turbines. In another embodiment, an article may be a fuselage component. Examples of aerospace components may include, without limitation, one or more of a fuselage shell, wing, fairing, doors, access panel, aerodynamic control surface, or tensioner. In another embodiment, an article may be an automotive component. Examples of automotive components may include, without limitation, one or more of a body panel, bumper, airfoil, truck bed, skid plate, hood, longitudinal rail, pillar, or door. Examples of industrial components may include, without limitation, one or more of platforms. Petition 870210098125, dated 10 / 25 / 2021, pp. 151 / 187 132 / 158 rising pipes, impact protection structures for oil and gas; bridge, pipes, pressure vessels, power poles, coils, containers, tanks, lining, containment vessels, articles for application in corrosive environments (e.g., chlor-alkali, caustic, acid, brine, etc.), centralizers (e.g., oilfield centralizer), electrolytic cell linings, reinforcing structures for concrete architectures and roads, or radiators. Examples of electrical components may include, without limitation, one or more wound articles, such as coils or electric motors, or insulating devices. In one embodiment, an article may be a shielding component for the swirl current of a magnetic resonance imaging system or a shielding component for any electromagnetic radiation.In one embodiment, an article may be a military component including, without limitation, ballistic-resistant armor for personnel or vehicles, or ballistic-resistant structures to protect personnel or equipment. In another embodiment, an article may be a component of sporting goods including, without limitation, an arrow shaft, a tennis racket surface, a hockey stick, compound bow arms, or a golf club handle.In one embodiment, an article may be an object used in offshore applications, wherein the object is at least partially coated with a ROMP composition of the invention, wherein the object includes but is not limited to pipes, tubing, pipe fittings, hoses, hose fittings, tanks, containers, drums, manifolds, riser pipes, field splices, configurations designated as Christmas trees (oilfield Christmas tree, subsea Christmas tree), bridges, reel parts, configurations designated as pipe end termination (PLET), configurations designated as pipe end multiplicity (PLEM), robotics, devices and vehicles used in offshore applications, configurations designated as subsea tuning box housings, and other subsea architectures and equipment. Petition 870210098125, dated 10 / 25 / 2021, pp. 152 / 187 133 / 158

[00258] The resin compositions according to the invention may further comprise a bonding composition, or be used to provide improved adhesion for substrate materials that are sized with certain commercial silanes commonly used in the industry. As is known in the art, glass fibers are typically treated with a chemical solution (e.g., a bonding composition) soon after their formation to reinforce the glass fibers and protect the mechanical integrity of the strands during composite processing and manufacturing. Bonding treatments compatible with olefin metathesis catalysts and polydicyclopentadiene composites have been described in U.S. Pat. Nos. 6,890,650 and 6,436,476, disclosures of both of which are incorporated herein by reference. However, these disclosures are based on the use of silane in specialized treatments that are not commonly used in industrial glass manufacturing.In comparison, the present invention can provide improved mechanical properties for glass polymer composites that are dimensioned with silanes commonly used in the industry.

[00259] Glass bonding formulations typically comprise at least one film former (typically a film-forming polymer), at least one silane, and at least one lubricant. Any components of a bonding formulation that do not interfere with or substantially diminish the effectiveness of the metathesis catalyst or olefin polymerization reaction are considered to be compatible with the present invention and may generally be used herein.

[00260] Film formers that are compatible with metathesis catalysts include epoxies, polyesters, polyurethanes, polyolefins, and / or polyvinyl acetates. Other common film formers that do not negatively affect the performance of the olefin metathesis catalyst may also be used. Film formers are typically used as non-ionic, aqueous emulsions. Petition 870210098125, dated 10 / 25 / 2021, pp. 153 / 187 134 / 158 More than one film former can be used in a given bonding formulation to achieve a desired balance of glass processability and composite mechanical properties.

[00261] More particularly, the film former may comprise a low molecular weight epoxy emulsion, defined as an epoxy monomer or oligomer having an epoxy group average molecular weight (EEW) of less than 500, and / or a high molecular weight epoxy emulsion, defined as an epoxy monomer or oligomer having an epoxy group average molecular weight (EEW) greater than 500. Examples of suitable low molecular weight products include aqueous epoxy emulsions produced by Franklin International, including Franklin K8 0203 (EEW ​​190) and Franklin E-102 (EEW ​​225 - 275). Other examples of low molecular weight epoxy emulsions are available from Hexion, including EPI-REZ™ 3510W-60 (EEW ​​185 - 215), and EPI-REZ™ 3515-W-60 (EEW ​​225 - 275). Other examples of low molecular weight epoxy emulsions are available from COIM, including Filco 309 (EEW ​​270) and Filco 306 (EEW ​​330).Other examples of low molecular weight epoxy emulsions are available from DSM, including Neoxil® 965 (EEW ​​220 to 280) and Neoxil® 4555 (EEW ​​220 to 260). Examples of suitable high molecular weight epoxy emulsion products include epoxy emulsions produced by Hexion, including EPI-REZ™ 3522-W-60 (EEW ​​615 to 715).

[00262] Aqueous emulsions of modified epoxies, polyesters, and polyurethanes can also be used in the film former. Examples of suitable modified epoxy products include emulsions produced by DSM, including Neoxil® 2626 (a plasticized epoxy with an EEW of 500 to 620), Neoxil® 962 / D (an epoxy-ester with an EEW of 470 to 550), Neoxil® 3613 (an epoxy-ester with an EEW of 500 to 800), Neoxil® 5716 (a novolac epoxy with an EEW of 210 to 290), Neoxil® 0035 (a plasticized epoxy-ester with an EEW of 2500), and Neoxil® 729 (a lubricated epoxy with an EEW of 200 to 800). Other examples of epoxy emulsions Petition 870210098125, dated 10 / 25 / 2021, pp. 154 / 187 Modified 135 / 158 emulsions are available from COIM, including Filco 339 (an unsaturated polyester-epoxy with an EEW of 2000) and Filco 362 (an epoxy-ester with an EEW of 530). Examples of suitable polyester products include emulsions produced by DSM, including Neoxil® 954 / D, Neoxil® 2635, and Neoxil® 4759 (unsaturated bisphenolic polyesters). Additional suitable DSM products include Neoxil® 9166 and Neoxil® 968 / 60 (adipate polyesters). Other examples of suitable products include emulsions produced by COIM, including Filco 354 / N (unsaturated bisphenol polyester), Filco 350 (unsaturated polyester), and Filco 368 (saturated polyester). Examples of suitable polyurethane products include emulsions produced by Bayer Material Science, including Baybond®330 and Baybond®401.

