Cyclic olefin compositions, ROMP compositions thereof, and applications thereof

Abstract

The invention relates to cyclic olefin compositions including a di-cyclopentadiene portion, a tri-cyclopentadiene portion, and an optional tetra-cyclopentadiene portion. The invention also relates to a resin composition including the cyclic olefin composition, and a ring-opening metathesis polymerization (ROMP) composition including the cyclic olefin composition or the resin composition and at least one catalyst composition including a metal carbene olefin metathesis catalyst. The invention also relates to methods for making and using the cyclic olefin compositions, resin compositions, and ROMP compositions. The invention further relates to ROMP polymers and curable and cured articles of manufacture comprising the ROMP compositions.

Description

CYCLIC OLEFIN COMPOSITIONS, ROMP COMPOSITIONS THEREOF, AND APPLICATIONS THEREOFCROSS-REFERENCE TO RELATED APPLICATION(S) AND CLAIM(S) OF PRIORITY

[0001] This application claims the benefit of priority of 63 / 649,632 entitled “ROMP Compositions Containing Di-Cyclopentadiene and Tri-Cyclopentadiene" filed in the U.S. Patent & Trademark Office on May 20, 2024, and 63 / 650,911 entitled “Liquid ROMP Compositions Containing Elevated Levels of Exo-Dicyclopentadiene and Applications Thereof’ filed in the U.S. Patent & Trademark Office on May 22, 2024, the complete disclosures of each of which are incorporated herein by reference.BACKGROUND

[0002] The molding of thermoset polymers is a technologically and commercially important processing technique. In one known version of this technique, a liquid cyclic olefin monomer resin is combined with at least one metal carbene olefin metathesis catalyst to form a ring-opening metathesis polymerization (ROMP) composition, and the ROMP composition is added (e.g., via pouring, casting, vacuum-infusion, pressure-injection, etc.) into a mold. The ROMP composition is subjected to conditions effective to polymerize the ROMP composition and on completion the molded article is subjected to any optional post cure processing that may be required to achieve a high degree of curing and / or the desired properties. Commercially important cyclic olefin monomer resins typically include readily available and inexpensive cyclic olefins such as norbornene monomers, particularly dicyclopentadiene (DCPD). Since high purity DCPD melts at 32 °C to 34 °C, other norbornene co-reactants, or monomers that are copolymerizable with DCPD such as trimer of cyclopentadiene (tricyclopentadiene (TCPD)) are often added to depress the melting point below room temperature. In fact, the addition of TCPD, and higher oligomers of cyclopentadiene such as tetracyclopentadiene (TeCPD) and further higher order oligomers of cyclopentadiene (e.g., pentacyclopentadiene, hexacyclopentadiene, etc.) are also useful to modulate specific properties of the final cured thermoset polymer part, such as the glass transition temperature, tensile modulus, and tensile elongation at break.

[0003] The use of copolymerization of various monomers to achieve various properties is well known within the polymer art. However, the use of monomers is also known to have limitations in resin cost and material availability. Therefore, it is desirable to modify properties of thermoset properties by other means.

[0004] Furthermore, there is a need for improved ring-opening metathesis polymerization (ROMP) compositions that include, optionally, exo-DCPD and TCPD and TeCPD isomers.Specifically, there is a need to modify the physical properties of the higher order oligomers (e.g. , melt point) and blends thereof such that they can be used in high concentrations in ROMP compositions. Such ROMP compositions described herein include a unique mixture of, optionally, exo- and endo-DCPD, and TCPD isomers and / or TeCPD isomers.SUMMARY

[0005] This Summary is provided to introduce a selection of representative concepts in a simplified form, which representative concepts are further described below in the Detailed Description. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it or the objects and benefits described herein intended to be used to limit the scope of the claimed subject matter.

[0006] A first aspect of the invention relates to a cyclic olefin composition, comprising, consisting essentially of, or consisting of:20 to 100 wt.% of a DCPD portion, and0 to 80 wt.% of a TCPD portion, based on the total weight of the DCPD and TCPD portions in the cyclic olefin composition; wherein the DCPD portion comprises consists essentially of, or consists of:0.3 to 60 wt.% of exo-DCPD, and40 to 99.7 wt.% of endo-DCPD, based on the total weight of the exo-DCPD and endo-DCPD in the DCPD portion; and wherein the TCPD portion, if present, comprises, consists essentially of, or consists of: 0.1 to 10 wt.% of TCPD-7,3 to 25 wt.% of TCPD-3,5 to 90 wt.% of TCPD-5, and5 to 85 wt.% of TCPD-1 , based on the total weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 in the TCPD portion.

[0007] A second aspect of the invention relates to a cyclic olefin composition, comprising, consisting essentially of, or consisting of:0.0001 to 99.9999 wt.% of a DCPD portion,0.0001 to 90 wt.% of a TCPD portion, and0 to 50 wt.% of a TeCPD portion,based on the total weight of the DCPD, TCPD, and TeCPD portions in the cyclic olefin composition; wherein the DCPD portion, if present, comprises, consists essentially of, or consists of:0.3 to 99 wt.% of exo-DCPD, and1 to 99 wt.% of endo-DCPD, based on the total weight of the exo-DCPD and endo-DCPD in the DCPD portion; wherein the TCPD portion comprises, consists essentially of, or consists of:0.1 to 10 wt.% of TCPD-7,3 to 25 wt.% of TCPD-3,5 to 90 wt.% of TCPD-5, and5 to 85 wt.% of TCPD-1 , based on the total weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 in the TCPD portion; and wherein the TeCPD portion comprises, consists essentially of, or consists of:O to 10 wt.% of TeCPD-1 ,0 to 15 wt.% of TeCPD-2,O to 30 wt.% of TeCPD-3,O to 5 wt.% of TeCPD-4,O to 5 wt.% of TeCPD-5,0 to 70 wt.% of TeCPD-6, andO to 90 wt.% of TeCPD-7, based on the total weight of the TeCPD-1 , TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, and TeCPD-7 in the TeCPD portion.

[0008] A third aspect of the invention relates to a cyclic olefin composition, comprising, consisting essentially of, or consisting of:0.0001 to 99.9998 wt.% of a DCPD portion,0.0001 to 99.9998 wt.% of a TCPD portion, and0.0001 to 50 wt.% of a TeCPD portion, based on the total weight of the DCPD, TCPD, and TeCPD portions in the cyclic olefin composition; wherein the DCPD portion, if present, comprises, consists essentially of, or consists of:0.3 to 99 wt.% of exo-DCPD, and1 to 99 wt.% of endo-DCPD, based on the total weight of the exo-DCPD and endo-DCPD in the DCPD portion;wherein the TCPD portion comprises, consists essentially of, or consists of:0.1 to 10 wt.% of TCPD-7,3 to 25 wt.% of TCPD-3,5 to 90 wt.% of TCPD-5, and5 to 85 wt.% of TCPD-1 , based on the total weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 in the TCPD portion; and wherein the TeCPD portion comprises, consists essentially of, or consists of:O to 10 wt.% of TeCPD-1 ,0 to 15 wt.% of TeCPD-2,0 to 30 wt.% of TeCPD-3,0 to 5 wt.% of TeCPD-4,0 to 5 wt.% of TeCPD-5,0 to 70 wt.% of TeCPD-6, and0 to 90 wt.% of TeCPD-7, based on the total weight of the TeCPD-1 , TeCPD-2, TeCPD-3, TeCPD-4, TeCPD- 5, TeCPD-6, and TeCPD-7 in the TeCPD portion.

[0009] A fourth aspect of the invention relates to a resin composition, comprising, consisting essentially of, or consisting of the cyclic olefin compositions of embodiments disclosed herein.

[0010] A fifth aspect of the invention relates to a ring-opening metathesis polymerization (ROMP) composition, comprising, consisting essentially of, or consisting of the cyclic olefin compositions of embodiments disclosed herein or the resin composition of embodiments disclosed herein and at least one catalyst composition comprising, consisting essentially of, or consisting of at least one metal carbene olefin metathesis catalyst.

[0011] A sixth aspect of the invention relates to a method of making the cyclic olefin compositions of embodiments disclosed herein.

[0012] A seventh aspect of the invention relates to a method of making the resin composition of embodiments disclosed herein.

[0013] An eighth aspect of the invention relates to a method of making the ROMP composition of embodiments disclosed herein.

[0014] A ninth aspect of the invention relates to a ROMP polymer, comprising, consisting essentially of, or consisting of the reaction product of the ROMP composition of embodiments disclosed herein, wherein the ROMP composition is subjected to conditions effective to polymerize the ROMP composition.

[0015] A tenth aspect of the invention relates to a method of making the ROMP polymer of embodiments disclosed herein.

[0016] A eleventh aspect of the invention relates to methods and uses of the ROMP composition of embodiments disclosed herein in various molding processes, such as vacuum assisted resin transfer molding (VARTM), resin transfer molding (RTM), and reaction injection molding (RIM), continuous sheet molding, composite manufacture, bath based pultrusion, plural injection pultrusion, spray coatings, and brushable coatings to polymerize the ROMP composition and form a cured article.

[0017] A twelfth aspect of the invention relates to a curable article of manufacture comprising the ROMP composition of embodiments disclosed herein.

[0018] A thirteenth aspect of the invention relates to a cured article of manufacture, wherein the curable article of manufacture of embodiments disclosed herein is cured.

[0019] A fourteenth aspect of the invention relates to a method of making the cured article of manufacture of embodiments disclosed herein.

[0020] A fifteenth aspect of the invention relates to a kit(s) comprising, consisting essentially of, or consisting of the cyclic olefin compositions of embodiments disclosed herein, the resin composition of embodiments disclosed herein, and / or the ROMP composition of embodiments disclosed herein.

[0021] It should be understood that objects, functions, and improvements discussed above and otherwise herein are desirable and may be achieved by one or more embodiments, but are not necessarily applicable to all embodiments and are not limiting.BRIEF DESCRIPTION OF THE DRAWINGS

[0022] The drawings referenced herein form a part of the specification, and are incorporated herein by reference. Features shown in the drawings are meant as illustrative of only some embodiments, and not of all embodiments, unless otherwise explicitly indicated .

[0023] FIG. 1 shows an example chromatogram of a cyclic olefin composition comprising the DCPD, TCPD, and TeCPD portions (including any other heavier oligomers and impurities) from Sample 8, described below.

[0024] FIG. 2 shows an example of the DCPD portion region of a chromatogram produced via Method A from Sample 8, described below.

[0025] FIG. 3 shows an example of the TCPD portion region of a chromatogram produced via Method A from Sample 8, described below.

[0026] FIG. 4 shows an example of the TeCPD portion region of a chromatogram produced via Method A from Sample 8, described below.

[0027] FIG. 5 shows an example of the endset determination of melt points for sample BL12, described below, at varying rates.

[0028] FIG. 6 shows the determination of the equilibrium melt point for sample BL12, described below, through extrapolation to zero rates.

[0029] FIG. 7 shows the phase diagram of mixtures of the DCPD component of varying exo- DCPD isomer concentration.

[0030] FIG. 8 shows the solubility of DCPD / TCPD / TeCPD mixtures at 70 wt.% TCPD in high exo-isomer content vs low exo-isomer content.

[0031] FIG. 9 shows the reactivity of high exo-DCPD vs low exo-DCPD.

[0032] FIG. 10 shows the Tg of Low and High (7%) exo-DCPD at varying concentrations of catalyst.DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS Terminology and Definitions

[0033] Unless otherwise indicated, the invention is not limited to specific reactants, substituents, catalysts, catalyst compositions, resin compositions, cyclic olefins, reaction conditions, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not to be interpreted as being limiting.

[0034] As used in the specification and the appended claims, the singular forms “a,” “an,” and "the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a substituent” encompasses a single substituent as well as two or more substituents, and the like.

[0035] As used in the specification and the appended claims, the terms “for example,” “for instance,” "such as,” or “including” are meant to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid for understanding the invention, and are not meant to be limiting in any fashion.

[0036] In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings:

[0037] The term “alkyl” as used herein refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to about 24 carbon atoms, such as 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, f-butyl,octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl, and the like. Generally, although again not necessarily, alkyl groups herein contain 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, such as 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 replaced with a heteroatom. If not otherwise indicated, the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkyl and lower alkyl, respectively.

[0038] The term “alkylene” as used herein refers to a difunctional linear, branched, or cyclic alkyl group, where “alkyl” is as defined above.

[0039] The term “alkenyl” as used herein refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 24 carbon atoms (e.g., 2 to about 12 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. 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, such as 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 replaced with a heteroatom. If not otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and / or heteroatom-containing alkenyl and lower alkenyl, respectively.

[0040] The term “alkenylene” as used herein refers to a difunctional linear, branched, or cyclic alkenyl group, where “alkenyl” is as defined above.

[0041] The term “alkynyl” as used herein refers to a linear or branched hydrocarbon group of 2 to about 24 carbon atoms (e.g., 2 to about 12 carbon atoms) containing at least one triple bond, such as ethynyl, n-propynyl, and the like. 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 replaced with a heteroatom. If not otherwise indicated, the terms “alkynyl” and “lower alkynyl” include linear, branched, unsubstituted, substituted, and / or heteroatom-containing alkynyl and lower alkynyl, respectively.

[0042] The term “alkoxy” as used herein refers to an alkyl group bound through a single, terminal ether linkage; that is, an "alkoxy” group may be represented as -O-alkyl where alkyl is asdefined above. A “lower alkoxy” group refers to an alkoxy group containing 1 to 6 carbon atoms. Analogously, “alkenyloxy” and “lower alkenyloxy’’ respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage, and “alkynyloxy” and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.

[0043] 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 indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). Aryl groups may contain 5 to 24 carbon atoms (e.g., 5 to 14 carbon atoms). Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether, 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 replaced with a heteroatom, as will be described in further detail infra.

[0044] The term “aryloxy” as used herein refers to an aryl group bound through a single, terminal ether linkage, wherein “aryl” is as defined above. An “aryloxy” group may be represented as -O-aryl where aryl is as defined above. Aryloxy groups may contain 5 to 24 carbon atoms (e.g., 5 to 14 carbon atoms). Examples of aryloxy groups include, without limitation, phenoxy, o-halo- phenoxy, m-halo-phenoxy, phalo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p- methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.

[0045] The term “alkaryl” 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. Alkaryl and aralkyl groups may contain 6 to 24 carbon atoms (e.g., 6 to 16 carbon atoms). Alkaryl groups include, without limitation, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7- dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1 ,4-diene, and the like. Examples of aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4- benzylcyclohexylmethyl, and the like. The terms “alkaryloxy” and “aralkyloxy” refer to substituents of the formula -OR wherein R is alkaryl or aralkyl, respectively, as just defined.

[0046] The term “acyl” refers to substituents having the formula -(CO)-alkyl, -(CO)-aryl, (CO)- aralkyl, -(CO)-alkaryl, -(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)-alkaryl, -O(CO)-alkenyl, -O(CO)-alkynyl wherein “alkyl,” “aryl,” “aralkyl,” “alkaryl,” “alkenyl,” and “alkynyl” are as defined above.

[0047] The terms “cyclic" and “ring” refer to alicyclic or aromatic groups that may or may not be substituted and / or heteroatom containing, and that 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.

[0048] The terms “halo” and “halogen” are used in the conventional sense to refer to a chloro, bromo, fluoro, or iodo substituent.

[0049] As used herein, the term “hydrocarbon” means a class of compounds containing hydrogen bound to carbon. The term "Cn” hydrocarbon means hydrocarbon having n carbon atom(s) per molecule, where n is a positive integer. The term “Cn+” hydrocarbon means hydrocarbon having at least n carbon atom(s) per molecule, where n is a positive integer. The term “Cn” hydrocarbon means hydrocarbon having no more than n number of carbon atom(s) per molecule, where n is a positive integer. “Hydrocarbon” encompasses (i) saturated hydrocarbon, (ii) unsaturated hydrocarbon, and (iii) mixtures of hydrocarbons, including mixtures of hydrocarbon compounds (saturated and / or unsaturated), including mixtures of hydrocarbon compounds having different values of n.

[0050] “Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, such as 1 to about 24 carbon atoms, such as 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” intends a hydrocarbyl group of 1 to 6 carbon atoms, such as 1 to 4 carbon atoms, and the term “hydrocarbylene” refers to a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, such as 1 to about 24 carbon atoms, such as 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species. The term “lower hydrocarbylene” refers to a hydrocarbylene group of 1 to 6 carbon atoms. “Substituted hydrocarbyl” refers to hydrocarbyl substituted with one or more substituent groups, 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” are to be interpreted as including substituted and / or heteroatom-containing hydrocarbyl and heteroatom-containing hydrocarbylene moieties, respectively.

[0051] 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 is replaced with an atom other than carbon, e.g., 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 further that “heterocycles” may be monocyclic, bicyclic, or polycyclic as described above with respect to the term “aryl.” Examples of heteroalkyl groups include without limitation alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, 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 heteroatom-containing alicyclic groups include without limitation pyrrolidine, morpholino, piperazino, piperidino, etc.

[0052] By "substituted” as in “substituted hydrocarbyl,” “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced 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 alkaryloxy, acyl (including C2-C24 alkylcarbonyl (-CO-alkyl) and CB-C24 arylcarbonyl (-CO-aryl)), acyloxy (-O-acyl, including C2-C24 alkylcarbonyloxy (-O-CO-alkyl) and C6-C24 arylcarbonyloxy (-O- CO-aryl)), C2-C24 alkoxycarbonyl (-(CO)-O-alkyl), C6-C24 aryloxycarbonyl (-(CO)-O-aryl), halocarbonyl (-CO)-X where X is halo), C2-C24 alkylcarbonato (-O-(CO)-O-alkyl), C6-C24 arylcarbonato (-O-(CO)-O-aryl), carboxy (-COOH), carboxylato (COO-), carbamoyl (-(CO)-NH2), mono-(C1-C24 alkyl)-substituted carbamoyl ((CO)-NH(C1-C24 alkyl)), di-(C1-C24 alkyl)-substituted carbamoyl (-(CO)-N(C1-C24 alkyl)2), mono-(C1-C24 haloalkyl)-substituted carbamoyl (-(CO)- NH(C1-C24 haloalkyl)), di-(C1-C24 haloalkyl)-substituted carbamoyl (-(CO)-N(C1-C24 haloalkyl)2), mono-(C5-C24 aryl)-substituted carbamoyl ((CO)-NH-aryl), di-(C5-C24 aryl)-substituted carbamoyl (-(CO)-N(C5-C24 aryl)2), di-N-(C1-C24 alkyl), 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(C1- C24 alkyl)2), mono-(C5-C24 aryl)-substituted thiocarbamoyl (-(CS)-NH-aryl), di(C5-C24 aryl)- substituted thiocarbamoyl (-(CS)-N(C5-C24 aryl)2), di-N-(C1-C24 alkyl), N-(C5-C24 aryl)-substitutedthiocarbamoyl (-(CS)-N(CI-C24 alkyl)(C5-C24 aryl), carbamido (-NH-(CO)-NH2), cyano (-C=N), cyanato (-O-C=N), thiocyanato (-S-CEN), isocyanate (-N=C=O), thioisocyanate (-N=C=S), formyl (-(CO)-H), thioformyl ((CS)-H), amino (-NH2), mono-(C1-C24 alkyl)-substituted amino (- NH(C1-C24 alkyl), di-(C1-C24 alkyl)-substituted amino (-N(C1-C24 alkyl)2), mono-(C5-C24 aryl)- substituted amino (-NH(C5-C24 aryl), di-(C5-C24 aryl)-substituted amino (-N(C5-C24 aryl)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, C6C24 alkaryl, C6-C24 aralkyl, etc.), C2-C20 alkylimino (CR=N(alkyl), where R includes without limitation hydrogen, C1C24 alkyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), arylimino (-CR=N(aryl), where R includes without limitation hydrogen, C1-C20 alkyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), nitro (-NO2), nitroso (NO), sulfo (-SO2-OH), sulfonato (-SO2-O-), C1-C24 alkylsulfanyl (-S-alkyl; also termed “alkylthio”), C5- C24 arylsulfanyl (-S-aryl; also termed “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), borono (-B(OH)2), boronato (-B(OR)2 where R includes without limitation alkyl or other hydrocarbyl), phosphono (-P(O)(OH)2), phosphonato (-P(O)(O")2), phosphinato (P(O)(O-)), phospho (-PO2), and phosphino (-PH2); and the hydrocarbyl moieties C1-C24 alkyl (e.g., C1-C12 alkyl, C1-C6 alkyl), C2-C24 alkenyl (e.g., C2-C12 alkenyl, C2-C6 alkenyl), C2-C24 alkynyl (e.g., C2-C12 alkynyl, C2-C6 alkynyl), C5-C24aryl (e.g., C5-C14 aryl), C6-C24 alkaryl (e.g., C6-C16 alkaryl), and C6- C24 aralkyl (e.g., C6-Ci6aralkyl).

[0053] By “functionalized” as in “functionalized hydrocarbyl,” “functionalized alkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more functional groups such as those described hereinabove. The term “functional group” is meant to include any functional species that is suitable for the uses described herein. In particular, as used herein, a functional group would necessarily possess the ability to react with or bond to corresponding functional groups on a substrate surface.

[0054] In addition, the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically mentioned above. Analogously, the above-mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties as noted above.

[0055] As disclosed herein, any material or compound illustrated by a chemical structure shall include, in addition to the chemical structure, any and all optical isomer(s) thereof, unless clearlyspecified otherwise. Thus, each of the exo-DCPD, endo-DCPD, TCPD-1 , TCPD-2, TCPD-3, TCPD-4, TCPD-5, TCPD-6, TCPD-7, TCPD-8, TeCPD-1 , TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, TeCPD-7, and the like, as defined and / or described herein shall include, in addition to the illustrated structure therefor, any and all optical isomer(s) of the illustrated structure.

[0056] The terms “cyclopentadiene” or “CPD” interchangeably mean cyclopenta-1 ,3-diene:

[0057] The terms “di-cyclopentadiene,” “dicyclopentadiene,” or “DCPD” interchangeably mean a molecule or a mixture of molecules each having a chemical formula C10H12 and obtainable via a Diels-Alder reaction between two CPD molecules. Thus, a DCPD molecule can be or can include an exo-DCPD stereo isomer, an endo-DCPD stereo isomer, or a mixture of both at any proportion. Exo-DCPD and endo-DCPD isomers can have structures as illustrated below, respectively:Exo-DCPD:Endo-DCPD:

[0058] The terms “tri-cyclopentadiene,” “tricyclopentadiene,” or “TCPD” interchangeably mean a molecule or a mixture of molecules each having a chemical formula C15H18 and obtainable via a Diels-Alder reaction between a DCPD molecule and a CPD molecule. Thus, a TCPD molecule can be or can include a single TCPD isomer, or a mixture of any two or more TCPD isomers.TCPD molecules can include the 6,5,6-isomersthe 6,6,5-isomerseach of which can include multiple stereo isomers. A TCPD can be or can include one or more of the following isomers TCPD-1 , TCPD-2, TCPD-3, TCPD-4, TCPD- 5, TCPD-6, TCPD-7, and TCPD-8 (also referred herein as TCPD I, TCPD II, TCPD III, TCPD IV, TCPD V, TCPD VI, TCPD VII, and TCPD-VIII, respectively), at various quantities thereof, which can be obtained via Diels-Alder reactions between a CPD molecule and an identified DCPD isomer at the identified DCPD reaction bond, shown in Table 1 below. A composition containing TCPD can include a single TCPD isomer, but typically include a mixture of multiple TCPD isomers.Table 1

[0059] The terms “tetra-cyclopentadiene,” “tetracyclopentadiene,” or “TeCPD” interchangeably mean a molecule or a mixture of molecules each having a chemical formula C20H24 and obtainable via a Diels-Alder reaction between a TCPD molecule and a CPD molecule. Thus, a TeCPD molecule can be a single TeCPD isomer, or a mixture of any two or more TeCPD isomers. The TeCPD isomers or mixture of two or more TeCPD isomers observed in one or more of the cyclic olefin compositions of embodiments disclosed herein are designated herein as TeCPD-1 (or TeCPD I), TeCPD-2 (or TeCPD II), TeCPD-3 (or TeCPD III), TeCPD-4 (or TeCPD IV), TeCPD-5 (or TeCPD V), TeCPD-6 (or TeCPD VI), and TeCPD-7 (or TeCPD VII) herein. As described below, these TeCPD isomers can be identified using gas chromatography.

[0060] “Optional” or “optionally” means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase “optionally substituted” means that a nonhydrogen substituent may or may not be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a nonhydrogen substituent is not present.

[0061] The term “substrate(s)” in the context of the invention refers to an object or a surface of an object upon which property deterioration or corrosion can occur, the surface of which can be protected by a coating. Substrates can be metals such as steel, stainless steel, aluminum, copper, alloys or nonmetals such as glass, concrete, ceramics, porcelain, brick, plastics, rubber, wood, cloth, fabrics, or composites such as reinforced plastics, electronic assemblies, etc.

[0062] The term “substrate material(s)” as used herein, refers to the material(s) of construction of a substrate.

[0063] As is known in the art, weight percent (wt.%) can be represented by gas chromatography (GC) percent area (area %). Hence, GO area% obtained from the GC was reported as wt.%, unless otherwise noted. Weight percent (wt.%) and percent by weight are used interchangeably herein. Mol percent (mol%) was calculated from the weight percent (wt.%) as is known in the art.CYCLIC OLEFIN COMPOSITION

[0064] In some embodiments, the invention relates to a cyclic olefin composition, comprising, consisting essentially of, or consisting of:20 to 100 wt.% (e.g., 21 to 99.999 wt.%, 22 to 99.99 wt.%, 23 to 99.9 wt.%, 25 to 99.5 wt.%, 30 to 99 wt.%, 35 to 95 wt.%, 40 to 90 wt.%, 45 to 85 wt.%, 50 to 80 wt.%, 55 to 75 wt.%, 60 to 70 wt.%) of a DCPD portion, and0 to 80 wt.% (e.g., 0.001 to 79 wt.%, 0.01 to 78 wt.%, 0.1 to 77 wt.%, 0.5 to 75 wt.%, 1 to 70 wt.%, 5 to 65 wt.%, 10 to 60 wt.%, 15 to 55 wt.%, 20 to 50 wt.%, 25 to 45 wt.%, 30 to 40 wt.%) of a TCPD portion, based on the total weight of the DCPD and TCPD portions in the cyclic olefin composition; wherein the DCPD portion comprises consists essentially of, or consists of:0.3 to 60 wt.% (e.g., 0.4 to 55 wt.%, 0.5 to 50 wt.%, 0.6 to 45 wt.%, 0.7 to 40 wt.%, 0.8 to 35 wt.%, 0.9 to 30 wt.%, 1 to 25 wt.%, 2 to 24 wt.%, 3 to 23 wt.%, 4 to 22 wt.%, 5 to 21 wt.%, 6 to 20 wt.%, 7 to 19 wt.%, 8 to 18 wt.%, 9 to 17 wt.%, 10 to 16 wt.%, 11 to 15 wt.%, 12 to 14 wt.%) of exo-DCPD, and40 to 99.7 wt.% (e.g., 45 to 99.6 wt.%, 50 to 99.5 wt.%, 55 to 99.4 wt.%, 60 to 99.3 wt.%, 65 to 99.2 wt.%, 70 to 99.1 wt.%, 75 to 99 wt.%, 76 to 98 wt.%, 77 to 97 wt.%, 78 to 96 wt.%, 79 to 95 wt.%, 80 to 94 wt.%, 81 to 93 wt.%, 82 to 92 wt.%, 83 to 91 wt.%, 84 to 90 wt.%, 85 to 89 wt.%, 86 to 88 wt.%) of endo-DCPD, based on the total weight of the exo-DCPD and endo-DCPD in the DCPD portion; and wherein the TCPD portion, if present, comprises, consists essentially of, or consists of:0.1 to 10 wt.% of (e.g., 0.2 to 9 wt.%, 0.3 to 8 wt.%, 0.4 to 7 wt.%, 0.5 to 6 wt.%, 0.6 to 5 wt.%, 0.7 to 4 wt.%, 0.8 to 3 wt.%, 0.9 to 2 wt.%, 1 to 1 ,5 wt.%) of TCPD-7,3 to 25 wt.% (e.g., 4 to 24 wt.%, 5 to 23 wt.%, 6 to 22 wt.%, 7 to 21 wt.%, 8 to 20 wt.%, 9 to 19 wt.%, 10 to 18 wt.%, 11 to 17 wt.%, 12 to 16 wt.%, 13 to 15 wt.%) of TCPD-3,5 to 90 wt.% (e.g., 7 to 89 wt.%, 9 to 87 wt.%, 11 to 85 wt.%, 13 to 83 wt.%, 15 to 81 wt.%, 17 to 79 wt.%, 20 to 75 wt.%, 25 to 70 wt.%, 30 to 65 wt.%, 35 to60 wt.%, 40 to 55 wt.%, 45 to 50 wt.%) of TCPD-5, and5 to 85 wt.% (e.g., 10 to 83 wt.%, 15 to 81 wt.%, 20 to 79 wt.%, 25 to 77 wt.%, 30 to 75 wt.%, 35 to 73 wt.%, 40 to 71 wt.%, 45 to 69 wt.%, 50 to 67 wt.%,55 to 65 wt.%, 60 to 63 wt.%, 61 to 62 wt.%) of TCPD-1 , based on the total weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 in the TCPD portion.

