METHOD FOR CONTROLLING THE FLOW OF LOW VISCOSITY RESINS IN VACUUM-ASSISTED RESIN TRANSFER MOLDING, VACUUM-ASSISTED RESIN TRANSFER MOLDING APPARATUS, AND MANUFACTURED ARTICLE

Abstract

A vacuum-assisted resin transfer molding (VARTM) method is disclosed, the method comprising: providing a vacuum-assisted resin transfer mold assembly comprising a mold having a first mold surface and a second mold surface arranged to enclose a laminate assembly within a space between the first and second mold surfaces when the laminate assembly is placed on the first mold surface; providing a laminate assembly comprising a laminate pre-form, a peel ply, and a resin distribution media pervious to the flow of a resin, the laminate pre-form having first and second surfaces, the first surface of the pre-form positioned to be in contact with the first mold surface, the peel ply positioned such that the second surface of the laminate pre-form is in contact with the peel ply, and the resin distribution media positioned to be contained within the first and second mold surfaces; positioning at least one resin flow control structure to modify the flow of resin within the resin distribution media; providing at least one inlet and at least one outlet in the laminate assembly such that the resin can be introduced into the assembly through the inlet; arranging and sealing the second mold surface to enclose the laminate assembly within the space between the first and second mold surfaces such that a vacuum can be pulled on the laminate assembly contained within the space between the first and second mold surfaces; applying a vacuum to the mold assembly; allowing the resin to flow into the laminate assembly through the at least one inlet such that the resin flows into the resin distribution media; allowing the resin to flow out of the laminate assembly through the at least one outlet; and allowing the resin to cure in the laminate assembly to form a laminate material. An article of manufacture made by said VARTM method.

Description

1 / 84 “METHOD FOR CONTROLLING THE FLOW OF LOW VISCOSITY RESINS IN VACUUM-ASSISTED RESIN TRANSFER MOLDING, VACUUM-ASSISTED RESIN TRANSFER MOLDING APPARATUS, AND MANUFACTURED ARTICLE” RELATED ORDERS

[001] This application claims the benefit of U.S. Provisional Patent Application No. 61 / 346,253, filed August 23, 2010, and U.S. Provisional Patent Application No. 61 / 497,880, filed June 16, 2011, the contents of which are incorporated herein by reference. TECHNICAL FIELD

[002] The present invention relates to methods for controlling the flow of low viscosity resins in resin transfer molding (RTM) processes, in particular vacuum assisted resin transfer molding (VARTM), to ensure a uniform and complete resin distribution in thick composite laminates. More particularly, the invention relates to incorporating resin flow control structures to moderate or control resin flow without external intervention. BACKGROUND

[003] Composite infusions, such as VARTM, are closed-mold molding processes for the fabrication of larger fiber-reinforced composite structures. In this simple manifestation of infusions, a laminated fiber preform is installed on the mold surface and sealed with an outer mold surface, for example, an outer sheet of flexible bagging material such as nylon or Mylar plastic. In VARTM, a vacuum is applied to remove trapped air from the preform, and then resin infusion into the preform and curing are allowed. As typical thermoset resins used for composite fabrication tend to have high viscosities (generally 150 centipoises (cp) or higher), processing techniques have been developed to improve speed and quality. Petition 870200096653, dated 03 / 08 / 2020, page 19 / 112 2 / 84 of the resin infusion. In particular, a variety of resin delivery media types have been developed to promote resin flow.

[004] There are three basic types of VARTM. Type 1 uses the resin distribution medium on top of the laminate, between the preform and the bagging material. Type 2 uses a sandwich core as a resin distribution medium within the laminate. Type 3 uses specialized materials within the laminate itself as a resin distribution medium which, unlike type 1, is located in the composite component. For example, in Type 1 VARTM, the material is loaded onto the laminate in the xy plane in the resin distribution medium (a very permeable layer) and allowed to filter or flow down into the laminate in the z direction through an easily separated layer (shell layer) to completely fill the laminate with resin. This minimizes the current layer flow required for the thickness or z direction.Typical infusion resins have high viscosities (typically 200-600 cp at 25°C), so choosing the correct resin delivery medium for flow above the top is required to achieve a balance between flow in the xy plane and flow through the layer in the z direction.

[005] As described in, for example, U.S. Provisional Patent Applications No. 5,840,238, 6,310,121, and 6,525,125, disclosures of which are incorporated herein by reference, polymers generated by olefin metathesis processes are attractive as composite matrix materials. Of particularly beneficial use are polymers generated by ring-opening metathesis polymerization (ROMP) of cyclic olefins. The low viscosity of cyclic olefin resin formulations and the ability to control ROMP kinetics (e.g., U.S. Pat. No. 4,708,969 and 5,939,504, disclosures of which are incorporated herein by reference) facilitate composite fabrication and processing, and the corrosion resistance and high toughness of ROMP polymers lead to good composite durability. Commercially important ROMP resin formulations are generally based on inexpensive and readily available cyclic olefins such as dicyclopentadiene (DCPD), norbornenes, Petition 870200096653, dated 03 / 08 / 2020, p. 20 / 112 3 / 84 cyclooctadiene (COD), and various cycloalkenes.

[006] Although the extremely low viscosity of ROMP resin formulations is attractive for fast VARTM processing, they also present unique challenges. For example, typical high viscosity resins tend to be slow-paced and self-correcting and forgiving. Voids and channels fill slowly and problems with competing flow rates due to differences in permeability within the laminate parts are minimized. However, when one switches to ROMP resins with viscosity of 1 / 10th to 1 / 20th or less, flow control issues are amplified and as a result most techniques used with the more viscous resins no longer yield acceptable results. Figure 1(a) shows a simple representation of a resin dispensing medium containing an infusion configuration (1), a reinforcement layer (2), and a mold surface (3).While the resin is introduced in this evacuated infusion configuration in Figure 1(b), the resin flows rapidly along the resin distribution medium (1) (xy plane) and infuses more slowly into the reinforcement layer (2) (z direction) due to permeability differences between the resin distribution medium layer (1) and the reinforcement layer (2). This permeability difference can create a severe lead-lag (4), leading to areas within the reinforcement layer (2) with poor resin impregnation and possible void formation. As shown in Figures 1(c) and 1(d), as the resin continues to flow along the distribution medium (1) (xy plane) and infuses into the reinforcement layer (2) (z direction), the lead-lag can lead to areas of poor resin impregnation (i.e., dry spots or voids) (5). These areas of poor resin impregnation can lead to poor results, reduced mechanical properties, rejected parts, etc.

[007] One of the dogmas of resin infusion methods, such as VARTM, or any process involving liquid movement through a permeable medium, is that the liquid will follow the path of least resistance. However, once such a path is established, grounding of unfilled areas is usually impossible. Petition 870200096653, dated 03 / 08 / 2020, page 21 / 112 4 / 84 In composites, an unfilled portion is a failed portion. While higher viscosity and thicker resins will be self-correcting in this respect, low viscosity resins (typically less than 100 cp at 40°C, for example, 1-50 cp, 525 cp, or 10-20 cp at 40°C) require greater control. The present invention describes the incorporation of lower permeability resin flow control structures to moderate resin flow (e.g., flow rates, flow direction, etc.) through the resin distribution medium layers and ensure complete “wetting” (i.e., infusion of a desired amount of resin within the laminate to achieve the desired fiber volume in the composite) of the entire sheet. However, these pause points must be a balance of retarding and promoting flow to allow complete infusion of the entire sheet.While most VARTM enhancements aim to promote flow (i.e., increase infusion rates due to the high viscosity of the resins), low-viscosity resins require a balance of resin flow rates to allow for optimal compound fill time while maintaining full and complete resin infusion into the reinforcing layers. Controlling the flow in this way ensures full and complete infusion without dry spots. One might recall that until the current generation of low-viscosity resins (e.g., ROMP resins), such resin flow techniques were unnecessary.

[008] The invention describes the incorporation of resin flow control structures into a process such as VART™ infusion, allowing for improved control of resin flow patterns with low-viscosity resins. The use of the resin delivery medium with high-permeability resin allows for rapid distribution of the resin to key areas of the compound. The addition of resin flow control structures allows for modification of the resin flow in the delivery medium, enabling control over resin lead-lag and resin channeling patterns to ensure complete resin impregnation into the compound and to prevent voids and dry spots. This control is a combination of materials, processes. Petition 870200096653, dated 03 / 08 / 2020, page 22 / 112 5 / 84 so, and technique. SUMMARY OF THE INVENTION

[009] The invention is directed to address one or more of the aforementioned concepts and relates to a group of related processing techniques that enable resin flow to be controlled in RTM, in particular, VARTM. In this case, acceleration and retardation have been found to be necessary to ensure complete filling in VARTM, especially for low viscosity resins (typically less than 100 cp at 40°C, for example, 1-50 cp, 525 cp, or 10-20 cp at 40°C). More particularly, the resin flow control structures of the invention serve to control the flow without other external intervention. Once incorporated into the configuration, the resin flow control structures of the invention can be used to control or moderate the flow rate, or transfer the flow to another area of ​​a composite or laminated material.

[010] In one embodiment, the invention is directed to a VART™ method, the method comprises: provide a VART™ mold assembly comprising a mold having a first mold surface and a second mold surface (e.g., a vacuum bag) arranged to attach a laminate assembly within a space between the first and second surfaces when the laminate assembly is placed on the first mold surface; To provide a laminate assembly comprising a laminate preform, a shell layer, and a resin distribution medium prior to resin flow, the laminate preform having a first and a second surface, the first surface of the preform optionally positioned to be in contact with the first mold surface, the shell layer positioned so that the second surface of the laminate preform is in contact with the shell layer, and the resin distribution medium positioned to be contained within the first and second surfaces; Petition 870200096653, dated 03 / 08 / 2020, page 23 / 112 6 / 84 Position at least one resin flow control structure to modify the resin within the distribution medium; to provide at least one inlet and at least one outlet in the laminate assembly so that resin can be introduced into the laminate assembly through the inlet; Arrange and seal the second mold surface to attach the laminate assembly within the space between the first and second mold surfaces so that the vacuum can be removed from the laminate assembly contained within the space between the first and second mold surfaces; Apply a vacuum to the mold assembly; to allow a resin to flow within a laminate assembly through at least one inlet so that the resin flows into the resin distribution medium; To allow the resin to flow out of the laminate assembly through at least one outlet; and to allow the resin to cure in the laminate assembly to form a laminated material.

[011] In another embodiment, the invention is directed to a VART™ apparatus, the apparatus comprising: a VART™ mold assembly comprising a mold having at least one first mold surface and one second mold surface arranged to attach a laminate assembly within a space between the first and second mold surfaces when the laminate assembly is placed on the first mold surface; A laminate assembly comprising a laminate preform, a shell layer, a permeable resin distribution medium for resin flow, an inlet port, and an outlet port, the laminate preform having a first and a second surface, with the first surface of the preform in contact with the first surface of the mold, the second surface of the preform in contact Petition 870200096653, dated 03 / 08 / 2020, page 24 / 112 7 / 84 with the shell layer, and the resin distribution medium contained within the laminate preform or in contact with the shell layer; at least one resin flow control structure to modify the resin flow within the resin distribution medium; means for extracting a vacuum in the assembly; and means for allowing resin to flow into the laminate assembly through the inlet port so that the resin flows into the resin distribution medium.

[012] In another embodiment, the invention is directed to articles manufactured using the disclosed method and / or apparatus, including, for example, composite articles made of a fiber-reinforced resin matrix. By way of example, such articles may include jet engine blades, jet engine nacelles, vehicle panels and articles including, for example, boat hulls, car bodies and components, wind turbine blades, aircraft structures such as wings, wing parts, radar domes, fuselage components, nose cones, landing flaps, landing gear and rear bulkhead.

[013] These and other aspects of the invention will be apparent to an expert by considering the following detailed description and examples. BRIEF DESCRIPTION OF THE DRAWINGS

[014] Figure 1(a)-1(d) depicts the flow of resin through the resin distribution medium in the laminated reinforced material leading to the formation of voids as described herein.

[015] Figure 2 depicts a side view of a VARTM infusion incorporating the resin control structures of the invention.

[016] Figure 3 depicts a top view of a VARTM infusion incorporating the resin control structures of the invention.

[017] Figure 4 depicts an enlarged view of a resin delivery means and two resin control structures of the invention.

[018] Figure 5 depicts an enlarged view of two distribution means of Petition 870200096653, dated 03 / 08 / 2020, page 25 / 112 8 / 84 resin and three resin control structures of the invention.

[019] Figure 6 depicts the flow of resin through the resin distribution medium, incorporating the resin flow control structures of the invention, in the reinforced laminate material leading to a substantially reduced lead-lag as described herein.

[020] Figure 7 depicts a top view of an exemplary VARTM fusion incorporating the resin flow control structures of the invention.

[021] Figure 7(a) depicts the first layer of figure 7.

[022] Figure 7(b) depicts the second layer of figure 7.

[023] Figure 7(c) depicts the third layer of figure 7.

[024] Figure 7(d) depicts the fourth layer of figure 7.

[025] Figure 7(e) depicts the fifth layer of figure 7.

[026] Figure 7(f) depicts the sixth layer of figure 7.

[027] Figure 7(g) depicts the seventh layer of figure 7.

[028] Figure 7(h) depicts the eighth layer of figure 7.

[029] Figure 7(i) depicts the ninth layer of figure 7.

[030] Figure 7(j) depicts the tenth layer of figure 7.

[031] Figure 8 depicts a top view of a VART™ infusion.

[032] Figure 9 depicts a top view of a VART™ infusion.

[033] Figure 10 depicts a top view of a VARTM infusion. DETAILED DESCRIPTION OF THE INVENTION Terminology and Definitions

[034] Unless otherwise indicated, the invention is not limited to specific reagents, substituents, catalysts, reaction conditions, or the like, as such may vary. It should also be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not to be construed as being limiting.

[035] As used in the specification and appended claims, as for Petition 870200096653, dated 03 / 08 / 2020, p. 26 / 112 9 / 84 but singulars “a”, “an” and “the” include plural references unless the context clearly indicates otherwise. Thus, for example, the reference to “an α-olefin” includes a single α-olefin as well as a combination or mixture of two or more α-olefins, the reference to “substituent” encompasses a single substituent as well as two or more substituents, and so on.