[00263] The film former may also comprise copolymers of polyolefins or polyolefin-acrylic, polyvinyl acetates, modified polyvinyl acetates, or polyolefin-acetate copolymers. Suitable polyolefins include, but are not limited to, polyethylenes, polypropylenes, polybutylenes, and copolymers thereof, and the polyolefins may be oxidized, maleated, or otherwise treated for effective use by the film former. Examples of suitable products include emulsions produced by Michelman, including Emulsion 91735 Michem®, Emulsion 35160 Michem®, Emulsion 42540 Michem®, Emulsion 69230 Michem®, Emulsion 34040M1 Michem®, Prime 4983R Michem®, and Prime 4982SC Michem®. Examples of suitable products include emulsions manufactured by HB Fuller, including PD 708H, PD 707, and PD 0166. Additional suitable products include emulsions manufactured by Franklin International, including Duracet® 637.Additional suitable products include emulsions manufactured by Celanese, including Vinamul® 8823 (plasticized polyvinyl acetate), Dur-O-Set® E-200 (ethylene vinyl acetate copolymer), Dur-O-Set® TX840 (ethylene vinyl acetate copolymer), and Resyn® 1971 (modified epoxy polyvinyl acetate).

[00264] Although not limited to this, preferred film formers include Petition 870210098125, dated 10 / 25 / 2021, pages 155 / 187 136 / 158 low and high molecular weight epoxies, saturated and unsaturated polyesters, and polyolefins, such as Franklin K80-203, Franklin E-102, Hexion 3510-W-60, Hexion 3515-W-60, and Michelman 35160.

[00265] Non-ionic lubricants can also be added to the bonding composition. Suitable non-ionic lubricants that are compatible with ROMP compositions include polyethylene glycol esters and ethylene oxide-propylene oxide block copolymer. More than one non-ionic lubricant can be used in a given bonding formulation if desired, for example, to achieve a desired balance of glass processability and composite mechanical properties.

[00266] Suitable lubricants may contain polyethylene glycol (PEG) units with an average molecular weight between 200 and 2000, preferably between 200 and 600. These PEG units may be esterified with one or more fatty acids, including oleate, thalate, laurate, stearate, and others. Particularly preferred lubricants include PEG 400 dilaurate, PEG 600 dilaurate, PEG 400 distearate, PEG 600 distearate, PEG 400 dioleate, and PEG 600 dioleate. Examples of suitable products include compounds produced by BASF, including MAPEG® 400 DO, MAPEG® 400 DOT, MAPEG® 600 DO, MAPEG® 600 DOT, and MAPEG® 600 DS. Suitable additional products include compounds manufactured by Zschimmer & Schwarz, including Mulsifan 200 DO, Mulsifan 400 DO, Mulsifan 600 DO, Mulsifan 200 DL, Mulsifan 400 DL, Mulsifan 600 DL, Mulsifan 200 DS, Mulsifan 400 DS, and Mulsifan 600 DS.Suitable additional products include compounds manufactured by Cognis, including Agnique® PEG 300 DO, Agnique® PEG 400 DO, and Agnique® PEG 600 DO.

[00267] Suitable non-ionic lubricants also include ethylene oxide and propylene oxide block copolymers. Examples of suitable products include compounds produced by BASF, including Pluronic®L62, Petition 870210098125, dated 10 / 25 / 2021, pp. 156 / 187 137 / 158 Pluronic® L101, Pluronic® P103, and Pluronic® P105.

[00268] Cationic lubricants can also be added to the bonding composition. Cationic lubricants that are ROMP compatible include modified polyethylene imines, such as Emery 6760L produced by Pulcra Chemicals.

[00269] The silane coupling agent may optionally be added to the adhesive composition, examples not including, but not limited to, methacrylate, acrylate, amino, or epoxy silanes functionalized together with alkyl, alkenyl, and norbornenyl silanes.

[00270] Optionally, the bonding composition may contain one or more additives to modify the pH of the bonding resin. A preferred pH modifier is acetic acid.

[00271] The bonding composition may optionally contain other additives useful in glass bonding compositions. Such additives may include emulsifiers, defoamers, cosolvents, biocides, antioxidants, and additives intended to improve the effectiveness of the bonding composition. The bonding composition may be prepared by any method and applied to substrate materials for use herein, such as glass fibers or fabric, by any technique or method.

[00272] In a preferred embodiment, the metathesis reactions disclosed herein are carried out under an inert, dry atmosphere. Such an atmosphere can be created using any inert gas, including gases such as nitrogen and argon. The use of an inert atmosphere is optimal in terms of promoting catalyst activity, and reactions carried out under an inert atmosphere are typically performed with a relatively low catalyst loading. The reactions disclosed herein can also be carried out in an atmosphere containing oxygen and / or one containing water, and in one embodiment, the reactions are carried out under ambient conditions. Petition 870210098125, dated 10 / 25 / 2021, pp. 157 / 187 138 / 158 The presence of oxygen or water in the reaction may, however, necessitate the use of higher catalyst charges compared to reactions carried out under an inert atmosphere. Where the vapor pressure of the reactants allows, the reactions disclosed here can also be carried out under reduced pressure.

[00273] The reactions disclosed here can be carried out in a solvent, and any solvent that is inert in the direction transverse to metathesis can be used. Generally, solvents that can be used in metathesis reactions include organic, protic, or aqueous solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. Examples of solvents include benzene, toluene, p-xylene, methylene chloride, 1,2-dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, methanol, ethanol, water, or mixtures thereof. In a preferred embodiment, the reactions disclosed here are carried out pure, that is, without the use of a solvent.

[00274] It will be evaluated that the temperature at which a metathesis reaction according to methods disclosed herein is conducted can be adjusted as necessary within a wide temperature range. With a highly active metathesis catalyst, olefin metathesis can occur at temperatures as low as -78 °C. With increasingly latent catalysts, olefin metathesis cannot be observed until temperatures of -40 °C, -10 °C, 0 °C, 10 °C, 20 °C, 25 °C, 35 °C, 50 °C, 70 °C, 100 °C, or 150 °C. In a preferred embodiment, the reactions are carried out at a temperature of at least about 35 °C, and in another preferred embodiment, the reactions are carried out at a temperature of at least about 50 °C.In certain embodiments, a mold or pre-mold can be filled with resin and catalyst at a temperature close to room temperature (for example, about 10 to 45 °C, or preferably 15 to 40 °C, or more preferably 20 to 35 °C) and then heated within a period of time to a. Petition 870210098125, dated 10 / 25 / 2021, pp. 158 / 187 139 / 158 higher temperature (e.g., about 50 to 200 °C, or preferably 70 to 150 °C, or more preferably 90 to 120 °C) to allow polymerization to complete more quickly. In certain embodiments, a mold or pre-mold may be preheated to a temperature considerably above room temperature (e.g., about 50 to 250 °C, or about 50 to 200 °C, or about 50 to 150 °C, or about 50 to 100 °C, or about 100 to 150 °C, or about 150 to 200 °C) and then rapidly filled with resin and catalyst to allow rapid cycle times.