[0065] In some embodiments, the invention relates to a cyclic olefin composition, comprising, consisting essentially of, or consisting of:0.0001 to 99.9999 wt.% (e.g, 0.001 to 99.9998 wt.%, 0.01 to 99.999 wt.%, 0.1 to 99.99 wt.%, 0.5 to 99.9 wt.%, 1 to 99.5 wt.%, 2 to 99 wt.%, 3 to 98 wt.%, 4 to 97 wt.%, 5 to 96 wt.%, 6 to 95 wt.%, 7 to 94 wt.%, 8 to 93 wt.%, 9 to 92 wt.%, 10 to 91 wt.%, 15 to 90 wt.%, 20 to 85 wt.%, 25 to 80 wt.%, 30 to 75 wt.%, 35 to 70 wt.%, 40 to 65 wt.%, 45 to 60 wt.%, 50 to 55 wt.%) of a DCPD portion,0.0001 to 90 wt.% (e.g., 0.001 to 89 wt.%, 0.01 to 88 wt.%, 0.1 to 87 wt.%, 0.5 to 86 wt.%, 1 to 85 wt.%, 2 to 80 wt.%, 3 to 75 wt.%, 4 to 70 wt.%, 5 to 65 wt.%, 6 to 60 wt.%, 7 to 55 wt.%, 8 to 50 wt.%, 9 to 45 wt.%, 10 to 40 wt.%, 15 to 35 wt.%, 20 to 30 wt.%) of a TCPD portion, and0 to 50 wt.% (e.g., 0.0001 to 49.9998 wt.%, 0.001 to 45 wt.%, 0.01 to 40 wt.%, 0.1 to 35 wt.%, 0.5 to 30 wt.%, 1 to 25 wt.%, 2 to 20 wt.%, 3 to 15 wt.%, 4 to 10 wt.%, 5 to 9 wt.%, 6 to 8 wt.%) of a TeCPD portion, based on the total weight of the DCPD, TCPD, and TeCPD portions in the cyclic olefin composition; wherein the DCPD portion, if present, comprises, consists essentially of, or consists of: 0.3 to 99 wt.% (e.g., 0.4 to 98 wt.%, 0.5 to 97 wt.%, 1 to 96 wt.%, 2 to 95 wt.%, 3 to 94 wt.%, 4 to 93 wt.%, 5 to 92 wt.%, 10 to 91 wt.%, 15 to 90 wt.%, 20 to 85 wt.%, 25 to 80 wt.%, 30 to 75 wt.%, 35 to 70 wt.%, 40 to 65 wt.%, 45 to 60 wt.%, 50 to 55 wt.%) of exo-DCPD, and1 to 99 wt.% (e.g., 2 to 98 wt.%, 3 to 97 wt.%, 4 to 96 wt.%, 5 to 95 wt.%, 10 to 94 wt.%, 15 to 93 wt.%, 20 to 92 wt.%, 25 to 91 wt.%, 30 to 90 wt.%, 35 to 89 wt.%, 40 to 88 wt.%, 45 to 87 wt.%, 50 to 86 wt.%, 55 to 85 wt.%, 65 to 80 wt.%, 70 to 75 wt.%) of endo-DCPD, based on the total weight of the exo-DCPD and endo-DCPD in the DCPD portion;wherein the TCPD portion comprises, consists essentially of, or consists of:0.1 to 10 wt.% (e.g., 0.2 to 9 wt.%, 0.3 to 8 wt.%, 0.4 to 7 wt.%, 0.5 to 6 wt.%, 0.6 to 5 wt.%, 0.7 to 4 wt.%, 0.8 to 3 wt.%, 0.9 to 2 wt.%, 1 to 1 ,5 wt.%) of TCPD-7,3 to 25 wt.% (e.g., 4 to 24 wt.%, 5 to 23 wt.%, 6 to 22 wt.%, 7 to 21 wt.%, 8 to 20 wt.%, 9 to 19 wt.%, 10 to 18 wt.%, 11 to 17 wt.%, 12 to 16 wt.%, 13 to 15 wt.%) of TCPD-3,5 to 90 wt.% (e.g., 6 to 85 wt.%, 7 to 80 wt.%, 8 to 75 wt.%, 9 to 70 wt.%, 10 to 65 wt.%, 15 to 60 wt.%, 20 to 55 wt.%, 25 to 50 wt.%, 30 to 45 wt.%, 35 to 40 wt.%) of TCPD-5, and5 to 85 wt.% (e.g., 6 to 80 wt.%, 7 to 75 wt.%, 8 to 70 wt.%, 9 to 65 wt.%, 10 to 60 wt.%, 15 to 55 wt.%, 20 to 50 wt.%, 25 to 45 wt.%, 30 to 40 wt.%) of TCPD-1 , based on the total weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 in the TCPD portion of the cyclic olefin composition; and wherein the TeCPD portion comprises, consists essentially of, or consists of:0 to 10 wt.% (e.g., 0.001 to 9 wt.%, 0.01 to 8 wt.%, 0.1 to 7 wt.%, 0.5 to 6 wt.%, 1 to 5 wt.%, 2 to 4 wt.%, 2.5 to 3 wt.%) of TeCPD-1 ,0 to 15 wt.% (e.g., 0.001 to 14 wt.%, 0.01 to 13 wt.%, 0.1 to 12 wt.%, 0.5 to 11 wt.%, 1 to 10 wt.%, 2 to 9 wt.%, 3 to 8 wt.%, 4 to 7 wt.%, 5 to 6 wt.%) of TeCPD-2,0 to 30 wt.% (e.g., 0.001 to 25 wt.%, 0.01 to 20 wt.%, 0.1 to 15 wt.%, 0.5 to 10 wt.%, 1 to 9 wt.%, 2 to 8 wt.%, 3 to 7 wt.%, 4 to 6 wt.%) of TeCPD-3,0 to 5 wt.% (e.g., 0.001 to 4 wt.%, 0.01 to 3 wt.%, 0.1 to 2 wt.%, 0.5 to 1 wt.%) of TeCPD-4,0 to 5 wt.% (e.g., 0.001 to 4 wt.%, 0.01 to 3 wt.%, 0.1 to 2 wt.%, 0.5 to 1 wt.%) of TeCPD-5,0 to 70 wt.% (e.g., 0.001 to 65 wt.%, 0.01 to 60 wt.%, 0.1 to 55 wt.%, 0.5 to 50 wt.%, 1 to 45 wt.%, 5 to 40 wt.%, 10 to 35 wt.%, 15 to 30 wt.%, 20 to 25 wt.%) of TeCPD-6, and0 to 90 wt.% (e.g., 0.001 to 85 wt.%, 0.01 to 80 wt.%, 0.1 to 75 wt.%, 0.5 to 70 wt.%, 1 to 65 wt.%, 5 to 60 wt.%, 10 to 55 wt.%, 15 to 50 wt.%, 20 to 45 wt.%, 25 to 40 wt.%, 30 to 35 wt.%) of TeCPD-7,based on the total weight of the TeCPD-1, TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, and TeCPD-7 in the TeCPD portion.

[0066] In some embodiments, the invention relates to a cyclic olefin composition, comprising, consisting essentially of, or consisting of:0.0001 to 99.9998 wt.% (e.g., 0.001 to 99.998 wt.%, 0.01 to 99.98 wt.%, 0.1 to 99.8 wt.%, 0.5 to 99 wt.%, 1 to 99.5 wt.%, 2 to 99 wt.%, 3 to 98 wt.%, 4 to 97 wt.%, 5 to 96 wt.%, 6 to 95 wt.%, 7 to 94 wt.%, 8 to 93 wt.%, 9 to 92 wt.%, 10 to 91 wt.%, 15 to 90 wt.%, 20 to 85 wt.%, 25 to 80 wt.%, 30 to 75 wt.%, 35 to 70 wt.%, 40 to 65 wt.%, 45 to 60 wt.%, 50 to 55 wt.%) of a DCPD portion,0.0001 to 99.9998 wt.% (e.g., 0.001 to 99.998 wt.%, 0.01 to 99.98 wt.%, 0.1 to 99.8 wt.%, 0.5 to 99 wt.%, 1 to 99.5 wt.%, 2 to 99 wt.%, 3 to 98 wt.%, 4 to 97 wt.%, 5 to 96 wt.%, 6 to 95 wt.%, 7 to 94 wt.%, 8 to 93 wt.%, 9 to 92 wt.%, 10 to 91 wt.%, 15 to 90 wt.%, 20 to 85 wt.%, 25 to 80 wt.%, 30 to 75 wt.%, 35 to 70 wt.%, 40 to 65 wt.%, 45 to 60 wt.%, 50 to 55 wt.%) of a TCPD portion, and0.0001 to 50 wt.% (e.g., 0.001 to 45 wt.%, 0.01 to 40 wt.%, 0.1 to 35 wt.%, 0.5 to 30 wt.%, 1 to 25 wt.%, 2 to 20 wt.%, 3 to 15 wt.%, 4 to 14 wt.%, 5 to 13 wt.%, 6 to 12 wt.%, 7 to 11 wt.%, 8 to 10 wt.%) of a TeCPD portion, based on the total weight of the DCPD, TCPD, and TeCPD portions in the cyclic olefin composition; wherein the DCPD portion comprises, consists essentially of, or consists of:0.3 to 99 wt.% (e.g., 0.4 to 98 wt.%, 0.5 to 97 wt.%, 1 to 96 wt.%, 2 to 95 wt.%, 3 to 94 wt.%, 4 to 93 wt.%, 5 to 92 wt.%, 10 to 91 wt.%, 15 to 90 wt.%, 20 to 85 wt.%, 25 to 80 wt.%, 30 to 75 wt.%, 35 to 70 wt.%, 40 to 65 wt.%, 45 to 60 wt.%, 50 to 55 wt.%) of exo-DCPD, and1 to 99 wt.% (e.g., 2 to 98 wt.%, 3 to 97 wt.%, 4 to 96 wt.%, 5 to 95 wt.%, 10 to 94 wt.%, 15 to 93 wt.%, 20 to 92 wt.%, 25 to 91 wt.%, 30 to 90 wt.%, 35 to 89 wt.%, 40 to 88 wt.%, 45 to 87 wt.%, 50 to 86 wt.%, 55 to 85 wt.%, 65 to 80 wt.%, 70 to 75 wt.%) of endo-DCPD, based on the total weight of the exo-DCPD and endo-DCPD in the DCPD portion; wherein the TCPD portion comprises, consists essentially of, or consists of:0.1 to 10 wt.% (e.g., 0.2 to 9 wt.%, 0.3 to 8 wt.%, 0.4 to 7 wt.%, 0.5 to 6 wt.%, 0.6 to 5 wt.%, 0.7 to 4 wt.%, 0.8 to 3 wt.%, 0.9 to 2 wt.%, 1 to 1 ,5 wt.%) of TCPD-7,3 to 25 wt.% (e.g 4 to 24 wt.%, 5 to 23 wt.%, 6 to 22 wt.%, 7 to 21 wt.%, 8 to 20 wt.%, 9 to 19 wt.%, 10 to 18 wt.%, 11 to 17 wt.%, 12 to 16 wt.%, 13 to 15 wt.%) of TCPD-3,5 to 90 wt.% (e.g., 6 to 85 wt.%, 7 to 80 wt.%, 8 to 75 wt.%, 9 to 70 wt.%, 10 to 65 wt.%, 15 to 60 wt.%, 20 to 55 wt.%, 25 to 50 wt.%, 30 to 45 wt.%, 35 to 40 wt.%) of TCPD-5, and5 to 85 wt.% (e.g., 6 to 80 wt.%, 7 to 75 wt.%, 8 to 70 wt.%, 9 to 65 wt.%, 10 to 60 wt.%, 15 to 55 wt .%, 20 to 50 wt.%, 25 to 45 wt.%, 30 to 40 wt .%) of TCPD-1 , based on the total weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 in the TCPD portion; and wherein the TeCPD portion comprises, consists essentially of, or consists of:0 to 10 wt.% (e.g., 0.001 to 9 wt.%, 0.01 to 8 wt.%, 0.1 to 7 wt.%, 0.5 to 6 wt.%, 1 to 5 wt.%, 2 to 4 wt.%, 2.5 to 3 wt.%) of TeCPD-1 ,0 to 15 wt.% (e.g., 0.001 to 14 wt.%, 0.01 to 13 wt.%, 0.1 to 12 wt.%, 0.5 to 11 wt.%, 1 to 10 wt.%, 2 to 9 wt.%, 3 to 8 wt.%, 4 to 7 wt.%, 5 to 6 wt.%) of TeCPD-2,0 to 30 wt.% (e.g., 0.001 to 25 wt.%, 0.01 to 20 wt.%, 0.1 to 15 wt.%, 0.5 to 10 wt.%, 1 to 9 wt.%, 2 to 8 wt.%, 3 to 7 wt.%, 4 to 6 wt.%) of TeCPD-3,0 to 5 wt.% (e.g., 0.001 to 4 wt.%, 0.01 to 3 wt.%, 0.1 to 2 wt.%, 0.5 to 1 wt.%) of TeCPD-4,0 to 5 wt.% (e.g., 0.001 to 4 wt.%, 0.01 to 3 wt.%, 0.1 to 2 wt.%, 0.5 to 1 wt.%) of TeCPD-5,0 to 70 wt.% (e.g., 0.001 to 65 wt.%, 0.01 to 60 wt.%, 0.1 to 55 wt.%, 0.5 to 50 wt.%, 1 to 45 wt.%, 5 to 40 wt.%, 10 to 35 wt.%, 15 to 30 wt.%, 20 to 25 wt.%) of TeCPD-6, and0 to 90 wt.% (e.g., 0.001 to 85 wt.%, 0.01 to 80 wt.%, 0.1 to 75 wt.%, 0.5 to 70 wt.%, 1 to 65 wt.%, 5 to 60 wt.%, 10 to 55 wt.%, 15 to 50 wt.%, 20 to 45 wt.%, 25 to 40 wt.%, 30 to 35 wt.%) of TeCPD-7, based on the total weight of the TeCPD-1, TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, and TeCPD-7 in the TeCPD portion.

[0067] In some embodiments, the exo-DCPD has a structurethe TCPD-3 has a structure

[0068] In some embodiments of the cyclic olefin composition, the exo-DCPD has a retention index of 1017 ±1 , and the endo-DCPD has a retention index of 1031 ±1. In some embodiments of the cyclic olefin composition, the TCPD-7 has a retention index of 1535 ±2, the TCPD-3 has a retention index of 1539 ±1 , the TCPD-5 has a retention index of 1585 ±1 , and the TCPD-1 has a retention index of 1579 ±1. In some embodiments of the cyclic olefin composition, the TeCPD-1 has a retention index of 2310 ±1 , the TeCPD-2 has a retention index of 2318 ±1 , the TeCPD-3 has a retention index of 2330 ±2, the TeCPD-4 has a retention index of 2354 ±1 , the TeCPD-5 has a retention index of 2363 ±1 , the TeCPD-6 has a retention index of 2370 ±1 , and the TeCPD- 7 has a retention index of 2382 ±1 . In some embodiments of the cyclic olefin composition, theretention indexes of the DCPD, TCPD, and / or TeCPD portions are determined using ASTM D2887 (Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography). In some embodiments of the cyclic olefin composition, the retention time of the DCPD and TCPD portions is measured by gas chromatography using an Agilent 8890 Gas Chromatography (GC) System according to Settings Method A (Table 2 below).

[0069] In some embodiments of the cyclic olefin composition, the exo-DCPD has a retention index of 1017 ±1 , the endo-DCPD has a retention index of 1031 ±1, the TCPD-7 has a retention index of 1535 ±2, the TCPD-3 has a retention index of 1539 ±1 , the TCPD-5 has a retention index of 1585 ±1 , and the TCPD-1 has a retention index of 1579 ±1 .In some embodiments of the cyclic olefin composition, the retention indexes of the DCPD and TCPD portions are determined using ASTM D2887 (Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography). In some embodiments of the cyclic olefin composition, the retention time of the DCPD and TCPD portions is measured by gas chromatography using an Agilent 8890 Gas Chromatography (GC) System according to Settings Method A (Table 2 below).

[0070] In some embodiments of the cyclic olefin composition, the exo-DCPD has a retention index of 1017 ±1 , the endo-DCPD has a retention index of 1031 ±1 , the TCPD-7 has a retention index of 1535 ±2, the TCPD-3 has a retention index of 1539 ±1 , the TCPD-5 has a retention index of 1585 ±1 , the TCPD-1 has a retention index of 1579 ±1 , the TeCPD-1 has a retention index of 2310 ±1 , the TeCPD-2 has a retention index of 2318 ±1 , the TeCPD-3 has a retention index of 2330 ±2, the TeCPD-4 has a retention index of 2354 ±1 , the TeCPD-5 has a retention index of 2363 ±1 , the TeCPD-6 has a retention index of 2370 ±1 , and the TeCPD-7 has a retention index of 2382 ±1.In some embodiments of the cyclic olefin composition, the retention indexes of the DCPD, TCPD, and TeCPD portions are determined using ASTM D2887 (Standard Test Method for BoilingRange Distribution of Petroleum Fractions by Gas Chromatography). In some embodiments of the cyclic olefin composition, the retention time of the DCPD, TCPD, and TeCPD portions is measured by gas chromatography using an Agilent 8890 Gas Chromatography (GC) System according to Settings Method A (Table 2 below).

[0071] In some embodiments, the TeCPD isomers in the TeCPD portion elute in the order of the TeCPD-1 first, the TeCPD-2 second, the TeCPD-3 third, the TeCPD-4 fourth, the TeCPD-5 fifth, the TeCPD-6 sixth, and the TeCPD-7 seventh when separated by gas chromatography under conditions sufficient to achieve baseline separation of the TeCPD isomers. Stated differently, the TeCPD-1 elutes first, the TeCPD-2 elutes after the TeCPD-1 elutes, the TeCPD-3 elutes after the TeCPD-2 elutes, the TeCPD-4 elutes after the TeCPD-3 elutes, the TeCPD-5 elutes after the TeCPD-4 elutes, the TeCPD-6 elutes after the TeCPD-5 elutes, and the TeCPD-7 elutes after the TeCPD-6 elutes. In some embodiments, the retention time is measured by gas chromatography using an Agilent 8890 Gas Chromatography (GC) System according to Settings Method A (Table 2 below).

[0072] In some embodiments, one or more of the cyclic olefin compositions comprises, consists essentially of, or consists of:50 to 99.999 wt.% (e.g., 50 to 99.99 wt.%, 50 to 99.9 wt.%, 50 to 99 wt.%, 55 to 98 wt.%, 60 to 97 wt.%, 65 to 96 wt.%, 70 to 95 wt.%, 75 to 94 wt.%, 80 to 93 wt.%, 85 to 92 wt.%, 90 to 91 wt.%) of the DCPD portion, and0.001 to 50 wt.% (e.g., 0.01 to 50 wt.%, 0.1 to 50 wt.%, 1 to 50 wt.%, 2 to 45 wt.%, 3 to 40 wt.%, 4 to 35 wt.%, 5 to 30 wt.%, 6 to 25 wt.%, 7 to 20 wt.%, 8 to 15 wt.%, 9 to 10 wt.%) of the TCPD portion.

[0073] In some embodiments, one or more of the cyclic olefin compositions comprises, consists essentially of, or consists of:50 to 99.999 wt.% (e.g., 50 to 99.99 wt.%, 50 to 99.9 wt.%, 50 to 99 wt.%, 50 to 98 wt.%, 55 to 97 wt.%, 60 to 96 wt.%, 65 to 95 wt.%, 70 to 94 wt.%, 75 to 93 wt.%, 80 to 92 wt.%, 85 to 91 wt.%) of the DCPD portion, and0.001 to 25 wt.% (e.g., 0.01 to 25 wt.%, 0.1 to 25 wt.%, 1 to 25 wt.%, 2 to 25 wt.%, 3 to 20 wt.%, 4 to 15 wt.%, 5 to 10 wt.%, 6 to 9 wt.%, 7 to 8 wt.%) of the TeCPD portion.

[0074] In some embodiments, one or more of the cyclic olefin compositions comprises, consists essentially of, or consists of:49.999 to 99.998 wt.% (e.g., 49.99 to 99.98 wt.%, 49.9 to 99.8 wt.%, 49 to 98 wt.%, 50 to 97 wt.%, 55 to 96 wt.%, 60 to 94 wt.%, 65 to 92 wt.%, 70 to 90 wt.%, 75 to 88 wt.%, 80 to 86 wt.%, 82 to 84 wt.%) of the DCPD portion,0.001 to 50 wt.% (e.g., 0.01 to 50 wt.%, 0.1 to 50 wt.%, 1 to 50 wt.%, 2 to 45 wt.%, 3 to 40 wt.%, 4 to 35 wt.%, 5 to 30 wt.%, 6 to 25 wt.%, 7 to 20 wt.%, 8 to 15 wt.%, 9 to 10 wt.%) of the TCPD portion, and0.001 to 25 wt.% (e.g., 0.01 to 25 wt.%, 0.1 to 25 wt.%, 1 to 25 wt.%, 2 to 25 wt.%, 3 to 20 wt.%, 4 to 15 wt.%, 5 to 10 wt.%, 6 to 9 wt.%, 7 to 8 wt.%) of the TeCPD portion.

[0075] In some embodiments, one or more of the cyclic olefin compositions comprises, consists essentially of, or consists of:0.001 to 49.999 wt.% (e.g., 0.01 to 49.99 wt.%, 0.1 to 49.9 wt.%, 1 to 49 wt.%, 2 to 45 wt.%, 3 to 40 wt.%, 4 to 35 wt.%, 5 to 30 wt.%, 6 to 25 wt.%, 7 to 20 wt.%, 8 to 15 wt.%, 9 to 10 wt.%) of the DCPD portion,50 to 99.998 wt.% (e.g., 50 to 99.98 wt.%, 50 to 99.8 wt.%, 50 to 98 wt.%, 55 to 96 wt.%, 60 to 94 wt.%, 65 to 92 wt.%, 70 to 90 wt.%, 75 to 88 wt.%, 80 to 86 wt.%, 82 to 84 wt.%) of the TCPD portion, and0.001 to 49.999 wt.% (e.g., 0.01 to 49.99 wt.%, 0.1 to 49.9 wt.%, 1 to 49 wt.%, 2 to 45 wt.%, 3 to 40 wt.%, 4 to 35 wt.%, 5 to 30 wt.%, 6 to 25 wt.%, 7 to 20 wt.%, 8 to 15 wt.%, 9 to 10 wt.%) of the TeCPD portion.

[0076] In some embodiments, one or more of the cyclic olefin compositions comprises ≥ 90 wt.% (e.g., ≥ 91 wt.%, ≥ 92 wt.%, ≥ 93 wt.%, ≥ 94 wt.%, ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, ≥ 99 wt.%, ≥ 99.1 wt.%, ≥ 99.2 wt.%, ≥ 99.3 wt.%, ≥ 99.4 wt.%, ≥ 99.5 wt.%, ≥ 99.6 wt.%, ≥ 99.7 wt.%, ≥ 99.8 wt.%, ≥ 99.9 wt.%) of the DCPD portion, based on the total weight of the cyclic olefin composition.

[0077] In some embodiments, one or more of the cyclic olefin compositions comprises ≥ 90 wt.% (e.g., ≥ 91 wt.%, ≥ 92 wt.%, ≥ 93 wt.%, ≥ 94 wt.%, ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, ≥ 99 wt.%, ≥ 99.1 wt.%, ≥ 99.2 wt.%, ≥ 99.3 wt.%, ≥ 99.4 wt.%, ≥ 99.5 wt.%, ≥ 99.6 wt.%, ≥ 99.7 wt.%, ≥ 99.8 wt.%, ≥ 99.9 wt.%) of a combined amount of the DCPD and TCPD portions, based on the total weight of the cyclic olefin composition.

[0078] In some embodiments, one or more of the cyclic olefin compositions comprises ≥ 90 wt.% (e.g., ≥ 91 wt.%, ≥ 92 wt.%, ≥ 93 wt.%, ≥ 94 wt.%, ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, ≥ 99 wt.%, ≥ 99.1 wt.%, ≥ 99.2 wt.%, ≥ 99.3 wt.%, ≥ 99.4 wt.%, ≥ 99.5 wt.%, ≥ 99.6 wt.%, ≥ 99.7 wt.%, ≥ 99.8 wt.%, ≥ 99.9 wt.%) of a combined amount of the DCPD, TCPD, and TeCPD portions, based on the total weight of the cyclic olefin composition.

[0079] In some embodiments, one or more of the cyclic olefin compositions comprises ≥ 70 wt.% (e.g., ≥71 wt.%, ≥ 72 wt.%, ≥ 73 wt.%, ≥ 74 wt.%, ≥ 75 wt.%, ≥ 76 wt.%, ≥ 77 wt.%, ≥ 78 wt.% ≥ 79 wt.%) of the TCPD portion, based on the total weight of the cyclic olefin composition.

[0080] In some embodiments, one or more of the cyclic olefin compositions comprises ≥ 90 wt.% (e.g., ≥ 91 wt.%, ≥ 92 wt.%, ≥ 93 wt.%, ≥ 94 wt.%, ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, ≥ 99 wt.%, ≥ 99.1 wt.%, ≥ 99.2 wt.%, ≥ 99.3 wt.%, ≥ 99.4 wt.%, ≥ 99.5 wt.%, ≥ 99.6 wt.%, ≥ 99.7 wt.%, ≥ 99.8 wt.%, ≥ 99.9 wt.%) of the TCPD portion, based on the total weight of the cyclic olefin composition.

[0081] In some embodiments, one or more of the cyclic olefin compositions comprises ≥ 90 wt.% (e.g., ≥ 91 wt.%, ≥ 92 wt.%, ≥ 93 wt.%, ≥ 94 wt.%, ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, ≥ 99 wt.%, ≥ 99.1 wt.%, ≥ 99.2 wt.%, ≥ 99.3 wt.%, ≥ 99.4 wt.%, ≥ 99.5 wt.%, ≥ 99.6 wt.%, ≥ 99.7 wt.%, ≥ 99.8 wt.%, ≥ 99.9 wt.%) of a combined amount of the TCPD and TeCPD portions, based on the total weight of the cyclic olefin composition.

[0082] In some embodiments, one or more of the cyclic olefin compositions comprises ≤ 7 wt.% (e.g., ≤ 6 wt.%, ≤ 5 wt.%, ≤ 4 wt.%, ≤ 3 wt.%, ≤ 2 wt.%, ≤ 1 wt.%, ≤ 0.1 wt.%, ≤ 0.01 wt.%, ≤ 0.001 wt.%, ≤ 0.0001 wt.%) of the TCPD portion, based on the total weight of the cyclic olefin composition.

[0083] In some embodiments, one or more of the cyclic olefin compositions comprises ≤ 7 wt.% (e.g., ≤ 6 wt.%, ≤ 5 wt.%, ≤ 4 wt.%, ≤ 3 wt.%, ≤ 2 wt.%, ≤ 1 wt.%, ≤ 0.1 wt.%, ≤ 0.01 wt.%, ≤ 0.001 wt.%, ≤ 0.0001 wt.%) of the TeCPD portion, based on the total weight of the cyclic olefin composition.

[0084] In some embodiments, one or more of the cyclic olefin compositions comprises ≤ 7 wt.% (e.g., ≤ 6 wt.%, ≤ 5 wt.%, < 4 wt.%, ≤ 3 wt.%, ≤ 2 wt.%, ≤ 1 wt.%, ≤ 0.1 wt.%, ≤ 0.01 wt.%, ≤ 0.001 wt.%, ≤ 0.0001 wt.%) of a combined amount of the TCPD and TeCPD portions, based on the total weight of the cyclic olefin composition.

[0085] In some embodiments, in one or more of the cyclic olefin compositions, the cyclic olefin composition comprises 0.001 to 5 wt.% (e.g., 0.01 to 4 wt.%, 0.1 to 3 wt.%, 0.5 to 2 wt.%, 1 to 1 .5 wt.%) of the DCPD portion, based on the total weight of the cyclic olefin composition, based on the total weight of the TCPD portion; the TCPD portion comprises < 70% TCPD-1 and > 15% TCPD 5; and the TeCPD portion comprises <55% TeCPD-6 and >13% TeCPD-7, based on the total weight of the TeCPD portion.

[0086] In some embodiments, one or more of the cyclic olefin compositions comprises 20 to 50 wt.% (e.g., 25 to 45 wt.%, 30 to 40 wt.%) of the DCPD portion, 50 to 80 wt.% (e.g., 55 to 75 wt.%, 60 to 70 wt.%) of the TCPD portion, and 0.1 to 7 wt.% (e.g., 1 to 6 wt.%, 2 to 5 wt.%, 3 to 4 wt.%) of TeCPD portion, based on the total weight of the cyclic olefin composition.

[0087] In some embodiments, one or more of the cyclic olefin compositions comprises a weight ratio of the TCPD portion to the DCPD portion of > 1 (e.g., > 5, > 10).

[0088] In some embodiments, one or more of the cyclic olefin compositions comprises a weight ratio of the DCPD portion to TeCPD portion of > 1 (e.g., > 5, > 10).

[0089] In some embodiments, one or more of the cyclic olefin compositions comprises a weight ratio of the TCPD portion to TeCPD portion of > 1 (e.g., > 5, > 10).

[0090] In some embodiments, one or more of the cyclic olefin compositions comprises 20 to 50 wt.% of the DCPD portion, 50 to 80 wt.% of the TCPD portion, and 0.1 to 7 wt.% of TeCPD portion, based on the total weight of the cyclic olefin composition.

[0091] In some embodiments, one or more of the cyclic olefin compositions comprises a weight ratio of the TCPD portion to the DCPD portion of 1 (e.g., > 5, > 10).

[0092] In some embodiments, one or more of the cyclic olefin compositions comprises a weight ratio of the DCPD portion to TeCPD portion of > 1 (e.g., > 5, > 10).

[0093] In some embodiments, one or more of the cyclic olefin compositions comprises a weight ratio of the TCPD portion to TeCPD portion of > 1 (e.g., > 5, > 10).

[0094] In some embodiments, one or more of the cyclic olefin compositions, the resin composition, and / or the ROMP composition do not comprise TCPD.

[0095] In some embodiments, one or more of the cyclic olefin compositions, the resin composition, and / or the ROMP composition do not comprise TeCPD.

[0096] In some embodiments, one or more of the cyclic olefin compositions, the resin composition, and / or the ROMP composition do not comprise a higher order oligomer of cyclopentadiene.

[0097] In some embodiments, one or more of the cyclic olefin compositions, the resin composition, and / or the ROMP composition do not comprise pentacyclopentadiene and hexacyclopentadiene.

[0098] In some embodiments, one or more of the cyclic olefin compositions, the resin composition, and / or the ROMP composition do not comprise pentacyclopentadiene.

[0099] In some embodiments, one or more of the cyclic olefin compositions, the resin composition, and / or the ROMP composition do not comprise hexacyclopentadiene.

[0100] In some embodiments, one or more of the cyclic olefin compositions, the resin composition, and / or the ROMP composition do not comprise any further multiunsaturated cyclic olefins and / or monounsaturated cyclic olefins.

[0101] In some embodiments, the cyclic olefin composition does not comprise any multiunsaturated cyclic olefin and / or monounsaturated cyclic olefin, other than the DCPD portion, the TCPD portion, and the TeCPD portion present in the cyclic olefin compositions. In some embodiments, the cyclic olefin composition does not comprise a multi unsaturated cyclic olefinand / or monounsaturated cyclic olefin, other than exo-DCPD, endo-DCPD, TCPD (e.g., TCPD-7, TCPD-3, TCPD-5, and TCPD-1 ), and TeCPD (e.g., TeCPD-1 , TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, and TeCPD-7). In some embodiments, the cyclic olefin composition does not comprise a multiunsaturated cyclic olefin, other than exo-DCPD, endo-DCPD, TCPD (e.g., TCPD-7, TCPD-3, TCPD-5, and TCPD-1 ), and TeCPD (e.g., TeCPD-1 , TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, and TeCPD-7).