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

[037] In this specification and in the claims that follow, reference will be made to a number of terms, which may be defined as having the following meanings:

[038] The term “alkyl” as used herein refers to a group of saturated cyclic hydrocarbons, branched or linear, typically though not necessarily containing from 1 to 24 carbon atoms, preferably from 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl, and the like. Generally, though again not necessarily, the alkyl groups herein contain from 1 to about 12 carbon atoms. The term “low 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 from 4 to 8, preferably from 5 to 7 carbon atoms.The term “substituted alkyl” refers to an alkyl substituted by one or more substituent groups, and the terms “heteroatom-containing alkyl” and “heteroalkyl” refer to an alkyl in which at least one carbon atom is substituted by a heteroatom. Unless otherwise indicated, the terms “alkyl” and “low alkyl” include a heteroatom-containing alkyl and a linear, branched, cyclic, unsubstituted, substituted low alkyl, respectively. Petition 870200096653, dated 03 / 08 / 2020, p. 27 / 112 10 / 84

[039] The term “alkylene” as used herein refers to a cyclic, branched or linear hydrocarbon group of 2 to about 24 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetraconsenyl, and the like. Preferred alkenyl groups contain from 2 to about 12 carbon atoms. The term “low alkenyl” refers to an alkenyl group of 2 to 6 carbon atoms, and the specific term “cycloalkenyl” refers to a cyclic alkenyl group, preferably having from 5 to 8 carbon atoms. The term "substituted alkenyl" refers to an alkenyl substituted by one or more substituent groups, and the terms "heteroatom-containing alkenyl" and "heteroatom" refer to an alkenyl in which at least one carbon atom is substituted by a heteroatom.Unless otherwise indicated, the terms "alkenyl" and "low alkenyl" include a heteroatom-containing alkenyl and a linear, branched, cyclic, unsubstituted, substituted low alkenyl, respectively.

[040] The term “alkenylene” as used here refers to a linear, branched or bifunctional cyclic alkenyl group, wherein the “alkenyl” is as defined above.

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

[042] The term “alkoxy” as used here refers to an alkyl group attached Petition 870200096653, dated 03 / 08 / 2020, p. 28 / 112 11 / 84 through a single-terminal ether linkage; that is, an “alkoxy” group can be represented as -O-alkyl where alkyl is as defined above. A “low alkoxy” group refers to an alkoxy group containing from 1 to 6 carbon atoms. Analogously, “alkenyloxy” and “low alkenyloxy” respectively refer to an alkenyl group and a low alkenyl group linked through a single-terminal ether linkage, and “alkynyloxy” and “alkynyloxy” respectively refer to an alkynyl group and a low alkynyl group linked through a single-terminal ether linkage.

[043] 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 (so that different aromatic rings are linked to a common group such as a methylene moiety or ethylene). Preferred aryl groups contain from 5 to 24 carbon atoms, and particularly preferred aryl groups contain from 5 to 14 carbon atoms. Exemplary aryl groups contain one or two fused or linked aromatic rings, for example, phenyl, naphthyl, biphenyl, diphenyl ether, diphenylamine, benzophenone, and the like. The term "substituted aryl" refers to an aryl moiety substituted by one or more substituent groups, and the terms "heteroatom-containing aryl" and "heteroaryl" refer to aryl substituents in which at least one carbon atom is substituted by a heteroatom, as will be described in more detail below.

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

[045] The term “alcaryl” refers to an aryl group with an alkyl substituent, and the Petition 870200096653, dated 03 / 08 / 2020, p. 29 / 112 12 / 84 The term “aralkyl” refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined above. Preferred alkyl and aralkyl groups contain from 6 to 24 carbon atoms, and particularly preferred alkyl and aralkyl groups contain from 6 to 16 carbon atoms. Exemplary alkyl groups include, without limitation, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethylcyclopenta-1,4-diene, and the like. Exemplary aralkyl groups include, without limitation, benzyl, 2-phenylethyl, 3-phenylethyl, 3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. The terms “alcaryloxy” and “aralkyloxy” refer to substituents of the formula -OR where R is an alkyl or aralkyl, respectively, as already defined.

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

[047] Additionally, the term “acyl” also refers to substituents having the formula -(CO)-alkaryl, -(CO)-alkenyl, or -(CO)-alkynyl and the term “acyloxy” also refers to substituents having the formula -O(CO)-alkaryl, -(CO)-alkenyl, or -(CO)alkynyl where “alkaryl”, “alkenyl”, and “alkynyl” are as defined above.

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

[049] The terms “halo” and “halogen” refer to univalent hydrocarbyl radicals containing from 1 to 30 carbon atoms, more preferably from 1 to 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like. The term “low hydrocarbyl” refers to a hydrocarbyl group of 1 to 6 carbon atoms. Petition 870200096653, dated 03 / 08 / 2020, page 30 / 112 13 / 84 preferably from 1 to 4 carbon atoms, and the term “hydrocarbylene” refers to a divalent hydrocarbyl moiety containing from 1 to about 30 carbon atoms, preferably from 1 to about 24 carbon atoms, more preferably from 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species. The term “low hydrocarbylene” refers to a hydrocarbyl group of 1 to 6 carbon atoms. “Substituted hydrocarbyl” refers to a hydrocarbyl substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer to a hydrocarbyl in which at least one carbon atom is substituted by a heteroatom.Similarly, "substituted hydrocarbylene" refers to a hydrocarbylene substituted by one or more substituent groups, and the terms "heteroatom-containing hydrocarbylene" and "heterocarbylene" refer to a hydrocarbylene in which at least one carbon atom is substituted by a heteroatom. Unless otherwise indicated, the terms "hydrocarbyl" and "hydrocarbylene" are to be interpreted as including hydrocarbylene halves and substituted heteroatom-containing hydrocarbyl, respectively.

[050] The term “heteroatom-containing” as in a “heteroatom-containing hydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms are replaced by an atom other than carbon, for example, nitrogen, oxygen, sulfur, phosphorus, or silicon, typically a nitrogen, an oxygen, or a sulfur. Similarly, the term “heteroalkyl” refers to an alkyl substituent that is a heteroatom-containing, the term “heterocyclic” refers to a cyclic substituent that is a heteroatom-containing, the terms “heteroaryl” and “heteroatomatic” 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 that heterocyclics can be monocyclic, bicyclic, or polycyclic as described above in relation to the term aryl.Examples of heteroalkyl groups include alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like. The examples of hete. Petition 870200096653, dated 03 / 08 / 2020, page 31 / 112 14 / 84 substituted roaryl groups include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc., and examples of alicyclic groups containing heteroatoms are pyrrolidine, morpholino, piperazine, piperidine, etc.

[051] By “substituted” as in “substituted hydrocarbyl”, “substituted alkyl”, “substituted aryl” and the like, as alluded to in some of the definitions mentioned above, means that in the hydrocarbyl, alkyl, aryl or other moiety, at least one hydrogen atom bonded to a carbon (or other) atom is substituted by one or more 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 C6-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 a halo), C2-C24 alkylcarbonate (-O(CO)-O-alkyl), C6-C24 arylcarbonate (-O-(CO)-O-aryl),carboxy (-COOH), carboxylate (COO-), carbamoyl (-(CO)-NH2), substituted mono-(C1-C24 alkyl)-carbamoyl (-(CO)NH(C1-C24 alkyl)), substituted di-(C1-C24 alkyl)-carbamoyl (-(CO)-N(C1-C24 alkyl)2), substituted mono-(C1-C24 haloalkyl)-carbamoyl (-(CO)-NH(C1-C24 haloalkyl)), substituted di-(C1-C24 haloalkyl)-carbamoyl (-(CO)-N(C1-C24 haloalkyl)2), substituted mono-(C5-C24 aryl)-carbamoyl (-(CO)-NH-aryl), substituted di-(C5-C24 aryl)-carbamoyl (-(CO)-N(C5-C24 aryl)2), thiocarbamoyl (-(CS)-NH2), substituted mono-(C1-C24 alkyl) thiocarbamoyl (-(CS)-NH(C1-C24 alkyl)), substituted di-(C1-C24 alkyl)-thiocarbamoyl ((CS)-N(C1-C24 alkyl)2), mono-(C5-C24 aryl)-thiocarbamoyl (-(CS)-NH-alkyl), di-(C5C24 aryl)-thiocarbamoyl (-(CS)-N(C5-C24 aryl)2), di-N-(C1-C24 alkyl), substituted N-(C5-C24 aryl)thiocarbamoyl (-(CS)-N(C1-C24 alkyl)(C5-C24 aryl), carbamido (-NH-(CO)NH2), cyano (^N), cyanate (-O-CΞN), thiocyanate (-S-CΞN), formyl (-(CO)-H), thioformyl ((CS)-H), amino (-NH2),substituted mono-(C1-C24 alkyl)-amino (-NH(C1-C24 alkyl), substituted di(C1-C24 alkyl)-amino (-N(C1-C24 alkyl)2), mono-(C5-C24 aryl)-amino, Petition 870200096653, dated 03 / 08 / 2020, p. 32 / 112 15 / 84 substituted (-NH(C5-C24 aryl), di-(C5-C24 aryl)-substituted amino (-N(C5-C24 aryl)2), alkylamino (-NH-(CO)-alkyl), C6-C24 arylamido (-NH-(CO)-aryl), imino (-CR=NH where R includes without limitation hydrogen, C1-C24 alkyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl, etc.), C2-C20 alkylimino (-CR=N(alkyl), where R includes without limitation hydrogen, C1-C24 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, C6C24 alkaryl, C6-C24 aralkyl, etc.), nitro (-NO2), nitroso (-NO), sulfo (-SO2-OH), sulfonate (-SO2-O-), C1-C24 alkylsulfanil (-S-alkyl; also called “alkylthio”), C5C24 arylsulfanil (-S-aryl;also called “arylthio”), C1-C24 alkylsulfinyl (-(SO)alkyl), C5-C24 arylsulfinyl (-(SO)-aryl), C1-C24 alkylsulfonyl (-(SO2-alkyl), C1-C24 C1-C24 monoalkylsulfonyl -SO2-N(H)alkyl), C1-C24 dialkylaminosulfonyl -SO2N(alkyl)2, C5-C24 arylsulfonyl (-SO2 aryl), boryl (-BH2), borono (-B(OH)2), boronate (B(OR)2, where R includes without limitation alkyl or other hydrocarbyl), phosphono (-P(O)(OH)2), phosphonate (-P(O)(O-)2), phospho ((-PO2), and phosphine (-PH2); and the C1-C24 alkyl hydrocarbyl moieties (preferably C1-C12 alkyl, more preferably C1-C6 alkyl), C2-C24 alkenyl (preferably C2-C12 alkenyl, more preferably C2-C6 alkenyl), C2-C24 alkynyl (preferably C2-C12 alkynyl, more preferably C2-C6 alkynyl), C5-C24 aryl (preferably C5-C14 aryl), C6-C24 alkaryl (preferably C6-C16 alkaryl), and C6-C24 alkaryl (preferably C6-C16 alkaryl).

[052] By “functionalized” as in “functionalized hydrocarbyl”, “functionalized alkyl”, “functionalized olefin”, “functionalized cyclic olefin” and the like, means that in the hydrocarbyl, alkyl, olefin, cyclic olefin or other moiety, at least one hydrogen atom bonded to a carbon (or other) atom is replaced by one or more functional groups such as those described above. The term “functional group” means any functional species that are compatible for use as described herein. In particular, a functional group would necessarily possess the capacity Petition 870200096653, dated 03 / 08 / 2020, page 33 / 112 16 / 84 ability to react with or bonded to the corresponding functional groups on a substrate surface.

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

[054] “Optional” or “optionally” means that the circumstance described subsequently may or may not occur, so that the description includes cases where the circumstances occur and cases where they do not. For example, the phrase “optionally substituted” means that a non-hydrogen substituent may or may not be present on a given atom, and thus the description includes structures where a non-hydrogen substituent is present and structures where a non-hydrogen substituent is not present.

[055] The term “laminate preform,” as used herein, generally refers to any material of those resin compositions as used herein in the invention that can be contacted with, applied to, or otherwise allowed to flow into the laminated material, such that the resin is contained within the laminated material. Without limitation, such materials include reinforcing materials such as filaments, fibers, slivers, mats, textures, fabrics, carbon fibers and fabrics, aramid fibers and fabrics, and polyolefins or other polymer fibers or fabrics. Other compatible materials include metallic density modulators, microparticle density modulators such as microspheres, and macroparticle density modulators such as glass or ceramic granules.

[056] The term “resin delivery medium”, as used herein, means any two-dimensional flow aid used for resin feeding, especially in vacuum infusion processes. The resin delivery medium is typically Petition 870200096653, dated 03 / 08 / 2020, page 34 / 112 17 / 84 A coarse, open-structured medium is initially used as a vacuum pathway to evacuate dry reinforcement prior to infusion. The resin distribution medium provides a relatively high permeability pathway for the resin introduced into the stored assembly to be rapidly distributed to the laminate preform. Non-limiting examples of resin distribution media / products include Enkafusion®, Airtech Greenflow® 75, Soric®, common nursery-type screen, fishing net, and non-woven inner media such as polypropylene, polyethylene, nylon or PET, continuous yarn carpet, or other similar materials.

[057] The term “preform”, as used herein, refers collectively to one or more layers of reinforcing materials that are to be infused with resin. The preform may contain multiple different types of reinforcing materials or different material constructions, and may also include cores and / or other structural layers. The preform may also contain non-structural layers as required for the production of the desired composite laminate.

[058] The term “store”, as used herein, refers to the combination of a reinforced preform with any part thereof or all of the additional infusion components, in particular a shell layer, a resin delivery medium, a resin flow control structure, a vacuum bagging material, and a mold surface.

[059] The term “lead-lag”, as used herein, refers to a phenomenon in which the use of resin distribution medium layers creates a fast-moving resin infusion front in the reinforced preform areas directly adjacent to the resin distribution layers, whereas the resin infusion front in areas further from the resin distribution layer may lag significantly.

[060] As used herein, the term “modify,” in the context of resin flow control structures, means to control (e.g., decrease) the resin flow rate in or through the resin distribution medium by changing the flow direction. Petition 870200096653, dated 03 / 08 / 2020, page 35 / 112 18 / 84 resin in or through the resin distribution medium to another area of ​​a composite or laminated material, changing the permeation characteristics of the resin distribution medium, obstructing the flow area in cross-section of the resin distribution medium, creating regions of lower permeability within or through the distribution medium, or some combination thereof. RESIN FLOW CONTROL STRUCTURES

[061] The flow control measures described herein typically include those in which the flow rate and / or the direction of the flow rate is modified to minimize void formation and ensure complete filling of the preform materials. The flow control structures of the invention allow for rapid resin flow through the resin distribution medium to the infusion parts, while slow resin flow in key regions creates a more uniform flow front and minimizes low resin impregnation areas of the reinforcement layers. The use of resin flow control structures to decrease flow in laminate regions allows for controlled resin flow fronts, for example, in areas prone to void formation, such as core fitting structures, ply drops, and curved shape areas.These techniques can be conveniently performed in a top flow layer arranged in such a way that it does not affect the part or the laminate itself.