[00275] It should be understood that although the invention has been described in conjunction with specific embodiments thereof, the above description as well as the examples that follow are intended to illustrate and not limit the scope of the invention. Other aspects, advantages, and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains. EXPERIMENTAL

[00276] In the following examples, efforts have been made to ensure accuracy with respect to numbers used (e.g., quantities, temperature, etc.) but some experimental error and deviation should be considered. Unless otherwise indicated, temperature is in degrees Celsius (°C), pressure is atmospheric or near atmospheric, viscosity is in centipoise (cP). Additives added to cyclic olefin compositions to form resin compositions are reported as ppm, which is defined as the weight in grams of additive per million grams of cyclic olefin composition, or as phr, which is defined as the weight in grams of additive per one hundred grams of cyclic olefin composition.

[00277] The following examples should be considered as not being limited to the invention as described herein, and instead are provided as representative examples of the compositions of the invention, methods for their use, and articles made of such compositions and methods. Petition 870210098125, dated 10 / 25 / 2021, pp. 159 / 187 140 / 158 EXAMPLES Materials and methods

[00278] All glassware was oven-dried and reactions were carried out under ambient conditions unless otherwise noted. All solvents and reagents were purchased from commercial suppliers and used as received unless otherwise noted. All cyclic olefin compositions were degassed for a minimum of 20 minutes under vacuum to remove cyclopentadiene (CPD) unless otherwise noted. Percent by weight of dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), and tetracyclopentadiene (TeCPD) present in the degassed cyclic olefin compositions were determined from percentage area values ​​obtained by gas chromatography (GC). DCPD (Ultrene® 99) was obtained from Cymetech Corporation. A representative batch of Ultrene® 99 comprising DCPD (99.83 percent by weight) and TCPD (0.17 percent by weight) as measured by GC.A modified DCPD-based resin (DCPDHT) containing between 20 and 25% TCPD (and small amounts of higher CPD homologs) was prepared by heat treatment of Ultrene® 99, generally as described in US Pat. No. 4,899,005. A representative batch of DCPD-HT prepared in this form comprised DCPD (73.98 percent by weight), TCPD (23.51 percent by weight), and TeCPD (2.51 percent by weight).

[00279] TCPD was prepared from DCPD-HT by removing DCPD and other low molecular weight, low-boiling hydrocarbons under vacuum to provide a composition comprising approximately 80% by weight of TCPD, which was further subjected to high vacuum distillation to provide the desired product as a white waxy solid when cooled to room temperature. A representative batch of TCPD (>99% purity) prepared in this form comprising DCPD (0.11 percent by weight), TCPD (99.72 percent by weight), and tetracyclopentadiene (0.17 percent by weight) as measured by GC. A second batch Petition 870210098125, dated 10 / 25 / 2021, pp. 160 / 187 141 / 158 representative of TCPD prepared in this form comprising DCPD (2.93 percent by weight), TCPD (97.03 percent by weight), and TeCPD (0.04 percent by weight).

[00280] Liquid MDI (50 / 50 mixture of 4,4'-MDI and 2,4'-MDI) was used as received from Bayer Material Science (Mondur® MLQ) and was used where indicated. The antioxidant Ethanox® 4702 (4,4'-methylenebis(2,6-di-tertiary-butylphenol), Albemarle Corporation) was used where indicated. Cristal Plus 70FG mineral oil, containing 2 phr Cab-o-sil TS610, was used to prepare the catalyst suspensions. Triphenylphosphine (TPP) was used as received from Arkema. 5-Vinyl-2-norbornene (> 99%) was used as received from JX Nippon Chemical Texas Inc. A carbene olefin metal metathesis catalyst tricyclohexylphosphine [1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene][2-thienylmethylene]ruthenium(II) dichloride) (catMETium® RF2 Evonik Industries; CAS No 1190427-49-6) was purchased from Strem Chemicals Inc.

[00281] Metal carbene olefin metathesis catalysts were prepared by standard methods and include [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinilidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine)ruthenium(II) (C827); 1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinilidene]dichloro(benzylidene)(tricyclohexylphosphine)ruthenium(II) (C848); [1,3-bis-(2,4,6-trimethylphenyl)-2imidazolidinylidene]dichloro(phenylindenylidene)(diethylphenylphosphine) ruthenium(II) (C835), [1,3bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro(phenylindenylidene) (tricyclohexylphosphine) ruthenium(II) (C949); and ruthenium (II) dichloro (3-methyl-2-butenylidene) bis(tricyclohexylphosphine) (C801)

[00282] The cyclic olefin composition (A): Ultrene® 99 DCPD was heat-treated as generally described in US Pat. No. 4,899,005 until the TCPD content reached 10 to 14% (as determined by GC). DCPD and other low molecular weight, low-boiling hydrocarbons were removed under vacuum to provide a composition comprising 54 to 56% by weight of TCPD. The desired TCPD / tetracyclopentadiene ratio was adjusted by adding TCPD (> 99% of Petition 870210098125, dated 10 / 25 / 2021, pp. 161 / 187 142 / 158 purity) and Ultrene® 99 DCPD to provide cyclic olefin composition (A) as a colorless, transparent homogeneous liquid at room temperature. The degassed cyclic olefin composition (A) comprising DCPD (42.99 percent by weight), TCPD (55.14 percent by weight), and tetracyclopentadiene (1.87 percent by weight) as measured by GC.

[00283] The cyclic olefin composition (B): Ultrene® 99 DCPD was heat-treated as generally described in US Pat. No. 4,899,005 until the TCPD content reached 10 to 14% (as determined by GC). DCPD and other low molecular weight, low-boiling hydrocarbons were removed under vacuum to provide a composition comprising 66 to 69% by weight of TCPD. The desired TCPD / tetracyclopentadiene ratio was adjusted by adding TCPD (>99% purity) and Ultrene® 99 DCPD to provide cyclic olefin composition (B) as a homogeneous, colorless, transparent liquid at room temperature. The degassed cyclic olefin composition (B) comprising DCPD (29.78 percent by weight), TCPD (67.57 percent by weight), and tetracyclopentadiene (2.65 percent by weight) as measured by GC.

[00284] The cyclic olefin composition (C): Ultrene® 99 DCPD was heat-treated as generally described in US Pat. No. 4,899,005 until the TCPD content reached 10 to 14% (as determined by GC). DCPD and other low molecular weight, low-boiling hydrocarbons were removed under vacuum to provide a composition comprising 54 to 56% by weight of TCPD. The desired TCPD / TeCPD ratio was adjusted by adding TCPD (> 99% purity) and Ultrene® 99 DCPD to provide cyclic olefin composition (C) as a homogeneous, colorless, transparent liquid at room temperature. The degassed cyclic olefin composition (C) comprising DCPD (37.17 percent by weight), TCPD (59.28 percent by weight), and TeCPD (3.55 percent by weight) as measured by GC.

[00285] The cyclic olefin composition (D): Ultrene® 99 DCPD was melted and Petition 870210098125, dated 10 / 25 / 2021, pp. 162 / 187 143 / 158 combined with a representative batch of TCPD comprising DCPD (2.93 percent by weight), TCPD (97.03 percent by weight), and TeCPD (0.04 percent by weight). The resulting degassed cyclic olefin composition (D) comprising DCPD (90.04 percent by weight) and TCPD (9.96 percent by weight) as measured by GC.