[0102] In some embodiments, the resin composition does not comprise any multiunsaturated cyclic olefin and / or monounsaturated cyclic olefin, other than the DCPD portion, the TCPD portion, and the TeCPD portion present in the cyclic olefin compositions. In some embodiments, the resin composition does not comprise a multi unsaturated cyclic olefin and / or monounsaturated cyclic olefin, other than exo-DCPD, endo-DCPD, TCPD (e.g., TCPD-7, TCPD-3, TCPD-5, and TCPD- 1 ), and TeCPD (e.g., TeCPD-1 , TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, and TeCPD-7). In some embodiments, the resin composition does not comprise a multiunsaturated cyclic olefin, other than exo-DCPD, endo-DCPD, TCPD (e.g., TCPD-7, TCPD-3, TCPD-5, and TCPD-1 ), and TeCPD (e.g., TeCPD-1 , TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, and TeCPD-7).

[0103] In some embodiments, the ROMP composition does not comprise any multiunsaturated cyclic olefin and / or monounsaturated cyclic olefin, other than the DCPD portion, the TCPD portion, and the TeCPD portion present in the cyclic olefin compositions. In some embodiments, the ROMP composition does not comprise a multiunsaturated cyclic olefin and / or monounsaturated cyclic olefin, other than exo-DCPD, endo-DCPD, TCPD (e.g., TCPD-7, TCPD-3, TCPD-5, and TCPD-1 ), and TeCPD (e.g., TeCPD-1 , TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, and TeCPD-7). In some embodiments, the ROMP composition does not comprise a multiunsaturated cyclic olefin, other than exo-DCPD, endo-DCPD, TCPD (e.g., TCPD-7, TCPD-3, TCPD-5, and TCPD-1 ), and TeCPD (e.g., TeCPD-1 , TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, and TeCPD-7).

[0104] In some embodiments, one or more of the cyclic olefin compositions further comprises at least one higher order oligomer of cyclopentadiene.

[0105] In some embodiments, one or more of the cyclic olefin compositions further comprises pentacyclopentadiene and hexacyclopentadiene.

[0106] In some embodiments, one or more of the cyclic olefin compositions further comprises pentacyclopentadiene.

[0107] In some embodiments, one or more of the cyclic olefin compositions further comprises hexacyclopentadiene.

[0108] In some embodiments, one or more of the cyclic olefin compositions are liquid at ≤ 50 °C (e.g., ≤ 40 °C, ≤ 30 °C, ≤ 25 °C, ≤ 20 °C).

[0109] In some embodiments, one or more of the cyclic olefin compositions are liquid at ≤ 0 °C (e.g., ≤ -5 °C, ≤ -10 °C, ≤ -20 °C, ≤ -30 °C).

[0110] In some embodiments, one or more of the cyclic olefin compositions are liquid at ≤ 50 °C (e.g., ≤ 40 °C, ≤ 30 °C, ≤ 25 °C, ≤ 20 °C) and the cyclic olefin composition comprises ≥ 70 wt.% (e.g., ≥ 72 wt.%, ≥ 74 wt.%, ≥ 76 wt.%, ≥ 78 wt.%) of the TCPD portion, based on the total weight of the cyclic olefin composition.

[0111] In some embodiments, one or more of the cyclic olefin compositions are liquid at ≤ 30 °C ( ≤ 25 °C, ≤ 20 °C) and the cyclic olefin composition comprises ≥ 70 wt.% (e.g., ≥ 75 wt.%, ≥ 80 wt.%, ≥ 85 wt.%, ≥ 89 wt.%) of the TCPD portion, based on the total weight of the cyclic olefin composition.

[0112] In some embodiments, one or more of the cyclic olefin compositions are liquid at ≤ 30 °C ( ≤ 25 °C, ≤ 20 °C) and the cyclic olefin composition comprises ≥ 90 wt.% (e.g., ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, ≥ 99 wt.%) of the TCPD portion, based on the total weight of the cyclic olefin composition.

[0113] In some embodiments, one or more of the cyclic olefin compositions are liquid at ≤ 50 °C (e.g., ≤ 40 °C, ≤ 30 °C, ≤ 25 °C, ≤ 20 °C) and wherein the cyclic olefin composition comprises ≥ 70 wt.% (e.g., ≥ 72 wt.%, ≥ 74 wt.%, ≥ 76 wt.%, ≥ 78 wt.%) of the combined TCPD and TeCPD portions, based on the total weight of the cyclic olefin composition.

[0114] In some embodiments, one or more of the cyclic olefin compositions are liquid at ≤ 30 °C ( ≤ 25 °C, ≤ 20 °C) and wherein the cyclic olefin composition comprises ≥ 70 wt.% (e.g., ≥ 75 wt.%, ≥ 80 wt.%, ≥ 85 wt.%, ≥ 89 wt.%) of the combined TCPD and TeCPD portions, based on the total weight of the cyclic olefin composition.

[0115] In some embodiments, one or more of the cyclic olefin compositions are liquid at ≤ 30 °C (< 25 °C, < 20 °C) and wherein the cyclic olefin composition comprises ≥ 90 wt.% (e.g., ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, ≥ 99 wt.%) of the combined TCPD and TeCPD portions, based on the total weight of the cyclic olefin composition.

[0116] In some embodiments, the cyclic olefin composition comprises additional ROMP-active cyclic olefins (e.g., norbornene, ethylidene norbornene, etc.) besides DCPD, TCPD, TeCPD, and heavier oligomers of cyclopentadiene (CPD) that further depress the melt point below those observed from cyclic olefin compositions of DCPD, TCPD, TeCPD, and heavier oligomers of CPD alone.

[0117] In some embodiments, the cyclic olefin composition is part of a mixture including additional molecules besides DCPD, TCPD, TeCPD, and heavier oligomers of CPD that further depress the melt point below those observed from cyclic olefin compositions of DCPD, TCPD, TeCPD, and heavier oligomers of CPD alone.

[0118] In some embodiments, one or more of the cyclic olefin compositions do not have an observed crystallization temperature.

[0119] In some embodiments, one or more of the cyclic olefin compositions have multiple observed crystallization temperatures.

[0120] The exo- and endo-DCPD used in the cyclic olefin compositions may be prepared according to any process known in the art.

[0121] The TCPD isomers used in the TCPD portion of the cyclic olefin compositions may be prepared according to any process known in the art, including the processes disclosed in PCT / US2022 / 081048, the complete disclosure of which is incorporated herein by reference.

[0122] The TCPD isomers used in the TCPD portion of the cyclic olefin compositions may also include those prepared by catalytic methods known in the art that differ in structure from those prepared via thermal methods.

[0123] The TeCPD isomers used in the TeCPD portion of the cyclic olefin compositions may be prepared according to any process known in the art, including via thermal or catalytic methods.

[0124] The TeCPD isomers used in the TeCPD portion of the cyclic olefin compositions may also include those prepared by catalytic methods known in the art that differ in structure from those prepared via thermal methods.

[0125] In some embodiments, the DCPD portion, the TCPD portion, and the TeCPD portion can be prepared by: introducing a hydrocarbon feed comprising CPD and DCPD into a reaction zone; subjecting the hydrocarbon feed to reaction conditions sufficient to effect reaction between the CPD and the DCPD within the reaction zone to produce a reactor effluent comprising TCPD, TeCPD, CPD, and DCPD; separating from the reactor effluent a first product, a second product, and a purge stream, wherein: the first product comprises DCPD, TCPD, and TeCPD, the second product comprises CPD and DCPD, and the purge stream comprises CPD, nitrogen, and oxygen; separating the second product into at least a first portion and a second portion; andintroducing the first portion of the second product into the reaction zone.

[0126] As discussed above, DCPD has two possible isomeric structures named endo-DCPD and exo-DCPD. Endo-DCPD is the predominant kinetic product (-99:1 ) in the dimerization of cyclopentadiene (CPD) and no producers of DCPD offer a DCPD product with an elevated level of exo-DCPD. Similarly, TCPD has multiple isomeric structures that are various versions of endo- type TCPD or exo-typo TCPD isomers. Additionally, TeCPD has multiple isomeric structures that are various versions of endo-type TeCPD or exo-type TeCPD

[0127] The inclusion of higher levels of exo-DCPD in the cyclic olefin compositions present in the ROMP compositions disclosed herein depresses the melt point of the olefin composition allowing for lower processing temperatures without the inclusion of other reactive or non -reactive diluents as melt-point depressants. Those diluents can be added in combination with exo-DCPD to achieve even further lowering of the melt-point of the olefinic resin. For example, the lower melting point of the cyclic olefin composition can be achieved through enrichment of exo-DCPD isomer and, optionally, through enrichment of endo and exo-TCPD isomers, and further optionally through the enrichment of endo and exo-TeCPD isomers. Unlike other melt-point depressants, such as ethylidene norbornene (ENB), the thermophysical properties of the polymerized ROMP compositions disclosed herein are not negatively impacted, and, in fact, are enhanced by inclusion of exo-DCPD. Furthermore, because of the higher reactivity of higher exo-product, lower catalyst loadings as compared to those needed for purely endo-based compositions can be leveraged to achieve the same reactivity and final cured part performance.

[0128] For example, a cyclic olefin composition comprised of only endo-rich DCPD requires the addition of reactive diluents, e.g., TCPD or alkyl norbornenes, or non-reactive diluents, e.g., solvent or hydrocarbon resins, to be processed at temperatures below 32 °C. Enrichment of exo- DCPD within the DCPD isomer split allows the ROMP compositions disclosed herein to be processed at significantly lower temperatures.

[0129] Similarly, endo-rich TCPD isomers have a melting point around 62 °C, and TCPD formulations with DCPD that are greater than -60 wt.% TCPD are solid at room temperature. Endo-based DCPD / TCPD with about 72 wt.% TCPD have a melting point of around 42 °C. Therefore, to leverage higher TCPD content and still maintain liquid process conditions, a diluent must be used. Through enrichment of the exo-based TCPD and / or exo-based DCPD, the melting point of the cyclic olefin composition used in the invention are reduced allowing for processing of the cyclic olefin compositions with higher than 60 wt.% TCPD at room temperature or lower. For cyclic olefin compositions comprising greater than 70 wt.% TCPD, liquid processing conditionsbecome possible at less than 20 °C. For cyclic olefin compositions comprising greater than 90 wt.% TCPD, liquid processing conditions become possible at lower than 30 °C.

[0130] Lower processing temperatures at specified loadings may be possible depending on the degree of isomer enrichment. For example, reaction injection molding (RIM) of endo-DPCD would require heat tracing and heated molds to transfer the material or would require that the material be diluted. Bath base pultrusion would require that the bath be heated or that the material be diluted with non-DCPD or TCPD material to achieve a liquid state. Enrichment of exo content for the DCPD portion and, optionally, the TCPD portion facilitates bath-based processes without the need for non-DCPD or non-TCPD diluents. For example, the coating of pipes in cold environments may require the use of heating lamps, heat tracing, and / or dilution with non exo-enriched cyclic olefin compositions. In contrast, the ROMP compositions disclosed herein may not require such measures for applications in similar environments. Other applications where dilution and added heat can be reduced or removed by using the ROMP compositions disclosed herein include, for example, vacuum assisted resin transfer molding (VARTM), resin transfer molding (RTM), RIM, casting, spray coating, brushable coatings, and box injection pultrusion.

[0131] Additionally, as the ROMP composition disclosed herein is enriched in exo-isomer of DCPD and, optionally, TCPD, the solubility of TeCPD and other higher order oligomers is further improved, allowing for higher conversion of DCPD to TCPD without solids formation of TeCPD. Therefore, enriched cyclic olefin compositions with up to 25 wt.% exo-DCPD may be able to involve TCPD:TeCPD ratios that are lower than the non-enriched cyclic olefin compositions (e.g., a ratio of TCPD:TeCPD of < 20, < 15, < 10, or < 5). At 40 °C, it may be possible to have a liquid ROMP composition disclosed herein composed of greater than 80 wt.% TCPD and 8 wt.% TeCPD and other higher order oligomers. Stiffness values of the cured part would be higher than otherwise, due to the higher TCPD and potential TeCPD content.

[0132] Furthermore, due to the higher reactivity of the ROMP compositions disclosed herein, the same reactivity performance may be achieved at lower catalyst loadings. For example, the reactivity of 100 grams exo-enriched cyclic olefin composition used in the ROMP compositions disclosed herein at 30 °C may require less than 80% (e.g., 70%, 60%, 50%, 40%) less catalyst to achieve the same reactivity performance of comparable non-enriched cyclic olefin compositions, depending on the concentration of exo isomers in the cyclic olefin composition. To achieve the same glass transition as cured endo-DCPD, the exo-enriched cyclic olefin composition used in the ROMP compositions disclosed herein may require less than 80% (e.g., 70%, 60%, 50%, 40%) less catalyst to achieve the same thermal properties of comparable non-enriched cyclic olefin compositions. For example, the same, faster, and / or hotter reactivity performance and the sameor higher thermal properties of non-enriched cyclic olefin composition at loading of 100 ppm of Second Generation Grubbs catalysts may be achieved in comparable exo-enriched cyclic olefin composition used in the ROMP compositions disclosed herein at less than 80 ppm (e.g., 70 ppm, 60 ppm, 50 ppm, or 40 ppm) of the same catalyst. Because of the faster reaction kinetics, it may be possible to cure the ROMP compositions disclosed herein at lower temperature or without added heat. For example, traditional reaction injection molding leverages heated molds to not just keep the reaction mixture liquid but to drive the reaction to completion. Exo-enriched cyclic olefin compositions used in the ROMP compositions disclosed herein may need reduced or no heat input during the molding process.

[0133] Due to less catalyst required to achieve the same reactivity and thermal properties, it may be possible to achieve higher toughness values for exo-enriched ROMP compositions disclosed herein than for non-enriched ROMP compositions. This may be due to lower crosslinking from lower catalyst loading and / or from the absence of diluents that would otherwise influence toughness. This toughness effect may be seen in rubber toughened blends and / or blends with TCPD and / or compositions with a reactive diluent. Enriched exo-isomers of DCPD and, optionally, TCPD allows for near room temperature ROMP compositions that were previously inaccessible without dilution.

[0134] In some embodiments, the cyclic olefin composition, the resin composition, and / or the ROMP composition do not comprise a melt-point depressant diluent. In some embodiments, the melt-point depressant diluent is selected from a reactive cycloolefin or cyclodiolefin monomer containing at least one norbornene structure, ora mixture of reactive monomers other than DCPD, TCPD, and TeCPD. In another embodiment, the melt-point depressant diluent is selected from 5- ethylidene-2-norbornene, methyl-^tetracyclododecene, methyl-dicyclopentadiene, and hexacycloheptadecene.RESIN COMPOSITION

[0135] In some embodiments, the invention also relates to a resin composition comprising, consisting essentially of, or consisting of the cyclic olefin composition disclosed herein.Additional Multiunsaturated and Monounsaturated Cyclic Olefins

[0136] In some embodiments, the resin composition further comprises at least one additional multiunsaturated cyclic olefin. In another embodiment, the resin composition further comprises at least one additional monounsaturated cyclic olefin. In another embodiment, the resin composition further comprises at least one additional multiunsaturated cyclic olefin and at least one additional monounsaturated cyclic olefin

[0137] The at least one additional multiunsaturated cyclic olefin, if present, and the at least one monounsaturated cyclic olefin, if present, in the resin composition may be, independent of one another, substituted or unsubstituted.

[0138] The at least one additional multiunsaturated cyclic olefin and the at least one monounsaturated cyclic olefin, if present, may be, independent of one another, substituted by hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, -(Z*)n-Fn wherein n is 0 or 1 , Fn is the functional group, and Z’ is a hydrocarbylene linking group such as an alkylene, substituted alkylene, heteroalkylene, substituted heteroalkene, arylene, substituted arylene, heteroarylene, or substituted heteroarylene linkage, and functional groups (Fn).

[0139] Non-limiting examples of the additional multiunsaturated and monounsaturated cyclic olefins that may be used in the resin composition include dicyclohexadiene; norbornene; 5- methyl-2-norbornene; 5-ethyl-2-norbornene; 5-isobutyl-2-norbornene; 5,6-dimethyl-2- norbornene; 5-tolyl-2-norbornene; 5-phenyl-2-norbornene; 5-benzylnorbornene; 5- acetylnorbornene; 5-methoxycarbonylnorbornene; 5-ethoxycarbonyl-1 -norbornene; 5-methyl-5- methoxy-carbonylnorbomene; 5-cyanonorbornene; 5,5,6-trimethyl-2-norbomene; cyclo- hexenylnorbornene; endo, exo-5,6-dimethoxynorbornene; endo, endo-5,6-dimethoxynorbornene; endo, exo-5-6-dimethoxycarbonylnorbornene; endo, endo-5,6-dimethoxycarbonylnorbornene; 2,3-dimethoxynorbomene; norbornadiene; tricycloundecene; tetracyclododecene; 8- methyltetracyclododecene; 8-ethyl-tetracyclododecene; 8-methoxycarbonyltetracyclododecene; 8-methyl-8-tetracyclo-dodecene; 8-cyanotetracyclododecene; pentacyclopentadecene; pentacyclohexadecene; higher order oligomers of cyclopentadiene such as cyclopentadiene pentamer, and the like; and C2-C12 hydrocarbyl substituted 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-ethylidene-2-norbornene; 5-isopropenyl-2-norbornene; 5- propenyl-2-norbornene; and 5-butenyl-2-norbornene, and the like. The additional multiunsaturated and monounsaturated cyclic olefins that may be used in the resin composition include those, for example, disclosed in PCT / US2021 / 045673, the complete disclosure of which is incorporated herein by reference.

[0140] Multiunsaturated cyclic olefins include 5-vinyl-2-norbornene, 5-ethylidene-2- norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, 5-butenyl-2-norbornene, and the like.

[0141] Multiunsaturated cyclic olefins include 5-vinyl-2-norbornene and 5-ethylidene-2- norbornene.

[0142] Multiunsaturated cyclic olefins include 5-ethylidene-2-norbornene.

[0143] Monounsaturated cyclic olefins, if present, include C2-C12 hydrocarbyl substituted norbornenes (e.g., C4-C12 hydrocarbyl substituted norbornenes, C6-C12 hydrocarbyl substituted norbornenes, Cg-C-io hydrocarbyl substituted norbornenes). Monounsaturated cyclic olefins include, for example, 5-tolyl-2-norbornene, 5-phenyl-2-norbornene, 5-butyl-2-norbornene, 5- hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene, and 5-dodecyl-2-norbornene.

[0144] In some embodiments, the at least one additional multiunsaturated cyclic olefin is present in the resin composition in an amount ranging from 0.1 to 90 wt.% (e g., 0.5 to 85 wt.%, 1 to 80 wt.%, 2 to 75 wt.%, 3 to 70 wt.%, 4 to 65 wt.%, 5 to 60 wt.%, 10 to 55 wt.%, 15 to 50 wt.%, 20 to 45 wt.%, 25 to 40 wt.%, 30 to 35 wt.%), based on the total weight of the resin composition. In another embodiment, the at least one additional monounsaturated cyclic olefin is present in the resin composition in an amount ranging from 0.1 to 90 wt.% (e.g., 0.5 to 85 wt.%, 1 to 80 wt.%, 2 to 75 wt.%, 3 to 70 wt.%, 4 to 65 wt.%, 5 to 60 wt.%, 10 to 55 wt.%, 15 to 50 wt.%, 20 to 45 wt.%, 25 to 40 wt.%, 30 to 35 wt.%), based on the total weight of the resin composition. In another embodiment, the at least one additional multiunsaturated cyclic olefin and the at least one additional monounsaturated cyclic olefin are present in the resin composition in a combined amount ranging from 0.1 to 90 wt.% (e.g., 0.5 to 85 wt.%, 1 to 80 wt.%, 2 to 75 wt.%, 3 to 70 wt.%, 4 to 65 wt.%, 5 to 60 wt.%, 10 to 55 wt.%, 15 to 50 wt.%, 20 to 45 wt.%, 25 to 40 wt.%, 30 to 35 wt.%), based on the total weight of the resin composition.Adhesion Promoter

[0145] In some embodiments, the resin composition further comprises at least one adhesion promoter.

[0146] In some embodiments, the at least one adhesion promoter is selected from an acid- functionalized polyolefin.

[0147] The acid-functionalized polyolefin that may be used as the adhesion promoter includes those disclosed in U.S. Pat. No. 7,465,773, the complete disclosure of which is incorporated herein by reference. For example, adhesion promoters may be an acid-functionalized polyolefin, such as a polyolefin comprising maleic anhydride (also referred to herein as maleic anhydride grafted polyolefin). The polyolefin may be unsaturated, comprising alkene moieties, such as polybutadiene. The polyolefin may have a vinyl content of no greater than 40, 35, or 30 wt.%. The polyolefin may have an average anhydride equivalent weight ranging from 200-5000 g / mole per anhydride group (e.g., no greater than 4000, 3000, 2000, 1000, or 500 g / mole per anhydride group). The polyolefin comprising maleic anhydride is a liquid, typically having a viscosity at 20 or 25 °C of at least 2000, 3000, 4000, or 5000 mPas. (DIN EN ISO 3219). The viscosity at 20 or25 °C may be no greater than 75,000 mPas (e.g., no greater than 30,000, 25,000, 20,000, or 15,000 or 10,000 mPas; less than 1000 or 500 mPas). The polyolefin may have a viscosity of at least 50,000; 75,000; 100,000; 125,000; or 150,000 mPas at 45, 50, or 55 °C. The viscosity is indicative of the molecular weight. The polyolefin may have a molecular weight (Mn) of no greater than 10,000; 9,000; 8,000; 7,000; 6,000; 5,000; 4,500; 4,000; 3,500; or 3,000 g / mole. The polyolefin may have a molecular weight (Mn) of at least 1 ,000, 1 ,100, 1 ,200, 1 ,300, 1 ,400, 1 ,500, 1 ,600, 1 ,700, 1 ,800, 1 ,900, or 2,000 g / mole. An acid-functionalized polyolefin that may be used as an adhesion promoter is polybutadiene comprising maleic anhydride (also referred to herein as maleic anhydride grafted polybutadiene).

[0148] In another embodiment, the adhesion promoter is selected from a silane-functionalized polyolefin, such as a polyolefin comprising silane (also referred to herein as silane grafted polyolefin). The polyolefin may be unsaturated, comprising alkene moieties, such as polybutadiene. The average silane functionality per polymer chain may be between 0.1 and 2. The polyolefin comprising silane is a liquid, typically having a viscosity at 20 or 25 °C of at least 2000, 3000, 4000, 5000, 7500, 15000, or 30000 mPas. (DIN EN ISO 3219). The viscosity at 20 or 25 °C may be no greater than 75,000 mPas (e.g., no greater than 30,000, 25,000, 20,000, or 15,000 or 10,000 mPas; less than 1000 or 500 mPas). The polyolefin may have a viscosity of at least 50,000; 75,000; 100,000; 125,000; or 150,000 mPas at 45, 50, or 55 °C. The viscosity is indicative of the molecular weight. The polyolefin may have a molecular weight (Mn) of no greater than 10,000; 9,000; 8,000; 7,000; 6,000; 5,000; 4,500; 4,000; 3,500; or 3,000 g / mole. The polyolefin may have a molecular weight (Mn) of at least 800, 900, 1 ,000, 1 ,100, 1 ,200, 1,300, 1 ,400, 1 ,500, 1,600, 1,700, 1,800, 1 ,900, or 2,000 g / mole. A silane-functionalized polyolefin that may be used as an adhesion promoter is silane functionalized polybutadiene (also referred to herein as silane grafted polybutadiene).

[0149] In another embodiment, the adhesion promoter is selected from any compound having at least two isocyanate groups. In some embodiments, the compound containing at least two isocyanate groups is selected from at least one diisocyanate, at least one triisocyanate, or at least one polyisocyanate (i.e., containing four or more isocyanate groups), and mixtures thereof. In a more particular aspect of the invention, the adhesion promoter comprises, or is limited to, a diisocyanate compound, or mixtures of diisocyanate compounds.

[0150] The compounds of the isocyanate compounds comprising at least two isocyanate groups may be selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functionalized hydrocarbyl compounds. As described above, suitable hydrocarbyl adhesion promoter compounds generallyinclude alkyl, cycloalkyl, alkylene, alkenyl, alkynyl, aryl, cycloalkyl, alkaryl, and aralkyl compounds. Substituted heteroatom-containing, and functionalized hydrocarbyl adhesion promoter compounds include the aforementioned hydrocarbyl compounds, as well as the variations thereof noted hereinabove.

[0151] In another embodiment, the at least one adhesion promoter is selected from an alkyl diisocyanate. An alkyl diisocyanate refers to a linear, branched, or cyclic saturated or unsaturated hydrocarbon group typically although not necessarily containing 1 to about 24 carbon atoms, such as a diisocyanate containing 2 to about 12 carbon atoms (e g., 6 to 12 carbon atoms such as hexamethylene diisocyanate (HDI), octamethylene diisocyanate, decamethylene diisocyanate, and the like). Cycloalkyl diisocyanates contain cyclic alkyl group, typically having 4 to 16 carbon atoms. A cycloalkyl diisocyanate containing 6 to about 12 carbon atoms are cyclohexyl, cyclooctyl, cyclodecyl, and the like. A cycloalkyl diisocyanate may originate as a condensation product of acetone called 5-isocyanato-1-(isocyanatomethyl)-1,3,3-trimethyl-cyclohexane, commonly known as Isophorone diisocyanate (IPDI) and the isomers of isocyanato- [(isocyanatocyclohexyl)methyl]cyclohexane (H12MDI). H12MDI is derived from the hydrogenated form of the aryl diisocyanate methylene diphenyl diisocyanate (MDI).

[0152] In another embodiment, the at least one adhesion promoter is selected from an aryl diisocyanate. Aryl diisocyanates refers 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 bound to a common group such as a methylene or ethylene moiety). Aryl diisocyanates may contain 5 to 24 carbon atoms (e.g., 5 to 14 carbon atoms). Exemplary aryl diisocyanates contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, tolyl, xylyl, naphthyl, biphenyl, diphenylether, benzophenone, and the like. Aromatic di isocyanates include toluene diisocyanates, tetramethylxylene diisocyanate (TMXDI), and methylene diphenyl diisocyanate (MDI), which may comprise any mixture of its three isomers, 2.2’-MDI, 2,4’-MDI, and 4,4’-MDL

[0153] In another embodiment, the at least one adhesion promoter is selected from a polymer- containing isocyanate, such as, for example, diisocyanates. Polymer-containing isocyanates refers to a polymer-containing two or more terminal and / or pendant alkyl or aryl isocyanate groups. The polymer-containing isocyanates generally have a minimal solubility in the resin composition to provide improved mechanical properties. Polymer-containing isocyanates include, but are not limited to, PM200 (poly MDI), Lupranate® (poly MDI from BASF), 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.

[0154] In another embodiment, the at least one adhesion promoter is selected from a trimer of alkyl diisocyanates and aryl diisocyanates. In its simplest form, any combination of polyisocyanate compounds may be trimerized to form an isocyanurate ring containing isocyanate functional groups. Trimers of alkyl diisocyanate and aryl diisocyanates may also be referred to as isocyanurates of alkyl diisocyanate or aryl diisocyanate. Alkyl diisocyanate and aryl diisocyanate trimers include, but are not limited to, hexamethylene diisocyanate trimer (HDIt), isophorone diisocyanate trimer, toluene diisocyanate trimer, tetramethylxylene diisocyanate trimer, methylene diphenyl diisocyanate trimers, and the like. Adhesion promoters include, but are not limited to, 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; hexamethylenediisocyanatetrimer (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® Ml); liquid MDI (Mondur® ML); and liquid MDI (Mondur® MLQ). Adhesion promoters may be 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; hexamethylenediisocyanatetrimer (HDIt); hexamethylene diisocyanate (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® Ml); liquid MDI (Mondur® ML); liquid MDI (Mondur® MLQ).

[0155] In another embodiment, the at least one adhesion promoter is selected from compositions comprising 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 a metathesis active olefin (e.g., 2- hydroxyethyl bicyclo[2.2.1]hept-2-ene-5-carboxylate (HENB), 2-hydroxyethyl acrylate (HEA), oleyl alcohol, 9-decen-1-ol), where the compounds may be combined in various ratios to form a pre-reacted mixture, For example, the pre-reacted mixtures include liquid MDI (Mondur® MLQ) and 2-hydroxyethyl bicycle[2.2.1]hept-2-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 The pre-reacted mixture may be used as the adhesion promoter in the invention. Further examples of such adhesion promoters are described in U.S. Pat. No. 9,527,982, thecomplete disclosure of which is incorporated herein by reference. It is also possible to use a mixture of HENB-MDI and excess, unreacted MDI as the adhesion promoter in the invention. An additional adhesion promoter may be HENB. An additional adhesion promoter may be any combination of the above.

[0156] In some embodiments, such as when a polyolefin comprising maleic anhydride is used as the adhesion promoter, the adhesion promoter does not comprise any isocyanate moieties. Furthermore, in some embodiments, the adhesion promoter does not contain any compound containing at least two isocyanate groups. And in other embodiments, the resin composition (and / or the cyclic olefin composition and / or the ROMP composition) does not contain any compound containing at least two isocyanate groups.

[0157] In another embodiment, the at least one adhesion promoter is selected from functionalized silanes of the formula Fn-(A)n-Si(Y*)3, wherein Y* is selected from halide (e.g., 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 substituted heteroatom- containing hydrocarbylene; n is 0 or 1 ; and R is selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl, such as lower alkyl (e.g., methyl, ethyl, or isopropyl); and a peroxide selected from dialkyl and diaryl peroxides.

[0158] In other embodiments, the at least one adhesion promoter is selected from those disclosed in PCT / US2012 / 042850 and PCT / US2016 / 017449, the complete disclosure of which are incorporated herein by reference.

[0159] One or more of any of the aforementioned adhesion promoters, in any combination, may be used in the resin composition. For example, at least one acid-functionalized polyolefin may be used in combination with at least one polyoctenamer.

[0160] In some embodiments, the at least one adhesion promoter is a liquid.

[0161] In some embodiments, the at least one adhesion promoter has an acid content of between 0.1 to 100 mgKOH / g (e.g., 1 to 75 mgKOH / g, 5 to 50 mgKOH / g, 10 to 25 mgKOH / g, 15 to 20 mgKOH / g).