[062] Although flat panels are used to illustrate non-limiting embodiments of the invention in the figures, the invention is not so limiting and can be used for panels of any geometry, including areas of curvature, changes in thickness of the reinforcement layer, and variable reinforcement materials or constructions. The resin control structures of the invention can be used in conjunction with any infusion methods known in the art (e.g., SCRIMP, RTM, VIP, VEC, and other forms of above-the-top and through-the-canvas infusion).

[063] In one embodiment of the invention, a smooth mold surface (10) is shown in figures 2 and 3, for example, although the mold surface may be of Petition 870200096653, dated 03 / 08 / 2020, page 36 / 112 19 / 84 any geometry, for example, curved. The mold can be constructed of any suitable material, including steel, aluminum, or composite, and can be of any dimension. The mold surface can be treated with release agents and / or sealants.

[064] One or more layers of fibrous reinforced material may be arranged on the surface of the mold (10) in any desired position and / or orientation to form a fibrous reinforced preform (11). The one or more layers of fibrous reinforced material may be of the same or different compositions and may be of the same or different dimensions (e.g., width, length, thickness, shape, etc.) and / or may be arranged (e.g., woven) in any construction or orientation. Compatible reinforcing materials include, for example, those that add the strength or stiffness of a polymer compound when incorporated with the polymer. Non-limiting examples of reinforcing materials may be in the form of filaments, fibers, wicks, mats, textures, fabrics, knitted material, cloths, PVC, PAN, PET, balsa, honeycomb paper, composite reinforcing honeycomb PP, glass, Kevlar®, Spectra®, graphite, basalt, boron, or other known structures.Compatible reinforcing materials include glass fibers and fabrics, carbon fibers and fabrics, aramid fibers and fabrics, polyolefin fibers or fabrics (including ultra-high molecular weight polyethylene fabrics such as those produced by Honeywell under the trade name Zylon®).

[065] Other examples of reinforcing materials include core materials, such as, for example, various polymer foams, Nida-Core DIAB PVD, Gurit Corecell®, Airex® PVC and PET, Armacell® PET, ProBalsa® balsa, and BALTEK® balsa.

[066] In other embodiments, gel coatings, such as, for example, urethane, polyester, vinyl ester, or epoxy, can be deposited between the mold surface (10) and the reinforced preform (11).

[067] The shell layer materials (12) are optionally porous films, which allow the resin to flow freely through the layer without binding to the ma Petition 870200096653, dated 03 / 08 / 2020, page 37 / 112 20 / 84 composite material formed in the infusion process. Compatible canvas drops include nylon, woven fabrics, polyester fabrics, glass fabrics, or any fabric with a fluoropolymer- or silicone polymer-based release coating. The canvas drop can be of any desired dimension.

[068] In other applications, lower tarp drop, such as, for example, released films such as Airtech WRIGHTLON® Blue, fluoropolymer, and others like Tedlar®, may be used.

[069] One or more resin distribution media (30) are arranged on the surface of the shell layer (12). The resin distribution media (30) is arranged to provide a high permeability resin flow to a portion of the infusion. In other embodiments, the resin distribution media may be positioned in only a portion of the shell layer and / or the reinforcement layer. In other embodiments, one or more resin distribution media may be positioned anywhere in the storage, for example, within the reinforcement layers themselves and / or between the mold surface and the reinforcement layer. Furthermore, the resin distribution media may be cut and separated by creating gaps or breaks in the media. For example, breaks in the resin distribution media may be created in the canvas drop zones, see the example discussed below.In figures 2 and 3, for example, the resin distribution medium (30) is positioned on top of the shell layer (12), which itself is positioned on top of the reinforcement layer (11), although any other desired arrangement is possible. Any distribution layer with greater permeability than the reinforcement layers (11) can be compatible as a resin distribution medium (30), although resin distribution media with greater filament spacing or more open structures are particularly well suited (as described below).

[070] Any thickness of resin distribution medium can be used, although thinner layers of resin distribution medium typically offer greater control for infusion with other low viscosity resins. The thicknesses Petition 870200096653, dated 03 / 08 / 2020, page 38 / 112 21 / 84 thicknesses of 1 mm to 4 mm are common, with 1 mm thickness preferred for most infusion setups. One or more resin delivery media may be the same or different, may be the same or a different dimension (e.g., width, length, thickness, shape, etc.), and may be layered directly on top of, or near, each other and / or separated by another structure.

[071] In areas where slower resin flow rates are desired in the resin distribution medium (30), a first resin flow control structure (21) can be placed below the resin distribution medium (30) and the same or a second different resin flow control structure (20) can be placed above the resin distribution medium (30) to create a resin distribution medium with resin flow control structures.

[072] The first resin flow structure (21) and the same or a second different resin flow control structure (20) may substantially overlap each other, have the same shape and dimensions, and typically extend across the entire width of the resin distribution medium, as shown, for example, in Figure 4, but they need not substantially overlap each other, have the same shape and / or dimensions, and / or extend across the entire width of the resin distribution medium. In other embodiments, the resin distribution medium may be positioned to cover the resin flow control structures completely, partially, or not entirely. Similarly, in other embodiments, the resin flow control structures may be positioned to cover the resin distribution medium completely, partially, or not entirely.

[073] In another embodiment, it is possible to use a plurality of resin flow control structures, which may be the same or different, to control the resin flow rate in one or more resin distribution media. For example, as shown in Figure 5, a first resin flow control structure (20) may be positioned on top of the surface of a first resin distribution medium (30), a second resin flow control structure (21), which may be the Petition 870200096653, dated 03 / 08 / 2020, page 39 / 112 22 / 84 same or different as the first resin flow control structure (20), can be positioned below the first resin flow structure (20), the second resin distribution medium (31), which can be the same or different as the first resin distribution medium (30), can then be positioned below the second resin flow control structure (21), and a third resin flow control structure (22), which can be the same or different as the first and / or second resin flow control structures (20 and 21), can then be positioned below the second resin distribution medium (31).As the resin flow control structures in Figure 4, the first, second, and third resin flow control structures (20, 21, and 22) in Figure 5 substantially overlap each other, have the same shape and dimensions, and extend across the width of the resin distribution medium, but in other embodiments they do not need to substantially overlap each other, have the same shape and / or dimensions, and / or extend across the width of the resin distribution medium. Additional layers of resin distribution medium and / or resin flow control structures are also possible. For example, more than one identical or different resin flow control structure can be positioned in the same resin distribution medium plane.

[074] The resin flow control structures of the invention modify the resin flow rate through the distribution medium (30 and 31), retarding the resin flow in the resin distribution medium plane (30 and 31), allowing resin flow in the reinforcement layers (11) to create a more uniform flow front with a reduced lead-lag between the different layers of the infusion.

[075] Figure 6(a)-6(d) depicts the use of the resin flow control structures of the invention to control or moderate the flow in the resin distribution medium and the infusion into the preform reinforcement material. Figures 6(a) and 6(b) are identical to Figures 1(a) and 1(b) previously discussed, other than the inclusion of the resin flow control structures (20 and 21) in Figures 6(a) and 6(b). As depicted in Figure Petition 870200096653, dated 03 / 08 / 2020, page 40 / 112 23 / 84 6(c), the resin flow control structures (20 and 21) restrict the resin flow in the resin distribution medium (1) (xy direction) so that the resin flow in the reinforcement layer (2) (z direction) dominates there, substantially reducing the lead-lag (4). The reduction in lead-lag (6) results in a substantially more uniform resin front which facilitates a more complete resin impregnation of the reinforcement layer (2), as shown in figure 6(d).

[076] The resin flow control structures of the invention may be formed of any material or construction capable of modifying the flow rate of the resin in the resin distribution medium. Preferably, the resin flow control structures are gas permeable to allow complete evacuation of the preform assembly. The resin flow control structures may be resin impermeable or resin permeable. Without wishing to be bound to any particular theory, it is believed that the materials of the resin flow control structures have sufficient thickness, straw, or compressibility, such that when the stored infusion is evacuated, the material of the resin flow control structures partially or completely fills the open structures of the resin distribution medium, thereby modifying the flow rate of the resin in the resin distribution medium.

[077] Compatible materials for resin flow control structures have sufficient flexibility and / or adaptability to simple or complex vacuum infusion structures. Resin flow control structures can be constructed from any compatible fibers, including nylon, polyester, acrylic polyamide, natural or other synthetic fibers. The fibers can be of any compatible construction, including nonwovens, stapled yarns, continuous fibers, felt weaves, woven fabrics, or combinations thereof. The resin flow control structure material may also contain additional elements such as honeycomb structures, foam structures, and thermoplastic or glass microspheres.

[078] The “grouped materials” (also known as “grain conveyor belt” Petition 870200096653, dated 03 / 08 / 2020, page 41 / 112 24 / 84 or “laminated bulk materials” are a class of nonwoven synthetics incorporating microspheres that are particularly compatible as resin flow control structures. “Grouped materials” include the products Lantor Coremat®, NidaCore matline®, and Sphere Core SphereTex®.

[079] Resin flow control frame materials must be of compatible thickness (z-direction) to modify the resin flow rate in the resin distribution medium. The thickness will depend on both the nature of the resin flow control frame material and the construction of the resin distribution medium. In the case of bundled materials, the thickness of the resin flow control frame material is typically at least twice the thickness of the resin distribution medium. The thickness can vary within the resin flow control frames themselves. For example, one part of the resin flow control frame might be 2 mm thick and the other part might be 1 mm thick. The thickness can also decrease as well within the resin flow control frames.

[080] The resin flow control structure materials must be of compatible width and / or length (x- or y- direction) to modify the resin flow rate in the resin distribution medium. Generally, the thicker the preform reinforcement layer (z- direction), the larger and / or longer the resin flow control structure (x- or y- direction) required to modify the resin flow rate in the resin distribution medium. In one embodiment, for example, the resin flow control structure has a width and / or length approximately three times greater than the thickness of the preform reinforcement layer. In other embodiments, the width of the resin flow control structures may vary within the resin flow control structures themselves. For example, one part of the resin flow control structure may be 6 mm wide and / or long and the other part may be 3 mm wide and / or long.The width and / or length can be reduced, as can the resin flow control structures.

[081] Any variation in thickness, width, and / or length in the materials Petition 870200096653, dated 03 / 08 / 2020, page 42 / 112 25 / 84 resin flow control structures that modify the resin flow rate in the resin distribution medium make the resin flow control structure compatible for controlling the resin flow in the resin distribution medium. For example, in one embodiment, the width or length of the resin flow control structures, depending on their orientation to the resin flow, extends to the outer edges and / or extends beyond the outer edges of the resin distribution medium.

[082] Resin flow control structures can be of any geometry, including, for example, rectangular, square, circular, oval, triangular, trapezoidal, etc., or any combination thereof.

[083] Resin flow control structures can be positioned above and / or below the resin dispensing medium with or without any adhesive. If no adhesive is used, the resin flow control structures can be held in place by, for example, vacuum bagging, which presses down on the resin flow control structures and the resin dispensing medium is drawn over the VART™ mold assembly. Alternatively, or in addition to not using any adhesive, any type of adhesive known in the art can be used to hold the position of the resin flow control structures. For example, any pressure-sensitive adhesive or adhesion promoter can be used, including, for example, acrylics, and polyester-based or epoxy-based contact adhesives. Compatible adhesives or adhesion promoters include, for example, NuTack® E, NuTack® Blu, NidaTack® NT-100, FusionTack, and 3M™ Super 77™.

[084] Resin flow control structures can be positioned in any way necessary to control the infusion of resin into the reinforcement layers. For example, resin flow control structures can, for instance, generally be positioned on both sides of the resin distribution medium and extend to the outer edges of the resin distribution medium to control the flow of resin into the resin distribution medium. The position, size, geometry, and Petition 870200096653, dated 03 / 08 / 2020, page 43 / 112 26 / 84 The dimensions of the resin flow control structures can also vary. For example, resin flow control structures can be positioned in any orientation and at any location in the resin distribution medium depending on the direction of resin flow, and do not need to extend to the outer edges of the resin distribution medium in order to control the resin flow in the resin distribution medium.

[085] The resin-impermeable material, such as, for example, a vacuum bagging film (15), is placed over the assembled stock and attached to the mold surface (10) by means of a sealant (e.g., Airtech AT® 200 Yellow tape, Era-Vac LTS® 90B). Compatible vacuum bag materials (15) include, for example, Airtech Stretchlon®, Aerovac Stretchvac®, AerovacVACFILM® 450V, and others. The vacuum bag (15), together with the mold surface (10), defines a mold assembly, and once sealed, the mold assembly creates a substantially airtight cavity (18) around the stock. Another resin delivery medium (e.g., Enkachannel, Diatex Omega Profile® ACIP50, and a common spiral wrap used to bundle yarns) (14) may be used as a supply channel or feeder for the resin. The vacuum bag (15) is equipped with one or more resin inlet ports (16) and one or more vacuum outlet ports (17).In other embodiments, breathable fabrics, such as nonwoven thermoplastics, including, for example, nylon, polyethylene, and polypropylene, may be used. In a typical VARTM infusion, the substantially airtight cavity (18) is evacuated by means of a vacuum applied at the vacuum port (17). The resin may be introduced and / or allowed into the storage assembly by any means known in the art, including, for example, the differential pressure created by the vacuum, so that the resin then flows into the resin distribution medium. For example, the resin is introduced at the resin inlet port (16), flow direction through the reinforcement layers (11). Once the infusion is complete, the resin is cured by any method known in the art to form a composite laminate material. Petition 870200096653, dated 03 / 08 / 2020, page 44 / 112 27 / 84

[086] In another embodiment, the resin flow control structures of the invention can be used to control the resin flow in the resin distribution medium in more varied and complex arrangements than those shown in Figures 2-5. For example, the resin flow control structures can be positioned perpendicular and / or parallel to the resin flow from the inlet to the outlet in the laminate assembly comprising, for example, a plurality of preform reinforcement layers and the resin distribution medium, each of which can have varying dimensions and can be oriented in any conceivable position. Such a complex arrangement is described in the example below. CYCLIC OLEFIN