[00286] The cyclic olefin composition (E): Ultrene® 99 DCPD was melted and combined with a representative batch of TCPD comprising DCPD (2.93 percent by weight), TCPD (97.03 percent by weight), and TeCPD (0.04 percent by weight). The resulting degassed cyclic olefin composition (E) comprising DCPD (79.88 percent by weight) and TCPD (20.12 percent by weight) as measured by GC.

[00287] Cyclic olefin composition (F): A representative batch of DCPDHT comprising DCPD (73.98 wt. percent), TCPD (23.51 wt. percent), and TeCPD (2.51 wt. percent) was combined with a representative batch of TCPD comprising DCPD (2.93 wt. percent), TCPD (97.03 wt. percent), and TeCPD (0.04 wt. percent). The resulting degassed cyclic olefin composition (F) comprising DCPD (66.00 wt. percent), TCPD (31.54 wt. percent), and TeCPD (2.46 wt. percent) as measured by GC.

[00288] Cyclic olefin composition (G): A representative batch of DCPDHT comprising DCPD (73.98 percent by weight), TCPD (23.51 percent by weight), and TeCPD (2.51 percent by weight) was combined with a representative batch of TCPD comprising DCPD (2.93 percent by weight), TCPD (97.03 percent by weight), and TeCPD (0.04 percent by weight). The resulting degassed cyclic olefin composition (G) comprising DCPD (58.58 percent by weight), TCPD (39.44 percent by weight), and TeCPD (1.98 percent by weight) as measured by GC.

[00289] The catalyst composition (A): C827 was suspended in mineral oil (Cristal Plus 500 FG) containing 2 phr Cab-o-sil TS610. The composition of Petition 870210098125, dated 10 / 25 / 2021, pp. 163 / 187 144 / 158 catalyst (A) was prepared to have a monomer to catalyst ratio of 45,000:1 at 2 grams of catalyst suspension per 100 grams of DCPD monomer.

[00290] Catalyst composition (B): C848 was suspended in mineral oil (Cristal Plus 500 FG) containing 2 phr Cab-o-sil TS610. Catalyst composition (B) was prepared to have a monomer to catalyst ratio of 90,000:1 to 2 grams of catalyst suspension per 100 grams of DCPD monomer.

[00291] Catalyst composition (C): C827 and C835 were suspended in mineral oil (Cristal Plus 500 FG) containing 2 phr Cab-o-sil TS610. The catalyst composition (C) was prepared to have a monomer to catalyst ratio of 45,000:1 for C827 and 150,000:1 for C835 at 2 grams of catalyst suspension per 100 grams of DCPD monomer.

[00292] Catalyst composition (D): C949 was suspended in mineral oil (Cristal Plus 500 FG) containing 2 phr Cab-o-sil TS610. Catalyst composition (D) was prepared to have a monomer to catalyst ratio of 30,000:1 for C949 at 2 grams of catalyst suspension per 100 grams of DCPD monomer.

[00293] Catalyst composition (E): C827 and C848 were suspended in mineral oil (Cristal Plus 500 FG) containing 2 phr Cab-o-sil TS610. The catalyst composition (E) was prepared to have a monomer to catalyst ratio of 45,000:1 for C827 and 500,000:1 for C848 at 2 grams of catalyst suspension per 100 grams of DCPD monomer.

[00294] Catalyst composition (F): catMETium® RF2 was dissolved in toluene. Catalyst composition (F) was prepared to have a monomer to catalyst ratio of 60,000:1 for CatMETium® RF2 at 2 grams of catalyst solution per 100 grams of DCPD monomer. Petition 870210098125, dated 10 / 25 / 2021, pp. 164 / 187 145 / 158

[00295] The catalyst composition (G): C801 was suspended in mineral oil (Cristal Plus 500 FG) containing 2 phr Cab-o-sil TS610. The catalyst composition (G) was prepared to have a monomer to catalyst ratio of 5.000:1 for C801 at 2 grams of catalyst suspension per 100 grams of DCPD monomer.

[00296] 2-Hydroxyethyl bicyclo[2,2,1]hept-2-ene-5-carboxylate (HENB) was prepared as described in WO 2012 / 174502.

[00297] The adhesion promoter of composition (A). Synthesized HENB (2-hydroxyethyl bicyclo[2,2,1]hept-2-ene-5-carboxylate) (0.10 mol eq., 338 g) was added to liquid MDI (Mondur® MLQ) (1.0 mol eq., 4646 g) at room temperature (22 to 25 °C) and stirred under an inert atmosphere for a minimum of 24 hours. The reaction mixture was used as prepared. EXAMPLES 1 to 4

[00298] Samples of cyclic olefin composition (A) or (B) were placed in a 1000 mL three-necked round-bottom flask, cooled to 23.5 °C, and degassed under vacuum for 20 minutes. The degassed cyclic olefin composition (A) comprising DCPD (42.99 wt percent), TCPD (55.14 wt percent), and tetracyclopentadiene (1.87 wt percent) as measured by GC. The degassed cyclic olefin composition (B) comprising DCPD (29.78 wt percent), TCPD (67.57 wt percent), and tetracyclopentadiene (2.65 wt percent) as measured by GC. Samples (100 g) of the degassed cyclic olefin compositions (A) or (B) were catalyzed by adding 2 grams of either catalyst composition (A) or (B) to form a ROMP composition, which was further degassed for 1 minute under vacuum at 23.5 °C.The degassed ROMP composition (23.5 °C) was poured into an aluminum mold (6 inches x 4 inches x 1 / 4 inches) preheated to 70 °C. None of the molded polymer panels had defects. Petition 870210098125, dated 10 / 25 / 2021, pp. 165 / 187 146 / 158 visible as summarized in Table 1: Table 1 Example Cyclic olefin composition Catalyst composition Result 1 AA no visible defects 2 AB no visible defects 3 BA no visible defects 4 BB no visible defects EXAMPLES 5 to 7

[00299] The Ultrene® 99 DCPD samples were melted and combined with cyclic olefin composition (A) or (B) to provide the new cyclic olefin compositions indicated in Table 2 below (100 grams). The resulting cyclic olefin compositions were placed in a jacketed 1000 mL three-necked round-bottom flask, cooled to 23.5 °C and degassed under vacuum for 20 minutes. The compositions (DCPD / TCPD / tetracyclopentadiene) of the resulting degassed cyclic olefin compositions as measured by GC are summarized in Table 2. The degassed cyclic olefin compositions were catalyzed by adding 2 grams of catalyst composition (A) or (B) to form a ROMP composition, which was further degassed for 1 minute under vacuum at 23.5 °C. The degassed ROMP composition (23.5 °C) was poured into a preheated aluminum mold (6 inches x 4 inches x 1 / 4 inches) as indicated in Table 3.The results for the resulting molded polymer panels are summarized in Table 3. Petition 870210098125, dated 10 / 25 / 2021, pp. 166 / 187 147 / 158 Table 2 Example Quantity of Ultrene 99 Cyclic olefin composition DCPD (% by weight) TCPD (% by weight) Tetracyclopentadiene (% by weight) A / B Quantity 5 63 g A 37 g 77.89 20.57 0.67 6 63 g A 37 g 77.70 20.65 0.67 7 45 g A 55 g 68.47 30.11 1.42 Table 3 Example Catalyst composition (A / B) Mold temperature Result 5 B 70 °C visible defects 6 A 70 °C visible defects 7 B 60 °C visible defects EXAMPLES 8 to 10