[0162] Any concentration of adhesion promoter is sufficient for the invention. In some embodiments, the at least one adhesion promoter is present in the resin composition in an amount ranging from 0.05 to 15 wt.% (e.g., 0.1 to 13 wt.%, 0.5 to 10 wt.%, 1 to 8 wt.%, 2 to 6 wt.%, 3 to 5 wt.%), based on the total weight of the resin composition. In another embodiment, the adhesion promoter comprises 0.1 to 10 wt.% (e.g., 0.5 to 9 wt.%, 1 to 8 wt.%, 2 to 7 wt.%, 3 to 6 wt.%, 4 to5 wt.%), based on the total weight of the resin composition, of the at least one acid-functionalized polyolefin, and 0.05 to 5 wt.% (e.g., 0.1 to 4 wt.%, 0.5 to 3 wt.%, 1 to 2 wt.%), based on the total weight of the resin composition, of at least one polyoctenamer.Antioxidant and Antiozonant

[0163] In some embodiments, the resin composition comprises at least one antioxidant and / or antiozonant including, without limitation, 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 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); miscellaneous 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); methylene bridged polyalkylphenol, 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 dicyclopentadiene, such as Wingstay L; tetrakis(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, e.g., Ethanox® 330 (Albemarle Corporation); 4,4'- methylenebis (2,6-di-tertiary-butylphenol), e.g., 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, phosphited phenols and bisphenols, such as Naugard® 492 (Chemtura Corporation), phosphite / phenolic antioxidant blends, 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, i.e., Irganox 1076, tetrakis(2,4-di-tert-butylphenyl)4,4'-biphenylylenediphosp honite, diphenylamine, and 4,4'- diemthoxydiphenylamine.

[0164] In some embodiments, the at least one antioxidant and / or antiozonant are present in the resin composition in an amount ranging from 0.001 to 10 wt.% (e.g., 0.01 to 9 wt.%, 0.1 to 8 wt.%, 0.5 to 7 wt.%, 1 to 6 wt.%, 2 to 5 wt.%, 3 to 4 wt.%), based on the total weight of the resin composition.Impact Modifier

[0165] In some embodiments, the resin composition comprises at least one impact modifier compound (also referred to herein as rubber toughener or elastomers) including, without limitation, butyl rubber, polyisobutylene, ethylene-propylene copolymer, styrene- ethylene / butylene-styrene copolymer, styrene-ethylene / propylene-styrene copolymer, ethylene- propylene-diene terpolymers, ethylene-vinyl acetate, and nitrile rubbers. Impact modifiers or elastomers may be polybutadiene Diene 55AC10 (Firestone), polybutadiene Diene 55AM5 (Firestone), EPDM Royalene 301 T, EPDM Buna T9650 (Bayer), styrene-ethylene / butylene- styrene copolymer Kraton G1651 H, Polysar Butyl 301 (Bayer), polybutadiene Taktene 710 (Bayer), styrene-ethylene / butylene-styrene Kraton G1726M, styrene-ethylene / butylene-styrene Kraton G1650, Ethylene-Octene Engage 8150 (DuPont-Dow), styrene-butadiene Kraton D1184, EPDM Nordel 1070 (DuPont-Dow), and polyisobutylene Vistanex MML-140 (Exxon). Various polar impact modifiers or elastomers can also be used.

[0166] In some embodiments, the at least one impact modifier compound is selected from a poly(styrene-ethylene-butylene-styrene), an ethylene-propylene copolymer, an ethylene- propylene diene terpolymer, and mixtures thereof. In another embodiment, the impact modifier compound is an ethylene-propylene copolymer. In another embodiment, the impact modifier compound is a poly(styrene-ethylene-butylene-styrene or poly(styrene-butadiene-styrene).

[0167] In some embodiments, the at least one impact modifier compound is present in the resin composition in an amount ranging from 0.01 to 30 wt.% (e.g., 0.1 to 25 wt.%, 1 to 20 wt.%, 5 to 15 wt.%, 7 to 12 wt.%), based on the total weight of the resin composition.Internal Mold Release

[0168] In some embodiments, the resin composition comprises at least one internal mold release.

[0169] In some embodiments, the at least one internal mold release is present in the resin composition in an amount ranging from 0.1 to 4 wt.% (e.g., 0.1 to 3 wt.%, 0.5 to 2 wt.%, 1 to 1.5 wt.%), based on the total weight of the resin composition.Gel Modifier

[0170] In some embodiments, the resin composition comprises at least one gel modifier - including, without limitation, an exogeneous inhibitor, a chelating diene, a hydroperoxide gel modifier, and mixtures thereof. For example, the gel modifier may be vinyl norbornene.

[0171] In some embodiments, exogenous inhibitors, or “gel modification additives,” for use in the resin composition are disclosed in U.S. Pat. No. 5,939,504, the complete disclosure of which are incorporated herein by reference. In some embodiments, hydroperoxide gel modifiers (e.g., cumene hydroperoxide) for use in the resin composition are disclosed in PCT / US2012 / 042850, the complete disclosure of which are incorporated herein by reference.

[0172] In some embodiments, the at least one gel modifier is present in the resin composition in an amount ranging from 0.01 to 5 wt.% (e.g., 0.1 to 4 wt.%, 0.5 to 3 wt.%, 1 to 2 wt.%), based on the total weight of the resin composition.Hydrocarbon Resin

[0173] In some embodiments, the resin composition comprises at least one hydrocarbon resin including, without limitation, pure monomer thermoplastic resin (PMR), C5 thermoplastic resin, C5 / C9 thermoplastic resin, C9 thermoplastic resin, terpene thermoplastic resin, indene- coumarone (IC) thermoplastic resin, dicyclopentadiene (DCPD) thermoplastic resin, hydrogenated or partially hydrogenated pure monomer (PMR) thermoplastic resin, hydrogenated or partially hydrogenated C5 thermoplastic resin, hydrogenated or partially hydrogenated C5 / C9 thermoplastic resin, hydrogenated or partially hydrogenated C9 thermoplastic resin, hydrogenated or partially hydrogenated dicyclopentadiene (DCPD) thermoplastic resin, terpene thermoplastic resin, modified indene-coumarone (IC) thermoplastic resin, and mixtures thereof.

[0174] In some embodiments, the at least one hydrocarbon resin used in the resin composition include, for example, the thermoplastic hydrocarbon resins disclosed in PCT / US2021 / 045673, the complete disclosure of which is incorporated herein by reference.

[0175] In some embodiments, the hydrocarbon resin has a number average molecular weight between 200 and 3000 g / mol.

[0176] In some embodiments, the hydrocarbon resin has a glass transition temperature in the range of 30 to 150 °C (e.g., 40 to 140 °C, 50 to 130 °C, 60 to 120 °C, 70 to 110 °C, 80 to 100 °C, 90 to 95 °C).

[0177] In some embodiments, the hydrocarbon resin is present in the resin composition in an amount ranging from 0.01 to 30 wt.% (e.g., 0.01 to 25 wt.%, 0.1 to 20 wt.%, 1 to 15 wt.%, 5 to 10 wt.%), based on the total weight of the resin composition.Plasticizer

[0178] In some embodiments, the resin composition comprises at least one plasticizer including, without limitation, any compound or substance that improves the flexibility, workability, or distensibility of a plastic or elastomer.

[0179] In some embodiments, the plasticizer compound is selected from a polybutene oil (PB), a polyalphaolefin oil, a hydrocarbon resin, and mixtures thereof. In some embodiments, the plasticizer compound is a PB oil.

[0180] PB oil is an oligomer or polymer made from butene monomers, such as 1 -butene and isobutene, or a mixture of butene monomers. PB oils possess the general repeat unit structure of (C4H8)n- PB oil made from isobutene monomer may be referred to as polyisobutene or polyisobutylene. PB oil made from 1 -butene may be referred to as poly(1 -butene). Commercial sources of polybutene oil that may be used in the invention include, for example, Indopol® H-15, H-25, H-50, H-100, H-300, H-1200, H-1500, H-1900, H-2100). Higher molecular weight polybutene oils may be semi solid at room temperature.

[0181] The polyalphaolefin oil may comprise oligomers of C5 to C18 olefins (e.g., C6 to C14, C8 to C12, C10); having a kinematic viscosity of 3 to 30 cSt or more at 100 °C. (e.g., 20 cSt or less, 4 cSt or more at 100 °C.); and a pour point of -10 °C. or less (e.g., -20 °C. or less, -30 °C. or less). For example, the polyalphaolefin oil may be Group IV hydrocarbon oil basestocks, polyisobutenes, wax isomerate lubricant oil basestocks, ethylene / butene copolymers, or mixtures thereof. For example, the polyalphaolefin oil may be Group IV hydrocarbon basestocks, such as those derived from linear alpha olefins. For example, polyalphaolefin oils derived from oligomerization of linear alpha olefins such as, but not limited to, C8, C10, C12, C14, C16, and C18. Typical molecular weights, as defined by number average molecular weight, Mn, defining polyalphaolefin oil are 250 g / mol to 10000 g / mol (e.g., 300 g / mol, 500 g / mol, 1000 g / mol, 2000 g / mol, 4000 g / mol, 6000 g / mol, 7000 g / mol, 9000 g / mol, 9500 g / mol). Commercial polyalphaolefin oils include SpectraSyn 100, SpectraSyn 40, SpectraSyn 10, SpectraSyn 8, SpectraSyn 6, SpectraSyn 5, SpectraSyn 4, SpectraSyn 2, and SpectraSyn Elite 300.

[0182] In some embodiments, the at least one plasticizer compound is present in the resin composition in an amount ranging from 1 to 40 wt.% (e.g., 5 to 45 wt.%, 10 to 40 wt.%, 25 to 35 wt.%), based on the total weight of the resin composition.ROMP COMPOSITION

[0183] The invention also relates to a ring-opening metathesis polymerization (ROMP) composition comprising, consisting essentially of, or consisting of the cyclic olefin compositiondisclosed herein and at least one catalyst composition comprising, consisting essentially of, or consisting of at least one metal carbene olefin metathesis catalyst.

[0184] The invention also relates to a ROMP composition comprising, consisting essentially of, or consisting of the resin composition disclosed herein and the at least one catalyst composition.CATALYST COMPOSITIONMetal Carbene Olefin Metathesis Catalyst

[0185] In some embodiments, the at least one catalyst composition used in the ROMP composition disclosed herein disclosed herein comprises, consists essentially of, or consists of at least one metal carbene olefin metathesis catalyst.

[0186] In some embodiments, the at least one metal carbene olefin metathesis catalyst is selected from a metathesis catalyst containing ruthenium, a metathesis catalyst containing osmium, a metathesis catalyst containing molybdenum, a metathesis catalyst containing tungsten, a metathesis catalyst containing titanium, a metathesis catalyst containing rhenium, a metathesis catalyst containing nickel, and mixtures thereof.

[0187] In some embodiments, the at least one metal carbene olefin metathesis catalyst is selected from a First Generation Grubbs-type olefin metathesis catalyst; a Second Generation Grubbs-type olefin metathesis catalyst; a First Generation Hoveyda-Grubbs-type olefin metathesis catalyst; a Second Generation Hoveyda-Grubbs-type olefin metathesis catalyst; a Schrock-type molybdenum olefin metathesis catalyst; a high -oxidation-state alkylidene complex of molybdenum; a high -oxidation -state alkylidene complex of tungsten; cyclic alkyl amino carbene (CAAC) ruthenium complexes; and mixtures thereof.

[0188] A metal carbene olefin metathesis catalyst that may be used in the catalyst composition disclosed herein is a Group 8 transition metal complex having the structure of formula (I)(I)wherein:M is a Group 8 transition metal;L1, L2, and L3are neutral electron donor ligands; n is 0 or 1 , such that L3may or may not be present; m is 0, 1 , or 2; k is 0 or 1 ;X1and X2are anionic ligands; andR1and R2are 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 R2can be taken together to form one or more cyclic groups, and further wherein any one or more of X1, X2, L1, L2, L3, R1, and R2may be attached to a support.

[0189] Additionally, in formula (I), one or both of R1and R2may have the structure -(W)n-U+V', wherein W is selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing 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 counterion; and n is 0 or 1 . Furthermore, R1and R2may be taken together to form an indenylidene moiety.

[0190] Catalysts may contain Ru or Os as the Group 8 transition metal, with Ru preferred.

[0191] Numerous embodiments of the catalysts useful in the reactions disclosed herein are described in more detail infra. For the sake of 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.

[0192] 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, and n, X1, X2, L1, L2, L3, R1, and R2are described as follows.

[0193] For the first group of catalysts, n is 0, and L1and L2are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, 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. Trisubstituted phosphines may be of the formula PRH1RH2RH3, where RH1, RH2, and RH3are each independently substituted or unsubstituted aryl or C1-C10 alkyl, particularly primary alkyl, secondary alkyl, or cycloalkyl. L1and L2may be independently selected from trimethylphosphine (PMe3), triethylphosphine (PEt3), tri-n- butylphosphine (PBu3), tri(ortho-tolyl)phosphine (P-o-tolyl3), tri-tert-butylphosphine (P-tert-Bu3), tricyclopentylphosphine (PCyclopentyl3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), trioctylphosphine (POct3), triisobutylphosphine, (P-i-Bu3), triphenylphosphine (PPh3),tri(pentafluorophenyl)phosphine (P(C6F5)3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph). Alternatively, L1and L2may be independently selected from phosphabicycloalkane (e.g., monosubstituted 9- phosphabicyclo-[3.3.1]nonane, or monosubstituted 9-phosphabicyclo[4.2.1 ]nonane] such as cyclohexylphoban, isopropylphoban, ethylphoban, methylphoban, butylphoban, pentylphoban and the like).

[0194] X1and X2are anionic ligands, and may be the same or different, or are linked together to form a cyclic group, typically although not necessarily a five- to eight-membered ring. X1and X2may be 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 alkylsulfonato, C5C24arylsulfonato, C1-C20 alkylsulfanyl, C5-C24 arylsulfanyl, C1-C20 alkylsulfinyl, NO3, -N=C=O, -N=C=S, or C5-C24 arylsulfinyl. Optionally, X1and X2may be substituted with one or more moieties selected from C1-C12 alkyl, C1-C12 alkoxy, C5-C24 aryl, and halide, which may, in turn, with the exception of halide, be further substituted with one or more groups selected from halide, Ci-C6alkyl, Ci-C6alkoxy, and phenyl. X1and X2may be halide, benzoate, C2-C6 acyl, C2-C6 alkoxycarbonyl, C1- C6 alkyl, phenoxy, Ci-Cs alkoxy, C1- C6 alkylsulfanyl, aryl, or C1- C6 alkylsulfonyl. X1and X2may each be halide, CF3CO2, CH3CO2, CFH2CO2, (CH3)3CO, (CF3)2(CH3)CO, (CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane-sulfonate. X1and X2may each be chloride.

[0195] R1and R2are independently selected from hydrogen, hydrocarbyl (e.g., C1-C20 alkyl, C2- C20 alkenyl, C2-C2o alkynyl, C5-C24aryl, C6-C24alkaryl, C6-C24 aralkyl, etc.), substituted hydrocarbyl (e.g., substituted C1-C2o alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, Ce-C24 alkaryl, Ce-C24 aralkyl, etc.), heteroatom-containing hydrocarbyl (e.g., heteroatom-containing C1-C20 alkyl, C2-C2Q alkenyl, C2-C2o alkynyl, C5-C24 aryl, C6-C24alkaryl, C6-C24aralkyl, etc.), and substituted heteroatom-containing hydrocarbyl (e.g., substituted heteroatom-containing C1C20 alkyl, C2-C20alkenyl, C2-C20alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24aralkyl, etc.), and functional groups. R1and R2may 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, such as 5, 6, 7, or 8 ring atoms.

[0196] In certain catalysts, R1is hydrogen and R2is selected from C1-C20 alkyl, C2-C2o alkenyl, and C5-C24aryl, such as Ci-C6alkyl, C2-C6alkenyl, and C5-C14 aryl. R2may be phenyl, vinyl, methyl, isopropyl, or t-butyl, optionally substituted with one or more moieties selected from C1- C6 alkyl, C1- C6 alkoxy, phenyl, and a functional group Fn as defined earlier herein. R2may be phenylor vinyl substituted with one or more moieties selected from methyl, ethyl, chloro, bromo, iodo, fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl. R2may be phenyl or -CH=C(CH3)2.

[0197] Any two or more (typically two, three, or four) of X1, X2, L1, L2, L3, R1, and R2can be taken together to form a cyclic group, including bidentate or multidentate ligands, as disclosed, for example, in U.S. Patent No. 5,312,940, the complete disclosure of which is incorporated herein by reference. When any of X1, X2, L1, L2, L3, R1, and R2are linked to form cyclic groups, those cyclic groups may contain 4 to 12, such as 4, 5, 6, 7 or 8 atoms, or may comprise two or three of such rings, which may be either 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.

[0198] A second group of catalysts, commonly referred to as Second Generation Grubbs-type catalysts, have the structure of formula (I), wherein L1is a carbene ligand having the structure of formula (II)such that the complex may have the structure of formula (III)wherein M, m, n, X1, X2, L2, L3, R1, and R2are 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 0 when X is O or S, q is necessarily 0 when Y is O or S, and k is 0 or 1 .However, when X is N or P, then p is 1 , and when Y is N or P, then q is 1 . Both X and Y may be N;Q1, Q2, Q3, and Q4are linkers, e.g., hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene, such as substituted and / or heteroatom-containing alkylene) or -(CO)-, and w, x, y, and z are independently 0 or 1 , meaning that each linker is optional, w, x, y, and z may all be 0. Further, two or more substituents on adjacent atoms within Q1, Q2, Q3, and Q4may be linked to form an additional cyclic group; andR3, R3A, R4, and R4Aare independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl. In addition, X and Y may be independently selected from carbon and one of the heteroatoms mentioned above, no more than one of X or Y may be carbon. Also, L2and L3may be taken together to form a single bindentate electron-donating heterocyclic ligand. Furthermore, R1and R2may be taken together to form an indenylidene moiety. Moreover, X1, X2, L2, L3, X and Y may be further coordinated to boron or to a carboxylate.

[0199] In addition, any two or more of X1, X2, L1, L2, L3, R1, R2, R3, R3A, R4, R4A, Q1, Q2, Q3, and Q4can 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 R4Amay be attached to a support. Any two or more of X1, X2, L1, L2, L3, R1, R2, R3, R3A, R4, and R4Acan also be taken to be -A-Fn, wherein “A” is a divalent hydrocarbon moiety selected from alkylene and arylalkylene, wherein the alkyl portion of the alkylene and arylalkylene groups can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the of arylalkylene can be substituted or unsubstituted, and wherein hetero atoms and / or functional groups may be present in either the aryl or the 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 R4Amay be attached to a support.

[0200] A particular class of carbene ligands having the structure of formula (II), where R3Aand R4Aare linked to form a cyclic group and at least one of X or Y is a nitrogen, or at least one of Q3or Q4is a heteroatom-containing hydrocarbylene or substituted heteroatom-containing hydrocarbylene, where at least one heteroatom is a nitrogen, are commonly referred to as N- heterocyclic carbene (NHC) ligands.

[0201] R3Aand R4Amay be linked to form a cyclic group so that the carbene ligand has the structure of formula (IV)(IV) wherein R3and R4are as defined for the second group of catalysts above, with at least one of R3and R4, such as both R3and R4, being alicyclic or aromatic of one to about five rings, and optionally containing one or more heteroatoms and / or substituents. Q is a linker, typically a hydrocarbylene linker, including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene linkers, wherein two or more substituents on adjacent atoms within Q may also be linked 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 often, although not necessarily, a two-atom linkage or a three-atom linkage.

[0202] Examples of N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands suitable as L1thus include, but are not limited to, the following where DIPP or DiPP is diisopropylphenyl and Mes is 2,4,6trimethylphenyl:

[0203] Additional examples of N-heterocyclic carbene (NHC) ligands and acyclic diaminocarbene ligands suitable as L1thus include, but are not limited to the following:wherein RW1, RW2, RW3, and RW4are independently hydrogen, unsubstituted hydrocarbyl, substituted hydrocarbyl, or heteroatom containing hydrocarbyl, and where one or both of RW3and RW4may be in independently selected from halogen, nitro, amido, carboxyl, alkoxy, aryloxy, sulfonyl, carbonyl, thio, or nitroso groups.

[0204] Additional examples of N-heterocyclic carbene (NHC) ligands suitable as L1are 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 complete disclosure of each of which is incorporated herein by reference.

[0205] Additionally, thermally activated N-Heterocyclic Carbene Precursors as disclosed in U.S. Pat. No. 6,838,489, the complete disclosure of which is incorporated herein by reference, may also be used with the invention.

[0206] When M is ruthenium, then, the complexes may have the structure of formula (V)wherein n, X1, X2, L2, L3, R1, and R2are as defined for the first group of catalysts, and k, R3, R4, and Q are as defined for the second group of catalysts.

[0207] More preferably, Q is a two-atom linkage having the structure -CR11R12-CR13R14- or - CR11=CR13-, such as -CR11R12-CR13R14-, wherein R11, R12, R13, and R14are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. Examples of functional groups here 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, C1C20 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 R14may be 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 R14may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., a C4-C12 alicyclic group or a C5or C6aryl group, which may itself be substituted, e.g., with linked or fused alicyclic or aromatic groups, or with other substituents. In one further aspect, any one or more of R11, R12, R13, and R14comprises one or more of the linkers. Additionally, R3and R4may 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, substituted C5-C24 aryl, C5-C24 heteroaryl, C6-C24aralkyl, C6-C24 alkaryl, or halide. Furthermore, X1and X2may be halogen.

[0208] When R3and R4are aromatic, they are typically although not necessarily composed of one or two aromatic rings, which may or may not be substituted, e.g., R3and R4may be phenyl, substituted phenyl, biphenyl, substituted biphenyl, or the like. R3and R4may be the same and are each unsubstituted phenyl or phenyl substituted 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 alkaryl, or halide. Anysubstituents present may be hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C5-C14 aryl, substituted C5-C14 aryl, or halide. As an example, R3and R4are mesityl (i.e. , Mes as defined herein).

[0209] In a third group of catalysts having the structure of formula (I), M, m, n, X1, X2, R1, and R2are as defined for the first group of catalysts, L1is a strongly coordinating neutral electron donor ligand such as any of those described for the first and second group of catalysts, and L2and L3are weakly coordinating neutral electron donor ligands in the form of optionally substituted heterocyclic groups. Again, n is 0 or 1 , such that L3may or may not be present. Generally, in the third group of catalysts, L2and L3are optionally substituted five- or six-membered monocyclic groups containing 1 to 4 (e.g., 1 to 3, 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 should not be substituted on a coordinating heteroatom, and any one cyclic moiety within a heterocyclic group will generally not be substituted with more than 3 substituents.

[0210] For the third group of catalysts, examples of L2and L3include, without limitation, heterocycles containing nitrogen, sulfur, oxygen, or a mixture thereof.

[0211] Examples of nitrogen-containing heterocycles appropriate for L2and L3include pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1 ,3,5-triazine, 1 ,2,4triazine, 1 ,2,3- triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1 ,2,3triazole, 1 ,2,4-triazole, indole, 3H-indole, 1 H-isoindole, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinnoline, quinazoline, naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine, purine, benzimidazole, bisimidazole, phenazine, acridine, and carbazole. Additionally, the nitrogen-containing heterocycles may be optionally substituted on a non-coordinating heteroatom with a non- hydrogen substitutent.

[0212] Examples of sulfur-containing heterocycles appropriate for L2and L3include thiophene, 1 ,2-dithiole, 1 ,3-dithiole, thiepin, benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene, 2H-thiopyran, 4H-thiopyran, and thioanthrene.

[0213] Examples of oxygen -containing heterocycles appropriate for L2and L3include 2Hpyran, 4H-pyran, 2-pyrone, 4-pyrone, 1 ,2-dioxin, 1 ,3-dioxin, oxepin, furan, 2H1 benzopyran, coumarin, coumarone, chromene, chroman-4-one, isochromen-1-one, isochromen-3-one, xanthene, tetrahydrofuran, 1,4-dioxan, and dibenzofuran.

[0214] Examples of mixed heterocycles appropriate for L2and L3include 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-oxathiole, 1 ,3-oxathiole, 4H-1 ,2-oxazine, 2H1 ,3-oxazine, 1 ,4-oxazine, 1 ,2,5-oxathiazine, o-isooxazine, phenoxazine, phenothiazine, pyrano[3,4- b]pyrrole, indoxazine, benzoxazole, anthranil, and morpholine.

[0215] L2and L3ligands may be aromatic nitrogen-containing and oxygen-containing heterocycles, such as monocyclic N-heteroaryl ligands that are optionally substituted with 1 to 3 (e.g., 1 or 2) substituents. Specific examples of L2and L3ligands are pyridine and substituted pyridines, such as 3bromopyridine, 4-bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6dibromopyridine, 3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine, 2,4,6trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine, 3,5-diiodopyridine, 3,5-dibromo-4- methylpyridine, 3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine,3,5dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine, 2,4,6-trimethylpyridine, 2,4,6triisopropylpyridine, 4-(fert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine, 3,5dichloro-4-phenylpyridine, and the like.

[0216] In general, any substituents present on L2and / or L3are selected from halo, C1-C20 alkyl, substituted C1-C2o alkyl, C1-C2o heteroalkyl, substituted C1-C2o heteroalkyl, C5-C24aryl, substituted C5-C24aryl, C5-C24heteroaryl, substituted C5-C24heteroaryl, C6-C24alkaryl, substituted C6-C24alkaryl, C6-C24heteroalkaryl, substituted C6-C24heteroalkaryl, C6-C24aralkyl, substituted C6-C24aralkyl, C6-C24heteroaralkyl, substituted C6-C24heteroaralkyl, and functional groups, with suitable functional groups including, without limitation, C1-C20 alkoxy, C6-C24aryloxy, C2-C2o alkylcarbonyl, C6-C24arylcarbonyl, C2-C20alkylcarbonyloxy, C6-C24arylcarbonyloxy, C2-C20alkoxycarbonyl, C6- C24aryloxycarbonyl, halocarbonyl, C2-C20alkylcarbonato, C6-C24arylcarbonato, carboxy, carboxylate, carbamoyl, mono-(C1-C2o alkyl)-substituted carbamoyl, di-(C1-C20alkyl)-substituted carbamoyl, di-N-(C1-C2o alkyl), N-(C6-C24aryl)-substituted carbamoyl, mono-(C6-C24aryl)- substituted carbamoyl, di-(C6-C24aryl)-substituted carbamoyl, thiocarbamoyl, mono-(C1-C2o alkyl)-substituted thiocarbamoyl, di(C1C20 alkyl)-substituted thiocarbamoyl, di-N-(C1-C2o alkyl)-N- (C6-C24aryl)-substituted thiocarbamoyl, mono-(C6-C24aryl)-substituted thiocarbamoyl, di-(C6-C24aryl)-substituted thiocarbamoyl, carbamide, formyl, thioformyl, amino, mono-(C1-C2o alkyl)- substituted amino, di-(C1-C2o alkyl)-substituted amino, mono-(C5-C24aryl)-substituted amino, di- (C5-C24 aryl)-substituted amino, di-N-(C1-C2o alkyl), N-(C6-C24aryl)-substituted amino, C2-C20 alkylamido, C6C24arylamido, imino, C1-C2o alkylimino, C6-C24arylimino, nitro, and nitroso. In addition, two adjacent substituents may 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.

[0217] Substituents on L2and L3include, without limitation, hate, C1-C12 alkyl, substituted C1- C12 alkyl, C1-C12 heteroalkyl, substituted C1-C12 heteroalkyl, C5-C14aryl, substituted C5-C14aryl,C5-C14 heteroaryl, substituted C5-C14 heteroaryl, Ce-Cie alkaryl, substituted C6-C16 alkaryl, Ce-Cie heteroalkaryl, substituted C6-C16 heteroalkaryl, 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, C6-C14 arylcarbonyloxy, C2-C12 alkoxycarbonyl, Ce- C14 aryloxycarbonyl, halocarbonyl, formyl, amino, mono-(Ci-Ci2 alkyl)-substituted amino, di-(Ci- C12 alkyl)-substituted amino, mono-(C5-C14 aryl)-substituted amino, di-(Cs-Ci4 aryl)-substituted amino, and nitro.

[0218] In another embodiment, the substituents are halo, C1- C6 alkyl, C1- C6 haloalkyl, C1- C6 alkoxy, phenyl, substituted phenyl, formyl, N,N-di(C1- C6 alkyl)amino, nitro, and nitrogen heterocycles as described above (including, for example, pyrrolidine, piperidine, piperazine, pyrazine, pyrimidine, pyridine, pyridazine, etc.).

[0219] L2and L3may also be taken together to form a bidentate or multidentate ligand containing two or more, generally two, coordinating heteroatoms such as N, O, S, or P, such as diimine ligands of the Brookhart type. One representative bidentate ligand has the structure of formula (VI)(VI)wherein R15, R16, R17, and R18hydrocarbyl (e.g., C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5- C24 aryl, C6-C24 alkaryl, or C6-C24 aralkyl), substituted hydrocarbyl (e.g., substituted C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, or C6-C24 aralkyl), heteroatom- containing hydrocarbyl (e.g., C1-C20 heteroalkyl, C5-C24 heteroaryl, heteroatom-containing C6-C24 aralkyl, or heteroatom-containing C6-C24 alkaryl), or substituted heteroatom-containing hydrocarbyl (e.g., substituted C1-C20 heteroalkyl, C5-C24 heteroaryl, heteroatom-containing C6-C24 aralkyl, or heteroatom-containing C6-C24 alkaryl), or (1 ) R15and R16, (2) R17and R18, (3) R16and R17, or (4) both R15and R16, and R17and R18, may be taken together to form a ring, i.e., an N- heterocycle. Cyclic groups in such a case may be five-and six-membered rings, typically aromatic rings.

[0220] In a fourth group of catalysts that have 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, pinacolate dianions, -P(CH32(CF)2P(CH3)2-, and -OC(CH3)2(CH3)2CO-. Bidentate ligands may be 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 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 optionally substituted with C2-C20 alkenyl, C2C20 alkynyl, C1-C20 alkyl, C5-C20 aryl, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, C5C20 aryloxy, C2-C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl, or C1-C20 alkylsulfinyl, each of which may be further substituted with CI-CB alkyl, halide, C1- C6 alkoxy or with a phenyl group optionally substituted with halide, C-i-Ce alkyl, or C1- C6 alkoxy. In compounds of this type, X, L1, and L2may be 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 halide, Ci-C6alkyl or CiC6alkoxy. X, L1and L2may 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.

[0221] In another embodiment, the metal carbene olefin metathesis catalyst is selected from complexes wherein Y is coordinated to the metals, and are commonly called “Grubbs-Hoveyda” catalysts. Grubbs-Hoveyda metathesis-active metal carbene complexes may be described by the formula (VII)wherein:M is a Group 8 transition metal, particularly Ru or Os, or, more particularly, Ru;X1, X2, and L1are as previously defined herein for the first and second groups of catalysts;Y is a heteroatom selected from N, O, S, and P; for example, Y is O or N;Rs, R6, R7, and R8are each, independently, selected from 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, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, wherein “A” and Fn have been defined above; and any combination of Y, Z, R5, R6, R7, and R8can be linked to form one or more cyclic groups; n is 0, 1 , or 2, such that n is 1 for the divalent heteroatoms O or S, and n is 2 for the trivalent heteroatoms N or P; andZ is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl where the functional group(s) may independently be one or more or 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 RBmay be linked to a support. Additionally, R5, RB, R7, R8, and Z may independently be thioisocyanate, cyanato, or thiocyanato.