[087] A class of resin compositions that can be used in the method of the invention disclosed herein includes one or more cyclic olefins. In general, any cyclic olefin compatible with the metatase reactions disclosed herein can be used. Such cyclic olefins may optionally be substituted, optionally containing heteroatom, mono-unsaturated, bi-unsaturated, or polyunsaturated C5 to C24 hydrocarbons that may be mono-, bi-, or polycyclic. The cyclic olefin may generally be any strained or non-strained cyclic olefin, provided that the cyclic olefin is capable of participating in the ROMP reaction either individually or as part of a ROMP cyclic olefin composition. While certain strain-free cyclic olefins such as cyclohexane are generally understood as not undergoing ROMP reactions on their own, under appropriate circumstances, such strain-free cyclic olefins can nevertheless be ROMP-active.For example, when present as a comonomer in a ROMP composition, strainless cyclic olefins can be ROMP active. Therefore, as used herein and as would be appreciated by experts, the term “strainless cyclic olefin” is intended to refer to those strainless cyclic olefins that can undergo a ROMP reaction under any conditions, or in any ROMP composition, provided that the strainless cyclic olefin is ROMP active. Petition 870200096653, dated 03 / 08 / 2020, page 45 / 112 28 / 84

[088] In general, the cyclic olefin can be represented by the structure of formula (A) where J and RA are as follows: frog RA is selected from a group consisting of hydrogen, hydrocarbyl (e.g., C1-C20 alkyl, C5-C20 aryl, C5-C30 aralkyl, or C5-C30 alkaryl), substituted hydrocarbanyl (e.g., C1-C20 alkyl, C5-C20 aryl, C5-C30 aralkyl, or C5-C30 substituted alkaryl), heteroatom-containing hydrocarbyl (e.g., C1-C20 heteroalkyl, C5-C20 heteroaryl, C5-C30 heteroatom-containing aralkyl, or C5-C30 heteroatom-containing alkaryl), and substituted heteroatom-containing hydrocarbyl (e.g., C1-C20 heteroalkyl, C5-C20 heteroaryl, C5-C30 heteroatom-containing aralkyl, or C5-C30 heteroatom-containing alkaryl), and whether the substituted hydrocarbyl or the Hydrocarbyl containing a substituted heteroatom, wherein the substituents may be functional groups (“Fn”) such as phosphonate, phosphoryl, phosfanyl, phosphine, sulfonate, C1-C20 alkylsulfanyl, C5-C20 aryl sulfanyl, C1-C20 alkylsulfonyl, C5-C20 arylsulfonyl, C1-C20 alkylsulfinyl, C5-C20 arylsulfinyl, sulfonamide, amino, amido, imino, nitro, nitroso,hydroxy, C1-C20 alkoxy, C5-C20 aryloxy, C2-C20 alkoxycarbonyl, C5-C20 aryloxycarbonyl, carboxyl, carboxylate, mercapto, formyl, C1-C20 thioester, cyano, cyanate, carbamoyl, epoxy, styrenyl, silyl, silyloxy, silanyl, siloxazanil, boronate, boryl, or halogen, or a metalloid-containing or metal-containing group (where the metal may be, for example, Sn or Ge). RA may itself be one of the two groups mentioned above, such that the Fn moiety is directly bonded to the olefinic carbon atom indicated in the structure. In the latter case, however, the functional group will generally not be directly attached to an olefinic carbon via a heteroatom containing one or more lone pairs of electrons, for example, an oxygen, sulfur, nitrogen, or phosphorus atom, or via a metal rich in, Petition 870200096653, dated 03 / 08 / 2020, page 46 / 112 29 / 84 electrons or metalloids such as Ge, Sn, As, Sb, Se, Te, etc. with such functional groups, there will normally be a Z* linkage intervention, so that RA then has the structure -(Z*)n-Fn where n is 1, Fn is a functional group, and Z* is a hydrocarbylene linkage group such as alkylene, substituted alkylene, heteroalkylene, substituted heteroalkene, arylene, substituted arylene, heteroarylene, or substituted heteroarylene. Additionally, the functional groups (“Fn”) can be thiocyanate, isocyanate, or thioisocyanate.

[089] J is a saturated or unsaturated hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene, where J is a substituted hydrocarbylene or a substituted heteroatom-containing hydrocarbylene, the substituents may include one or more (Z*)n-Fn groups, where n is zero or 1, and Fn and Z* are previously defined. Additionally, two or more substituents are attached to the ring of carbon atoms (or other) together with J may be linked to form a bicyclic or polycyclic olefin. J will generally contain in the range of approximately 5 to 14 rings of atoms, typically 5 to 8 rings of atoms, for a monocyclic olefin, and for bicyclic and polycyclic olefins, each ring will generally contain 4 to 8, typically 5 to 7, rings of atoms.

[090] The reacting monounsaturated cyclic olefins enclosed by structure (A) can be represented by structure (B) where b is generally an integer, though not necessarily in the range of 1 to 10, typically 1 to 5, RA is as defined above for structure (A), and RB1, RB2, RB3, RB4, RB5, and RB6 are independently selected from a group Petition 870200096653, dated 03 / 08 / 2020, page 47 / 112 30 / 84 consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl and -(Z*)n-Fn where η, Z* and Fn are previously defined, and where if either half of RB1 to RB6 is a substituted hydrocarbyl or a substituted heteroatom-containing hydrocarbyl, the substituents may include one or more -(Z*)n-Fn groups. Therefore, RB1, RB2, RB3, RB4, RB5, and RB6 may be, for example, hydrogen, hydroxyl, C1-C20 alkyl, C5-C20 aryl, C5-C20 alkoxy, C5-C20 aryloxy, C2-C20 alkoxycarbonyl, C5-C20 aryloxycarbonyl, amino, amido, nitro, etc.

[091] Furthermore, any of the RB1, RB2, RB3, RB4, RB5, and RB6 moieties may be linked to any other RB1, RB2, RB3, RB4, RB5, and RB6 moieties to provide a bicyclic or polycyclic olefin, and the linkage may include without limitation functional groups or heteroatoms, for example, the linkage may include an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety.

[092] Examples of monounsaturated monocyclic olefins encompassed by structure (B) include, without limitation, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cycloundecene, cyclododecene, tricyclodecene, tetracyclodecene, octacyclodecene, and cycloeicosene, and substituted versions thereof such as 1-methylcyclopentene, 1-ethylcyclopentene, 1-isopropylcyclohexene, 1-chloropentene, 1-fluorocyclopentene, 4-methylcyclopentene, 4-methoxycyclopentene, 4-ethoxycyclopentene, cyclopent-3-enethiol, cyclopent-3-ene, 4-methylsulfanylcyclopentene, 3-methylcyclohexene, 1-methylcyclooctene, 1,5-dimethylcyclooctene, etc. The monocyclic diene reagents enclosed by structure (A) can generally be represented by structure (C). Petition 870200096653, dated 03 / 08 / 2020, page 48 / 112 31 / 84 where ced are integers independently in the range of 1 to about 8, typically 2 to 4, preferably 2 (so that the reagent is a cyclooctadiene), RA is as defined above for structure (A), and RC1, RC2, RC3, RC4, RC5, and RC6 are defined for RB1 to RB6. In this case, it is preferred that RC3 and RC4 be non-hydrogen substituents, in which case the second olefinic moiety is tetrasubstituted. Examples of monocyclic diene reagents include, without limitation, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclohexadiene, 5-ethyl-1,3-cyclohexadiene, 1,3-cycloheptadiene, cyclohexadiene, 1,5-cyclooctadiene, 1,3-cyclooctadiene, and substituted analogues thereof. Triene reagents are analogous to the diene (C) structure, and will generally contain at least one methylene linkage between any two olefinic segments.Additionally, any of the RC1, RC2, RC3, RC4, RC5, and RC6 moieties may be linked to any other RC1, RC2, RC3, RC4, RC5, and RC6 moieties to provide a bicyclic or polycyclic olefin, and a linkage may include, without limitation, functional groups and heteroatoms, for example, the linkage may include an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety.

[093] The bicyclic and polycyclic olefinic reagents encompassed by structure (A) can generally be represented by structure (D)RD2rD3 where e is an integer in the range of 1 to 8, typically 2 to 4, f is generally 1 or 2, T is a low alkylene or a low alkenylene, generally a substituted or unsubstituted ethyl or methyl group, RA is as defined above for structure (A), and RD1, RD2, RD3 and RD4 are defined for RB1 to RB6. Additionally, any of the halves of RD1, RD2, RD3 and RD4 can be linked to any other halves of RD1, RD2, RD3 and RD4 to provide a bicyclic or polycyclic olefin, and the linkage may include Petition 870200096653, dated 03 / 08 / 2020, p. 49 / 112 32 / 84 functional groups and heteroatoms, for example, the linkage may include, without limitation, an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety.

[094] The preferred olefinic reagents encompassed by structure (D) are of the norbornene family, having the general structure (E) where RA is as defined above, RE1, RE2, RE3 and RE6 have the same definitions as rbiarb6, θ re4 θ res are defined as for RE2 and RE3, respectively. Additionally, any halves of RE1, RE2, RE3, RE4, RE5 and RE6 may be linked to any of the other halves RE1, RE2, RE3, RE4, RE5 and RE6 to provide a bicyclic or polycyclic olefin, and the linkage may include functional groups or heteroatoms, for example, the linkage may include without limitation an ether, ester, thioether, amino, alkylamino, imino, or anhydride moiety.

[095] Examples of bicyclic and polycyclic olefinic reagents thus include, without limitation, dicyclopentadiene, tricyclopentadiene, dicyclohexadiene, norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5-isobutyl-2-norbornene, 5,6-dimethyl-2-norbornene, 5-phenylnorbornene, 5-benzylnorbornene, 5-acetylnorbornene, 5-methoxycarbonylnorbornene, 5,5,6-trimethyl-2-norbornene, cyclohexenylnorbornene, endo, exo-5,6-dimethoxynorbornene, endo, endo-5,6-dimethoxynorbornene, endo, exo-5,6-dimethoxycarbonylnorbornene, endo, endo-5,6-dimethoxycarbonylnorbornene, 2,3-dimethoxynorbornene, norbornadiene, tricyloundecene, tetracyclododecene, 8methyltetracyclododecene, 8-ethyl-tetracyclododecene, 8-methoxycarbonyltetracyclododecene, 8-methyl-8-tetracyclododecene, 8-cyanotetracyclododecene, pentacyclopentadecene, pentacyclohexadecene, and the like.Additionally, the aforementioned bicyclic and polycyclic olefinic reagents include their stereoisomers and mixtures thereof. Petition 870200096653, dated 03 / 08 / 2020, page 50 / 112. 33 / 84 mos.

[096] Preferred cyclic olefins include C5 to C24 unsaturated hydrocarbons. Also preferred are C5 to C24 cyclic hydrocarbons containing one or more (typically 2 to 12) heteroatoms such as O, N, S, or P. For example, crown ether cyclic olefins may include several O heteroatoms throughout the ring, and these are within the scope of the invention. Furthermore, preferred cyclic olefins are C5 to C24 hydrocarbons containing one or more (typically 2 or 3) olefins. For example, the cyclic olefin may be mono-, di-, or tri-unsaturated. Examples of cyclic olefins include, but are not limited to, cyclooctene, cyclododecene, and (c,t,t)-1,5,9-cyclododecatriene.

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

[098] Cyclic olefins can also be substituted, for example, a C5 to C24 cyclic hydrocarbon where one or more (typically 2, 3, 4 or 5) of the hydrogens are replaced by non-hydrogen substituents. Compatible non-hydrogen substituents can be chosen from the substituents described above. For example, functionalized cyclic olefins, i.e., C5 to C24 cyclic hydrocarbons where one or more (typically 2, 3, 4 or 5) of the hydrogens are replaced by functional groups described above. For example, a cyclic olefin functionalized with an alcohol group can be used to prepare a telechellic polymer comprising pendant alcohol groups. The functional groups in cyclic olefins can be protected in cases where the functional group interferes with the metatase catalyst, and any of the protecting groups commonly used in the art can be employed.Acceptable protective groups can be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3rd edition. (New York: Wiley, . Petition 870200096653, dated 03 / 08 / 2020, page 51 / 112 34 / 84 1999). Examples of functionalized cyclic olefins include, but are not limited to, 2-hydroxymethyl-5-norbornene, 2-[(2-hydroxyethyl)carboxylate]-5-norbornene, cidecanol, 5-nhexyl-2-norbornene, 5-n-butyl-2-norbornene.

[099] Cyclic olefins incorporating any combination of the above-mentioned features (i.e., heteroatoms, substituents, multiple olefins, multiple rings) are compatible with the methods disclosed herein.

[0100] Cyclic olefins useful in the methods disclosed herein may be strained or unstrained. It will be appreciated that the amount of ring strain varies for each cyclic olefin compound and depends on a number of factors including ring size, the presence and identity of substituents, and the presence of multiple rings. Ring strain is a factor in determining the reactivity of a molecule toward ring-opening olefin metatase reactions. Highly strained cyclic olefins, such as certain bicyclic compounds, readily undergo ring-opening reactions with olefin metatase catalysts. Less strained cyclic olefins, such as certain unsubstituted hydrocarbon monocyclic olefins, are generally less reactive.In some cases, ring-opening reactions of relatively unstressed (and therefore relatively unreactive) cyclic olefins may become possible when carried out in the presence of olefinic compounds disclosed herein.

[0101] A plurality of cyclic olefins can be used to prepare metatase polymers from an olefinic compound. For example, two cyclic olefins selected from cyclic olefins described above can be employed in order to form metatase products incorporating both cyclic olefins. Where two or more cyclic olefins are used, an example of a second cyclic olefin is a cyclic alkenol, that is, a C5 to C24 cyclic hydrocarbon where at least one of the hydrogen substituents is replaced by an alcohol or a protected alcohol moiety to yield a functionalized cyclic olefin.

[0102] The use of a plurality of cyclic olefins, and in particular when Petition 870200096653, dated 03 / 08 / 2020, page 52 / 112 35 / 84 If at least one of the cyclic olefins is functionalized, it allows further control over the positioning of functional groups within the products. For example, the density of cross-linked points can be controlled in polymers and macromonomers prepared using the methods disclosed herein. Control over the quantity and density of substituents and functional groups also allows control over the physical properties (e.g., melting point, tensile strength, glass transition temperature, etc.) of the products. Control over these and other properties is possible for reactions using only a single olefin, but it will be appreciated that the use of a plurality of cyclic olefins further increases the rate of possible metatase products and polymers formed. OLEFIN METATASE CATALYSTS

[0103] The olefin metatase catalyst complexes that may be present in the resins used in the method of the invention disclosed herein are preferably a Group 8 transition metal complex having the structure of formula (I) (I) where: M is a Group 8 transition metal; L1, L2 and L3 are neutral electron-donating ligands; n is either 0 or 1, so L3 may or may not be present; m is 0, 1, or 2; k is 0 or 1; X1 and X2 are anionic ligands; and R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, hydrocarbyl-containing hepToxin, Petition 870200096653, dated 03 / 08 / 2020, page 53 / 112 36 / 84 substituted teratom, and functional groups; where any two or more of X1, X2, L1, L2, L3, R1, and R2 can be taken together to form one or more cyclic groups, and further where any one or more of X1, X2, L1, L2, L3, R1, and R2 can be attached to a support.