[00300] The Ultrene® 99 DCPD samples were melted and combined with cyclic olefin composition (A) or (B) to provide the new cyclic olefin compositions indicated in Table 4 below (100 grams). The resulting cyclic olefin compositions were placed in a jacketed 1000 mL three-necked round-bottom flask, cooled to 23.5 °C and degassed under vacuum for 20 minutes. The compositions (DCPD / TCPD / tetracyclopentadiene) of the resulting degassed cyclic olefin compositions as measured by GC are summarized in Table 4. Triphenylphosphine (0.6 grams), liquid MDI (4.0 grams), Ethanox 4702 (2.0 grams), and 5-vinyl-2-norbornene (1.0 grams) were added to the cyclic olefin composition to provide a resin composition. The resin composition was placed in a jacketed 1000 mL three-necked round-bottom flask, cooled to 23.5°C, and degassed under vacuum for 20 minutes.The resin composition was catalyzed by the addition of catalyst composition (C) (2 grams) to form. Petition 870210098125, dated 10 / 25 / 2021, pp. 167 / 187 148 / 158 a ROMP composition, which was further degassed for 1 minute under vacuum at 23.5°C. The degassed ROMP composition (23.5°C) was poured into a preheated aluminum mold (6 inches x 4 inches x 1 / 4 inches) as indicated in Table 5. The results for the resulting molded polymer panels are summarized in Table 5. Table 4 Example Quantity of Ultrene 99 Cyclic olefin composition DCPD (% by weight) TCPD (% by weight) Tetracyclopentadiene (% by weight) A / B Quantity 8 81.7 g A 18.3 g 89.47 g 10.23 g 0.29 g 9 8 g A 92 g 47.48 g 50.78 g 1.74 g 10 13 g B 87 g 38.87 g 58.83 g 2.30 g Table 5 Example: Catalyst Composition, Mold Temperature, Result. 8°C 90°C visible defects; 9°C 90°C invisible defects; 10°C 90°C invisible defects. EXAMPLE 11

[00301] The bottom mold surface of a laminated composite consisting of a sealed and treated aluminum plate. The aluminum plate had mechanically fixed inlet and outlet ports on the bottom surface of the aluminum plate for resin infusion and attached vacuum source, respectively. A shell layer (Bron Aerotech; PTFE coated) was placed on the surface of the aluminum plate. A laminated glass composite was constructed by cutting and Petition 870210098125, dated 10 / 25 / 2021, pp. 168 / 187 149 / 158 arranging fifty layers of glass fabric, each layer having dimensions of 3” x 6”, on the top surface of the shell layer to obtain approximately 1.5” of laminate thickness. The glass fabric was used as supplied by Vectorply (E-LT 3500 - 10) based on PPG Hybon® 2026 (“Vectorply Glass Fabric”). A shell layer (Bron Aerotech; PTFE coated) was again placed on top of fifty layers of glass fabric reinforcement material. Nylon resin distribution media (Airtech Greenflow 75) were positioned on top of the shell layer at opposite ends of the laminated composite corresponding to the inlet and outlet port positions, respectively. A sheet of vacuum bagging film (Umeco Process Materials Stretch-Vac 2000) was placed over the completed layup.The vacuum bagging film was attached to the mold surface using sealant tape (Airtech AT200-Y tape), and a vacuum was applied to the outlet port to evacuate air from the layup to a vacuum level between 28 inches-Hg and 29 inches-Hg.

[00302] Ultrene® 99 DCPD (44 grams) was melted and combined with cyclic olefin composition (B) (356 grams) which, after degassing, comprised DCPD (37.50 percent by weight), TCPD (59.96 percent by weight), and tetracyclopentadiene (2.54 percent by weight). TPP (2.4 grams), liquid MDI (16.0 grams), Ethanox 4702 (8.0 grams), and 5-vinyl-2-norbornene (4.0 grams) were then added to provide a formulated resin composition, which was then degassed under vacuum for 20 minutes at room temperature (20 to 25 °C) with stirring. The resin composition was catalyzed by the addition of catalyst composition (C) (8 grams) to form a ROMP composition, which was further degassed for at least one minute under vacuum at room temperature (20 to 25 °C) with stirring. After at least one minute, stirring of the ROMP composition was stopped, the vacuum source was clamped off, and the ROMP composition was filled with argon.The composition of ROMP (20 to 25 °C) was then... Petition 870210098125, dated 10 / 25 / 2021, pp. 169 / 187 150 / 158 infused into the glass tissue, regulated by the pressure gradient between ambient pressure and the evacuated glass tissue layup. After infusion was complete, the glass laminate composite was heated to 100 °C at a heating rate of 1 °C / min and held at 100 °C for 1 hour, then allowed to cool to room temperature (20 to 25 °C) and subsequently demolded. The demolded glass laminate composite had no visible defects. EXAMPLE 12

[00303] The cyclic olefin composition (A) (100.0 grams) was placed in a jacketed 1000 mL three-necked round-bottom flask. The degassed cyclic olefin composition (A) comprising DCPD (42.99 wt percent), TCPD (55.14 wt percent), and tetracyclopentadiene (1.87 wt percent) as measured by GC. TPP (0.6 grams), adhesion promoter of composition (A) (4.0 grams), Ethanox 4702 (2.0 grams), and 5-vinyl-2-norbornene (1.0 gram) were added to the cyclic olefin composition (A) to provide a resin composition. The resin composition was cooled to 23.5°C and degassed under vacuum for 20 minutes. The resin composition was catalyzed by the addition of catalyst composition (C) (2 grams) to form a ROMP composition, which was further degassed for 1 minute under vacuum at 23.5°C. The degassed ROMP composition (23.5°C) was poured into an aluminum mold (6 inches x 4 inches x 1 / 4 inches) preheated to 90°C.The molded polymer panel has no visible defects. EXAMPLE 13

[00304] The bottom mold surface of a laminated composite consisting of a sealed and treated aluminum plate. The aluminum plate had inlet and outlet ports mechanically attached to the bottom surface of the aluminum plate by resin infusion and attached vacuum source, respectively. A shell layer (Bron Aerotech; PTFE coated) was placed on the surface of the plate. Petition 870210098125, dated 10 / 25 / 2021, pp. 170 / 187 151 / 158 aluminum. A glass laminate composite was constructed by cutting and arranging fifty layers of glass fabric, each layer having dimensions of 3” x 6”, on the top surface of the shell layer to obtain approximately 1.5” of laminate thickness. The glass fabric was used as supplied by Vectorply (E-LT 3500 10) based on PPG Hybon® 2026 (“Vectorply Glass Fabric”). A shell layer (Bron Aerotech; PTFE coated) was placed over the fifty layers of glass fabric reinforcement material. Nylon resin distribution media (Airtech Greenflow 75) were positioned on top of the shell layer at opposite ends of the laminate composite corresponding to the inlet and outlet port positions, respectively. A sheet of vacuum bagging film (Umeco Process Materials Stretch-Vac 2000) was placed over the completed layup.The vacuum bagging film was attached to the mold surface using sealant tape (Airtech AT200-Y tape), and a vacuum was applied to the outlet port to evacuate air from the layup to a vacuum level between 28 inches-Hg and 29 inches-Hg.