[0222] Examples of complexes comprising Grubbs-Hoveyda ligands suitable in the invention include:wherein L1, X1, X2, and M are as described for any of the other groups of catalysts. Suitable chelating carbenes and carbene precursors are further described by Pederson et al. (U.S. Pat.Nos. 7,026,495 and 6,620,955, the complete disclosure of both of which is incorporated herein by reference) and Hoveyda et al. (U.S. Pat. No. 6,921 ,735 and WO0214376, the complete disclosure of both of which is incorporated herein by reference).

[0223] Other useful complexes include structures wherein L2and R2according to formulae (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 trialkoxysilyl functionalized moiety include, but are not limited to, the following:

[0224] Further examples of complexes having linked 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 L2ligand, a neutral NHC ligand and an L3ligand, an anionic ligand and an alkylidine ligand, and any combination thereof. While the possible structures are too numerous to list herein, some suitable structures based on formula (III) include:

[0225] In addition to the catalysts that have the structure of formula (I), as described above, other transition metal carbene 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 the general formula (IX);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 the 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 the general formula (XII)(IX)(X)(XI)(XII) wherein:M, X1, X2, L1, L2, L3, R1, and R2are as defined for any of the previously defined four groups of catalysts; r and s are independently 0 or 1 ; t is an integer in the range of 0 to 5; k is an integer in the range of 0 to 1 ;Y is any non-coordinating anion (e.g., a halide ion, BFZT, etc.);Z1and Z2are independently selected 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 linkage;Z3is any cationic moiety such as -P(R2)3+or -N(R2)a+; and any two or more of X1, X2, L1, L2, L3, Z1, Z2, Z3, R1, and R2may be taken together to form a cyclic group, e.g., a multidentate ligand, and wherein any one or more of X1, X2, L1, L2, L3, Z1, Z2, Z3, R1, and R2may be attached to a support.

[0226] Additionally, another group of metal carbene olefin metathesis catalysts that may be used in the catalyst composition disclosed herein, is a Group 8 transition metal complex having the structure of formula (XIII):(XIII)wherein:M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly, ruthenium;X1, X2, L1and L2are as defined for the first and second groups of catalysts defined above; andRG1, RG2, RG3, RG4, RG5, and RG6are each independently selected from 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, cyanato, thiocyanato, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen-substituted 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 can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene can besubstituted or unsubstituted, and wherein hetero atoms and / or functional groups may be present in either the aryl orthe alkyl portions of the alkylene and arylalkylene groups, and Fn is a functional group, or any one or more of the RG1, RG2, RG3, RG4, RG5, and RG6may be linked together to form a cyclic group, or any one or more of the RG1, RG2, RG3, RG4, RG5, and RG6may be attached to a support.

[0227] Additionally, one Group 8 transition metal complex of formula XIII is a Group 8 transition metal complex of formula (XIV):(XIV)wherein:M, X1, X2, L1, L2, are as defined above for Group 8 transition metal complex of formula XIII; andRG7, RG8, RG9, RG1°, RG11, RG12, RG13, RG14, RG15, and RG16are as defined above for RG1, RG2, RG3, RG4, RG5, and RG6for Group 8 transition metal complex of formula XIII or any one or more of the RG7, RG8, RG9, RG1°, RG11, RG12, RG13, RG14, RG15, and RG16may be linked together to form a cyclic group, or any one or more of the RG7, RGB, RG9, RG1°, RG11, RG1Z, RG13, RG14, RG15, and RG16may be attached to a support.

[0228] Additionally, another Group 8 transition metal complex of formula XIII is a Group 8 transition metal complex of formula (XV):(XV)wherein M, X1, X2, L1, and L2are as defined above for Group 8 transition metal comp lex of formulaXIII.

[0229] Additionally, another group of olefin metathesis catalysts that may be used in the catalyst composition disclosed herein, is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (XVI):(XVI)wherein:M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly, ruthenium;X1and L1are as defined for the first and second groups of catalysts defined above;Z is selected from oxygen, sulfur, selenium, NRJ11, PRJ11, AsRJ11, and SbRJ11; andRJ1, RJ2, RJ3, RJ4, RJ5, RJ6, RJ7, RJ8, RJ9, RJ1°, and RJ11are each independently selected from 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, cyanato, thiocyanato, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen-substituted amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, wherein “A” is a divalenthydrocarbon moiety selected from alkylene and arylalkylene, wherein the alkyl portion of the alkylene and arylalkylene groups can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene can be substituted or unsubstituted, and wherein hetero atoms and / or functional groups may be present in either the aryl or the alkyl portions of the alkylene and arylalkylene groups, and Fn is a functional group, or any one or more of the RJ1, RJ2, RJ3, RJ4, RJ5, RJ6, RJ7, RJB, RJ9, RJ1°, and RJ11may be linked together to form a cyclic group, or any one or more of the RJ1, RJ2, RJ3, RJ4, RJ5, RJ6, RJ7,attached to a support.

[0230] Additionally, one Group 8 transition metal complex of formula (XVI) is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (XVII):wherein:M, X1, L1, Z, RJ7, RJ8, RJ9, RJ1°, and RJ11are as defined above for Group 8 transition metal complex of formula XVI; andRJ12, RJ13, RJ14, RJ15, RJ16, RJ17, RJ18, RJ19, RJ2°, and RJ21are as defined above for RJ1, RJ2, RJ3, RJ4, RJ5, and RJ6for Group 8 transition metal complex of formula XVI, or any one or more of the RJ7, RJ8, RJ9, RJ1°, RJ11, RJ12, RJ13, RJ14, RJ15, RJ16, RJ17, RJ1B, RJ19, RJ2°, and RJ21may be linked together to form a cyclic group, or any one or more of the RJ7, RJB, RJ9, RJ1°, RJ11, RJ12, RJ13, RJ14, RJ15, RJ1B, RJ17, RJ18, RJ19, RJ2°, and RJ21may be attached to a support.

[0231] Additionally, another Group 8 transition metal complex of formula (XVI) is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (XVIII):(XVIII)wherein M, X1, L1, Z, RJ7, RJ8, RJ9, RJ1°, and RJ11are as defined above for Group 8 transition metal complex of formula (XVI).

[0232] Additionally, another group of olefin metathesis catalysts that may be used in the catalyst composition disclosed herein, is a Group 8 transition metal complex comprising a Schiff base ligand having the structure of formula (XIX):(XIX)wherein:M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly, ruthenium;X1, L1, R1, and R2are as defined for the first and second groups of catalysts defined above;Z is selected from oxygen, sulfur, selenium, NRK5, PRK5, AsRK5, and SbRK5; m is 0, 1 , or 2; andRK1, RK2, RK3, RK4, and RK5are each independently selected from 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, cyanato, thiocyanato, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, amide, halogen-substituted 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 can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the arylalkylene can be substituted or unsubstituted, and wherein hetero atoms and / or functional groups may be present in either the aryl or the alkyl portions of the alkylene and arylalkylene groups, and Fn is a functional group, or any one or more of the RK1, RK2, RK3, RK4, and RK5may be linked together to form a cyclic group, or any one or more of the RK1, R142, RK3, RK4, and RK5may be attached to a support.

[0233] In addition, catalysts of formulas (XVI) to (XIX) may be optionally contacted with an activating compound, where at least partial cleavage of a bond between the Group 8 transition metal and at least one Schiff base ligand occurs, wherein the activating compound is either a metal or silicon compound selected from copper (I) halides; zinc compounds of the formula Zn(RY1)2, wherein RY1is halogen, C1-C7 alkyl or aryl; tin compounds represented by the formula SnRY2RY3RY4RY5wherein each of R^, RY3, RY4and RY5is independently selected from halogen, C1-C20 alkyl, C3-C10 cycloalkyl, aryl, benzyl and C2-C7 alkenyl; and silicon compounds represented by the formula SiRY6RY7RY8RY9wherein each of RY6, RY7, RYB, RY9is independently selected from hydrogen, halogen, C1-C20 alkyl, halo, C1-C7 alkyl, aryl, heteroaryl, and vinyl. In addition, catalysts of formulas (XVI) to (XIX) may be optionally contacted with an activating compound where at least partial cleavage of a bond between the Group 8 transition metal and at least one Schiff base 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, HOCIO, HOCIO2 and HOIO3. In addition, catalysts of formulas (XVI) to (XIX) may be optionally contacted with an activating compound where at least partial cleavage of a bond between the Group 8 transition metal and at least one Schiff base 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, napthalenesulfonic 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, dihydroxybenzoic acid, dihydroxymalic acid, dihydroxytartaric acid, dinicotinic acid, diphenylacetic acid, fluorobenzoic acid, formic acid, furan carboxylic acid, furoic acid, glycolic acid, hippuric acid, iodoacetic acid, iodobenzoic acid,lactic acid, lutidinic acid, mandelic acid, a-naphtoic acid, nitrobenzoic acid, nitrophenylacetic acid, o-phenylbenzoic acid, thioacetic acid, thiophene-carboxylic acid, trichloroacetic acid, and trihydroxybenzoic acid; and other acidic substances such as but not limited to picric acid and uric acid.

[0234] In addition, other examples of catalysts that may be used in the catalyst composition disclosed herein are located in the following disclosures, the complete disclosure of 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. App. Nos. 12 / 303,615; 10 / 590,380; 11 / 465,651 (Publication No.: US 2007 / 0043188); and 11 / 465,651 (Publication No.: US 2008 / 0293905 Corrected Publication); and European Pat. Nos. EP1757613B1 and EP1577282B1.

[0235] Non-limiting examples of catalysts that may be used to prepare supported 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:

[0236] In the foregoing molecular structures and formulae, Ph represents phenyl, Cy represents cyclohexyl, Cp represents cyclopentyl, Me represents methyl, Bu represents n-butyl, t-Bu represents fert-butyl, / -Pr represents isopropyl, py represents pyridine (coordinated through the N atom), Mes represents mesityl (i.e., 2,4,6-trimethylphenyl), DiPP and DIPP represents 2,6- diisopropylphenyl, and MiPP respresents 2-isopropylphenyl.

[0237] Further examples of catalysts useful to prepare supported 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-2butenylidene) bis(tricyclohexylphosphine) (C801 ); ruthenium (II) dichloro(phenylmethylene) bis(tricyclohexylphosphine) (C823); ruthenium (II) (1 ,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene) dichloro (phenylmethylene) (triphenylphosphine) (C830); ruthenium (II) dichloro (phenylvinylidene) bis(tricyclohexylphosphine) (C835); ruthenium (II) dichloro (tricyclohexylphosphine) (o-isopropoxyphenylmethylene) (C601); ruthenium (II) (1 ,3-bis-(2, 4,6- trimethylphenyl)-2-imidazolidinylidene) dichloro (phenylmethylene) bis(3bromopyridine) (C884); [1 ,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(o- isopropoxyphenylmethylene)ruthenium(ll) (C627); [1 ,3-bis-(2,4,6-trimethylphenyl)-2- imidazolidinylidene] dichloro (benzylidene) (triphenylphosphine) ruthenium(ll) (C831 ); [1 ,3-bis- (2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro(benzylidene)(methyldiphenylphosphine)ruthenium(ll) (C769);[1 ,3-bis-(2,4,6-trimethylphenyl)-2- imidazolidinylidene]dichloro(benzylidene)(tricyclohexylphosphine)ruthenium(ll) (C848);[1 ,3-bis- (2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro(benzylidene) (diethylphenylphosphine) ruthenium(ll) (C735);[1 ,3-bis-(2,4,6-trimethylphenyl)-2- imidazolidinylidene]dichloro(benzylidene)(tri-n-butylphosphine)ruthenium(ll) (C771 );[1 ,3-bis- (2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2- butenylidene)(triphenylphosphine)ruthenium(ll) (C809); [1 ,3-bis-(2,4,6-trimethylphenyl)-2- imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(methyldiphenylphosphine)ruthenium(ll) (C747);[1 ,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene) (tricyclohexylphosphine) ruthenium(ll) (C827);[1 ,3-bis-(2,4,6-trimethylphenyl)-2- imidazolidinylidene] dichloro(3-methyl-2-butenylidene)(diethylphenylphosphine)ruthenium(ll) (C713); [1 ,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro (3-methyl-2-butenylidene) (tri-n-butylphosphine)ruthenium(ll) (C749); [1 ,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro(phenylindenylidene)(triphenylphosphine)rutheniurn(ll) (C931 ); [1 ,3-bis-(2,4,6- trimethylphenyl)-2-imidazolidinylidene] dichloro (phenylindenylidene) (methylphenylphosphine) ruthenium(ll) (C869); [1 ,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene] dichloro (phenylindenylidene) (tricyclohexylphosphine) ruthenium(ll) (C949); [1 ,3-bis-(2,4,6- trimethylphenyl)-2- imidazolidinylidene]dichloro(phenylindenylidene)(diethylphenylphosphine)ruthenium(ll) (C835); and [1 ,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(phenylindenylidene)(tri-n- butylphosphine)ruthenium(ll) (C871 ).

[0238] Still further catalysts useful in ROMP reactions, and / or in other metathesis reactions, such as ring-closing metathesis, cross metathesis, ring-opening cross metathesis, self- metathesis, ethenolysis, alkenolysis, acyclic diene metathesis polymerization, and combinations thereof, include the following structures:

[0239] 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, U.S. Pat. No. 5,312,940, and U.S. Pat. No. 5,342,909, the complete disclosure of each of which are incorporated herein by reference. Also see U.S. Pat. Pub. No. 2003 / 0055262 to Grubbs et al., WO 02 / 079208, and U.S. Pat. No. 6,613,910 to Grubbs et al., the complete disclosure of each of which are incorporated herein by reference. Synthetic methods are described in WO 03 / 11455A1 to Grubbs et al., the complete disclosure of which is incorporated herein by reference.

[0240] Metal carbene olefin metathesis catalysts may be 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 “Grubbs-Hoveyda” catalysts.

[0241] Metal carbene olefin metathesis catalysts may have the structure of formula (I)(I)wherein:M is a Group 8 transition metal;L1, L2, and L3are neutral electron donor ligands; n is 0 or 1 ; m is 0, 1 , or 2; k is 0 or 1 ;X1and X2are anionic ligands;R1and R2are 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 R2can be taken together to form one or more cyclic groups, and further wherein any one or more of X1, X2, L1, L2, L3, R1, and R2may be attached to a support; and formula (VII)(VII) wherein:M is a Group 8 transition metal;L1is a neutral electron donor ligand;X1and X2are anionic ligands;Y is a heteroatom selected from O or N;R5, R6, R7, and R8are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom -containing hydrocarbyl, and functional groups; n is 0,1 , or 2; andZ 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 R8can be linked to form one or more cyclic groups, and further wherein any combination of X1, X2, L1, Y, Z, R5,R6, R7, and R8may be attached to a support.

[0242] Metal carbene olefin metathesis catalysts may have the structure of formula (I)(I) wherein:M is ruthenium; n is 0; m is 0; k is 1 ;L1and L2are trisubstituted phosphines independently selected from tri-n-butylphosphine (Pn-Bua), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N- heterocyclic carbene selected from 1 ,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1 ,3- bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1 ,3-bis(2,6-di-isopropylphenyl)-2- imidazolidinylidene, and 1 ,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L2is a trisubstituted phosphine selected from tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPha), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from 1 ,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene, 1 ,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1 ,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene;X1and X2are chloride; andR1is hydrogen and R2is phenyl or -CH=C(CH3)2or thienyl; or R1and R2are taken together to form 3-phenyl-1 H-indene; and formula (VII)(VII)wherein:M is ruthenium;L1is a trisubstituted phosphine selected from tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCpa), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Prs), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1 ,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1 ,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1 ,3-bis(2,6-di- isopropylphenyl)imidazol-2-ylidene;X1and X2are chloride;Y is oxygen;R3, R6, R7, and R8are each hydrogen; n is 1 ; andZ is isopropyl.

[0243] An example of metal carbene olefin metathesis catalysts having the structure of formula(I)wherein:M is ruthenium; n is 0; m is 0; k is 1 ;L1and L2are trisubstituted phosphines independently selected from tri-n-butylphosphine (Pn-Bua), tricyclopentylphosphine (PCpa), tricyclohexylphosphine (PCya), triisopropylphosphine (P-i-Pra), triphenylphosphine (PPha), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N- heterocyclic carbene selected from 1 ,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1 ,3- bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1 ,3-bis(2,6-di-isopropylphenyl)-2- imidazolidinylidene, and 1 ,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L2is a trisubstituted phosphine selected from tri-n-butylphosphine (Pn-Bua), tricyclopentylphosphine (PCpa), tricyclohexylphosphine (PCya), triisopropylphosphine (P-i-Pra), triphenylphosphine (PPha), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from 1 ,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene, 1 ,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1 ,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene;X1and X2are chloride; andR1is hydrogen and R2is phenyl or -CH=C(CH3)2or thienyl; or R1and R2are taken together to form an indenylidene moiety.

[0244] An example of metal carbene olefin metathesis catalysts having the structure of formula (VII)wherein:M is ruthenium;L1is a trisubstituted phosphine selected from tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N-heterocyclic carbene selected from 1 ,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2- ylidene, 1 ,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1 ,3-bis(2,6-di- isopropylphenyl)imidazol-2-ylidene;X1and X2are chloride;Y is oxygen;R5, RB, R7, and R8are each hydrogen; n is 1 ; andZ is isopropyl.

[0245] An example of a metal carbene olefin metathesis catalyst having the structure of formula (XV):(XV)wherein:M is ruthenium;X1and X2are chloride; andL1and L2are trisubstituted phosphines independently selected from tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1is an N- heterocyclic carbene selected from 1 ,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1 ,3- bis(2,4,6-trimethylphenyl)imidazol-2-ylidene, 1 ,3-bis(2,6-di-isopropylphenyl)-2- imidazolidinylidene, and 1 ,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene and L2is a trisubstituted phosphine selected from tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); or L1and L2are N-heterocyclic carbenes independently selected from 1 ,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene, 1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene, 1 ,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, and 1 ,3-bis(2,6-di-isopropylphenyl)imidazol-2-ylidene.

[0246] Metal carbene olefin metathesis catalysts include, for example, Umicore’s Ruthenium Metathesis Grubbs Catalysts® 1st Generation M101 (dichloro(3-phenyl-1 H-inden-1- ylidene)bis(tricyclohexylphosphine)ruthenium(ll)) M102(dichloro(benzylidene)bis(tricyclohexylphosphine)ruthenium(ll)), M103 (dichloro(3-methyl-2- butenylidene)bis(tricyclohexylphosphine)ruthenium(ll)), M104 (dichloro(2- thienylmethylene)bis(tricyclohexylphosphine)ruthenium(ll)), and M110(dichlorobis(isobutylphobane)(3-phenyl-1 H-indenylidene)ruthenium(ll)); Umicore’s Ruthenium Metathesis Grubbs Catalysts® 2nd Generation M200 ([1 ,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene]dichloro(3-phenyl-1 H-inden-1-ylidene)(triphenylphosphine)ruthenium(ll)),M201 ([1 ,3-bis(2,6-diisopropylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1 H-inden-1 - ylidene)(triphenylphosphine) ruthenium(ll)), M202 ([1 ,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene]dichloro(3-phenyl-1 H-inden-1 -ylidene)(tricyclohexylphosphine)ruthenium(l I)), M203 ([1 ,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene]dichloro(3-phenyl-1 H-inden-1 - ylidene)(tricyclohexylphosphine)ruthenium(ll)), M204 ([1 ,3-Bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene]dichloro(benzylidene)(tricyclohexylphosphine)ruthenium(ll)), M206 ([1 ,3- bis(2,6-diisopropylphenyl)-2-imidazolidinylidene]- dichloro(benzylidene)(tricyclohexylphosphine)ruthenium(ll)), M207 ([1 ,3-Bis(2,4,6- trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2- butenylidene)(tricyclohexylphosphine)ruthenium(ll)), M208 ([4,5-Dimethyl-1 ,3-bis(2,4,6- trimethylphenyl)imidazol-2-ylidene]-dichloro(2- thienylmethylene)(tricyclohexylphosphine)ruthenium(ll)), M209 ([1 ,3-Bis(2,4,6- trimethylphenyl)imidazol-2-ylidene]dichloro(2- thienylmethylene)(tricyclohexylphosphine)ruthenium(ll)), and M220 (cis-[1 ,3-bis(2,4,6- trimethylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1 H-inden-1 - ylidene)(triisopropylphosphite)ruthenium(ll)); Umicore’s Ruthenium Metathesis Grubbs Catalysts® 2nd Generation (N ligands) M310 ([1 ,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene]dichloro(3-phenyl-1 H-inden-1 -ylidene)(pyridyl)ruthenium(l I)) and M350 (1 ,3- bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-[2-[[(2-methylphenyl)imino]methyl]-phenolyl]-[3- phenyl-1 H-inden-1 -ylidene](chloro)ruthenium(l I)); Umicore’s Ruthenium Metathesis Hoveyda- Grubbs Catalysts® 1st / 2nd Generation M700 (dichloro(2- isopropoxybenzylidene)(tricyclohexylphosphine)ruthenium(ll)), M710 ([1 ,3-bis(2,4,6- trimethylphenyl)-2-imidazolidinylidene]dichloro[(2-isopropoxy)(5- trifluoroacetamido)benzylidene]ruthenium(ll)), M711 ([1 ,3-bis(2,6-diisopropylphenyl)-2- imidazolidinylidene]dichloro[(2-isopropoxy)(5-trifluoroacetamido)benzylidene]ruthenium(ll)), M720 ([1 ,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(2- isopropoxybenzylidene)ruthenium(ll)), M721 ([1,3-bis-(2-tolyl)-2-imidazolidinylidene]dichloro(2- isopropoxybenzylidene)ruthenium(ll)), M722 ([1 ,3-bis-(2,6-diisopropylphenyl)-2- imidazolidinylidene]dichloro(2-isopropoxybenzylidene)ruthenium(ll)), M730 ([1 ,3-bis(2,4,6- trimethylphenyl)-2-imidazolidinylidene]dichloro[5-(isobutoxycarbonylamido)-2- isopropoxybenzylidene]ruthenium(ll)), and M731 ([1,3-bis(2,6-diisopropylphenyl)-2- imidazolidinylidene]dichloro[5-(isobutoxycarbonylamido)-2- isopropoxybenzylidene]ruthenium(ll)); Umicore’s Bis-NHC Ruthenium Metathesis Grubbs Catalysts® 2nd Generation M800 (bis[1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-phenyl-1 H-inden-1 -ylidene)ruthenium(ll)); and Umicore’s Z- Selective Ruthenium Metathesis Hoveyda-Grubbs Catalysts® 2nd Generation M2001 (1-[Rel- (2R,5R,7R)-adamantane-2,1 -diyl][3-(2,4,6-trimethylphenyl)]2-imidazolidinylylidene](nitrato- O,O')(o-isopropoxybenzylidene)ruthenium(ll)).

[0247] The metal carbene olefin metathesis catalyst that may also be used in the invention include those, for example, disclosed in PCT / US2021 / 045673, the complete disclosure of which is incorporated herein by reference.

[0248] Suitable supports for any of the catalysts described herein may be of synthetic, semi- synthetic, or naturally occurring materials, which may be organic or inorganic, e.g., polymeric, ceramic, or metallic. Attachment to the support will generally, although not necessarily, be covalent, and the covalent linkage may be direct or indirect. Indirect covalent linkages 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 on the metal complexes coupled with supports containing cationic groups, or combinations of one or more cationic groups on the metal complexes coupled with supports containing anionic groups.

[0249] When utilized, 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, cellulosic polymers amylose, amylosic polymers, or a combination thereof. The support may comprise silica, a silicate, or a combination thereof.

[0250] It is also possible to use a support that has been treated to include functional groups, inert moieties, and / or excess ligands. Any of the functional groups described herein are suitable for incorporation on the support, and may be generally accomplished through techniques known in the art. Inert moieties may also be incorporated on the support to generally reduce the available attachment sites on the support, e.g., to control the placement, or amount, of a complex linked to the support.

[0251] The catalyst compositions comprising at least one metal carbene olefin metathesis catalyst may be utilized in olefin metathesis reactions according to techniques known in the art. The catalyst compositions disclosed herein are typically added to the cyclic olefin composition and / or resin composition as a solid, a solution, or as a suspension. When the catalyst composition disclosed herein is added to the cyclic olefin composition and / or resin composition as a suspension, the at least one metal carbene olefin metathesis catalyst is suspended in a carrier oil, such as mineral oil, paraffin oil, soybean oil, tri-isopropylbenzene, or any hydrophobic liquid which has a sufficiently high viscosity so as to permit effective dispersion of the catalyst(s), andwhich is sufficiently inert and which has a sufficiently high boiling point so that is does not act as a low-boiling impurity in the olefin metathesis reaction.

[0252] The catalyst compositions may be utilized in olefin metathesis reactions according to techniques known in the art. The metathesis reactions disclosed herein may be carried out under a dry, inert atmosphere. Such an atmosphere may be created using any inert gas, including such gases as nitrogen and argon. The use of an inert atmosphere is optimal in terms of promoting catalyst activity, and reactions performed under an inert atmosphere typically are performed with relatively low catalyst loading. The reactions disclosed herein may also be carried out in an oxygen-containing and / or a water-containing atmosphere, and the reactions may be carried out under ambient conditions. The presence of oxygen or water in the reaction may, however, necessitate the use of higher catalyst loadings as compared with reactions performed under an inert atmosphere. Where the vapor pressure of the reactants allows, the reactions disclosed herein may also be carried out under reduced pressure.

[0253] The reactions disclosed herein may be carried out in a solvent, and any solvent that is inert towards cross-metathesis may be employed. Generally, solvents that may be used in the metathesis reactions include organic, protic, or aqueous solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. Example solvents include benzene, toluene, p-xylene, methylene chloride, 1 ,2- dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, methanol, ethanol, water, or mixtures thereof. The reactions disclosed herein may be carried out neat, i.e. , without the use of a solvent.

[0254] The temperature at which a metathesis reaction according to methods disclosed herein is conducted can be adjusted as needed, and may be at least about 78 °C, 40 °C, -10 °C, 0 °C, 10 °C, 20 °C, 25 °C, 35 °C, 50 °C, 70 °C, 100 °C, or 150 °C, or the temperature may be in a range that has any of these values as the upper or lower bounds. The reactions may be carried out at a temperature of at least about 35 °C, or the reactions are carried out at a temperature of at least about 50 °C.

[0255] The amount of catalyst that is used (i.e., the “catalyst loading”) in the reaction is dependent upon a variety of factors such as the identity of the reactants and the reaction conditions that are employed. It is therefore understood that catalyst loading may be optimally and independently chosen for each reaction. In general, however, the catalyst will be present in an amount that ranges from a low of about 0.1 ppm, 1 ppm, or 5 ppm, to a high 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.

[0256] The catalyst will generally be present in an amount that ranges from a low of about 0.00001 mol%, 0.0001 mol%, or 0.0005 mol%, to a high 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 cyclic olefin(s) present in the cyclic olefin composition and / or resin composition.

[0257] When expressed as the molar ratio of monomer to catalyst, the catalyst (the “monomer to catalyst ratio”), loading will generally be present in an amount that ranges from a low of about 10,000,000:1 , 1 ,000,000:1 , or 200,00:1 , to a high of about 100,000:1 66,667:1 , 40,000:1 , 20,000:1 , 10,000:1 , 5,000:1 , or 1 ,000:1.

[0258] When expressed as the wt.% of catalyst, the at least one metal carbene olefin metathesis catalyst may be present in an amount ranging from 0.001 to 40 wt.% (e.g., 0.01 to 35 wt.%, 0.1 to 30 wt.%, 0.5 to 25 wt.%, 1 to 20 wt.%, 5 to 15 wt.%), based on the total weight of the catalyst composition.Viscosity Modifier

[0259] In some embodiments, the catalyst composition further comprises at least one viscosity modifier.

[0260] The at least one viscosity modifier may be a thixotropic agent, such as fumed silica, a polymer, such as a polyolefin, such as an ethylene-propylene copolymer, styrene-ethylene- butene-styrene (SEBS), polyol SEBS, or mixtures thereof. In some embodiments, the at least one viscosity modifier is present in the catalyst composition in an amount ranging from 0.01 to 5 wt.% (e.g., 0.1 to 4 wt.%, 0.5 to 3 wt.%, 1 to 2 wt.%), based on the total weight of the catalyst composition.

[0261] The invention also relates to a method of making the ROMP composition disclosed herein, comprising, consisting essentially of, or consisting of combining the cyclic olefin composition disclosed herein with the catalyst composition to form the ROMP composition.

[0262] invention also relates to a method of making the ROMP composition disclosed herein, comprising, consisting essentially of, or consisting of combining the resin composition disclosed herein with the catalyst composition to form the ROMP composition.Other Optional Components

[0263] The ROMP compositions disclosed herein may further contain a metal or non-metal substrate material, including, for example, a plastic or polymer substrate, a polymer-coated substrate (e.g., primer-coated steel), a glass fiber substrate, a carbon fiber substrate, a natural fiber substrate, and a metal oxide substrate.

[0264] The ROMP compositions disclosed herein may also contain at least one additive known in the art. Suitable additives include, but are not limited to, hardness modulators, fillers, binders,rheology modifiers and anti-settling agents, dispersants, wetting agents, pigments, flame retardants, dyes, fibers, reinforcement materials, coupling agents (e.g., silane coupling agents), film formers, lubricants, and stabilizers such as, for example, UV absorbers, and UV light stabilizers and other stabilizers known in the art. Furthermore, the amount of an additive added to the ROMP compositions may vary, depending on the particular type of additive. The additive and the additive loading should not interfere with polymerizing / curing the ROMP composition disclosed herein. Care should be taken when using chemistries that are known to inhibit ROMP. In some embodiments, the at least one additive is present in the ROMP composition in an amount ranging from 0.001 to 95 wt.% (e.g., 0.1 to 75 wt.%, 1 to 60 wt.%, 5 to 70 wt.%, 10 to 60 wt.%, 20 to 60 wt.%), based on the total weight of the ROMP composition.