[0104] Preferred catalysts contain Ru or Os as a Group 8 transition metal, with Ru being particularly preferred.

[0105] Several embodiments of the catalysts useful in the reactions disclosed herein are described in more detail below. For convenience, the catalysts are described in groups, but it should be emphasized that these groups are not intended 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.

[0106] 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 group in is 0, 1 or 2, en, X1, X2, L1, L2, L3, R1, and R2 are described as follows.

[0107] For the first group of catalysts, n is 0, and L1 and L2 are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibnite, ether, amino, amido, imino, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, and thioether. Exemplary ligands are trisubstituted phosphines of the formula PRH1RH2RH3, where RH1, RH2, and RH3 are each independently an aryl or a C1-C10 alkyl, particularly a primary alkyl, a secondary alkyl, or a cycloalkyl.In the most preferred embodiments, L1 and L2 are selected independently from a group consisting of trimethylphosphine (Pme3), triethylphosphine (Pet3), tri-n-butylphosphine (Pbu3), tri(orthotolyl)phosphine (Po-tolyl3), tri-tert-butylphosphine (P-tert-Bu3), tricyclopentylphosphine (Pcyclopentyl3), tricyclohexylphosphine (Pci3), triisopropylphosphine (Pi-Pr3), triisobutylphosphine, trioctylphosphine (Poct3), triphenylphosphine (PPh3), tri(pentafluorophenyl)phosphine (P(C6 F5)3), methyldiphenylphosphine (PmePh2), dimethylphenylphosphine (Pme2Ph), and diethylphenylphosphine (Pet2Ph). Petition 870200096653, dated 03 / 08 / 2020, p. 54 / 112 37 / 84

[0108] Alternatively, L1 and L2 are independently selected from a phosphabicycloalkane (e.g., monosubstituted 9-phosphabicyclo[3.3.1]nonane, or monosubstituted 9-phosphabicyclo[4.2.1]nonane) such as cyclohexylfoban, isopropylfoban, ethylfoban, methylfoban, butylfoban, pentifoban and the like).

[0109] X1 and X2 are anionic ligands, and may be the same or different, or are linked together to form a cyclic group, typically though not necessarily an eight-membered ring. In preferred embodiments, X1 and X2 are each independently a hydrogen, a 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 alkyloxy, C1-C20 alkylsulfonate, C5-C24 arylsulfonate, C1-C20 alkylsulfanyl, C5-C24 arylsulfanil, C1-C20 alkylsulfinyl, or C5-C24 arylsulfinyl. Optimally, X1 and X2 can be replaced by one or more halves selected from groups selected from a halide, C1-C12 alkyl, C1-C12 alkoxy, C5-C24 aryl, and halide, which can, in part, with the exception of the halide, be further replaced by one or more groups selected from C1-C6 alkyl, C1-C6 alkoxy, and phenyl halide.In more preferred embodiments, X1 and X2 are halide, benzoate, C2-C6 acyl, C2-C6 alkoxycarbonyl, C1-C6 alkyl, phenoxy, C1-C6 alkoxy, C1-C6 alkylsulfanyl, or C1-C6 alkylsulfonyl. In even more preferred embodiments, X1 and X2 are each a halide, CF3CO2, CH3CO2, CFH2CO2, (CH3)3CO, (CF3)2(CH)CO, (CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethanesulfonate. In the most preferred embodiments, X1 and X2 are each a chloride. Alternatively, X1 and X2 are independently NO3, -N=C=O, or N=C=S.

[0110] R1 and R2 are independently selected from a hydrogen, hydrocarbyl (example,

[0111] C1-C20 alkyl, C2-C20 alkenyl, C5-C24 alkynyl, C5-C24 aryl, C6-C24 alkaryl, etc.), substituted hydrocarbanyl (example, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl etc.), hydrocarbyl containing heteroatom (example, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6 Petition 870200096653, dated 03 / 08 / 2020, p. 55 / 112 38 / 84 C24 aralkyl etc. containing heteroatom), and hydrocarbyl containing substituted heteroatom (e.g., C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, C6-C24 aralkyl etc. containing substituted heteroatom), and functional groups. R1 and R2 may also be linked to form a cyclic group, which may be aliphatic or aromatic, and may contain substituents and / or heteroatoms. Generally, such a cyclic group will contain 4 to 12, preferably 5, 6, 7, or 8 ring atoms.

[0112] In preferred catalysts, R1 is a hydrogen and R2 is selected from C1-C20 alkyl, C2-C20 alkenyl and C5-C24 aryl, more preferably C1-C6 alkyl, C2-C6 alkenyl and C5-C14 aryl. Even more preferably, R1 is a phenyl, vinyl, methyl, isopropyl, or t-butyl, optionally substituted by one or more halves selected from C1-C6 alkyl, C1-C6 alkoxy, phenyl and a functional group Fn as defined above. More preferably, R2 is a phenyl or vinyl substituted by one or more halves selected from methyl, ethyl, chlorine, bromine, iodine, fluorine, nitro, dimethylamino, methyl, methoxy, and phenyl. Optimally, R2 is a phenyl or -C=C(CH3)2.

[0113] Any two or more (typically two, three, or four) of X1, X2, L1, L2, L3, R1, and R2 may be taken together to form a cyclic group, including bidentate and multidentate ligands, as disclosed, for example, in U.S. Patent No. 5,312,940, the disclosure of which is incorporated herein by reference. When any of the X1, X2, L1, L2, L3, R1, and R2 are linked to form cyclic groups, those cyclic groups may contain from 4 to 12, preferably 4, 5, 6, 7, or 8 atoms, or may comprise two or three 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 groups 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 aryl ketonates.

[0114] A second group of catalysts, commonly referred to as Second Generation Grubbs-type catalysts, has the structure of formula (I), where L1 is Petition 870200096653, dated 03 / 08 / 2020, p. 56 / 112 39 / 84 a carbene ligand having the structure of formula (II) (π) (QV3* R3—(Q1)x—X (Q4)2-R4A.Y----(Q2)y—R4 so that the complex can have the structure of formula (III) r3--(Q1)x---χ where M, m, η, X1, X2, L2, L3, R1, and R2 are defined for the first group of catalysts, and the remaining substituents are as follows; X and Y are heteroatoms typically selected from N, O, S, and P. Since O and S are divalent, p is necessarily zero when X is O or S, q is necessarily zero when Y is O or S, and k is zero or 1. However, when X is N or P, then p is 1, and when Y is N or P, then q is 1. In a preferred embodiment, both X and Y are N; Q1, Q2, Q3, and Q4 are linkers, for example, hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene and / or heteroatom-containing alkylene) or -(CO)-, ew, x, yez are independently zero or 1, meaning that each linker is optional. Preferably, w, x, yez are all zero. Furthermore, two or more substituents on adjacent atoms within Q1, Q2, Q3, and Q4 may be attached to form an additional cyclic group; and R3, R3A, R4, and R4A are independently selected from hydrogen, hydrocarbonyl, substituted hydrocarbonyl, heteroatom-containing hydrocarbonyl, and substituted heteroatom-containing hydrocarbonyl. Petition 870200096653, dated 03 / 08 / 2020, p. 57 / 112 40 / 84

[0115] Furthermore, any two or more of X1, X2, L1, L2, L3, R1, R2, R3, R3A, R4 and R4A may be taken together to form a cyclic group, and any one or more of X1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R2, R3, R3A, R4, and R4A may be attached to a support.Any two or more of X1, X2, L1, L2, L3, R1, R2, R3, R3A, R4, and R4A may also be taken as -A-Fn, where “A” is a divalent hydrocarbon moiety selected from an alkylene and arylalkylene, where the alkyl part of the alkylene and arylalkylene groups may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, where the aryl part of the arylalkylene may be substituted or unsubstituted, and where heteroatoms and / or functional groups may be present in both the aryl and alkyl parts of the alkylene and arylalkylene groups, and Fn is a functional group, or joined to form a cyclic group, and any one or more of X1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R2, R3, R3A, R4, and R4A may to be attached to a support.

[0116] Preferably, R3A and R4A are linked to form a cyclic group so that the carbene ligand has the structure of formula (IV) where R3 and R4 are as defined for the second group of catalysts above, preferably with at least one of the R3 and R4, and more preferably both R3 and R4, being alicyclic or aromatic from 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 linkers, heteroatom-containing hydrocarbylene linkers, and substituted heteroatom-containing hydrocarbylene linkers, where two or more substituents on adjacent atoms within Q may also be attached to form an additional cyclic structure or may be similarly substituted to provide a fused polycyclic structure of two to about five cyclic groups. Petition 870200096653, dated 03 / 08 / 2020, p. 58 / 112 41 / 84 cos. Q is generally, though not necessarily, a two-atom bond or a three-atom bond.

[0117] Examples of N-heterocyclic carbene (NHC) ligands and compatible acyclic diaminocarbene ligands such as L1 include, but are not limited to, the following where DIPP is a diisopropylphenyl and Ms is a 2,4,6-trimethylphenyl: r3—N r3Ar4A DIPP DIPP Month Month

[0118] Additional examples of N-heterocyclic carbene (NHC) ligands and compatible acyclic diaminocarbene ligands such as L1 include, but are not limited to, the following: Petition 870200096653, dated 03 / 08 / 2020, p. 59 / 112 42 / 84 where RW1, RW2, RW3 and RW4 are independently hydrogens, unsubstituted hydrocarbyl, substituted hydrocarbyl, and heteroatom-containing hydrocarbyl, and where one or both of RW3 and RW4 may be independently selected from nitroso, halogen, nitro, carboxyl, alkoxy, aryloxy, sulfonyl, carbonyl or thio groups.

[0119] Additional examples of N-heterocyclic carbene (NHC) ligands compatible with L1 are further described in US Patent Numbers 7,378,528; 7,652,145; 7,294,717; 6,787,620; 6,635,768; and 6,552,139, disclosures of which are incorporated herein by reference. Additionally, thermally activated N-heterocyclic carbene precursors as disclosed in US Patent Number 6,838,489, the contents of which are incorporated herein by reference, may also be used with the present invention.

[0120] When M is a ruthenium, then the preferred complexes have the structure of formula (V) (V) Petition 870200096653, dated 03 / 08 / 2020, pp. 60 / 112 43 / 84

[0121] In a more preferred embodiment, Q is a bond of two atoms having the structure -CR^R^-CR13R14- or -CR11=CR13-, preferably -CR R CR R -, where R11, R12, R13 and R14 are independently selected from a hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. Examples of functional groups include, without limitation, carboxyl, C1-C20 alkoxy, C5-C24 aryloxy, C2C20 alkoxycarbonyl, C5-C24 alkoxycarbonyl, C2-C24 acyloxy, C1-C20 alkylthio, C5-C24 arylthio, C1-C20 alkylsulfonyl, and C1-C20 alkylsulfinyl, optionally substituted by one or more halves selected from C1-C12 alkyl, C1-C12 alkoxy, C5-C14 aryl, hydroxy, sulfhydryl, formyl, and halide. R11, R12, R13, and R14 are preferably independently selected from hydrogen, C1-C12 alkyl, substituted C1-C12 alkyl, C1-C12 heteroalkyl, substituted C1-C12 heteroalkyl, phenyl, and substituted phenyl.Alternatively, any two of R11, R12, R13, and R14 can be linked together to form a saturated or unsaturated, substituted or unsubstituted ring structure, for example, with fused or bonded aromatic or alicyclic groups, or with other substituents. In another aspect, any one or more of R11, R12, R13, and R14 comprise one or more of the linkers. Additionally, L2 can be L2(k), where k is zero or 1.

[0122] When R3 and R4 are aromatic, they are typically, though not necessarily, compounds of one or more aromatic rings, which may or may not be substituted, for example, R3 and R4 may be phenyl, substituted phenyl, biphenyl, substituted biphenyl, or the like. In a preferred embodiment, R3 and R4 are the same and each is an unsubstituted phenyl or a phenyl substituted with up to three substituents selected from C1-C20 alkyl, C1-C20 substituted alkyl, C1-C20 heteroalkyl, C1-C20 substituted heteroalkyl, C5-C24 aryl, C5-C24 substituted aryl, C5-C24 heteroaryl, C6-C24 aralkyl, C6-C24 alcaryl, or helide. Preferably, any substituents present are hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C5-C24 aryl, substituted C5-C24 aryl, or halide. As an example, R3 and R4 are mesityl (i.e., M as defined here).

[0123] A third group of catalysts having the structure of formula (I), M, Petition 870200096653, dated 03 / 08 / 2020, pp. 61 / 112 44 / 84 m, n, X1, X2, R1 and R2 are as defined for the first group of catalysts, L1 is a strongly coordinating neutral electron-donating ligand such as any of those described for the first and second groups of catalysts, and L2 and L3 are weakly coordinating neutral electron-donating ligands in the form of optionally substituted heterocyclic groups. Again, n is zero or 1, so L3 may or may not be present. Generally, in the third group of catalysts, L2 and L3 are optionally substituted monocyclic groups with five- or six members, or are optionally substituted polycyclic or bicyclic structures composed of 2 to 5 such five- or six-membered monocyclic groups. If the heterocyclic group is substituted, it must not be substituted on a coordinating heteroatom, and any cyclic half within a heterocyclic group will generally not be substituted by more than three substituents.

[0124] For the third group of catalysts, examples of L2 and L3 include, without limitation, heterocycles containing nitrogen, sulfur, oxygen, or a mixture thereof.

[0125] Examples of nitrogen-containing heterocycles suitable for L2 and L3 include pyridine, bipyridine, pyridazine, pyrimidine, bipyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinoline, quinazoline, naftiridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolimimine, purine, benzimidazole, bisimidazole, phenazine, acridine and carbazole.

[0126] Examples of sulfur-containing heterocycles suitable for L2 and L3 include thiophene, 1,2-dithiole, 1,3-dithiole, tiepine, benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene, 2H-thiopyran, 4H-thiopyran, and thioanthrene.

[0127] Examples of oxygen-containing heterocycles suitable for L2 and L3 include 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin, oxepin, furan, 2H-1-benzopyran, coumarin, coumarone, chromene, chroman-4-one, isochromene Petition 870200096653, dated 03 / 08 / 2020, pages 62 / 112 45 / 84 1-one, isochromen-3-one, xanthene, tetrahydrofuran, 1,4-dioxane, and dibenzofuran.