[00305] The cyclic olefin composition (A) (500.0 grams) was placed in a 1000 mL three-necked round-bottom flask. The degassed cyclic olefin composition (A) comprising DCPD (42.99 wt percent), TCPD (55.14 wt percent), and tetracyclopentadiene (1.87 wt percent) as measured by GC. TPP (3.0 grams), adhesion promoter of composition (A) (20.0 grams), Ethanox 4702 (10.0 grams), and 5-vinyl-2-norbornene (5.0 grams) were added to the cyclic olefin composition (A) to provide a resin composition. The resin composition was degassed under vacuum for 20 minutes at room temperature (20 to 25°C) with stirring. The resin composition was catalyzed by the addition of catalyst composition (C) (10 grams) to form a ROMP composition, which was further degassed for at least one minute under vacuum at room temperature (20 to 25°C) with stirring. After at least one minute, Petition 870210098125, dated 10 / 25 / 2021, pp. 171 / 187 152 / 158 The agitation of the ROMP composition was stopped, the vacuum source was pinched off, and the ROMP composition was filled with argon. The ROMP composition (20 to 25°C) was then infused into the glass tissue, regulated by the pressure gradient between ambient pressure and the evacuated glass tissue layup. After the infusion was complete, the glass laminate composite was heated to 100°C at a heating rate of 1°C / min and held at 100°C for 1 hour, then allowed to cool to room temperature (20 to 25°C) and subsequently demolded. The demolded glass laminate composite had no visible defects. EXAMPLE 14

[00306] The bottom mold surface of a laminated composite consisting of a sealed and treated epoxy composite material. Two layers of ELT-3500 unidirectional glass fabric (12.5” x 26”) were placed on the epoxy composite plate. Two 1” thick sections of PVC core material (12.5” x 12.5”) were placed on one half of the ELT-3500 glass fabric section. 100 layers of ELT-1800 unidirectional glass fabric (12.5” x 12.5”) were placed on the other half of the ELT-3500 glass fabric section. Two layers of ELT3500 glass fabric (12.5” x 28”) were placed on top of the PVC core material and stack of ELT-1800 glass fabric. The shell layer was placed over the core of the PVC glass fabric composite layup. Two layers of infusion media (11.5” x 27.5”) were placed on top of the shell layer. A sheet of vacuum bagging film (Umeco Process Materials Stretch-Vac 2000) was placed over the completed layup.The vacuum bagging film was attached to the mold surface using sealant tape (Airtech AT200-Y tape), and a vacuum was applied to the outlet port to evacuate air from the layup to a vacuum level between 28 inches-Hg and 29 inches-Hg.

[00307] A first cyclic olefin composition (7132 grams) comprising DCPD (30.05 percent by weight), TCPD (64.97 percent by weight, Petition 870210098125, dated 10 / 25 / 2021, pp. 172 / 187 153 / 158 and tetracyclopentadiene (4.97 wt percent) as measured by GC was combined with a second cyclic olefin composition (2868 grams) comprising DCPD (75.19 wt percent), TCPD (22.33 wt percent), and tetracyclopentadiene (2.47 wt percent) as measured by GC to provide a new cyclic olefin composition (10 kg) comprising DCPD (43.00 wt percent), TCPD (52.74 wt percent), and tetracyclopentadiene (4.26 wt percent) as calculated. The new cyclic olefin composition was a heterogeneous mixture at room temperature (20 to 25°C) (i.e., a clear liquid containing white solids). TPP (66 grams), adhesion promoter of composition (A) (400 grams), Ethanox 4702 (200 grams), and 5-vinyl-2-norbornene (100 grams) were added to the new cyclic olefin composition to provide a resin composition. The resin composition was degassed under vacuum for 20 minutes with stirring.The resin composition was catalyzed by the addition of catalyst composition (A) (200 grams) to form a ROMP composition, which was further degassed for at least one minute under vacuum with stirring. After at least one minute, the stirring of the ROMP composition was stopped, the vacuum source was pinched off, and the ROMP composition was filled with ambient air. The ROMP composition (20 to 25°C) was then infused into the composite layup regulated by the pressure gradient between ambient pressure and the evacuated composite layup. After the infusion was complete, the composite layup was heated to 100°C at a heating rate of 1°C / min and held at 100°C for 30 minutes and then allowed to cool to room temperature (20 to 25°C) and subsequently demolded. The demolded glass laminate composite had visible defects.Furthermore, during the infusion, white solids separated by precipitation from the ROMP composition and difficulties were created during the infusion, particularly the white solids collected in the resin infusion media, thus delaying the resin flow in the composite layup (post-catalysis infusion time was 90 minutes). Petition 870210098125, dated 10 / 25 / 2021, pp. 173 / 187 154 / 158 EXAMPLES 15 to 20

[00308] The cyclic olefin composition (C) was degassed under vacuum for 20 minutes at room temperature (20 to 25°C). The degassed cyclic olefin composition (C) comprised DCPD (37.17 wt percent), TCPD (59.28 wt percent), and TeCPD (3.55 wt percent) as measured by GC. Six separate samples (100 grams per sample) of the degassed cyclic olefin composition (C) were catalyzed by the addition of 2 grams of catalyst composition (A), (B), (D), (E), (F), or (G) to form six independent ROMP compositions at room temperature (20 to 25°C). The six independent ROMP compositions were each poured into six separate aluminum molds (6 inches x 4 inches x 1 / 4 inches) preheated to 70°C. The results for the resulting molded polymer panels are summarized in Table 6. Table 6 Example Catalyst Composition Result 15 A Substantially free of defects 16 B Defects not visible 17 D Defects not visible 18 E Defects not visible 19 F Defects not visible 20 G Defects not visible EXAMPLE 21

[00309] The cyclic olefin composition (E) was degassed under vacuum for 20 minutes at room temperature (20 to 25°C). The degassed cyclic olefin composition (E) comprised DCPD (79.88 wt percent) and TCPD (20.12 wt percent) as measured by GC. The degassed cyclic olefin composition (E) (100 grams) was catalyzed by the addition of 2 grams of catalyst composition (D) to form a ROMP composition at the temperature Petition 870210098125, dated 10 / 25 / 2021, pp. 174 / 187 155 / 158 ambient (20 to 25°C). The ROMP composition was poured into an aluminum mold (6 inches x 4 inches x 1 / 4 inches) preheated to 70°C. The molded polymer panel had visible defects. EXAMPLES 22 to 23

[00310] The cyclic olefin composition (C) was degassed under vacuum for 20 minutes at room temperature (20 to 25°C). The degassed cyclic olefin composition (C) comprised DCPD (37.17 wt percent), TCPD (59.28 wt percent), and TeCPD (3.55 wt percent) as measured by GC. The degassed cyclic olefin composition (C) (600 grams) was catalyzed by the addition of 12 grams of catalyst composition (D) to form a ROMP composition at room temperature (20 to 25°C). The ROMP composition was poured into an aluminum mold (1.5 inches x 1.5 inches x 12 inches) preheated to 70°C. The result of the resulting molded polymer panel is summarized in Table 7.