[0265] As mentioned above, UV absorbers and UV light stabilizers are two examples of the type of stabilizers which may be used in the ROMP compositions disclosed herein. Suitable UV absorbers include nickel quenchers, benzophenones, benzotriazoles, benzyldene malonates, triazines, etc. Suitable UV light stabilizers include hindered amines, etc. The blend of various UV absorbers and UV light stabilizers are also suitable to provide protection against UV. Some suitable UV absorbers include 2-(2H-benzotriazol-2-yl)-p-cresol, 2-tert-Butyl-6-(5-chloro-2H- benzotriazol-2-yl)-4-methylphenol, and 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1 ,1 ,3,3- tetramethylbutyl)phenol], 2-hydroxy-4-methoxybenzophenone and 2-hydroxy-4- octyloxybenzophenone, as 2-(4,6-diphenyl-1 ,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol; oxanilide UV absorbers such as N-(2-ethoxyphenyl)-N'-(2-ethylphenyl)oxamide, dimethyl 2-(4- methoxybenzylidene)malonate, bis(1 ,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1 ,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis(1,2,2,6,6-pentamethyl-4-pperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, LOWILITE® Q84 and POLYBATCH® LLUVS 110, Tinuvin 1130, Tinuvin 171, Tinuvin 328, Tinuvin 384-2, Tinuvin 900, Tinuvin 928, Tinuvin 99, Tinuvin 5050, Tinuvin 5060, Tinuvin 5151 , Tinuvin 5248, Tinuvin 5251 , Tinuvin 5350, Tinuvin 123, Tinuvin 144, Tinuvin 152, Tinuvin 249, Tinuvin 292, Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479 (BASF), Chimassorb 81, Chimassorb 944, Chimassorb 2020 (BASF), KEMISORB 10, KEMISORB 11, KEMISORB 111 (Chemipro Kasei Ksisha), BP-2, BP-3, BP-6, BP-9 (Dalian Richfortune Chemicals), Ultra V 301 (Dover, ICI Industries), Grandsorb BP-1, Grandsorb BP-2, Grandsorb BP-4, Grandsorb BP-6 (Hongkun Group), SpeedBlock UV-6 (Lamsson), Maxgard 1000, Maxgard 300, Maxgard 400, Maxgard 500, Maxgard 600, Maxgard 700 (Lycus), Cyasorb UV-3346, Hostavin N 30 and the like. Such stabilizers can be used as individual components or in combination with other stabilizers known in the art for compositions. In some embodiments, the UV absorbers and / or UV light stabilizers are present in the ROMPcomposition in an amount ranging from 0.1 to 10 wt.% (e.g., 0.1 to 5 wt.%, 0.5 to 4 wt.%, 1 to 3 wt.%), based on the total weight of the ROMP composition.

[0266] Suitable fillers include, for example, microparticulate density modulators, such as, microspheres, or macroparticulate density modulators, for example: glass or ceramic beads. Other suitable fillers are inorganic fillers such as, for example, aluminum powder, aluminum flakes (e.g., aluminum flake paste), glass flakes, micaceous iron oxide, calcium carbonate, dolomite, silicas, silicates, talc, kaolin, mica, feldspar, barium sulfate and wollastonites, carbon nanotubes, graphene. Preferred inorganic fillers include aluminum powder, aluminum flakes, micaceous iron oxide, mica, glass fibers, wollastonite, calcium carbonate, silica and mixtures thereof, with flake- like fillers also being preferred. Preferably, the filler is aluminum powder or aluminum flakes (e.g ., aluminum flake paste), or alloys thereof. The aluminum powder or aluminum flake may be used alone or in combination with other fillers, such as those mentioned previously. For example, aluminum flake paste may be used alone or in combination with micaceous iron oxide. In some embodiments, the fillers, particularly the preferred fillers, are present in the ROMP composition in an amount ranging from 0.01 to 95 wt.% (e.g., 1 to 95 wt.%, 5 to 95 wt.%, 1 to 30 wt.%, 0.01 to 25 wt.%, 10 to 80 wt.%, 5 to 70 wt.%, 10 to 60 wt.%, 20 to 50 wt.%, 15 to 40 wt.%), based on the total weight of the ROMP composition. The aluminum flakes may have a particle size ranging from about 2 - 50 microns (e.g., 5 to 30 microns, 10 to 20 microns). Metallic flakes such as zinc, aluminum, magnesium, nickel, etc. can be added as inorganic fillers to compositions as sacrificial anodes to provide cathodic protection. They can also be used in combination with electrically conducting fillers as taught in US Patent 7,794,626, the complete disclosure of which is incorporated herein by reference, to provide galvanic anti-corrosion protection to the substrates.

[0267] One particular preferred inorganic filler is Mica C3000, which may be present in the ROMP composition in an amount ranging from 0.01 to 95 wt.% (e.g., 10 to 90 wt.%, 20 to 60 wt.%, 30 to 50 wt.%), based on the total weight of the ROMP composition.

[0268] Suitable dyes or pigments include MO 02294 black, M0-80406BV-Yellow from Chromaflo, and white pigment powder TI-PURE from Dupont.

[0269] Suitable rheology modifiers and anti-settling agents include inorganic and organic rheology modifiers. Inorganic rheology modifiers include clays and organoclays of hectorite, bentonite, attapulgite, kaoline, pyrophilite and talc; minerals such as fumed silica, precipitated silica, precipitated calcium carbonate, and montmorillonite, metal organic gellants such as zirconates, aluminates. Organic rheology modifiers include castor oil derivatives, modified polyurea, polyamides, calcium sulfonates, cellulose, shydrophobic ethoxylated urethane resins. Examples of suitable rheology modifiers include fumed silica such as Cab-O-Sil TS61Q, TS720from Cabot Corp and AEROSIL 972, AEROSIL 974 from Evonik. organoclay such as BENTOLITE L~10, BENTOLITE-WH, CLAYTONE 40, CLAYTONE AF, MINERAL COLLOID BP, Garamita 7303 from BYK Chemte, USA; Bentonite 149, Bentonite 329, Bentonite 331 , Bentonite 344 from Brentag Specialities, Attagel from BASF and the like, polyaminoamide phosphate, high molecular weight carboxylic acid salts of polyamine amides, and alkylene amine salts of an unsaturated fatty acid, all available from BYK Chemte USA as ANTI TERRA™, polyamide modified castor oil derivatives such as Luvotix ZH5, Luvitix ZH50 from Lehmann & Vass; micronized amide wax such as Crayvailac SUPER from Arkema.

[0270] Suitable coupling agents include, for example, silane coupling agents known in the art. Examples of silane coupling agents include (3-glycidoxypropyl)trimethoxysilane (Silquest A187), (3-glycidoxypropyl)triethoxysilane (Silquest A1871 ), vinyltrimethoxysilane (Silquest A171 ), vinyltriethoxysilane (Silquest A151 ), methacryloxpropyltrimethoxysilane (Silquest A174NT), N-(2- aminoethyl)-3-aminopropyltrimethoxysilane (Silquest A1120), 3-aminopropyltrimethoxysilane (Silquest A1110), hexadecylltrimethoxysilane, isooctyltriethoxysilane, n-octyltriethoxysilane, isobutyltriethoxysilane, methyltrimethoxysilane, and N-ethyl-amino isobutyl trimethoxysilane (Silquest A-Link 15 Silane).

[0271] ROMP compositions disclosed herein may contain additives such as dispersants / dispersing agents (surfactants) known in the art. Examples of dispersing agents and surfactants include sodium bis(tridecyl) sulfosuccinnate, di(2 -ethylhexyl) sodium sulfosuccinnate, sodium dihexylsulfosuccinnate, sodium dicyclohexyl sulfosuccinnate, diamyl sodium sulfosuccinnate, sodium diisobutyl sulfosuccinate, disodium isodecyl sulfosuccinnate, disodium ethoxylated alcohol half ester of sulfosuccinnic acid, disodium alkyl amido polyethoxy sulfosuccinnate, tetrasodium N-(1 ,2-dicarboxy-ethyl)-N-oxtadecyl sulfosuccinnamate, disodium N-octasulfosuccinnamate, sulfated ethoxylated nonylphenol, 2-amino-2-methyl-1 -propanol, and the like.ROMP POLYMER

[0272] The invention also relates to a ROMP polymer, comprising, consisting essentially of, or consisting of the reaction product of the ROMP composition disclosed herein, wherein the ROMP composition is subjected to conditions effective to polymerize the ROMP composition.

[0273] The invention further relates to a method of making the ROMP polymer comprising, consisting essentially of, or consisting of subjecting the ROMP composition disclosed herein to conditions effective to polymerize the ROMP composition to form the ROMP polymer.ARTICLES OF MANUFACTURE

[0274] The invention also relates to the method and use of the ROMP composition disclosed herein in various molding processes, such as vacuum assisted resin transfer molding (VARTM), resin transfer molding (RTM), reaction injection molding (RIM), bath based pultrusion, plural injection pultrusion, spray coatings, and brushable coatings to polymerize the ROMP composition and form a cured article.

[0275] The invention also relates to a curable article of manufacture comprising the ROMP composition disclosed herein. The invention further relates to a cured article of manufacture, wherein the curable article of manufacture comprising the ROMP composition disclosed herein is cured. Cured articles disclosed herein include, without limitation, composites (e.g., rebar via pultrusion, cured laminates via VARTM), insulation materials (e.g., insulation material cured via RTM), coatings (e.g., thin films (<10 mm) by spray coating or brush), cured cast parts via RTM, and cured composite articles via RTM.

[0276] ROMP compositions disclosed herein suitable for the manufacture of composite articles (also referred to herein as ROMP polymer composites) may be prepared by starting with pre- catalyzed ROMP compositions disclosed herein comprising, consisting essentially of, or consisting of the at least one catalyst composition and the at least one cyclic olefin composition or the at least one resin composition. The composite formulations disclosed herein can be applied to the reinforcement fabric through a vacuum infusion process; these may include large composite structures, such as wind blades, in which the manufacture of thick laminate structures is enabled by the low viscosity of the ROMP compositions described herein.

[0277] The manufacture of large composite structures is further enabled by the ROMP compositions disclosed herein due to their cure behavior. The catalyzed compositions undergo a rapid transition from liquid to solid phase at temperatures above 40 °C, exhibiting “snap cure” characteristics, after which point the temperature may be increased to the target post-cure temperature. The low enthalpy of reaction results in low exotherm temperatures even in thick laminate sections, allowing for a fast, controlled curing process.

[0278] ROMP compositions disclosed herein may have a maximum heat flow of <5.6 W / g, <4.6 W / g, or <3.9 W / g by dynamic scanning calorimetry (DSC). Alternatively (or in addition to), a ROMP composition disclosed herein may have a reduced maximum heat flow (e.g., <5%, <10%, <15%, <20%, <25%, <30%) as compared to a comparable ROMP composition, wherein the ROMP composition disclosed herein and the comparable ROMP composition are equivalent except the comparable ROMP composition does not contain the DCPD portion and, optionally, TCPD portion used in the ROMP compositions disclosed herein. A reduction in the maximum heat flow maytranslate to an overall reduction in the maximum temperature rise observed in thick castings, which may or may not include reinforcements. This has the benefit of enabling thick castings with controlled exotherm behavior.

[0279] The ROMP compositions disclosed herein s may have viscosities of <100 cP, < 125 cP, or < 150 cP at ambient temperatures. Addition of polymeric or oligomeric additives to resin are known to increase viscosity, so it is unexpected that the viscosity remains low at high loadings of thermoplastic hydrocarbon resins, such as loadings of 40 phr (approximately 30 wt.%). The retention of low viscosity even at high loadings of thermoplastic hydrocarbon resin enables fast infusion of thick laminates for the ROMP compositions disclosed herein used to prepare composite laminates.

[0280] The ROMP compositions disclosed herein additionally have a low viscosity under a range of temperatures. For example, loadings of 40 phr (approximately 30 wt.%) of the cyclic olefin compositions result in a resin viscosity of < 55 cP at a temperature of 40 °C, a resin viscosity of < 75 cP at 30 °C, and a resin viscosity of <105 at 20 °C. The relatively modest changes in viscosity over a broad range of temperatures enables fast infusion of thick laminates for the ROMP compositions disclosed herein used to prepare composite laminates, even at cooler resin temperatures.

[0281] To be sprayable as a coating, the viscosity at high shear rate (> 103sec1) is important. When a coating composition disclosed herein is forced through a spray nozzle and atomized, the coatings need to exhibit shear-thinning rheology. Proper coating additives such as dispersants and rheology modifier can modify the coatings of high filler loading to attain sprayable viscosity and the shear-thinning rheology.

[0282] The invention also relates to a cured article of manufacture, comprising, consisting essentially of, or consisting of the ROMP composition disclosed herein. The cured article of manufacture may, but does not need to, contain a reinforcement material, such as, for example, a substrate. Thus, the invention relates to cured articles of manufacture, comprising, consisting essentially of, or consisting of the ROMP composition disclosed herein, wherein the cured article does not contain a reinforcement material, such as, for example, a substrate.

[0283] The invention further relates to a method of making a cured article of manufacture, comprising, consisting essentially of, or consisting of: combining the catalyst composition disclosed herein and the cyclic olefin composition disclosed herein to form the ROMP composition disclosed herein; subjecting the ROMP composition to conditions effective to polymerize the ROMP composition to form the ROMP polymer disclosed herein; andsubjecting the ROMP polymer to conditions effective to cure the ROMP polymer to make the cured article of manufacture.

[0284] The invention further relates to a method of making a cured article of manufacture, comprising, consisting essentially of, or consisting of: combining the catalyst composition disclosed herein and the resin composition disclosed herein to form the ROMP composition disclosed herein; subjecting the ROMP composition to conditions effective to polymerize the ROMP composition to form the ROMP polymer disclosed herein; and subjecting the ROMP polymer to conditions effective to cure the ROMP polymer to make the cured article of manufacture.Insulation Materials

[0285] The invention also relates to insulation materials comprising, consisting essentially of, or consisting of the ROMP composition, ROMP polymer, or ROMP polymer composite disclosed herein.

[0286] The invention also relates to an object at least partially encased and / or coated by an insulation material, where the insulation material comprises, consists essentially of, or consists of the ROMP composition, ROMP polymer, or ROMP polymer composite disclosed herein.

[0287] The invention also relates to an insulation material for use in coating, encasing, or insulating (1 ) an object; (2) at least a portion of an object; and / or (3) at least a portion of at least one surface of an object, wherein the insulation material comprises the ROMP composition, ROMP polymer, or ROMP polymer composite disclosed herein.

[0288] The invention also relates to a method of insulating an object from a surrounding fluid, the method comprising interposing an insulation material between the object and the fluid where the insulation material comprises the ROMP polymer or ROMP polymer composite disclosed herein.

[0289] The invention also relates to a method for coating, encasing, or insulating (1 ) an object; (2) at least a portion of an object; and / or (3) at least a portion of at least one surface of an object, with an insulation material, wherein the insulation material is the ROMP polymer or ROMP polymer composite disclosed herein.Coating Compositions

[0290] The invention also relates to coating compositions comprising, consisting essentially of, or consisting of the ROMP compositions disclosed herein.

[0291] The ROMP compositions of this invention may be optionally formulated with other reactive chemistries to form co-cured coatings. The co-curing process may form interpenetrating polymer networks; for example, a co-cured polyurethane can form from a polyol and a diisocyanate; a co-cured epoxy can form from a bisepoxide and a hardener such as an anhydride, amine, or thiol. Care should be taken when using chemistries that are known to inhibit ROMP. Copolymeric coatings may be formed if multifunctional monomers are incorporated; for example, isocyanate- or alcohol-containing olefinic comonomers can copolymerize urethanes with the ROMP compositions disclosed herein, and epoxide-containing comonomers can copolymerize epoxies with the ROMP compositions disclosed herein. Other polymers such as polysiloxanes, polyureas, and acrylics can be incorporated into the ROMP compositions disclosed herein.

[0292] The invention also relates to a method for coating at least a portion of at least one surface of a substrate or object with a coating composition disclosed herein, comprising contacting at least a portion of the at least one surface of the substrate with the coating composition disclosed herein, and subjecting the coated substrate to conditions effective to promote an olefin metathesis reaction of the at least one cyclic olefin composition in the presence of the at least one catalyst composition. The substrate surface is preferably a clean surface, but coating compositions disclosed herein may also be applied to “dirtier” surfaces than conventional epoxy-based coating compositions. A method disclosed herein may also apply a UV resistance topcoat over the coatings to provide protection against UV degradation as known in the art. A method disclosed herein accordingly produces an article of manufacture coated with a cured coating composition disclosed herein.

[0293] The adhesion to the substrate can be achieved by priming the substrate with an adhesion promoter or by adding an adhesion promoter as a coating additive to the coating formulation.

[0294] The invention also relates to a method for coating a steel substrate material, comprising, consisting essentially of, or consisting of: blasting the steel surface with blasting media according to SSPC SP10 standards; optionally applying an adhesion promoter onto the steel surface; applying a coating composition disclosed herein and at least one additive (preferably, aluminum powder or aluminum flakes); curing the coating applied on the steel surface at a temperature between 5 °C to 150 °C.

[0295] The substrates or objects to be coated may be of any configuration, any weight, any size, any thickness, and / or any geometric shape. Furthermore, the substrates or objects to be coated may be constructed of any material including but not limited to metal such as steel,stainless steel, aluminum, copper, metal alloys, iron, nickel, titanium, and silver as well as stone, plastics, rubbers, polymers, wood, cloth, ceramics, glass, carbon, brick, fabrics, cement, concrete, or composites, such as reinforced plastics and electronic assemblies.

[0296] The substrate or object surfaces to be coated may be partially or fully coated.

[0297] The coating compositions disclosed herein can be applied to the substrate material or object to be coated / protected by any method known in the art, including, without limitation, spraying, brushing, dipping, or rolling. The coating composition can be applied on the substrate material or object to be coated with a paint brush. The coating composition can also be sprayed on the substrate material or object to be coated with a film spray gun, a conventional spray gun, a plural component sprayer, a high-volume low pressure (HVLP) or an airless applicator.KITS

[0298] The invention further provides a kit comprising, consisting of, or consisting essentially of at least one container; the first container comprising, consisting of, or consisting essentially of the cyclic olefin composition; and, optionally, instructions for administration of the at least one container. In another embodiment, the first container comprises, consists of, or consists essentially of the resin composition. In another embodiment, the first container comprises, consists of, or consists essentially of the ROMP composition.

[0299] The invention further provides a kit comprising, consisting of, or consisting essentially of at least two containers; the first container comprising, consisting of, or consisting essentially of the catalyst composition; the second container comprising, consisting of, or consisting essentially of the cyclic olefin composition or the resin composition; and, optionally, instructions for administration of the containers.

[0300] As used herein, the term “instructions" when used in the context of a kit includes a publication, a recording, a diagram, or any other medium of expression which can be used to communicate the usefulness of the kit for its designated use. The instructions can, for example, be affixed to or included within a container for the kit.

[0301] The term “container” as used herein refers to any receptacle or applicator means capable of holding, storing, and / or applying the cyclic olefin composition, the resin composition, the catalyst composition, and / or the ROMP composition(or their individual components). Such a container may be in any container configuration known to a person skilled in the art, such as, but not limited to, a cartridge, a bottle, a drum, an intermediate bulk container (IBC), a Jerry Can, a flexi tank container, IBC tote tank, or an ISO tank container. The containers may be made of any material suitable for the materials contained therein and additionally suitable for short and / or longterm storage under any kind of temperature. Such materials indude, by way of example, inorganic materials, such as Type I glass (including amber colored glass), ceramics, metals (e.g., steel, aluminum, tin), etc., and organic materials such as inert polymers including polyolefins (e.g., high density polyethylene), fluorinated polyolefins, and the like. Suitable containers include those that maintain the sterility and integrity of their contents, for example, by providing a barrier to moisture. The suitable containers may have an appropriate applicator means to dispense and / or mix the materials contained therein. The containers may be sealed as separate articles or are combined into a single article of manufacture having a barrier between the containers. This barrier can either be removed or destroyed allowing mixing of the materials in each of their respective containers at the appropriate time.Exemplary Embodiments

[0302] E1 ) A cyclic olefin composition, comprising, consisting essentially of, or consisting of: 20 to 100 wt.% (e.g., 21 to 99.999 wt.%, 22 to 99.99 wt.%, 23 to 99.9 wt.%, 25 to 99.5 wt.%, 30 to 99 wt.%, 35 to 95 wt.%, 40 to 90 wt.%, 45 to 85 wt.%, 50 to 80 wt.%, 55 to 75 wt.%, 60 to 70 wt.%) of a di-cyclopentadiene (DCPD) portion, and0 to 80 wt.% (e.g., 0.001 to 79 wt.%, 0.01 to 78 wt.%, 0.1 to 77 wt.%, 0.5 to 75 wt.%, 1 to 70 wt.%, 5 to 65 wt.%, 10 to 60 wt.%, 15 to 55 wt.%, 20 to 50 wt.%, 25 to 45 wt.%, 30 to 40 wt.%) of a tri-cyclopentad iene (TCPD) portion, based on the total weight of the DCPD and TCPD portions in the cyclic olefin composition; wherein the DCPD portion comprises, consists essentially of, or consists of:0.3 to 60 wt.% (e.g., 0.4 to 55 wt.%, 0.5 to 50 wt.%, 0.6 to 45 wt.%, 0.7 to 40 wt.%, 0.8 to 35 wt.%, 0.9 to 30 wt.%, 1 to 25 wt.%, 2 to 24 wt.%, 3 to 23 wt.%, 4 to 22 wt.%, 5 to 21 wt.%, 6 to 20 wt.%, 7 to 19 wt.%, 8 to 18 wt.%, 9 to 17 wt.%, 10 to 16 wt.%, 11 to 15 wt.%, 12 to 14 wt.%) of exo-DCPD, and40 to 99.7 wt.% (e.g., 45 to 99.6 wt.%, 50 to 99.5 wt.%, 55 to 99.4 wt.%, 60 to 99.3 wt.%, 65 to 99.2 wt.%, 70 to 99.1 wt.%, 75 to 99 wt.%, 76 to 98 wt.%, 77 to 97 wt.%, 78 to 96 wt.%, 79 to 95 wt.%, 80 to 94 wt.%, 81 to 93 wt.%, 82 to 92 wt.%, 83 to 91 wt.%, 84 to 90 wt.%, 85 to 89 wt.%, 86 to 88 wt.%) of endo-DCPD, based on the total weight of the exo-DCPD and endo-DCPD in the DCPD portion; and wherein the TCPD portion, if present, comprises, consists essentially of, or consists of:0.1 to 10 wt.% (e.g., 0.2 to 9 wt.%, 0.3 to 8 wt.%, 0.4 to 7 wt.%, 0.5 to 6 wt.%, 0.6 to 5 wt.%, 0.7 to 4 wt.%, 0.8 to 3 wt.%, 0.9 to 2 wt.%, 1 to 1 ,5 wt.%) of TCPD-7,3 to 25 wt.% (e.g., 4 to 24 wt.%, 5 to 23 wt.%, 6 to 22 wt.%, 7 to 21 wt.%, 8 to 20 wt.%, 9 to 19 wt.%, 10 to 18 wt.%, 11 to 17 wt.%, 12 to 16 wt.%, 13 to 15 wt.%) of TCPD-3,5 to 90 wt.% (e.g., 7 to 89 wt.%, 9 to 87 wt.%, 11 to 85 wt.%, 13 to 83 wt.%, 15 to 81 wt.%, 17 to 79 wt.%, 20 to 75 wt.%, 25 to 70 wt.%, 30 to 65 wt.%, 35 to 60 wt.%, 40 to 55 wt.%, 45 to 50 wt.%) of TCPD-5, and5 to 85 wt.% (e.g., 10 to 83 wt.%, 15 to 81 wt.%, 20 to 79 wt.%, 25 to 77 wt.%, 30 to 75 wt.%, 35 to 73 wt.%, 40 to 71 wt.%, 45 to 69 wt.%, 50 to 67 wt.%, 55 to 65 wt.%, 60 to 63 wt.%, 61 to 62 wt.%) of TCPD-1 , based on the total weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 in the TCPD portion.

[0303] E2) A cyclic olefin composition, comprising, consisting essentially of, or consisting of: 0.0001 to 99.9999 wt.% (e.g, 0.001 to 99.9998 wt.%, 0.01 to 99.999 wt.%, 0.1 to 99.99 wt.%, 0.5 to 99.9 wt.%, 1 to 99.5 wt.%, 2 to 99 wt.%, 3 to 98 wt.%, 4 to 97 wt.%, 5 to 96 wt.%, 6 to 95 wt.%, 7 to 94 wt.%, 8 to 93 wt.%, 9 to 92 wt.%, 10 to 91 wt.%, 15 to 90 wt.%, 20 to 85 wt.%, 25 to 80 wt.%, 30 to 75 wt.%, 35 to 70 wt.%, 40 to 65 wt.%, 45 to 60 wt.%, 50 to 55 wt.%) of a DCPD portion,0.0001 to 90 wt.% (e.g., 0.001 to 89 wt.%, 0.01 to 88 wt.%, 0.1 to 87 wt.%, 0.5 to 86 wt.%, 1 to 85 wt.%, 2 to 80 wt.%, 3 to 75 wt.%, 4 to 70 wt.%, 5 to 65 wt.%, 6 to 60 wt.%, 7 to 55 wt.%, 8 to 50 wt.%, 9 to 45 wt.%, 10 to 40 wt.%, 15 to 35 wt.%, 20 to 30 wt.%) of a TCPD portion, and 0 to 50 wt.% (e.g., 0.0001 to 49.9998 wt.%, 0.001 to 45 wt.%, 0.01 to 40 wt.%, 0.1 to 35 wt.%, 0.5 to 30 wt.%, 1 to 25 wt.%, 2 to 20 wt.%, 3 to 15 wt.%, 4 to 10 wt.%, 5 to 9 wt.%, 6 to 8 wt.%) of a TeCPD portion, based on the total weight of the DCPD, TCPD, and TeCPD portions in the cyclic olefin composition; wherein the DCPD portion comprises, consists essentially of, or consists of:0.3 to 99 wt.% (e.g., 0.4 to 98 wt.%, 0.5 to 97 wt.%, 1 to 96 wt.%, 2 to 95 wt.%, 3 to 94 wt.%, 4 to 93 wt.%, 5 to 92 wt.%, 10 to 91 wt.%, 15 to 90 wt.%, 20 to 85 wt.%, 25 to 80 wt.%, 30 to 75 wt.%, 35 to 70 wt.%, 40 to 65 wt.%, 45 to 60 wt.%, 50 to 55 wt.%) of exo-DCPD, and1 to 99 wt.% (e.g 2 to 98 wt.%, 3 to 97 wt.%, 4 to 96 wt.%, 5 to 95 wt.%, 10 to 94 wt.%, 15 to 93 wt.%, 20 to 92 wt.%, 25 to 91 wt.%, 30 to 90 wt.%, 35 to 89 wt.%, 40 to 88 wt.%, 45 to 87 wt.%, 50 to 86 wt.%, 55 to 85 wt.%, 65 to 80 wt.%, 70 to 75 wt.%) of endo-DCPD, based on the total weight of the exo-DCPD and endo-DCPD in the DCPD portion; wherein the TCPD portion comprises, consists essentially of, or consists of:0.1 to 10 wt.% (e g, 0.2 to 9 wt .%, 0.3 to 8 wt.%, 0.4 to 7 wt.%, 0.5 to 6 wt.%, 0.6 to 5 wt.%, 0.7 to 4 wt.%, 0.8 to 3 wt.%, 0.9 to 2 wt.%, 1 to 1 ,5 wt.%) of TCPD-7,3 to 25 wt.% (e.g., 4 to 24 wt.%, 5 to 23 wt.%, 6 to 22 wt.%, 7 to 21 wt.%, 8 to 20 wt.%, 9 to 19 wt.%, 10 to 18 wt.%, 11 to 17 wt.%, 12 to 16 wt.%, 13 to 15 wt.%) of TCPD-3,5 to 90 wt.% (e.g., 6 to 85 wt.%, 7 to 80 wt.%, 8 to 75 wt.%, 9 to 70 wt.%, 10 to 65 wt.%, 15 to 60 wt.%, 20 to 55 wt.%, 25 to 50 wt.%, 30 to 45 wt.%, 35 to 40 wt.%) of TCPD-5, and5 to 85 wt.% (e.g., 6 to 80 wt.%, 7 to 75 wt.%, 8 to 70 wt.%, 9 to 65 wt.%, 10 to 60 wt.%, 15 to 55 wt.%, 20 to 50 wt.%, 25 to 45 wt.%, 30 to 40 wt.%) of TCPD-1 , based on the total weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 in the TCPD portion; and wherein the TeCPD portion, if present, comprises, consists essentially of, or consists of:0 to 10 wt.% (e.g., 0.001 to 9 wt.%, 0.01 to 8 wt.%, 0.1 to 7 wt.%, 0.5 to 6 wt.%, 1 to 5 wt.%, 2 to 4 wt.%, 2.5 to 3 wt.%) of TeCPD-1 ,0 to 15 wt.% (e.g., 0.001 to 14 wt.%, 0.01 to 13 wt.%, 0.1 to 12 wt.%, 0.5 to 11 wt.%, 1 to 10 wt.%, 2 to 9 wt.%, 3 to 8 wt.%, 4 to 7 wt.%, 5 to 6 wt.%) of TeCPD-2,0 to 30 wt.% (e.g., 0.001 to 25 wt.%, 0.01 to 20 wt.%, 0.1 to 15 wt.%, 0.5 to 10 wt.%, 1 to 9 wt.%, 2 to 8 wt.%, 3 to 7 wt.%, 4 to 6 wt.%) of TeCPD-3,0 to 5 wt.% (e.g., 0.001 to 4 wt.%, 0.01 to 3 wt.%, 0.1 to 2 wt.%, 0.5 to 1 wt.%) of TeCPD-4,0 to 5 wt.% (e.g., 0.001 to 4 wt.%, 0.01 to 3 wt.%, 0.1 to 2 wt.%, 0.5 to 1 wt.%) of TeCPD-5,0 to 70 wt.% (e.g., 0.001 to 65 wt.%, 0.01 to 60 wt.%, 0.1 to 55 wt.%, 0.5 to 50 wt.%, 1 to 45 wt.%, 5 to 40 wt.%, 10 to 35 wt.%, 15 to 30 wt.%, 20 to 25 wt.%) of TeCPD-6, and0 to 90 wt.% (e.g., 0.001 to 85 wt.%, 0.01 to 80 wt.%, 0.1 to 75 wt.%, 0.5 to 70 wt.%, 1 to 65 wt.%, 5 to 60 wt.%, 10 to 55 wt.%, 15 to 50 wt.%, 20 to 45 wt.%, 25 to 40 wt.%, 30 to 35 wt.%) of TeCPD-7, based on the total weight of the TeCPD-1, TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, and TeCPD-7 in the TeCPD portion.