[0128] Examples of mixed heterocycles suitable for L2 and L3 include isoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxatiol, 1,3-oxatiol, 4H-1,2-oxazine, 2H-1,3-oxazine, 1,4-oxazine, 1,2,5-oxathiazine, isooxazine, phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, and morpholine.

[0129] Preferred ligands for L2 and L3 are oxygen-containing and nitrogen-containing heterocycles, and particularly preferred ligands for L2 and L3 are monocyclic N-heteroaryl ligands that are optionally substituted by 1 to 3, preferably 1 or 2, substituents. Specific examples of particularly preferred L2 and L3 ligands are pyridine and substituted pyridines, such as 3-bromopyridine, 4-bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine, 3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine, 2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine, 3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine, 3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine, 3,5-dimethylpyridine, 4-methylpyridine, 3,5-diidopropylpyridine, 2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine, 4-(tertbutyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine, 3,5-dichloro-4-phenylpyridine, and the like.

[0130] In general, any substituents present in L2e / or L3 are selected from a halo, C1-C20 alkyl, substituted C1-C20 alkyl, C1-C20 heteroalkyl, substituted C1-C20 heteroalkyl, C5-C24 aryl, substituted C5-C24 aryl, C5-C24 heteroaryl, substituted C5C24 heteroaryl, C6-C24 alkoxy, C6-C24 heteroalkyl, substituted C6-C24 heteroalkyl, C6-C24 aralkyl, substituted C6-C24 aralkyl, C6-C24 heteroaralkyl, substituted C6-C24 heteroaralkyl, and functional groups, with compatible functional groups including, without limitation, C1-C20 alkoxy, C5-C24 aryloxy, C2-C20 alkylcarbinyl, C6-C24 arylcarbonyl, C2C20 alkylcarbonyloxy, C6-C24 arylcarbonyloxy, C2-C20 alkoxycarbonyl, C6-C24 aryloxycarbonyl, halocarbonyl, C2-C20 alkylcarbonate, C6-C24 arylcarbonate, carboxy, carboxylate, carbamoyl, mono-(C1-C20 alkyl)-substituted carbamoyl, di-(C1-C20 alkyl)-substituted carbamoyl Petition 870200096653, dated 03 / 08 / 2020, page 63 / 112 46 / 84 acid, di-N-(C1-C20 alkyl), N-(C5-C24 aryl)-substituted carbamoyl, substituted mono-(C5-C24 aryl)carbamoyl, substituted di-(C6-C24 aryl)-carbamiol, thiocarbamoyl, substituted mono-(C1-C20 alkyl)-thiocarbamoyl, di-(C1-C20 substituted alkyl)-thiocarbamoyl, substituted di-N-(C1-C20 alkyl)-N-(C6-C24 aryl)-thiocarbamoyl, substituted mono-(C6-C24 aryl)-thiocarbamoyl, substituted di-(C6-C24 aryl)-thiocarbamoyl, carbamido, formyl, thioformyl, amino, substituted mono(C1-C20 alkyl)-amino, substituted di-(C1-C20 alkyl)-amino, Substituted mono-(C5-C24 aryl)-amino, substituted di-(C5-C24 aryl)-amino, di-N-(C1-C20 alkyl), N-(C5-C24 aryl)-amino, C2-C20 alkylamido, C6-C24 arylamido, C1-C20 alkylimino, C5-C24 arylimino, nitro, and nitroso. Furthermore, two adjacent substituents can be taken together to form a ring, generally an aryl or alicyclic ring with five or six members, optionally containing from 1 to 3 heteroatoms and from 1 to 3 substituents as above.

[0131] Preferred substituents on L2 and L3 include, without limitation, a halo, C1-C12 alkyl, substituted C1-C12 alkyl, C1-C12 heteroalkyl, substituted C1-C12 heteroalkyl, C5-C14 aryl, substituted C5-C14 aryl, C5-C14 heteroaryl, substituted C5-C14 heteroaryl, C6-C16 alkoxy, substituted C6-C16 alkoxy, C6-C16 heteroalkoxy, substituted C6-C16 heteroalkoxy, C1-C12 alkoxy, C5-C14 aryloxy, C2-C12 alkylcarbamiol, C6-C14 arylcarbamoyl, C2-C12 alkylcarbonyloxy, C6-C14 arylcarbonyloxy, C2-C12 alkoxycarbonyl, C6-C14 aryloxycarbonyl, halocarbonyl, formyl, amino, substituted mono-(C1-C12 alkyl)amino, substituted di-(C1-C12 alkyl)amino, substituted mono-(C5-C14 aryl)amino, substituted di-(C5-C14 aryl)amino, and nitro.

[0132] Of the above mentioned, the most preferred substituents are halo, C1-C12 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, phenyl, substituted phenyl, formyl, NN-di(C1-C6 alkyl)amino, nitro, and nitrogen heterocycles as described above (including, for example, pyrrolidine, piperidine, piperazine, pyrazine, pyrimidine, pyridine, pyridazine, etc.).

[0133] In certain embodiments, L2 and L3 may also be taken together to form a bidentate or multidentate binder containing two or more, usually two, Petition 870200096653, dated 03 / 08 / 2020, pp. 64 / 112 47 / 84 coordination heteroatoms such as N, O, S, or P, with such ligands preferably being Brookhart-type diimine ligands. A representative bidentate ligand has the structure of formula (VI) (VI) where R15, R16, R17, and R18hydrocarbyl (example, C1-C20 alkyl, C2-C2oalkenyl, C2C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, or C6-C24 aralkyl), substituted hydrocarbyl (example, C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C5-C24 aryl, C6-C24 alkaryl, or C6-C24 substituted aralkyl), heteroatom-containing hydrocarbanyl (e.g., C1-C20 heteroalkyl, C5-C24 heteroaryl, C6-C24 heteroatom-containing aralkyl, or C6-C24 heteroatom-containing alkaryl), or substituted heteroatom-containing hydrocarbyl (example, CiC20 heteroalkyl, C5-C24 heteroaryl, C6-C24 aralkyl containing heteroatom, or C6-C24 alkaryl containing substituted heteroatom), or (1) R15 and R16, (2) R17 and R18, (3) R16 and R17, or (4) both R15 and R16, and R17 and R18, can be taken together to form a ring, that is, an N-heterocycle. Preferred cyclic groups in such a case are five- and six-membered rings, typically aromatic rings.

[0134] In a fourth group of catalysts having the structure of formula (I), two of the substituents are taken together to form a bidentate ligand or a tridentate ligand. Examples of bidentate ligands include, but are not limited to, biophosphines, dialkoxides, alkyldiketonates, and aryldiketonates. Specific examples include -P(Ph)2CH2CH2P(Ph)2-, -As(Ph)2CH2CH2As(Ph2)-, P(Ph)2CH2CH2C(CF3)2O-, binaftholate dianions, pinacolalate dianions, P(CH3)2(CH2)2P(CH3)2-, and -OC(CH3)2(CH3)2CO-. Preferred bidentate ligands are -P(Ph)2CH2CH2P(Ph)2- and -P(OH3)2(OH2)2P(OH3)2-. Tridentate ligands include, but are not limited to, (OH3)2NOH2OH2P(OH)OH2OH2NO(OH3)2. Other preferred tridentate ligands are those in which any three of X1, X2, L1, L2, R1, and R2 Petition 870200096653, dated 03 / 08 / 2020, pp. 65 / 112 48 / 84 (for example, X1, L1, and L2) are taken together to be cyclopentadienyl, indenyl, or fluorenyl, each optionally substituted by C2-C20 alkenyl, C2-C20 alkynyl, C1-C20 alkyl, C5-C20 aryl, C1-C20 alkoxy, C2-C20 alkenyloxy, C2-C20 alkynyloxy, C5-C20 aryloxy, C2C20 alkoxycarbonyl, C1-C20 alkylthio, C1-C20 alkylsulfonyl, or C1-C20 alkylsulfinyl, each of which may be further substituted by C1-C20 alkyl, halide, C1-C1e alkoxy or a phenyl group optionally substituted by halide, C1-C1e alkyl, or C1-C1e alkoxy. More preferably, in compounds of this type, X, L1, and L2 are taken together to be cyclopentadienyl or indenyl, each optionally substituted with vinyl, C1-C10 alkyl, C5-C20 aryl, C1-C10 carboxylate, C2-C10 alkoxycarbonyl, C1-C10 alkoxy, or C5-C20 aryloxy, each optionally substituted with C1-Oθ alkyl, halide, C1-Ce alkoxy, or with a phenyl group optionally substituted with halide, C1-Oθ alkyl, or C1-Oθ alkoxy.More preferably, X, L1, and L2 can be taken together to be cyclopentadienyl, optionally substituted with vinyl, hydrogen, methyl, or phenyl. Tetradentate ligands include, but are not limited to, O2C(CH2)2P(Ph)(CH2)2P(Ph)(CH2)2CO2, phthalocyanines, and porphyrins.

[0135] Complexes where Y is coordinated to the metal are examples of a fifth group of catalysts, and are commonly called “Grubbs-Hoveyda” catalysts. Metatase-activated Grubbs-Hoveyda metal carbene complexes can be described by formula (VII) Where, M is a Group 8 transition metal, particularly Ru or Os, or more particularly, Ru; X1e, X2e, and L1 are as previously defined here for 0 first and 0 second. Petition 870200096653, dated 03 / 08 / 2020, p. 66 / 112 49 / 84 of the catalyst group; Y is a heteroatom selected from N, O, S, and P; preferably Y is O or N; R5, R6, R7, and R8 are each independently selected from the groups consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, substituted halogen amide, trifluoramide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, where “A” and Fn has been defined above; and any combination of Y, Z, R5, R6, R7, and R8 that can be linked to form one or more cyclic groups; n is 0, 1, or 2, such that n is 1 for divalent heteroatoms O or S, en is 2 for trivalent heteroatoms N or P; and Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl where the functional group(s) may independently be one or more of the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoramide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl, and trimethylsilyl; and where any combination or combinations of X1, X2, L1, Y, Z, R5, R6, R7, and R8 may be attached to a support.

[0136] Additionally, R5, R6, R7, and R8 are each independently selected from a group consisting of thioisocyanate, cyanate, or thiocyanate. Additionally, Z can be independently selected from thioisocyanate, cyanate, or thiocyanate. Additionally, Z can be independently a thioisocyanate, cyanate, or thiocyanate. Petition 870200096653, dated 03 / 08 / 2020, p. 67 / 112 50 / 84

[0137] In general, Grubbs-Hoveyda complexes useful in the invention contain a chelating alkylidene moiety of formula (VIII) (VIII) where Y, η, Z, R5, R6, R7, and R8 are as previously defined here for catalysts of the fifth group; Y, Z, and R5 can optionally be linked to form a cyclic structure; and

[0138] R9 and R10 are each independently selected from a hydrogen or a substituent group selected from alkyl, aryl, alkoxy, aryloxy, C2-C20 alkoxycarbonyl, or C1-C20 trialkylsilyl, wherein each of the substituent groups is substituted or unsubstituted; and wherein any combination or combinations of Z, Y, R5, R6, R7, R8, R9 and R10 may be connected to a holder.

[0139] Examples of complexes comprising compatible GubbsHoveyda ligands in the invention include: where L1, X1, X2 and M are as described for any other catalytic groups. Petition 870200096653, dated 03 / 08 / 2020, p. 68 / 112 51 / 84 sadores. Carbene precursors and compatible chelating carbenes are further described by Pederson et al. (US Pat. Nos. 7,026,495 and 6,620,955, both disclosures of which are incorporated herein by reference) and Hoveyda et al. (US Pat. No. 6,921,725 ​​and WO0214376, both disclosures of which are incorporated herein by reference).

[0140] Other useful complexes include structures where L1 and R2 according to formula (I), (III) or (V) are linked, such as styrenic compounds that also include a functional group for attachment to a support. Examples where the functional group is a functionalized half of trialkoxysilyl include, but are not limited to, the following: Petition 870200096653, dated 03 / 08 / 2020, pp. 69 / 112 52 / 84

[0141] Other examples of complexes having ligands linked include those having linkages between a neutral NHC ligand and an anionic ligand, a neutral NHC ligand and an alkylidine ligand, a neutral NHC ligand and an L2 ligand, a neutral NHC ligand and an L3 ligand, an anionic ligand and an alkylidine ligand, and any combination thereof. While the possible structures are too numerous to list here, some compatible structures based on formula (III) include: [(Q^-R3^ p |(Q4)z-R4A|q R3-(Q')xX .Y—(O2)y-R4 Petition 870200096653, dated 03 / 08 / 2020, pages 70 / 112 53 / 84

[0142] In addition to catalysts having the structure of formula (I), as described above, other transition metal carbene complexes include, but are not limited to: Neutral carbene osmium or ruthenium complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 16, are penta-coordinated, and are of general formula (IX); Neutral carbene osmium or ruthenium 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 carbene osmium or ruthenium 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); Cationic carbene osmium or ruthenium 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) Petition 870200096653, dated 03 / 08 / 2020, pp. 71 / 112 54 / 84 (XII) where; M, X1, X2, L1, L2, L3, R1, and R2 are as defined by any of the four previously defined groups of catalysts; The values ​​are independently either zero or 1; t is an integer in the range of zero to 5; k is an integer in the range of zero to 1; Y is any non-coordinated anion (for example, a halide ion, BF4_, etc.); Z and Z are selected independently of a -O-, -S-, -NR2-, PR2-, P(=O)R2-, -P(OR2)-, -P(=O)(OR2)-, -C(=O)-, -C(=O)O-, -OC(=O)-, -00(=O)0-, S(=O)-, -S(=O)2; Z is any cationic half such as -P(R2)3+ or -N(R2)3+; and any two or more of X1, X2, L1, L2, L3, Z1, Z2, Z3, R1, and R2 can be taken together to form a cyclic group, for example, a multidentate ligand, and where any one or more of X1, X2, L1, L2, L3, Z1, Z2, Z3, R1, and R2 can be attached to a support. Z1 and Z2 can also be a C1-C20 hydrocarbylene bond containing optionally and / or optionally substituted heteroatoms.

[0143] Additionally, another group of olefin metatase catalysts that can be used in the invention disclosed herein is a Group 8 transition metal complex having the structure of formula (XIII): where M is a Group 8 transition metal, particularly ruthenium or osmium, Petition 870200096653, dated 03 / 08 / 2020, pp. 72 / 112 55 / 84 or more particularly, ruthenium: X1, X2, L1 and L2 are as defined for the first and second groups of catalysts defined above; RG1, RG2, RG3, R4, RG5, and RG6 are each independently selected from a group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanate, thiocyanate, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, imide, halogen-substituted starch, trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn,where “A” is a divalent hydrocarbon moiety selected from an alkylene and arylalkylene, wherein the alkyl moiety of the alkylene and arylalkylene groups may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, wherein the aryl moiety of the arylalkylene may be substituted or unsubstituted, and wherein functional groups and / or heteroatoms may be present in both the aryl and alkyl moieties of the alkylene and arylalkylene groups, and Fn is a functional group, or any one or more of RG1, RG2, RG3, RG4, RG5, and RG6 may be linked together to form a cyclic group, or any one or more of RG1, RG2, RG3, RG4, RG5, and RG6 may be attached to a support.