[00311] The cyclic olefin composition (F) was degassed under vacuum for 20 minutes at room temperature (20 to 25°C). The degassed cyclic olefin composition (F) comprised DCPD (66.00 wt percent), TCPD (31.54 wt percent), and TeCPD (2.46 wt percent) as measured by GC. The degassed cyclic olefin composition (F) (600 grams) was catalyzed by the addition of 12 grams of catalyst composition (D) to form a ROMP composition at room temperature (20 to 25°C). The ROMP composition was poured into an aluminum mold (1.5 inches x 1.5 inches x 12 inches) preheated to 70°C. The result of the resulting molded polymer panel is summarized in Table 7. Table 7 Example: Catalyst composition; Cyclic olefin composition; Result Petition 870210098125, dated 10 / 25 / 2021, pages 175 / 187 156 / 158 22 DC non-visible defects 23 DF visible defects EXAMPLE 24

[00312] The cyclic olefin composition (G) was degassed under vacuum for 20 minutes at room temperature (20 to 25°C). The degassed cyclic olefin composition (G) comprised DCPD (58.58 wt percent), TCPD (39.44 wt percent), and TeCPD (1.98 wt percent) as measured by GC. The degassed cyclic olefin composition (G) (100 grams) was catalyzed by the addition of 2 grams of catalyst composition (G) to form a ROMP composition at room temperature (20 to 25°C). The ROMP composition was poured into an aluminum mold (6 inches x 4 inches x 1 / 4 inches) preheated to 70°C. The molded polymer panel had no visible defects. EXAMPLE 25

[00313] The cyclic olefin composition (C) was degassed under vacuum for 20 minutes at room temperature (20 to 25°C). The degassed cyclic olefin composition (C) comprised DCPD (37.17 wt percent), TCPD (59.28 wt percent), and TeCPD (3.55 wt percent) as measured by GC. The degassed cyclic olefin composition (C) (50 grams) was catalyzed by the addition of 1 gram of catalyst composition (G) to form a ROMP composition at room temperature (20 to 25°C). The ROMP composition was poured into an aluminum mold (6 inches x 4 inches x 1 / 8 inches) preheated to 70°C. The molded polymer panel had no visible defects. EXAMPLE 26

[00314] The cyclic olefin composition (D) was degassed under vacuum for 20 minutes at room temperature (20 to 25°C). The degassed cyclic olefin composition (D) comprising DCPD (90.04 percent by weight) and TCPD (9.96 Petition 870210098125, dated 10 / 25 / 2021, pp. 176 / 187 157 / 158 percent by weight) as measured by GC. The degassed cyclic olefin composition (D) (100 grams) was catalyzed by the addition of 2 grams of catalyst composition (G) to form a ROMP composition at room temperature (20 to 25°C). The ROMP composition was poured into an aluminum mold (6 inches x 4 inches x 1 / 4 inches) preheated to 70°C. The molded polymer panel had no visible defects. EXAMPLES 27 to 29

[00315] Measurements of the vaporization point of DCPD resins showing an increase in the flash point with a decrease in DCPD content as measured according to ASTM D93 (Pensky-Martens method), Table 8. Table 8 Example DCPD content (% by weight) Flash point (°C) 27 74.0 41 28 41.0 58 29 26.0 60 EXAMPLES 30 to 31

[00316] Flash point measurements of resin compositions showing an increase in flash point with increasing TCPD content (decreasing DCPD content) as measured according to ASTM D93 (Pensky-Martens method), Table 9. Table 9 Example DCPD (% by weight) TCPD (% by weight) TeCPD (% by weight) Additive Package (% by weight) Flash point (°C) 30 39.0 50.3 3.6 7.1 54 31 20.0 70.0 2.9 7.1 66 a = Ethanox 4702 (2 phr); 5-vinyl-2-norbornene (1 phr); promoting composition of Petition 870210098125, dated 10 / 25 / 2021, pages 177 / 187 158 / 158 adhesion (A) (4 phr); TPP (0.6 phr) EXAMPLE 32

[00317] The degassed cyclic olefin composition (G) comprising DCPD (58.58 wt percent), TCPD (39.44 wt percent), and TeCPD (1.98 wt percent) as measured by GC was a clear, colorless homogeneous liquid at room temperature (20 to 25°C). Two (10 mL aliquots) of cyclic olefin composition (G) were placed in separate glass vials and sealed with screw-top caps. One aliquot was stored at room temperature (20 to 25°C), the other aliquot was stored at 10°C. After 24 hours both aliquots were clear, colorless homogeneous liquids.

[00318] A cyclic olefin composition (26 grams) comprising 25% by weight DCPD and 75% by weight TCPD as calculated was heated to 70°C to prepare a clear, colorless, homogeneous liquid. Two (10 mL aliquots) of this cyclic olefin composition (25% by weight DCPD and 75% by weight TCPD) were placed in separate glass vials and sealed with screw-top caps. One aliquot was stored at room temperature (20 to 25°C), the other aliquot was stored at 10°C. After 5 hours, the aliquot stored at room temperature (20 to 25°C) was a heterogeneous mixture containing a clear, colorless white solid liquid and precipitate. After 5 hours, the aliquot stored at 10°C was a white solid.