[0304] E3) A cyclic olefin composition, comprising, consisting essentially of, or consisting of: 0.0001 to 99.9998 wt.% (e.g., 0.001 to 99.998 wt.%, 0.01 to 99.98 wt.%, 0.1 to 99.8 wt.%, 0.5 to 99 wt.%, 1 to 99.5 wt.%, 2 to 99 wt.%, 3 to 98 wt.%, 4 to 97 wt.%, 5 to 96 wt.%, 6 to 95 wt.%, 7 to 94 wt.%, 8 to 93 wt.%, 9 to 92 wt.%, 10 to 91 wt.%, 15 to 90 wt.%, 20 to 85 wt.%, 25 to 80 wt.%, 30 to 75 wt.%, 35 to 70 wt.%, 40 to 65 wt.%, 45 to 60 wt.%, 50 to 55 wt.%) of a DCPD portion,0.0001 to 99.9998 wt.% (e.g., 0.001 to 99.998 wt.%, 0.01 to 99.98 wt.%, 0.1 to 99.8 wt.%, 0.5 to 99 wt.%, 1 to 99.5 wt.%, 2 to 99 wt.%, 3 to 98 wt.%, 4 to 97 wt.%, 5 to 96 wt.%, 6 to 95 wt.%, 7 to 94 wt.%, 8 to 93 wt.%, 9 to 92 wt.%, 10 to 91 wt.%, 15 to 90 wt.%, 20 to 85 wt.%, 25 to 80 wt.%, 30 to 75 wt.%, 35 to 70 wt.%, 40 to 65 wt.%, 45 to 60 wt.%, 50 to 55 wt.%) of a TCPD portion, and0.0001 to 50 wt.% (e.g., 0.001 to 45 wt.%, 0.01 to 40 wt.%, 0.1 to 35 wt.%, 0.5 to 30 wt.%, 1 to 25 wt.%, 2 to 20 wt.%, 3 to 15 wt.%, 4 to 14 wt.%, 5 to 13 wt.%, 6 to 12 wt.%, 7 to 11 wt.%, 8 to 10 wt.%) of a TeCPD portion, based on the total weight of the DCPD, TCPD, and TeCPD portions in the cyclic olefin composition; wherein the DCPD portion comprises, consists essentially of, or consists of:0.3 to 99 wt.% (e.g., 0.4 to 98 wt.%, 0.5 to 97 wt.%, 1 to 96 wt.%, 2 to 95 wt.%, 3 to 94 wt.%, 4 to 93 wt.%, 5 to 92 wt.%, 10 to 91 wt.%, 15 to 90 wt.%, 20 to 85 wt.%, 25 to 80 wt.%, 30 to 75 wt.%, 35 to 70 wt.%, 40 to 65 wt.%, 45 to 60 wt.%, 50 to 55 wt.%) of exo-DCPD, and1 to 99 wt.% (e.g., 2 to 98 wt.%, 3 to 97 wt.%, 4 to 96 wt.%, 5 to 95 wt.%, 10 to 94 wt.%, 15 to 93 wt.%, 20 to 92 wt.%, 25 to 91 wt.%, 30 to 90 wt.%, 35 to 89 wt.%, 40 to 88 wt.%, 45 to 87 wt.%, 50 to 86 wt.%, 55 to 85 wt.%, 65 to 80 wt.%, 70 to 75 wt.%) of endo-DCPD,based on the total weight of the exo-DCPD and endo-DCPD in the DCPD portion; wherein the TCPD portion comprises, consists essentially of, or consists of:0.1 to 10 wt.% (e.g., 0.2 to 9 wt.%, 0.3 to 8 wt.%, 0.4 to 7 wt.%, 0.5 to 6 wt.%, 0.6 to 5 wt.%, 0.7 to 4 wt.%, 0.8 to 3 wt.%, 0.9 to 2 wt.%, 1 to 1 ,5 wt.%) of TCPD-73 to 25 wt.% (e.g., 4 to 24 wt.%, 5 to 23 wt.%, 6 to 22 wt.%, 7 to 21 wt.%, 8 to 20 wt.%, 9 to 19 wt.%, 10 to 18 wt.%, 11 to 17 wt .%, 12 to 16 wt.%, 13 to 15 wt.%) of TCPD-3,5 to 90 wt.% (e.g., 6 to 85 wt.%, 7 to 80 wt.%, 8 to 75 wt.%, 9 to 70 wt.%, 10 to 65 wt.%, 15 to 60 wt.%, 20 to 55 wt.%, 25 to 50 wt.%, 30 to 45 wt.%, 35 to 40 wt.%) of TCPD-5, and5 to 85 wt.% (e.g., 6 to 80 wt.%, 7 to 75 wt.%, 8 to 70 wt.%, 9 to 65 wt.%, 10 to 60 wt.%, 15 to 55 wt.%, 20 to 50 wt.%, 25 to 45 wt.%, 30 to 40 wt.%) of TCPD-1 , based on the total weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 in the TCPD portion; and wherein the TeCPD portion comprises, consists essentially of, or consists of:0 to 10 wt.% (e.g., 0.001 to 9 wt.%, 0.01 to 8 wt.%, 0.1 to 7 wt.%, 0.5 to 6 wt.%, 1 to 5 wt.%, 2 to 4 wt.%, 2.5 to 3 wt.%) of TeCPD-1 ,0 to 15 wt.% (e.g., 0.001 to 14 wt.%, 0.01 to 13 wt.%, 0.1 to 12 wt.%, 0.5 to 11 wt.%, 1 to 10 wt.%, 2 to 9 wt.%, 3 to 8 wt.%, 4 to 7 wt.%, 5 to 6 wt.%) of TeCPD-2,0 to 30 wt.% (e.g., 0.001 to 25 wt.%, 0.01 to 20 wt.%, 0.1 to 15 wt.%, 0.5 to 10 wt.%, 1 to 9 wt.%, 2 to 8 wt.%, 3 to 7 wt.%, 4 to 6 wt.%) of TeCPD-3,0 to 5 wt.% (e.g., 0.001 to 4 wt.%, 0.01 to 3 wt.%, 0.1 to 2 wt.%, 0.5 to 1 wt.%) of TeCPD-4,0 to 5 wt.% (e.g., 0.001 to 4 wt.%, 0.01 to 3 wt.%, 0.1 to 2 wt.%, 0.5 to 1 wt.%) of TeCPD-5,0 to 70 wt.% (e.g., 0.001 to 65 wt.%, 0.01 to 60 wt.%, 0.1 to 55 wt.%, 0.5 to 50 wt.%, 1 to 45 wt.%, 5 to 40 wt.%, 10 to 35 wt.%, 15 to 30 wt.%, 20 to 25 wt.%) of TeCPD-6, and0 to 90 wt.% (e.g., 0.001 to 85 wt.%, 0.01 to 80 wt.%, 0.1 to 75 wt.%, 0.5 to 70 wt.%, 1 to 65 wt.%, 5 to 60 wt.%, 10 to 55 wt.%, 15 to 50 wt.%, 20 to 45 wt.%, 25 to 40 wt.%, 30 to 35 wt.%) of TeCPD-7, based on the total weight of the TeCPD-1, TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, and TeCPD-7 in the TeCPD portion.

[0305] E4) The cyclic olefin composition of any one of E1 -3, wherein: the exo-DCPD has a structurethe TCPD-3 has a structure

[0306] E5) The cyclic olefin composition of E1 , wherein: the exo-DCPD has a retention index of 1017 ±1 , the endo-DCPD has a retention index of 1031 ±1 ,the TCPD-7 has a retention index of 1535 ±2, the TCPD-3 has a retention index of 1539 ±1 , the TCPD-5 has a retention index of 1585 ±1 , and the TCPD-1 has a retention index of 1579 ±1 .

[0307] E6) The cyclic olefin composition of E2 or E3, wherein: the exo-DCPD has a retention index of 1017 ±1 , the endo-DCPD has a retention index of 1031 ±1 , the TCPD-7 has a retention index of 1535 ±2, the TCPD-3 has a retention index of 1539 ±1 , the TCPD-5 has a retention index of 1585 ±1 , the TCPD-1 has a retention index of 1579 ±1 , the TeCPD-1 has a retention index of 2310 ±1 , the TeCPD-2 has a retention index of 2318 ±1, the TeCPD-3 has a retention index of 2330 +2, the TeCPD-4 has a retention index of 2354 +1, the TeCPD-5 has a retention index of 2363 ±1, the TeCPD-6 has a retention index of 2370 ±1, and the TeCPD-7 has a retention index of 2382 ±1.

[0308] E7) The cyclic olefin composition of E5 or E6, wherein the retention indexes are determined using ASTM D2887 (Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography).

[0309] E8) The cyclic olefin composition of E2 or E3, wherein the TeCPD isomers in the TeCPD portion elute in the following order:1. the TeCPD-1 ,2. the TeCPD-2,3. the TeCPD-3,4. the TeCPD A5. the TeCPD-5,6. the TeCPD-6, and7. the TeCPD-7.

[0310] E9) The cyclic olefin composition of any one of E5-E8, wherein the retention time is measured by gas chromatography using an Agilent 8890 Gas Chromatography (GC) System according to Settings Method A:

[0311] E10) The cyclic olefin composition of E1 or E2, comprising, consisting essentially of, or consisting of:50 to 99.999 wt.% (e.g., 50 to 99.99 wt.%, 50 to 99.9 wt.%, 50 to 99 wt.%, 55 to 98 wt.%, 60 to 97 wt.%, 65 to 96 wt.%, 70 to 95 wt.%, 75 to 94 wt.%, 80 to 93 wt.%, 85 to 92 wt.%, 90 to 91 wt.%) of the DCPD portion, and0.001 to 50 wt.% (e.g., 0.01 to 50 wt.%, 0.1 to 50 wt.%, 1 to 50 wt.%, 2 to 45 wt.%, 3 to 40 wt.%, 4 to 35 wt.%, 5 to 30 wt.%, 6 to 25 wt.%, 7 to 20 wt.%, 8 to 15 wt.%, 9 to 10 wt.%) of the TCPD portion.

[0312] E11 ) The cyclic olefin composition of E2 or E3, comprising, consisting essentially of, or consisting of:50 to 99.999 wt.% (e.g., 50 to 99.99 wt.%, 50 to 99.9 wt.%, 50 to 99 wt.%, 50 to 98 wt.%, 55 to 97 wt.%, 60 to 96 wt.%, 65 to 95 wt.%, 70 to 94 wt.%, 75 to 93 wt.%, 80 to 92 wt.%, 85 to 91 wt.%) of the DCPD portion, and0.001 to 25 wt.% (e.g., 0.01 to 25 wt.%, 0.1 to 25 wt.%, 1 to 25 wt.%, 2 to 25 wt.%, 3 to 20 wt.%, 4 to 15 wt.%, 5 to 10 wt.%, 6 to 9 wt.%, 7 to 8 wt.%) of the TeCPD portion.

[0313] E12) The cyclic olefin composition of E2 or E3, comprising, consisting essentially of, or consisting of:49.999 to 99.998 wt.% (e.g., 49.99 to 99.98 wt.%, 49.9 to 99.8 wt.%, 49 to 98 wt.%, 50 to 97 wt.%, 55 to 96 wt.%, 60 to 94 wt.%, 65 to 92 wt.%, 70 to 90 wt.%, 75 to 88 wt.%, 80 to 86 wt.%, 82 to 84 wt.%) of the DCPD portion,0.001 to 50 wt.% (e.g., 0.01 to 50 wt.%, 0.1 to 50 wt.%, 1 to 50 wt.%, 2 to 45 wt.%, 3 to 40 wt.%, 4 to 35 wt.%, 5 to 30 wt.%, 6 to 25 wt.%, 7 to 20 wt.%, 8 to 15 wt.%, 9 to 10 wt.%) of the TCPD portion, and0.001 to 25 wt.% (e.g., 0.01 to 25 wt.%, 0.1 to 25 wt.%, 1 to 25 wt.%, 2 to 25 wt.%, 3 to 20 wt.%, 4 to 15 wt.%, 5 to 10 wt.%, 6 to 9 wt.%, 7 to 8 wt.%) of the TeCPD portion.

[0314] E13) The cyclic olefin composition of E3, comprising, consisting essentially of, or consisting of:0.001 to 49.999 wt.% (e.g., 0.01 to 49.99 wt.%, 0.1 to 49.9 wt.%, 1 to 49 wt.%, 2 to 45 wt.%, 3 to 40 wt.%, 4 to 35 wt.%, 5 to 30 wt.%, 6 to 25 wt.%, 7 to 20 wt.%, 8 to 15 wt.%, 9 to 10 wt.%) of the DCPD portion,50 to 99.998 wt.% e.g., 50 to 99.98 wt.%, 50 to 99.8 wt.%, 50 to 98 wt.%, 55 to 96 wt.%, 60 to 94 wt.%, 65 to 92 wt.%, 70 to 90 wt.%, 75 to 88 wt.%, 80 to 86 wt.%, 82 to 84 wt.%) of the TCPD portion, and0.001 to 49.999 wt.% (e.g., 0.01 to 49.99 wt.%, 0.1 to 49.9 wt.%, 1 to 49 wt.%, 2 to 45 wt.%, 3 to 40 wt.%, 4 to 35 wt.%, 5 to 30 wt.%, 6 to 25 wt.%, 7 to 20 wt.%, 8 to 15 wt.%, 9 to 10 wt.%) of the TeCPD portion.

[0315] E14) The cyclic olefin composition of any one of E1-E3, wherein the cyclic olefin composition comprises ≥ 90 wt.% (e.g., ≥ 91 wt.%, ≥ 92 wt.%, ≥ 93 wt.%, ≥ 94 wt.%, ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, ≥ 99 wt.%, ≥ 99.1 wt.%, ≥ 99.2 wt.%, ≥ 99.3 wt.%, ≥ 99.4 wt.%, ≥ 99.5 wt.%, ≥ 99.6 wt.%, ≥ 99.7 wt.%, ≥ 99.8 wt.%, ≥ 99.9 wt.%) of the DCPD portion, based on the total weight of the cyclic olefin composition.

[0316] E15) The cyclic olefin composition of any one of E1-E3, wherein the cyclic olefin composition comprises ≥ 90 wt.% (e.g., ≥ 91 wt.%, ≥ 92 wt.%, ≥ 93 wt.%, ≥ 94 wt.%, ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, ≥ 99 wt.%, ≥ 99.1 wt.%, ≥ 99.2 wt.%, ≥ 99.3 wt.%, ≥ 99.4 wt.%, ≥ 99.5 wt.%, ≥ 99.6 wt.%, ≥ 99.7 wt.%, ≥ 99.8 wt.%, ≥ 99.9 wt.%) of a combined amount of the DCPD and TCPD portions, based on the total weight of the cyclic olefin composition.

[0317] E16) The cyclic olefin composition of E2 or E3, wherein the cyclic olefin composition comprises ≥ 90 wt.% (e.g., ≥ 91 wt.%, ≥ 92 wt.%, ≥ 93 wt.%, ≥ 94 wt.%, ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, ≥ 99 wt.%, ≥ 99.1 wt.%, ≥ 99.2 wt.%, ≥ 99.3 wt.%, ≥ 99.4 wt.%, ≥ 99.5 wt.%, ≥ 99.6 wt.%, ≥ 99.7 wt.%, ≥ 99.8 wt.%, ≥ 99.9 wt.%) of a combined amount of the DCPD, TCPD, and TeCPD portions, based on the total weight of the cyclic olefin composition.

[0318] E17) The cyclic olefin composition of any one of E1-E3, wherein the cyclic olefin composition comprises ≥ 70 wt.% (e.g., ≥ 71 wt.%, ≥ 72 wt.%, ≥ 73 wt.%, ≥ 74 wt.%, ≥ 75 wt.%, ≥ 76 wt.%, ≥ 77 wt.%, ≥ 78 wt.% ≥ 79 wt.%) of the TCPD portion, based on the total weight of the cyclic olefin composition.

[0319] E18) The cyclic olefin composition of E3, wherein the cyclic olefin composition comprises ≥ 90 wt.% (e g., ≥ 91 wt.%, ≥ 92 wt.%, ≥ 93 wt.%, ≥ 94 wt.%, ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, ≥ 99 wt.%, ≥ 99.1 wt.%, ≥ 99.2 wt.%, ≥ 99.3 wt.%, ≥ 99.4 wt.%, ≥ 99.5 wt.%, ≥ 99.6 wt.%, ≥ 99.7 wt.%, ≥ 99.8 wt.%, ≥ 99.9 wt.%) of the TCPD portion, based on the total weight of the cyclic olefin composition.

[0320] E19) The cyclic olefin composition of E3, wherein the cyclic olefin composition comprises ≥ 90 wt.% (e g., ≥ 91 wt.%, ≥ 92 wt.%, ≥ 93 wt.%, ≥ 94 wt.%, ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, ≥ 99 wt.%, ≥ 99.1 wt.%, ≥ 99.2 wt.%, ≥ 99.3 wt.%, ≥ 99.4 wt.%, ≥ 99.5 wt.%, ≥ 99.6 wt.%, ≥ 99.7 wt.%, ≥ 99.8 wt.%, > 99.9 wt.%) of a combined amount of the TCPD and TeCPD portions, based on the total weight of the cyclic olefin composition.

[0321] E20) The cyclic olefin composition of any one of E1-E3, wherein the cyclic olefin composition comprises ≤ 7 wt.% (e.g., ≤ 6 wt.%, ≤ 5 wt.%, ≤ 4 wt.%, ≤ 3 wt.%, ≤ 2 wt.%, ≤ 1 wt.%, ≤ 0.1 wt.%, ≤ 0.01 wt.%, ≤ 0.001 wt.%, ≤ 0.0001 wt.%) of the TCPD portion, based on the total weight of the cyclic olefin composition.

[0322] E21 ) The cyclic olefin composition of E2 or E3, wherein the cyclic olefin composition comprises ≤ 7 wt.% (e.g., ≤ 6 wt.%, ≤ 5 wt.%, ≤ 4 wt.%, ≤ 3 wt.%, ≤ 2 wt.%, ≤ 1 wt.%, ≤ 0.1 wt.%, ≤ 0.01 wt.%, ≤ 0.001 wt.%, ≤ 0.0001 wt.%) of the TeCPD portion, based on the total weight of the cyclic olefin composition.

[0323] E22) The cyclic olefin composition of E2 or E3, wherein the cyclic olefin composition comprises ≤ 7 wt.% (e.g., ≤ 6 wt.%, ≤ 5 wt.%, ≤ 4 wt.%, ≤ 3 wt.%, ≤ 2 wt.%, ≤ 1 wt.%, ≤ 0.1 wt.%, ≤ 0.01 wt.%, ≤ 0.001 wt.%, < 0.0001 wt.%) of a combined amount of the TCPD and TeCPD portions, based on the total weight of the cyclic olefin composition.

[0324] E23) The cyclic olefin composition of E2 or E3, wherein: the cyclic olefin composition comprises 0.001 to 5 wt.% (e.g., 0.01 to 4 wt.%, 0.1 to 3 wt.%, 0.5 to 2 wt.%, 1 to 1 .5 wt.%) of the DCPD portion, based on the total weight of the cyclic olefin composition; the TCPD portion comprises < 70% TCPD-1 and > 15% TCPD 5, based on the total weight of the TCPD portion; and the TeCPD portion comprises <55% TeCPD-6 and >13% TeCPD-7, based on the total weight of the TeCPD portion.

[0325] E24) The cyclic olefin composition of E2 or E3, comprising 20 to 50 wt.% (e.g., 25 to 45 wt.%, 30 to 40 wt.%) of the DCPD portion, 50 to 80 wt.% (e.g., 55 to 75 wt.%, 60 to 70 wt.%) of the TCPD portion, and 0.1 to 7 wt.% (e.g., 1 to 6 wt.%, 2 to 5 wt.%, 3 to 4 wt.%) of TeCPD portion, based on the total weight of the cyclic olefin composition.

[0326] E25) The cyclic olefin composition of any one of E1 -E3, comprising a weight ratio of the TCPD portion to the DCPD portion of ≥ 1 (e.g., > 5, > 10).

[0327] E26) The cyclic olefin composition of E2 or E3, comprising a weight ratio of the DCPD portion to TeCPD portion of > 1 (e.g., > 5, > 10).

[0328] E27) The cyclic olefin composition of E2 or E3, comprising a weight ratio of the TCPD portion to TeCPD portion of > 1 (e.g., > 5, > 10).

[0329] E28) The cyclic olefin composition of E1 , wherein the cyclic olefin composition does not comprise TCPD.

[0330] E29) The cyclic olefin composition of E2, wherein the cyclic olefin composition does not comprise TeCPD.

[0331] E30) The cyclic olefin composition of any one of E1-E29, wherein the cyclic olefin composition does not comprise a higher order oligomer of cyclopentadiene.

[0332] E31 ) The cyclic olefin composition of any one of E1-E29, wherein the cyclic olefin composition does not comprise pentacyclopentadiene and hexacyclopentadiene.

[0333] E32) The cyclic olefin composition of any one of E1-E29, wherein the cyclic olefin composition does not comprise pentacyclopentadiene.

[0334] E33) The cyclic olefin composition of any one of E1-E29, wherein the cyclic olefin composition does not comprise hexacyclopentadiene.

[0335] E34) The cyclic olefin composition of any one of E1-E29, wherein the cyclic olefin composition does not comprise any further multiunsaturated cyclic olefins and / or monounsaturated cyclic olefins.

[0336] E35) The cyclic olefin composition of any one of E1-E29, wherein the cyclic olefin composition further comprises at least one higher order oligomer of cyclopentadiene.

[0337] E36) The cyclic olefin composition of any one of E1-E29, wherein the cyclic olefin composition further comprises pentacyclopentadiene and hexacyclopentadiene.

[0338] E37) The cyclic olefin composition of any one of E1-E29, wherein the cyclic olefin composition further comprises pentacyclopentadiene.

[0339] E38) The cyclic olefin composition of any one of E1-E29, wherein the cyclic olefin composition further comprises hexacyclopentadiene.

[0340] E39) The cyclic olefin composition of any one of E1-E38, wherein the cyclic olefin composition is liquid at ≤ 50 °C (e.g., ≤ 40 °C, ≤ 30 °C, ≤ 25 °C, ≤ 20 °C).

[0341] E40) The cyclic olefin composition of any one of E1-E38, wherein the cyclic olefin composition is liquid at ≤ 0 °C (e.g., ≤ -5 °C, ≤ -10 °C, ≤ -20 °C, ≤ -30 °C).

[0342] E41 ) The cyclic olefin composition of any one of E1-E38, wherein the cyclic olefin composition is liquid at ≤ 50 °C (e.g., ≤ 40 °C, ≤ 30 °C, ≤ 25 °C, ≤ 20 °C) and wherein the cyclic olefin composition comprises ≥ 70 wt.% (e.g., ≥ 72 wt.%, ≥ 74 wt.%, ≥ 76 wt.%, ≥ 78 wt.%) of the TCPD portion, based on the total weight of the cyclic olefin composition.

[0343] E42) The cyclic olefin composition of E2 or E3, wherein the cyclic olefin composition is liquid at ≤ 30 °C ( ≤ 25 °C, ≤ 20 °C) and wherein the cyclic olefin composition comprises ≥ 70 wt.% (e.g., ≥ 75 wt.%, ≥ 80 wt.%, ≥ 85 wt.%, ≥ 89 wt.%) of the TCPD portion, based on the total weight of the cyclic olefin composition.

[0344] E43) The cyclic olefin composition of E3, wherein the cyclic olefin composition is liquid at ≤ 30 °C ( ≤ 25 °C, ≤ 20 °C) and wherein the cyclic olefin composition comprises ≥ 90 wt.% (e.g., ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, ≥ 99 wt.%) of the TCPD portion, based on the total weight of the cyclic olefin composition.

[0345] E44) The cyclic olefin composition of any one of E1 -E3, wherein the cyclic olefin composition is liquid at ≤ 50 °C (e.g., ≤ 40 °C, ≤ 30 °C, ≤ 25 °C, ≤ 20 °C) and wherein the cyclic olefin composition comprises ≥ 70 wt.% (e.g., ≥ 72 wt.%, ≥ 74 wt.%, ≥ 76 wt.%, ≥ 78 wt.%) of the combined TCPD and TeCPD portions, based on the total weight of the cyclic olefin composition.

[0346] E45) The cyclic olefin composition of E2 or E3, wherein the cyclic olefin composition is liquid at ≤ 30 °C ( ≤ 25 °C, ≤ 20 °C) and wherein the cyclic olefin composition comprises ≥ 70 wt.% (e.g., ≥ 75 wt.%, ≥ 80 wt.%, ≥ 85 wt.%, ≥ 89 wt.%) of the combined TCPD and TeCPD portions, based on the total weight of the cyclic olefin composition.

[0347] E46) The cyclic olefin composition of E3, wherein the cyclic olefin composition is liquid at ≤ 30 °C ( ≤ 25 °C, < 20 °C) and wherein the cyclic olefin composition comprises ≥ 90 wt.% (e.g., ≥ 95 wt.%, ≥ 96 wt.%, ≥ 97 wt.%, ≥ 98 wt.%, > 99 wt.%) of the combined TCPD and TeCPD portions, based on the total weight of the cyclic olefin composition.

[0348] E47) A resin composition, comprising, consisting essentially of, or consisting of the cyclic olefin composition of any one of E1-E46.

[0349] E48) The resin composition of E47, wherein the resin composition further comprises at least one additional multiunsaturated cyclic olefin.

[0350] E49) The resin composition of E47 or E48, wherein the resin composition further comprises at least one monounsaturated cyclic olefin.

[0351] E50) The resin composition of any one of E47-E49, wherein the resin composition further comprises at least one adhesion promoter.

[0352] E51 ) The resin composition of any one of E47-E50, wherein the resin composition further comprises at least one antioxidant and / or at least one antiozonant.

[0353] E52) The resin composition of any one of E47-E51 , wherein the resin composition further comprises at least one impact modifier.

[0354] E53) The resin composition of any one of E47-E52, wherein the resin composition further comprises at least one internal mold release.

[0355] E54) The resin composition of any one of E47-E53, wherein the resin composition further comprises at least one gel modifier.

[0356] E55) The resin composition of any one of E47-E54, wherein the resin composition further comprises at least one hydrocarbon resin.

[0357] E56) The resin composition of any one of E47-E55, wherein the resin composition further comprises at least one plasticizer.

[0358] E57) The resin composition of any one of E47-E56, wherein the resin composition does not comprise a melt-point depressant diluent.

[0359] E58) The resin composition of E57, wherein the melt-point depressant diluent is selected from a reactive cycloolefin or cyclodiolefin monomer containing at least one norbornene structure, or a mixture of reactive monomers other than DCPD, TCPD, and TeCPD.

[0360] E59) The resin composition of E58, wherein the melt-point depressant diluent is selected from 5-ethylidene-2-norbornene, methyl-^tetracyclododecene, methyl- dicyclopentadiene, and hexacycloheptadecene.

[0361] E60) A ring-opening metathesis polymerization (ROMP) composition, comprising, consisting essentially of, or consisting of the cyclic olefin composition of any one of E1-E46 or the resin composition of any one of E47-E59 and at least one catalyst composition comprising, consisting essentially of, or consisting of at least one metal carbene olefin metathesis catalyst.

[0362] E61 ) The ROMP composition of E60, wherein the at least one metal carbene olefin metathesis catalyst is a metathesis catalyst containing ruthenium, molybdenum, tungsten, or titanium.

[0363] E62) The ROMP composition of E60, wherein the at least one metal carbene olefin metathesis catalyst is selected from a First Generation Grubbs-type olefin metathesis catalyst; a Second Generation Grubbs-type olefin metathesis catalyst; a First Generation Hoveyda-Grubbs- type olefin metathesis catalyst; a Second Generation Hoveyda-Grubbs-type olefin metathesis catalyst; a Schrock-type molybdenum olefin metathesis catalyst; a high -oxidation-state alkylidenecomplex of molybdenum; a high-oxidation-state alkylidene complex of tungsten; and mixtures thereof.

[0364] E63) The ROMP composition of E60, wherein the at least one metal carbene olefin metathesis catalyst is a Group 8 transition metal complex having the structure of formula (I):(i)wherein:M is a Group 8 transition metal;L1, L2, and L3are neutral electron donor ligands; n is 0 or 1 , such that L3may or may not be present; m is 0, 1 , or 2; k is 0 or 1 ;X1and X2are anionic ligands; andR1and R2are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, wherein any two or more of X1, X2, L1, L2, L3, R1, and R2can be taken together to form one or more cyclic groups, and further wherein any one or more of X1, X2, L1, L2, L3, R1, and R2may be attached to a support.

[0365] E64) The ROMP composition of E63, wherein the at least one metal carbene olefin metathesis catalyst is a Group 8 transition metal complex having the structure of formula (I), wherein:M is ruthenium; n is 0; m is 0; k is 1 ;L1and L2are trisubstituted phosphines independently selected from tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMe2Ph), and diethylphenylphosphine (PEt2Ph); orL1is an N-heterocyclic carbene selected from 1 ,3-bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene, 1 ,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, 1 ,3-bis(2,4,6-trimethylphenyl)-2-imidazol-2-ylidene, and 1 ,3-bis(2,6-di-isopropylphenyl)-2-imidazol-2-ylidene; and L2is a trisubstituted phosphine selected from tri-n-butylphosphine (Pn-Bu3), tricyclopentylphosphine (PCp3), tricyclohexylphosphine (PCy3), triisopropylphosphine (P-i-Pr3), triphenylphosphine (PPh3), methyldiphenylphosphine (PMePh2), dimethylphenylphosphine (PMejPh), and diethylphenylphosphine (PEt2Ph); orL1and L2are N-heterocyclic carbenes independently selected from 1 ,3-bis(2,4,6- trimethylphenyl)-2-imidazolidinylidene, 1 ,3-bis(2,6-di-isopropylphenyl)-2-imidazolidinylidene, 1 ,3- bis(2,4,6-trimethylphenyl)-2-imidazol-2-ylidene, and 1 ,3-bis(2,6-di-isopropylphenyl)-2-imidazol-2- ylidene;X1and X2are chlorine; andR1is hydrogen and R2is phenyl or -CH=C(CH3)2; or R1and R2are taken together to form an indenylidene moiety.

[0366] E65) The ROMP composition of E60, wherein the at least one metal carbene olefin metathesis catalyst is a Group 8 transition metal complex having the structure of formula (VII):(VII)wherein:M is a Group 8 transition metal;X1and X2are anionic ligands;L1is a neutral electron donor ligand;Y is a heteroatom selected from N, O, S, and P;R5, R6, R7, and R8are each, independently, selected from 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, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, wherein A is a divalent hydrocarbon moiety selectedfrom alkylene and arylalkylene, wherein the alkyl portion of the alkylene and arylalkylene groups can be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl portion of the of arylalkylene can be substituted or unsubstituted, and wherein hetero atoms and / or functional groups may be present in either the aryl or the alkyl portions of the alkylene and arylalkylene groups, and Fn is a functional group; and any combination of R5, R6, R7, and RBcan be linked to form one or more cyclic groups; n is 1 or 2, such that n is 1 for the divalent heteroatoms O or S, and n is 2 for the trivalent heteroatoms N or P; andZ is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl where the functional group may independently be one or more or the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, 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, V, Z, R5, R6, R7, and R8may be linked to a support.