[0144] Additionally, a preferred embodiment of the Group 8 transition metal complex of formula XIII is a Group 8 transition metal complex of formula XIV: Petition 870200096653, dated 03 / 08 / 2020, pp. 73 / 112 56 / 84 where M, X1, X2, L1 and L2 are as defined above for the Group 8 transition metal complex of formula XIII; RG7, RG8, RG9, RG1°, RG11, RG12, RG13, RG14, RG15 and RG16 are defined above for RG1, RG2, RG3, RG4, RG5, and RG6 for the Group 8 transition metal complex of formula XIII or any one or more of RG7, RG8, RG9, RG1°, RG11, RG12, RG13, RG14, RG15 and RG16 may be linked together to form a cyclic group, or any one or more of RG7, RG8, RG9, RG1°, RG11, RG12, RG13, RG14, RG15 and RG16 may be attached to a support.

[0145] Additionally, another preferred embodiment of the Group 8 transition metal complex of formula XIII is the Group 8 transition metal complex of formula XV: where M, X1, X2, L1 and L2 are as defined above for the Group 8 transition metal complex of formula XIII.

[0146] Additionally, another group of olefin metatase catalysts that can be used in the invention disclosed herein is a transition metal complex having the structure of formula (XVI): where M is a Group 8 transition metal, particularly a ruthenium or Petition 870200096653, dated 03 / 08 / 2020, pp. 74 / 112 57 / 84 osmium, or more particularly, ruthenium; X1 and L1 are as defined for the first and second groups of catalysts defined above; Z is selected from a group consisting of oxygen, sulfur, selenium, NRJ11, PRJ11, AsRJ11, and SbRJ1; and RJ1, RJ2, RJ3, RJ4, RJ5, RJ6, RJ7, RJ8, RJ9, RJ10 and RJ11 are each independently selected from a group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanate, thiocyanate, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, imide, halogen-substituted starch, trifluoroamide, sulfide, disulfide, sulfonate,carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, where “A” is a divalent hydrocarbon moiety selected from an alkylene and arylalkylene, where the alkyl part of the alkylene and arylalkylene groups may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, where the aryl part of the arylalkylene may be substituted or unsubstituted, and where functional groups and / or heteroatoms may be present in both the aryl and alkyl parts of the alkylene and arylalkylene groups, and Fn is a functional group, or any one or more of RJ1, RJ2, RJ3, RJ4, RJ5, RJ6, RJ7, RJ8, RJ9, RJ10 and RJ11 may be linked together to form a cyclic group, or any one or more of RJ1, RJ2, RJ3, RJ4, RJ5, RJ6, RJ7, RJ8, RJ9, RJ10 and RJ11 connectors can be attached to a bracket.

[0147] Additionally, a preferred embodiment of the Group 8 transition metal complex of formula XXI is a Group 8 transition metal complex of formula XVII: Petition 870200096653, dated 03 / 08 / 2020, pp. 75 / 112 58 / 84 (XVII) where M, X1, L1, Z, RJ7, RJ8, RJ9, RJ1° and RJ11 are as defined above for the Group 8 transition metal complex of formula XVI; and RJ12, RJ13, RJ14, RJ15, RJ16, rji7, RJW Rjw rj2o, θ Rj2isg0 CO as defined above for RJ1, RJ2, RJ3, RJ4, RJ5 and RJ6, for the Group 8 transition metal complex of formula XVI, or any one or more of RJ7, RJ8, RJ9, RJ1°, RJ11, RJ12, RJ13, RJ14, RJ15, RJ16, RJ17, RJ18, RJ19, RJ2°, and RJ21 may be linked together to form a cyclic group, or any one or more of RJ7, RJ8, RJ9, RJ1°, RJ11, RJ12, RJ13, RJ14, RJ15, RJ16, RJ17, RJ18, RJ19, RJ2°, and RJ21 may be attached to a support.

[0148] Additionally, another preferred embodiment of the Group 8 transition metal complex of formula XVI is a Group 8 transition metal complex of formula XVIII: (XVIII) where M, X1, L1, Z, RJ7, RJ8, RJ9, RJ1° and RJ11 are as defined above for the Group 8 transition metal complex of formula XVI.

[0149] Additionally, another group of olefin metatase catalysts that can be used in the invention disclosed herein is a Group 8 transition metal complex having the structure of formula (XIX): Petition 870200096653, dated 03 / 08 / 2020, pp. 76 / 112 59 / 84 (XIX): (19) where M is a Group 8 transition metal, particularly ruthenium or osmium, or more particularly ruthenium; X1 and L1, R2 are as defined for the first and second groups of catalysts defined above; Z is selected from a group consisting of oxygen, sulfur, selenium, NRK5, PRK5, AsRK5, and SbRK5; m is 0, 1 or 2; RK1, RK2, RK3, RK4, and RK5 are each independently selected from a group consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanate, thiocyanate, hydroxyl, ester, ether, thioether, amine, alkylamine, imine, imide, halogen-substituted starch,trifluoroamide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, borate, or -A-Fn, where “A” is a divalent hydrocarbon moiety selected from an alkylene and arylalkylene, where the alkyl part of the alkylene and arylalkylene groups may be linear or branched, saturated or unsaturated, cyclic or acyclic, and substituted or unsubstituted, where the aryl part of the arylalkylene may be substituted or unsubstituted, and where functional groups and / or heteroatoms may be present in both the aryl and alkyl parts of the alkylene and arylalkylene groups, and Fn is a functional group, or any one or more of RK1, RK2, RK3, RK4, and RK5 may be linked together to form a cyclic group, or any one or more of RK1, RK2, RK3, RK4, and RK5s can be attached to a bracket. Petition 870200096653, dated 03 / 08 / 2020, pp. 77 / 112 60 / 84

[0150] In addition, other examples of catalysts that can be used with the present invention are located in the following disclosures, each of which is incorporated herein by reference, U.S. Patent Nos. 7,687,635; 7,671,224 and 5,977,393; International Publication Number WO2010 / 037550; and U.S. Patent Application Numbers 12 / 303,615; 10 / 590,380; 11 / 465,651 (Publication Number: U.S. 2007 / 0043188); and 11 / 465,651 (Publication Number: U.S. 2008 / 0293905 Correct Publication).

[0151] Non-limiting examples of catalysts that can be used to prepare the supported complexes and in the reactions disclosed here include the following, some of which for convenience are identified throughout this disclosure by reference to their molecular weight: C884 C727 Petition 870200096653, dated 03 / 08 / 2020, pp. 78 / 112 61 / 84 C916 C727 PCy3 I^CIpy—► Ru— pyPh C701 C577 C646 C801 C811 C767-m Petition 870200096653, dated 03 / 08 / 2020, pp. 79 / 112 62 / 84 Petition 870200096653, dated 03 / 08 / 2020, pp. 80 / 112 63 / 84 DIPP DIPP CH3—NN—CH3| .Cl Rl / -=\cΛph Mes—NN—Mes DIPP DIPP Month Month Mes—NN—Mes Petition 870200096653, dated 03 / 08 / 2020, pp. 81 / 112 64 / 84 Y = O, S, NH

[0152] In the above-mentioned molecular structures and formulas, Ph represents phenyl, Cy represents cyclohexyl, Me represents methyl, t-Bu represents tert-butyl, Bu represents n-butyl, i-Pr represents isopropyl, py represents pyridine (coordinated through the N atom), Me represents mesityl (i.e., 2,4,6-trimethylphenyl), DiPP and DIPP represent 2,6-diidopropylphenyl, and MiPP represents 2-isopropylphenyl.

[0153] Other examples of useful catalysts for preparing the supporting complexes and in the reactions disclosed herein include the following: ruthenium(II)dichloro(3-methyl-1,2-butenylidene)bis(tricyclopentylphosphine) (C716); ruthenium(II)dichloro(3-methyl-1,2-butenylidene)bis(tricyclohexylphosphine) (801); ruthenium(II)dichloro(phenylmethylene)bis(tricyclohexylphosphine) (C823); ruthenium(II)(1,3-bis-(2,4,6-trimethylphenyl)-2imidazolidinilidene)dichloro(phenylmethylene)(triphenylphosphine) (C830), and ruthenium(II)dichloro(phenylvinylidine)bis(tricyclohexylphosphine) (C835); ruthenium (II) dichloro (tricyclohexylphosphine) (oisopropoxyphenylmethylene) (C601), and ruthenium (II) (1,3-bis-(2,4,6-trimethylphenyl)-2imidazolidene) dichloro (phenylmethylene) bis(3-bromopyridine (C884)). Petition 870200096653, dated 03 / 08 / 2020, pages 82 / 112 65 / 84

[0154] Yet another useful catalyst in ROMP reactions, and / or in other metatase reactions, such as ring-closing metatase, cross-metatase, ring-opening cross-metatase, self-metatase, ethenolysis, alkenolysis, acyclic diene metatase polymerization, and combinations thereof, include the following structures: Petition 870200096653, dated 03 / 08 / 2020, page 83 / 112 66 / 84

[0155] In addition, non-limiting examples of catalysts that can be used to prepare the supported complexes and in the reactions disclosed here include the following Petition 870200096653, dated 03 / 08 / 2020, pages 84 / 112 67 / 84

[0156] 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, US Pat. No. 5,312,940, and US Pat. No. 5,342,909, disclosures of which are incorporated herein by reference. See also US Pat. Pub. No. 2003 / 0055262 for Gubbs et al., WO02 / 079208, and US Pat. No. 6,613,910 for Grubbs et al., the disclosures of which are incorporated herein by reference. The preferred synthetic methods are described in WO 03 / 11455A1 for Grubbs et al., the disclosure of which is incorporated herein by reference.

[0157] Compatible supports for any of the catalysts described herein may be synthetic, semi-synthetic, or naturally occurring materials, which may be organic or inorganic, for example, polymeric, ceramic, or metallic. The ane Petition 870200096653, dated 03 / 08 / 2020, pages 85 / 112 68 / 84 Attachment to the support will generally, though not necessarily, be covalent, and the covalent bond can be direct or indirect. Direct covalent bonds are typically, though not necessarily, through a functional group on a support surface. Ionic attachments are also compatible, including combinations of one or more anionic groups in metal complexes coupled with supports containing cationic groups, or combinations of one or more cationic groups in metal complexes coupled with supports containing anionic groups.

[0158] When used, compatible supports may be selected from silicas, silicates, aluminas, aluminum oxides, silica-alumina, aluminosilicates, zeolites, titanias, titanium dioxide, magnetite, magnesium oxides, boron oxides, clays, zirconium, zirconium dioxide, carbon, polymers, cellulose, amylose, cellulosic polymers, amylosic polymers, or a combination thereof. The support preferably comprises a silica, a silicate, or a combination thereof.

[0159] In certain embodiments, it is also possible to use a support that has been treated to include the functional groups, inert halves and / or excess binders. Any of the functional groups described here are compatible for incorporation into the support, and this can generally be accomplished through techniques known in the art. Inert halves can also be incorporated into the support to generally reduce the attachment sites available on the support, for example, in order to control the placement, or quantity, of a complex bonded to the support.

[0160] The metatase catalysts described below can be used in olefin metatase reactions according to techniques known in the art. The catalyst is typically added to the reaction medium as a solid, or as a suspension where the catalyst is suspended in a suitable liquid. It will be appreciated that the amount of catalyst used (i.e., the “catalyst loading”) in the reaction is dependent on a variety of factors such as the identity of the reactants and the reaction conditions employed. It is understood, therefore, that Petition 870200096653, dated 03 / 08 / 2020, pages 86 / 112 69 / 84 The catalyst loading can be optimally and independently chosen for each reaction. In general, however, the catalyst will be present in an amount ranging from one below about 0.1 ppm, 1 ppm, or 5 ppm, to one above 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.

[0161] The catalyst will generally be present in an amount ranging from one below about 0.00001 mol%, 0.0001 mol%, or 0.0005 mol%, to one above about 0.001 mol%, 0.0015 mol%, 0.0025 mol%, 0.005 mol%, 0.01 mol%, 0.05 mol%, or 0.1 mol% relative to the olefinic substrate.

[0162] When expressed as a molar ratio of monomer to catalyst, the catalyst (the “monomer to catalyst ratio”), the feedstock will generally be present in an amount ranging from one below about 10,000,000:1, 1,000,000:1, or 200,000:1, to one above about 100,000:1, 66,667:1, 40,000:1, 20,000:1, 10,000:1, 5,000:1, or 1,000:1. CYCLIC OLEFIN (RESIN) ARTICLES AND COMPOSITIONS

[0163] Cyclic olefin resin compositions, particularly ROMP, that can be used in the method of the invention disclosed herein generally comprise one or more cyclic olefins and an olefin metatase catalyst. The cyclic olefins described above are compatible for use and may be functionalized or non-functionalized, and may be substituted or non-substituted.

[0164] Compatible resin compositions for use with this invention having a viscosity at 25°C ranging from about 1 centipoise to about 200 centipoise (1 cp - 200 cp). Viscosities typically range from 1-150 cp, 1-100 cp, 5-100 cp, 5-150 cp, 5-25 cp, 5-50 cp, 5-15 cp, 5-20 cp at 25°C. At other temperatures -20°C, -10°C, 0°C, 5°C, 15°C, 25°C, 30°C, 40°C, 50°C, 60°C, viscosities can vary from 1-150 cp, 1-100 cp, 5-100 cp, 5-150 cp, 5-25 cp, 5-50 cp, 5-15 cp, 5-20 cp.

[0165] The resin compositions of the invention may optionally be formulated with additives. Compatible additives include, but are not limited to, Petition 870200096653, dated 03 / 08 / 2020, p. 87 / 112 70 / 84 gels, modifications, hardness modulators, antioxidants, stabilizers, fillers, binders, coupling agents, impact modifiers, thixotropy, wetting agents, biocides, plasticizers, pigments, flame retardants, dyes, fibers and reinforcing materials, including dimensioned reinforcements and substrates, such as those treated with finishers, coatings, coupling agents, film formers and / or lubricants.