Claims

1. Ring-opening metathesis (ROMP) polymerization composition, CHARACTERIZED in that it comprises a catalyst composition comprising a metal carbene olefin metathesis catalyst, and a resin composition comprising a cyclic olefin composition, wherein the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene and 64.99% to 26.00% by weight of dicyclopentadiene; wherein the metal carbene olefin metathesis catalyst is selected from a Ru catalyst of the following formula (I), (V) or (VII): LRX1 / i ;>ι=(θ„=σ X^l\ LR d) (LZK wherein: M is Ru.L1, L2, and L3 are neutral electron-donating ligands; n is 0 or 1; m is 0, 1, or 2; k is 0 or 1; X1 and X2 are anionic ligands; R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein any two or more of X1, X2, L1, L2, L3, R1, and R2 may be taken together to form one or more cyclic groups, and wherein any one or more of X1, X2, L1, L2, L3, R1, and R2 may be attached to a support; Petition 870260077680, dated 04 / 08 / 2026, p.16 / 22 2 / 7 wherein: Q is a two-atom bond having the structure -CR11R12-CR13R14- or CR11=CR13-, wherein R11, R12, R13 and R14 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl and functional groups; R3 and R4 are the same and are each unsubstituted phenyl or substituted phenyl with up to three substituents selected from C1-C20 alkyl, substituted C1C20 alkyl, C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, C5-C24 aryl, substituted C5-C24 aryl, C5-C24 heteroaryl, C6-C24 aralkyl, C6-C24 alkaryl or halide; and L2, L3, n, k, R1, R2, X1 and X2 are defined in formula (I); where: M is Ru; L1 is a neutral electron-donating ligand; X1 and X2 are anionic ligands; Petition 870260077680, dated 04 / 08 / 2026, p.17 / 22 3 / 7 Y is a heteroatom selected from O or N; R5, R6, R7, and R8 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups; n is 0, 1, or 2; and Z is selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, wherein any combination of Y, Z, R5, R6, R7, and R8 can be linked to form one or more cyclic groups, and wherein any combination of X1, X2, L1, Y, Z, R5, R6, R7, and R8 can be linked to a support.

2. ROMP composition, according to claim 1, CHARACTERIZED in that the resin composition comprises 55% to 58% by weight of tricyclopentadiene, 0.01% to 3.6% by weight of tetracyclopentadiene and 38% to 42% by weight of dicyclopentadiene.

3. ROMP composition, according to claim 1 or 2, CHARACTERIZED in that it further comprises one or more additives.

4. ROMP composition, according to claim 3, CHARACTERIZED in that the additive is selected from gel modifiers, hardness modulators, impact modifiers, elastomers, antioxidants, antiozonants, stabilizers, crosslinkers, fillers, binders, coupling agents, thixotropes, wetting agents, biocides, plasticizers, pigments, flame retardants, dyes, fibers and reinforcing materials.

5. ROMP composition according to claim 1, CHARACTERIZED in that the carbene olefin metal metathesis catalyst is selected from formula (I) and in which R1 and R2 can be taken together to form an indenylidene moiety. Petition 870260077680, dated 04 / 08 / 2026, p. 18 / 22 4 / 7 6. ROMP composition according to claim 5, CHARACTERIZED in that L1 is a carbene ligand having the structure of formula (II): (II) wherein: X and Y are heteroatoms selected from N, O, S or P; p is zero when X is O or S, ep is 1 when X is N or P; q is zero when Y is O or S, eq is 1 when Y is N or P; Q1, Q2, Q3 and Q4 are ligands selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene or substituted heteroatom-containing hydrocarbylene and -(CO)-, and wherein two or more substituents on adjacent atoms in Q1, Q2, Q3 and Q4 may be attached to form an additional cyclic group; w, x, y and z are independently zero or 1;and R3, R3A, R4 and R4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl, wherein any two or more of X1, X2, L1, L2, L3, R1, R2, R3, R3A, R4, R4A, Q1, Q2, Q3 and Q4 may be taken together to form a cyclic group, and any one or more of X1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R2, R3, R3A, R4, and R4A may be attached to a support.

7. ROMP composition according to claim 1, CHARACTERIZED in that the carbene olefin metal metathesis catalyst is selected from formula (I) and wherein L1 is an N-heterocyclic carbene ligand. Petition 870260077680, dated 04 / 08 / 2026, page 19 / 22 5 / 7 8. ROMP composition according to claim 1, CHARACTERIZED in that the olefin carbene metal metathesis catalyst is selected from formula (I): (L')k (I) wherein: M is ruthenium; n is 0; m is 0; k is 1; L1 is an N-heterocyclic carbene selected from the group consisting of 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinilidene, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)-2-imidazolidinilidene and 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; L2 is a trisubstituted phosphine selected from the group consisting of tri-butylphosphine (Pn-Bus), tricyclopentylphosphine (PCps), tricyclohexylphosphine (PCys), triisopropylphosphine (Pi-Prs), triphenylphosphine (PPhs), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph) and diethylphenylphosphine (PEt2Ph); X1 and X2 are chloride; and R1 is hydrogen and R2 is phenyl or -CH=C(CH3)2 or thienyl; or R1 and R2 are taken together to form 3-phenyl 1-1H-indene.

9. Method for manufacturing a polymer by ring-opening metathesis polymerization (ROMP) CHARACTERIZED in that it comprises: subjecting the ROMP composition, as defined in claim 1, to conditions effective in promoting the polymerization of the ROMP composition. Petition 870260077680, dated 04 / 08 / 2026, page 20 / 22 6 / 7 10. Method for manufacturing a polymer composite by ring-opening metathesis polymerization (ROMP) CHARACTERIZED in that it comprises: contacting the ROMP composition, as defined in claim 1, with a substrate material; and subjecting the ROMP composition to conditions effective in promoting the polymerization of the ROMP composition.

11. Article of manufacture CHARACTERIZED in that it comprises the ROMP composition as defined in claim 1.

12. Article of manufacture CHARACTERIZED in that it is manufactured by the methods as defined in claim 9 or 10.

13. Method according to claim 9 or 10, or article of manufacture according to claim 11 or 12, CHARACTERIZED in that the cyclic olefin composition comprises 35.00% to 70.00% by weight of tricyclopentadiene, 0.01% to 4.00% by weight of tetracyclopentadiene.

14. Method according to claim 9 or 10, CHARACTERIZED in that the carbene olefin metal metathesis catalyst is selected from formula (I) and in which R1 and R2 are taken together to form an indenylidene moiety.

15. Method according to claim 14, CHARACTERIZED in that L1 is carbene ligand having the structure of formula (II): (II) wherein: X and Y are heteroatoms selected from N, O, S or P; Petition 870260077680, dated 04 / 08 / 2026, p.21 / 22 7 / 7 p is zero when X is O or S, ep is 1 when X is N or P; q is zero when Y is O or S, eq is 1 when Y is N or P; Q1, Q2, Q3 and Q4 are ligands selected from hydrocarbylene, substituted hydrocarbylene, hydrocarbylene containing a heteroatom or hydrocarbylene containing a substituted heteroatom and -(CO)-, and wherein two or more substituents on adjacent atoms in Q1, Q2, Q3 and Q4 may be attached to form an additional cyclic group; w, x, y and z are independently zero or 1; and R3, R3A, R4 and R4A are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl or substituted heteroatom-containing hydrocarbyl, wherein any two or more of X1, X2, L1, L2, L3, R1, R2, R3, R3A, R4, R4A, Q1, Q2, Q3 and Q4 may be taken together to form a cyclic group, and any one or more of X1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R2, R3, R3A, R4 and R4A may be connected to a holder.

16. Method according to claim 9 or 10, CHARACTERIZED in that the carbene olefin metal metathesis catalyst is selected from formula (I) and wherein L1 is an N-heterocyclic carbene ligand.