[0367] E66) The ROMP composition of any one of E60-E65, wherein the at least one metal carbene olefin metathesis catalyst is present in an amount ranging from 0.01 to 40 wt.% (e.g., 0.1 to 35 wt.%, 1 to 35 wt.%, 5 to 25 wt.%, 10 to 20 wt.%), based on the total weight of the catalyst composition.

[0368] E67) The ROMP composition of any one of E60-E66, wherein the catalyst composition further comprises at least one viscosity modifier.

[0369] E68) The ROMP composition of E67, wherein the at least one viscosity modifier is a thixotropic agent.

[0370] E69) The ROMP composition of E68, wherein the thixotropic agent is fumed silica.

[0371] E70) The ROMP composition of any one of E67-E69, wherein the at least one viscosity modifier is present in an amount ranging from 0.01 to 5 wt.% (e.g., 0.1 to 4 wt.%, 0.5 to 3 wt.%, 1 to 2 wt.%), based on the total weight of the catalyst composition.

[0372] E71 ) A method of making the ROMP composition of E60-E70, comprising, consisting essentially of, or consisting of: combining the cyclic olefin composition of any one of E1-E46 or the resin composition of any one of E47-E59 with the catalyst composition of any one of E60-E66 to form the ROMP composition.

[0373] E72) A ROMP polymer, comprising, consisting essentially of, or consisting of the reaction product of the ROMP composition of any one of E60-E70, wherein the ROMP composition is subjected to conditions effective to polymerize the ROMP composition.

[0374] E73) A method of making a ROMP polymer, comprising, consisting essentially of, or consisting of: subjecting the ROMP composition of any one of E60-E70 to conditions effective to polymerize the ROMP composition to form the ROMP polymer.

[0375] E74) A curable article of manufacture comprising, consisting essentially of, or consisting of the ROMP composition of any one of E60-E70.

[0376] E75) A cured article of manufacture, wherein the curable article of manufacture of E69 is cured.

[0377] E76) The cured article of manufacture of E75, wherein the cured article of manufacture is a composite, an insulation material, a coating, or a cast part.

[0378] E77) A method of making a cured article of manufacture, comprising, consisting essentially of, or consisting of: subjecting the ROMP composition of any one of E60-E70 to conditions effective to polymerize the ROMP composition to form a ROMP polymer; and subjecting the ROMP polymer to conditions effective to cure the ROMP polymer to make the cured article of manufacture.

[0379] E78) A kit comprising, consisting essentially of, or consisting of the cyclic olefin composition of any one of E1 -E46.

[0380] E79) A kit comprising, consisting essentially of, or consisting of the resin composition of any one of E47-E59.

[0381] E80) A kit comprising, consisting essentially of, or consisting of the ROMP composition of any one of E60-E70.EXPERIMENTAL

[0382] In the following examples, efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, temperature, etc.) but some experimental error and deviation should be accounted for. Unless indicated otherwise, temperature is in degrees Celsius (°C), pressure is at or near atmospheric, viscosity is in centipoise (cP). Additives added to the ROMP compositions are reported as ppm, which is defined as the weight in grams of additive per milliongrams of cyclic olefin composition, or as phr, which is defined as the weight in grams of the additive per hundred grams of cyclic olefin composition.

[0383] The following examples are to be considered as not being limiting of the invention as described herein, and are instead provided as representative examples of compositions of the embodiments disclosed herein and methods for their use, and articles made from such compositions and methods.EXAMPLESMaterials and Methods

[0384] All glassware was oven dried and reactions were performed under ambient conditions unless otherwise noted. All solvents and reagents were purchased from commercial suppliers and used as received unless otherwise noted.

[0385] It is to be understood that while the invention has been described in conjunction with specific embodiments thereof, that the description above 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.

[0386] Cyclic olefin composition “DCPD” was obtained from Cymetech Corporation (ULTRENE™) and is typically >99% dicyclopentadiene (DCPD). Generally, enriched exo-DCPD feeds (e.g., F1, F2, F3) were generated via heat soaking DCPD in an autoclave at temperatures >150 °C, and isolating the DCPD fraction of the resulting reaction via distillation. If needed, distillate was heat soaked again to further enrich the exo-DCPD in the DCPD fraction. This could be achieved by a continuous process. For example, a process, comprising: (1) introducing a hydrocarbon feed comprising cyclopentadiene and dicyclopentadiene into a reaction zone; (2) subjecting the hydrocarbon feed to reaction conditions sufficient to effect reaction between the CPD and the DCPD within the reaction zone to produce a reactor effluent comprising TCPD, TeCPD, CPD, and DCPD; (3) separating from the reactor effluent a first product, a second product, and a purge stream, wherein: the first product comprises DCPD, TCPD, and TeCPD, the second product comprises CPD and DCPD, and the purge stream comprises CPD, nitrogen, and oxygen; separating the second product into at least a first portion and a second portion; and introducing the first portion of the second product into the reaction zone.

[0387] During production of TCPD, TeCPD production is controlled through reactor conditions (e.g., residence time, temperature, etc.). Through control of the exo content of the DCPD feed and reactor conditions, the isomer distributions of TCPD and TeCPD may be predominantlycontrolled. All of the cyclic olefin compositions can be reacted with metal carbene olefin metathesis catalysts known in the art, such as those disclosed herein. All of the cyclic olefin compositions can be blended with various other additives used in the art (e.g., melt point depressants, rubbers, etc.) and reacted with metal carbene olefin metathesis catalysts, such as those disclosed herein, using methods known in the art.

[0388] Metal carbene olefin metathesis catalysts were purchased from Umicore and include 2ndgeneration Grubbs Catalysts.

[0389] An ASTM D2887 n-paraffin standard was purchased from Aqua Solutions.

[0390] General Procedure

[0391] Heat soaking was conducted in a Parr reactor on a hot plate with a 600 mL capacity, equipped with a cross stir bar and connected to an N2line. 400-450 g of DCPD with varying exo- DCPD content was sparged with N2and added to the reactor at 80 °C. The reactor was purged with N2 three times to ensure an inert atmosphere and placed under N2pressure (50-100 psi). The reaction mixture was equilibrated at 80 °C and then the external temperature on the hot plate was set to 200-240 °C such that the internal temperature could reach 150-180 °C. Optimal stirring was maintained at 150-170 RPM. The reaction was heated for 60-130 minutes after reaching 145 °C, depending on the desired % conversion (i.e. TCPD + TeCPD concentration). The reaction was stopped after the desired time and allowed to cool. The pressure was then released, and the reaction product was isolated from the reactor. This was done as many times as necessary to generate sufficient material for distillation. Samples were analyzed via GC to track isomer content and distribution.

[0392] Distillation was conducted in lab glassware. A 2L flask was charged with -1 ,5kg of the DCPD heat soak reaction and distilled via vacuum pressure at 1-4 torr. The pot temperature was held at 65-95 °C and a head temperature of 45-55 °C. The distillation was stopped when the purity of the bottoms reached <5% DCPD, ideally <1%, and was composed of TCPD, TeCPD, and further heavier oligomers.

[0393] Blends were then made by mixing the distillate (e.g., 1 D, 2D, 3D, etc.) and bottoms (e.g., 1 B, 2B, 3B, etc.) products at varying ratios. In this naming structure, 1 D and 1B are the distillate and bottoms respectively generated from the distillation of sample 1. In some cases, mild heating (<60 °C) was needed to melt the samples before blending. The blend compositions varied in 10% increments of bottoms product (e.g., 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%). These blends were then analyzed for their physical properties.

[0394] All samples were analyzed via GC using an Agilent 8890 GC system according to Method A described in the following Table 2:Table 2. Gas Chromatography Method A

[0395] An example chromatogram of a cyclic olefin composition comprising DCPD, TCPD, and TeCPD (including any other heavier oligomers and impurities) is shown in FIG. 1 from Sample 8, described below. The elution time ranges of the DCPD, TCPD, and TeCPD regions are described in

[0396] Table 3. The elution time ranges of the DCPD, TCPD, and TeCPD isomer peaks are described in Table 4. The chromatogram was analyzed using Agilent Openlab Chemstation (chromatography data system) integrating all peaks baseline to baseline, normalizing the peakarea to report as peak area %. All compositional data herein is reported as peak area %. The response factor for all isomers was assumed to be 1 . The percentage of DCPD in the sample was measured by taking the integration sum of the DCPD peaks (endo-DCPD and exo-DCPD) in the DCPD region divided by the sum of all of the peaks in the chromatogram produced via Method A. The percentage of TCPD in the sample was measured by taking the integration sum of the TCPD peaks in the TCPD region divided by the sum of all of the peaks in the chromatogram produced via Method A. The percentage of TeCPD in the sample was measured by taking the integration sum of the TeCPD peaks in the TeCPD region divided by the sum of all the peaks in the chromatogram produced via Method A.Table 3Table 4

[0397] Percentages of endo-DCPD and exo-DCPD of the DCPD fraction of the cyclic olefin compositions were measured by integrating the endo-DCPD and exo-DCPD peaks in the chromatogram produced via Method A and dividing by the sum of all DCPD isomers in the DCPD region for each peak, respectively. An example of the DCPD region of a chromatogram produced via Method A is shown in FIG. 2 from Sample 8, described below.

[0398] Percentages of the various isomers of TCPD in the TCPD fraction of the cyclic olefin compositions were measured by integrating the TCPD peaks in the chromatogram produced via Method A and dividing by the sum of all isomers in the TCPD region for each peak, respectively. An example of the TCPD region of a chromatogram produced via Method A is shown in FIG. 3 from Sample 8, described below.

[0399] Percentages of the various isomers of TeCPD in the TeCPD fraction of the cyclic olefin compositions were measured by integrating the TeCPD peaks in the chromatogram produced via Method A and dividing by the sum of all isomers in the TeCPD region for each peak, respectively. An example of the TeCPD region of a chromatogram produced via Method A is shown in FIG. 4 from Sample 8, described below.

[0400] It is appreciated that column age and sample loading can affect the retention times and peak qualities of the chromatograms of samples analyzed via Method A and GC methods in general. The method was run while ensuring the column was clean and free of anything other than the samples being analyzed. It is preferred that samples are diluted with a solvent (e.g., cyclohexane or toluene) before being used for GC analysis at a weight ratio of 5:1 up to 15:1 of solvent to sample. If a solvent is used, the solvent peak is omitted from the analysis of the chromatogram. A solvent should also have no molecules that co-elute with the cyclic olefin composition so as to obscure or cause misinterpretation of the chromatogram . It is appreciated that modifying the method may cause peaks to overlap or to cause a single peak to separate into multiple peaks if there are multiple isomers present that elute at similar times. For example, TeCPD III appears to be two co-eluting isomers, but they have been summed together for the purposes of the analysis described herein, and neither isomer was separately quantified. It is possible that other TCPD and TeCPD isomers could be in fact one or more other isomers that co- elute using Method A. If such isomers can be separated using a different method or other equipment, they should be summed together to achieve substantially the same results as Method A. There may also be other peaks in the chromatogram of small quantity that appear given the impurity profile of the reaction mixture. These additional peaks should not cause a change in the interpretation of the chromatogram. For example, it appears that there is a small peak between TeCPD III and TeCPD IV and between TeCPD VI and TeCPD VII. These peaks were not includedin measurements of TeCPD isomers, though the possibility that they are TeCPD isomers cannot be excluded. A substantially pure sample of DCPD (e.g., >99.9% purity) and the cyclic olefin compositions produced therefrom can be used to calibrate one’s method to achieve substantially similar or equivalent results as Method A.

[0401] Retention Index for DCPD, TCPD, and TeCPD

[0402] A retention index (Rl) in chromatography, specifically gas chromatography, compares the retention times of different compounds to a standard series of n-alkanes. The retention index of a chemical compound is calculated by interpolating its retention time between two adjacent n- alkanes. For example, if a compound elutes between n-decane (10 carbons) and n-undecane (11 carbons), its retention index would be a value between 1000 and 1100.

[0403] While retention times vary with the individual chromatographic system (e.g., column length, film thickness, diameter, and inlet pressure), the derived retention indices are independent of these parameters and allow comparing values measured by different analytical laboratories under varying conditions and analysis times from seconds to hours. Tables of retention indices are used to identify peaks by comparing measured retention indices with the tabulated values.

[0404] An Rl for each DCPD, TCPD, and TeCPD isomer was determined using ASTM D2887 (Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas ChromatographySee Table 5). The n-paraffin mix from Aqua Solutions was analyzed utilizing the same GC conditions as the samples. RIs were calculated using Kovats Index equation defined by IUPAC for temperature programmed chromatography:where: h is defined as the retention index of the chemical compound of interest, n is defined as the carbon number of n-alkane peak heading peak, t, is defined as retention times of the chemical compound of interest, tnis defined as the retention times of the reference n-alkane hydrocarbons eluting immediately before the chemical compound of interest, and tn+i is defined as the retention times of the reference n-alkane hydrocarbons eluting immediately after the chemical compound of interest.

[0405] The retention index for each of the compounds was independently determined on three different GC instruments using Method A with the same D2887 standard from Aqua Solutions and heat soaked samples.Table 5

[0406] The retention times for the n-paraffin timing mix obtained from Aqua Solutions is shown in Table 6.Table 6. Retention Time of n-Paraffins from D2887 Standard

[0407] Differential scanning calorimetry (DSC)

[0408] The melt point or assumed equilibrium melt point of the cyclic olefin composition disclosed herein was determined via DSC using a TA Instruments DSC 2500. The samples were sealed in TA hermetic lids and pans to ensure that volatilization did not occur in the DSC. The sample mass prepared in each pan was between 5 and 15 milligrams before being hermetically sealed. The general procedure to determine melt point is outlined in the article "DSC Method for Determining the Liquidus Temperature of Glass-Forming Systems,” J. Am. Ceram. Soc., 93(11 ):3757-3763 (2010), the complete disclosure of which is incorporated herein by reference, where the equilibrium melt point is determined via extrapolation of the melt point associated to various rates. For these samples discussed herein, the following general procedure was used.1 . Ramp up to 60 °C at 50 °C / min to melt the sample and remove thermal history2. Isothermal for 2 minutes3. Ramp 20 °C / min to -70.00 °C4. Isothermal 5.0 min5. Ramp 50 °C / min to 60.00 °C6. Isothermal 2.0 min7. Repeat 3 for 1 time8. Ramp 20 °C / min to -70.00 °C9. Isothermal 5.0 min10. Ramp 20 °C / min to 60.00 °C11. Isothermal 2.0 min12. Ramp 20 °C / min to -70.00 °C13. Isothermal 5.0 min14. Ramp 10 °C / min to 60.00 °C15. Isothermal 2.0 min16. Ramp 20 °C / min to -70.00 °C17. Isothermal 5.0 min18. Ramp 5 °C / min to 60 °C

[0409] The melt point for each ramp up was determine via the endset method , (an example using sample BL12, disclosed herein, is shown in FIG. 5). The equilibrium melt point was then determined through extrapolation to zero rates (BL12 example shown in FIG. 6). For samples where there was not sufficient time for the sample to crystallize during cooling, an isothermal temperature was held at -40 °C for 30 minutes on the ramp downs (e.g., steps 3, 8, 12, and 16) to facilitate crystallization of the sample before continuing the run. For samples with multiple melt points, an isothermal temperature was held at a temperature between the highest two melt points on the ramps downs (e.g., steps 3, 8, 12, and 16) to facilitate crystallization corresponding to the highest melt point. For samples where none of the above methods and modification yielded a clear melt point, it was assumed that the material would not crystallize in the conditions explored - these samples or blends have a blank (“-") where their melt point is described in Table 13.

[0410] The feed compositions are shown in Table 7.Table 7. Feed Compositions in wt%.

[0411] The heat soaking reaction conditions used to generate cyclic olefin compositions as described in the general heat soak procedure are shown in Table 8. Conversion is calculated by subtracting the total DCPD in the heat soaked samples from the total DCPD in the feed of the reaction.Table 8. Reaction Conditions Used to Make Cyclic Olefin Compositions

[0412] The heat soak generated cyclic olefin sample compositions are shown in Table 9.Table 9. Cyclic Olefin Sample Compositions in wt%

[0413] The TCPD portion of cyclic olefin samples are shown in Table 10.Table 10. TCPD Isomer Composition in wt % of the TCPD portion of the Cyclic Olefin Samples

[0414] The TeCPD portion of cyclic olefin samples are shown in Table 11 .Table 11 . TeCPD Isomer Composition in wt % of the TeCPD portion of the Cyclic Olefin Samples

[0415] The distillate and bottoms compositions of cyclic olefin samples are shown in Table 12.Table 12. Distillate and Bottoms Compositions of Cyclic Olefin Samples in wt%.

[0416] The cyclic olefin blends compositions and melt points are shown in Table 13.Table 13. Cyclic Olefin Blends Compositions in wt% and Melt Points

[0417] Physical properties:

[0418] Varying concentrations of exo-DCPD in pure DCPD was tested for its impact on physical characteristics. Exo-DCPD changed the phase behavior of pure DCPD and lowered the melting point of DCPD significantly. The melting point was depressed to 5 °C from 35 °C at 14% exo- DCPD (FIG. 7). Other norbornene molecules such as 2-ethylidene-5 norbornene have a similar property, but can negatively impact product performance. Exo-DCPD lowered the melting point and improved product performance via faster reactivity and better crosslinking and curing.

[0419] Exo-DCPD and the change in isomers distributions of the heavier molecules improved the solubility of heavier molecules, such as TCPD and TeCPD, that are used for crosslinking (FIG. 8). By incorporating exo-DCPD into the DCPD fraction, the heavier molecules were solubilized for longer periods of time and at lower temperatures. This can also be used to increase the concentration of heavier molecules in the formulation before precipitation is observed.

[0420] Reactivity:

[0421] Exo-DCPD significantly accelerated the ROMP reaction in DCPD systems (FIG. 9).

[0422] At 7% exo-DCPD, the reaction time was halved from -11 minutes to ~5 minutes. This increased reactivity can be leveraged in multiple ways - faster cure times, reduced catalyst usage,and offsetting the deactivation of molecules that would otherwise slow the reactivity of the catalyst to unacceptable rates.

[0423] Reducing the catalyst concentration by 25% and 50% resulted in the control samples slowed down substantially from ~11 mins to 28 mins with a low peak exotherm temperature, indicative of pure cure. See Table 14. The 7% exo-DCPD samples were also slowed substantially after catalyst reduction, but the starting point was much faster. Thus, with 50% catalyst, the reaction was as ast and complete as the control with 100% catalyst. The Tg of the samples were also measured, and a similar result was achieved - at 50% catalyst, the high exo-DCPD sample had a similar Tg as the control with 100% catalyst (FIG. 10).Table 14. Comparison of reaction rates / peak exotherm of ROMP catalysts at varying catalyst concentration vs exo-DCPD content* C25 is a commercially available suspension of 2ndgeneration Grubbs from Proxxima and used as received.

[0424] While particular embodiments have been shown and described, it will be obvious to those skilled in the art that, based upon the teachings herein, changes, and modifications may be made without departing from the embodiments and the broader aspects of the disclosure. Therefore, the appended claims are to encompass within their scope all such changes and modifications as are within the true spirit and scope of the embodiments. Furthermore, it is to be understood that the embodiments are solely defined by the appended claims. It will be understood by those with skill in the art that if a specific number of an introduced claim element is intended, such intent will be explicitly recited in the claim, and in the absence of such recitation no suchlimitation is present. For a non-limiting example, as an aid to understanding, the following appended claims contain usage of the introductory phrases “at least one” and “one or more” to introduce claim elements. However, the use of such phrases should not be construed to imply that the introduction of a claim element by the indefinite articles “a” or “an” limits any particular claim containing such introduced claim element to embodiments containing only one such element, even when the same claim includes the introductory phrases “one or more” or “at least one” and indefinite articles such as “a” or “an”; the same holds true for the use in the claims of definite articles. As used herein, the term “and / or” means either or both (or any combination or all of the terms or expressed referred to), e.g., “A, B, and / or C” encompasses A alone, B alone, C alone, A and B, A and C, B and C, and A, B, and C.

[0425] It is to be understood that while the invention has been described in conjunction with specific embodiments thereof, that the description above 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.

Claims

The claimed invention is:1 . A cyclic olefin composition, comprising:20 to 100 wt.% of a di-cyclopentad iene (DCPD) portion, and0 to 80 wt.% of a tri-cyclopentadiene (TCPD) portion, based on the total weight of the DCPD and TCPD portions in the cyclic olefin composition; wherein the DCPD portion comprises:0.3 to 60 wt.% of exo-DCPD, and40 to 99.7 wt.% of endo-DCPD, based on the total weight of the exo-DCPD and endo-DCPD in the DCPD portion; and wherein the TCPD portion, if present, comprises:0.1 to 10 wt.% of TCPD-7,3 to 25 wt.% of TCPD-3,5 to 45 wt.% of TCPD-5, and40 to 85 wt.% of TCPD-1 , based on the total weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 in the TCPD portion.

2. A cyclic olefin composition, comprising:0.0001 to 99.9999 wt.% of a di-cyclopentadiene (DCPD) portion,0.0001 to 90 wt.% of a tri-cyclopentadiene (TCPD) portion, and0 to 50 wt.% of a tetra-cyclopentad iene (TeCPD) portion, based on the total weight of the DCPD, TCPD, and TeCPD portions in the cyclic olefin composition; wherein the DCPD portion comprises:0.3 to 99 wt.% of exo-DCPD, and1 to 99 wt.% of endo-DCPD, based on the total weight of the exo-DCPD and endo-DCPD in the DCPD portion; wherein the TCPD portion comprises:0.1 to 10 wt.% of TCPD-7,3 to 25 wt.% of TCPD-3,5 to 90 wt.% of TCPD-5, and5 to 85 wt.% of TCPD-1 , based on the total weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 in the TCPD portion; and wherein the TeCPD portion, if present, comprises:O to 10 wt.% of TeCPD-1 ,0 to 15 wt.% of TeCPD-2,0 to 30 wt.% of TeCPD-3,0 to 5 wt.% of TeCPD-4,0 to 5 wt.% of TeCPD-5,0 to 70 wt.% of TeCPD-6, and0 to 90 wt.% of TeCPD-7, based on the total weight of the TeCPD-1, TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, and TeCPD-7 in the TeCPD portion.

3. A cyclic olefin composition, comprising:0.0001 to 99.9998 wt.% of a di-cyclopentadiene (DCPD) portion,0.0001 to 99.9998 wt.% of a tri-cyclopentadiene (TCPD) portion, and0.0001 to 50 wt.% of a tetra-cyclopentad iene (TeCPD) portion, based on the total weight of the DCPD, TCPD, and TeCPD portions in the cyclic olefin composition; wherein the DCPD portion comprises:0.3 to 99 wt.% of exo-DCPD, and1 to 99 wt.% of endo-DCPD, based on the total weight of the exo-DCPD and endo-DCPD in the DCPD portion; wherein the TCPD portion comprises:0.1 to 10 wt.% of TCPD-7,3 to 25 wt.% of TCPD-3,5 to 90 wt.% of TCPD-5, and5 to 85 wt.% of TCPD-1 , based on the total weight of the TCPD-7, TCPD-3, TCPD-5, and TCPD-1 in the TCPD portion; and wherein the TeCPD portion comprises:O to 10 wt.% of TeCPD-1 ,0 to 15 wt.% of TeCPD-2,0 to 30 wt.% of TeCPD-3,0 to 5 wt.% of TeCPD-4,0 to 5 wt.% of TeCPD-5,0 to 70 wt.% of TeCPD-6, and0 to 90 wt.% of TeCPD-7, based on the total weight of the TeCPD-1, TeCPD-2, TeCPD-3, TeCPD-4, TeCPD-5, TeCPD-6, and TeCPD-7 in the TeCPD portion.

4. The cyclic olefin composition of any one of claims 1 -3, wherein: the exo-DCPD has a structurethe TCPD-3 has a structurethe TCPD-5 has a structurethe TCPD-1 has a structure5. The cyclic olefin composition of claim 1 , wherein: the exo-DCPD has a retention index of 1017 ±1 , the endo-DCPD has a retention index of 1031 ±1 , the TCPD-7 has a retention index of 1535 ±2, the TCPD-3 has a retention index of 1539 ±1 , the TCPD-5 has a retention index of 1585 ±1 , and the TCPD-1 has a retention index of 1579 ±1 .

6. The cyclic olefin composition of claim 2 or claim 3, wherein: the exo-DCPD has a retention index of 1017 ±1 , the endo-DCPD has a retention index of 1031 ±1 , the TCPD-7 has a retention index of 1535 ±2, the TCPD-3 has a retention index of 1539 ±1 , the TCPD-5 has a retention index of 1585 ±1 , the TCPD-1 has a retention index of 1579 ±1 , the TeCPD-1 has a retention index of 2310 ±1 , the TeCPD-2 has a retention index of 2318 ±1, the TeCPD-3 has a retention index of 2330 +2, the TeCPD-4 has a retention index of 2354 ±1, the TeCPD-5 has a retention index of 2363 ±1, the TeCPD-6 has a retention index of 2370 ±1 , and the TeCPD-7 has a retention index of 2382 ±1.

7. The cyclic olefin composition of claim 5 or claim 6, wherein the retention indexes are determined using ASTM D2887 (Standard Test Method for Boiling Range Distribution of Petroleum Fractions by Gas Chromatography).

8. The cyclic olefin composition of claim 2 or claim 3, wherein the TeCPD isomers in the TeCPD portion elute in the following order:

1. the TeCPD-1 ,2. the TeCPD-2,3. the TeCPD-3,4. the TeCPD-4,5. the TeCPD-5,6. the TeCPD-6, and7. the TeCPD-7.

9. The cyclic olefin composition any one of claims 5-8, wherein retention times are measured by gas chromatography according to GC Method A:

10. The cyclic olefin composition of claim 1 or claim 2, comprising:50 to 99.999 wt.% of the DCPD portion, and0.001 to 50 wt.% of the TCPD portion.11 . The cyclic olefin composition of claim 2 or claim 3, comprising:50 to 99.999 wt.% of the DCPD portion, and0.001 to 25 wt.% of the TeCPD portion.

12. The cyclic olefin composition of claim 2 or claim 3, comprising:49.999 to 99.998 wt.% of the DCPD portion,0.001 to 50 wt.% of the TCPD portion, and0.001 to 25 wt.% of the TeCPD portion.

13. The cyclic olefin composition of claim 3, comprising:0.001 to 49.999 wt.% of the DCPD portion,50 to 99.998 wt.% of the TCPD portion, and0.001 to 49.999 wt.% of the TeCPD portion.

14. The cyclic olefin composition of any one of claims 1 -3, wherein the cyclic olefin composition comprises ≥ 90 wt.% of the DCPD portion, based on the total weight of the cyclic olefin composition.

15. The cyclic olefin composition of any one of claims 1 -3, wherein the cyclic olefin composition comprises ≥ 90 wt.% of a combined amount of the DCPD and TCPD portions, based on the total weight of the cyclic olefin composition.

16. The cyclic olefin composition of claim 2 or claim 3, wherein the cyclic olefin composition comprises ≥ 90 wt.% of a combined amount of the DCPD, TCPD, and TeCPD portions, based on the total weight of the cyclic olefin composition.

17. The cyclic olefin composition of any one of claims 1-3, wherein the cyclic olefin composition comprises ≥ 70 wt.% of the TCPD portion, based on the total weight of the cyclic olefin composition.

18. The cyclic olefin composition of claim 3, wherein the cyclic olefin composition comprises ≥ 90 wt.% of the TCPD portion, based on the total weight of the cyclic olefin composition.

19. The cyclic olefin composition of claim 3, wherein the cyclic olefin composition comprises ≥ 90 wt.% of a combined amount of the TCPD and TeCPD portions, based on the total weight of the cyclic olefin composition.

20. The cyclic olefin composition of any one of claims 1 -3, wherein the cyclic olefin composition comprises ≤ 7 wt.% of the TCPD portion, based on the total weight of the cyclic olefin composition.

21. The cyclic olefin composition of claim 2 or claim 3, wherein the cyclic olefin composition comprises ≤ 7 wt.% of the TeCPD portion, based on the total weight of the cyclic olefin composition.

22. The cyclic olefin composition of claim 2 or claim 3, wherein the cyclic olefin composition comprises ≤ 7 wt.% of a combined amount of the TCPD and TeCPD portions, based on the total weight of the cyclic olefin composition.

23. The cyclic olefin composition of claim 2 or claim 3, wherein: the cyclic olefin composition comprises 0.001 to 5 wt.% of the DCPD portion, based on the total weight of the cyclic olefin composition; the TCPD portion comprises < 70% TCPD-1 and > 15% TCPD 5, based on the total weight of the TCPD portion; and the TeCPD portion comprises <55% TeCPD-6 and >13% TeCPD-7, based on the total weight of the TeCPD portion.

24. The cyclic olefin composition of claim 2 or claim 3, comprising 20 to 50 wt.% of the DCPD portion, 50 to 80 wt.% of the TCPD portion, and 0.1 to 7 wt.% of TeCPD portion, based on the total weight of the cyclic olefin composition.

25. The cyclic olefin composition of any one of claims 1 -3, wherein the cyclic olefin composition is liquid at < 50 °C.

26. The cyclic olefin composition of any one of claims 1-3, wherein the cyclic olefin composition is liquid at < 50 °C and wherein the cyclic olefin composition comprises ≥ 70 wt.% of the TCPD portion, based on the total weight of the cyclic olefin composition.

27. A resin composition, comprising the cyclic olefin composition of any one of claims 1 -3.

28. A ring-opening metathesis polymerization (ROMP) composition, comprising the cyclic olefin composition of any one of claims 1-3 or the resin composition of claim 27 and at least one catalyst composition comprising at least one metal carbene olefin metathesis catalyst.

29. A method of making the ROMP composition of claim 28, comprising: combining the cyclic olefin composition of any one of claims 1 -3 or the resin composition of claim 27 with at least one catalyst composition comprising at least one metal carbene olefin metathesis catalyst to form the ROMP composition.

30. A ROMP polymer, comprising the reaction product of the ROMP composition of claim 28, wherein the ROMP composition is subjected to conditions effective to polymerize theROMP composition.31 . A method of making a ROMP polymer, comprising: subjecting the ROMP composition of claim 28 to conditions effective to polymerize the ROMP composition to form the ROMP polymer.

32. A curable article of manufacture comprising the ROMP composition of claim 28.

33. A cured article of manufacture, wherein the curable article of manufacture of claim 32 is cured.

34. A method of making a cured article of manufacture, comprising: subjecting the ROMP composition of claim 28 to conditions effective to polymerize the ROMP composition to form a ROMP polymer; and subjecting the ROMP polymer to conditions effective to cure the ROMP polymer to make the cured article of manufacture.

35. A kit comprising the cyclic olefin composition of any one of claims 1 -3, the resin composition of claim 27, or the ROMP composition of claim 28.

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