[0166] Compatible reinforcing materials include those that add to the strength or stiffness of a polymer compound when incorporated with the polymer. Reinforcing materials may be in the form of filaments, fibers, slivers, mats, textures, fabrics, knitted material, cloth, or other known structures. Compatible reinforcing materials include glass fibers and fabrics, carbon fibers and fabrics, aramid fibers and fabrics, polyolefin fibers or fabrics (including ultra-high molecular weight polyethylene fabrics such as those produced by Honeywell under the trade name Spectra), and polyoxazole fibers or fabrics (such as those produced by Toyobo Corporation under the trade name Zylon).

[0167] Other compatible fillers include, for example, metallic density modulators, microparticulate density modulators, such as, for example, microspheres, and macroparticulate density modulators, such as, for example, glass or ceramic granules. Metallic density modulators include, but are not limited to, powdered, sintered, shaved, flake, filed, particulate, or granular materials, metal oxides, metal nitrites, and / or metal carbides, and the like. Preferred metallic density modulators include, among others, tungsten, tungsten carbide, aluminum, titanium, iron, lead, silicon oxide, aluminum oxide, boron carbide, and silicon carbide. Microparticulate density modulators include, but are not limited to, glass, metal, thermoplastic (both expandable and pre-expanded) or thermosetting materials, and / or ceramic / silicate microspheres.Macroparticulate density modulators include, but are not limited to, glass, plastic, or ceramic granules; Petition 870200096653, dated 03 / 08 / 2020, page 88 / 112. 71 / 84 metal parts, blocks, pieces, or doses; hollow glass, ceramic, plastic, or metal spheres, balls, or tubes; and similar items.

[0168] The invention is also directed to articles manufactured from a resin composition comprising a cyclic olefin and an olefin metatase catalyst, such as the ROMP catalyst, using the methods of the invention. Furthermore, the compositions and articles of manufacture of the invention are not limited to a single polymer surface interface, but also include multilayers and laminates containing multiple polymer surface interfaces. The invention is also compatible for the manufacture of articles by infusing the resin into a porous material. Such porous materials include, but are not limited to, wood, cement, concrete, cross-linked and open-cell foams and sponges, papers, cardboard, felts, ropes or braids of natural or synthetic fibers, and various sintered materials.

[0169] In a preferred embodiment, the metatase reactions disclosed herein are carried out under a dry, inert atmosphere. Such an atmosphere can be created using any inert gas, including gases such as nitrogen and argon. The use of an inert atmosphere is optimal in terms of promoting catalytic activity, and reactions carried out under an inert atmosphere are typically performed with a relatively low catalyst loading. The reactions disclosed herein can also be carried out in an atmosphere containing water and / or containing oxygen, and in one embodiment, the reactions are carried out under ambient conditions. The presence of oxygen or water in the reaction may, however, necessitate the use of higher catalyst loadings compared to reactions carried out under an inert atmosphere. Where the vapor pressure of the reactants permits, the reactions disclosed herein can also be carried out under reduced pressure.

[0170] The reactions disclosed here can also be carried out in a solvent, and any solvent that is inert towards cross-metastasis can be used. Generally, solvents that can be used in metastasis reactions include organic, protic, or aqueous solvents, such as hydrocarbons. Petition 870200096653, dated 03 / 08 / 2020, pages 89 / 112 72 / 84 aromatics, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof.

[0171] Examples of solvents include benzene, toluene, p-xylene, methylene chloride, 1,2-dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethyl ether, pentane, methanol, ethanol, water, or mixtures thereof. In a preferred embodiment, the reactions disclosed herein are carried out pure, i.e., without the use of a solvent.

[0172] It will be appreciated that the temperature at which the metatase reaction, according to the methods disclosed herein, is conducted can be adjusted when necessary and can 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 another temperature can be in a variation that has any of these values ​​as links above and below. In preferred embodiments, the reactions are carried out at a temperature of at least about 35°C, and in another preferred embodiment, the reactions are carried out at a temperature of at least 50°C. EXAMPLES

[0173] Figure 7 depicts an example of a complex laminate assembly that uses a plurality of resin flow control structures with varying dimensions and positioning to control resin flow in a plurality of resin distribution media in a laminate assembly that contains a plurality of preform reinforcement layers having varying positions and dimensions.

[0174] Two zones, (A) and (B), are shown in Figure 7 and indicate two different storages, which constitute a complete article. In particular, the thickness of zone (A) is greater than the thickness of zone (B). As discussed below, in addition to the differences in thickness, the two zones contain varying reinforcement layers, both in number, dimensions, and composition. With infusion methods as previously described in the art, a composite of the complex construction of Figure 7, for example, contains a high content of unacceptable voids when infused with resin. Petition 870200096653, dated 03 / 08 / 2020, pages 90 / 112 73 / 84 in low viscosity resins. With high viscosity resins, it is common to infuse zones (A) and (B) in Figure 7 as sequential infusions and curing steps in order to control the resin flow pattern in each zone. Incorporating the resin flow control structures of the invention into the resin delivery medium allows both zones to be infused simultaneously with low viscosity resin (typically less than 100 cp at 40°C, for example, 1-50 cp, 5-25 cp, or 10-20 cp at 40°C) with improved control over resin flow patterns and to minimize voids and areas of poor resin impregnation.

[0175] Figure 7(a) shows the lower layer of Figure 7, consisting of a release-treated and sealed mold surface made of aluminum (40) having dimensions of 36”x36”. Three layers of one-way glass fabric reinforcement material (41) having dimensions of 24”x24” were positioned on top of the mold surface (40).

[0176] As shown in figure 7(b), the second layer of figure 7, the PET core material (42), having dimensions of 8”x19”, was positioned on top of the one-way glass fabric (41) in zone (B). Twelve layers of one-way glass fabric reinforcement material (43), having dimensions of 12”x24”, were positioned on top of the one-way glass fabric reinforcement material (41) in zone (A).

[0177] As shown in figure 7(c), the third layer of figure 7, three additional layers of one-way glass fabric reinforcement material (44), having dimensions of 24”x24”, were positioned on top of the PET core material (42) and one-way glass fabric reinforcement material (43) in both zones (A) and (B), creating a canvas drop between zones (A) and (B).

[0178] As shown in figure 7(d), the fourth layer of figure 7, a shell layer (45), having dimensions of 28”x27”, was positioned on top of the one-way glass fabric reinforcement material (44).

[0179] As shown in figure 7(e), the fifth layer of figure 7, the resin flow control structures (Coremat by Lantor; 4mm thick), having dimensions of 12”x3” (46(a)), 28”x4” (46(b)), 9”x11” (46(c)), 25”x2” (46(d)), were positioned Petition 870200096653, dated 03 / 08 / 2020, pages 91 / 112 74 / 84 located on top of the shell layer (45). This first layer of resin flow control structures was arranged across the canvas drop area between zones (A) and (B), extending the length of the storage, parallel to the planned resin flow direction in both zones (A) and (B). A 12”x3” resin flow control structure (46(a)) was arranged perpendicular to the planned resin flow in zone (A), starting 1.5” from the location of the selected vacuum outlet port (60(a)). Zone (B) had a 9”x11” resin flow control structure (46(c)) arranged perpendicular to the planned resin flow in zone (B), starting 1.5” from the location of the desired vacuum outlet port (60(b)). Zone (B) had an additional 25”x2” resin flow control structure (46(d)) arranged along the right side of the zone, parallel to the desired resin flow.Another 8”x2” resin flow control structure (46(e)) was placed along the resin entry edge of zone (B). The four sections of resin flow control structures in zone (B) protrude substantially from the edges of the PET core material (42) deeper in the storage structure.

[0180] As shown in figure 7(f), the sixth layer of figure 7, two independent layers of resin distribution medium (i.e., Enkafusion Infusion Media), having dimensions of 28”x11” (47(a)) and 28’x9” (47(b)), were positioned on top of the storage described in the previous figures. No distribution medium was positioned in the folded shell zone, so that there is a gap between the two resin distribution media 47(a) and 47(b).

[0181] As shown in Figure 7(g), the seventh layer of Figure 7, a second layer of five resin flow control structures (Coremat by Lantor; 4 mm thick) having dimensions of 12”x3” (48(a)), 28”x4” (48(b)), 9”x11” (48(c)), 25”x2” (48(d)), and 8”x2” (48(e)), were positioned on top of the resin distribution medium (47(a) and 47(b)) so that the second layer of resin flow control structures (48(a)-(e)) substantially overlaps the corresponding first layer of resin flow control structures having the same dimensions. Petition 870200096653, dated 03 / 08 / 2020, pages 92 / 112 75 / 84 below them (that is, 46(a)-(e)).

[0182] As shown in figure 7(h), the eighth layer of figure 7, the two additional independent layers of resin distribution medium (i.e., Enkafusion Infusion Media), having dimensions of 28”x11” (49(a)) and 28”x9” (49(b)), were positioned on top of the storage described in the previous figures. No distribution medium was positioned in the folded shell zone, so that there is a gap between the two resin distribution media 49(a) and 49(b).

[0183] As shown in figure 7(i), the ninth layer of figure 7, a third layer of resin flow control structures (Coremat by Lantor; 4 mm thick) having dimensions of 12”x3” (50(a)), 28”x4” (50(b)), 9”x11” (50(c)), 25”x2” (50(d)), and 8”x2” (50(e)), were positioned on top of the resin distribution medium (49(a) and 49(b)) so that the third layer of resin flow control structures (50(a)-(e)) substantially overlaps the corresponding first and second layers of resin flow control structures having the same dimensions below them (i.e., 48(a)-(e) and 46(a)-(e)).

[0184] As shown in figure 7(j), the tenth layer of figure 7, Colbond Enkachannels (51) was positioned on top of the second layer of resin distribution medium (49(a) and 49(b)). A vacuum bag (52) was placed over the entire storage. The inlet ports (61(a) and 61(c) in zone (A) and 61(b) in zone (B)) and the outlet ports (60(a) for zone (A) and 60(b) for zone (B)) were installed through the vacuum bag and positioned on top of the Colbond Enkachannels (51). The vacuum bag was affixed to the mold surface (40) using a sealant (i.e., Airtech AT® 200 Yellow tape) and vacuum was applied at 60(a) and 60(b) to evacuate air from the storage.

[0185] Viscosity measurements: uncatalyzed resin samples (100 g) were equilibrated at 25°C and viscosities were measured using a Brookfield DV-II viscometer (S62 shaft at 150 rpm).

[0186] Example 1: A low viscosity mixture (10-15 centipoise at 25°C) Petition 870200096653, dated 03 / 08 / 2020, pages 93 / 112 76 / 84 of resin containing dicyclopentadiene (containing 20-25% tricyclopentadiene), 2 phr Ethanox® 4702 and ruthenium [1,3-bis-(2,4,6-trimethylphenyl)-2imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine) ruthenium(II) (C827, available from Materia, Inc.) (monomer to catalyst in a 30,000:1 ratio) suspended in paraffin oil was introduced into storage (as shown in Figure 7 and described in Figures 7a-7j) through entry ports 61a-61(c). After the preform was determined to be completely impregnated with the resin, the resin was cured to form a composite laminate. Visual inspection confirmed the absence of any voids or areas of low resin impregnation in the composite laminate.

[0187] Example 2: This example used a modification to the storage shown in Figure 7 and described in Figures 7a-7j. In this example, the resin distribution medium (i.e., Eukafusion Infusion Media) in Zone (A) (47(a) & 49(a)) had dimensions 24”x11” so that the end of the distribution medium stopped 4” near the end of the complex laminate near the exit port 60(a) located in Zone (A). Additionally, a separate 2”x11” piece of resin distribution medium was placed at the end of the complex laminate in Zone (A), near the exit port to create a physical gap (2”x11”) between the resin distribution medium (47(a) & 49(a) having dimensions of 24”x11” and a 2”x11” piece of resin distribution medium placed at the end of the complex laminate in Zone (A).Also in this example the resin distribution medium in Zone (B) (49(a) & 49(b)) had dimensions of 21”x7” so that the end of the resin distribution medium stopped 7” near the end of the complex laminate in Zone (B). Furthermore, a separate 2”x7” piece of resin distribution medium was placed at the end of the complex laminate in Zone (B) to create a physical gap (5”x7”) between the resin distribution medium (47(b) & 49(b) having dimensions of 21”x7” and a 2”x7” piece of resin distribution medium placed at the end of the complex laminate. Additionally, the modified storage in this example does not contain an exit port 60(b) in the. Petition 870200096653, dated 03 / 08 / 2020, pages 94 / 112 77 / 84 Zone (B). Additionally, the modified storage in this example of the flow control structures 46(a) - 46(e), 48(a) - 46(e), or 50(a) - 50(e)). The remaining components comprising the stored data, as shown in Figure 7 and described in Figures 7a-7j, were present in the modified storage in this example. A low viscosity mixture (10-15 centipoise at 25°C) of dicyclopentadiene-containing resin (containing 20-25% tricyclopentadiene), 2 phr Ethanox® 4702 and ruthenium [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine) ruthenium(II) (C827, available from Materia, Inc.) (monomer to catalyst in a 30,000:1 ratio) suspended in paraffin oil was introduced into the modified storage of this example through inlet ports 61a-61(c). The resin reached outlet port 60(a) without complete impregnation of the preform.The resin was cured to form a composite laminate, and visual inspection confirmed significant voids and areas of low resin impregnation in the composite laminate.

[0188] After the preform was determined to be completely impregnated with the resin, the resin was cured to form a composite laminate. Visual inspection confirmed the absence of any voids or areas of low resin impregnation in the composite laminate.

[0189] Example 3: A moderate viscosity resin (150 centipoise at 25°C) was created by dissolving styrene / ethylene / butylene (SEBS) thermoplastic block copolymer (2 phr) in dicyclopentadiene (containing 20-25% tricyclopentadiene) and 2 phr Ethanox® 4702. The resin and ruthenium [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine) ruthenium(II) (C827, available from Materia, Inc.) catalyst monomer in a 30,000:1 ratio) suspended in paraffin oil mixture was introduced into storage (as shown in Figure 7 and described in Figures 7a-7j) through inlet ports 61(a) - 61(c). After the preform was determined to be completely impregnated with the resin, the resin was cured to Petition 870200096653, dated 03 / 08 / 2020, pages 95 / 112 78 / 84 form a composite laminate. Visual inspection confirmed the absence of any voids or areas of low resin impregnation in the composite laminate.

[0190] Example 4: This example used a modification to the storage shown in Figure 7 and described in Figures 7a-7j. The modified storage in this example does not contain the flow control structures 46(a) - 46(e), 48(a) - 46(e), or 50(a) - 50(e)). The remaining components comprising the storage, as shown in Figure 7 and described in Figures 7a-7j, were present in the modified storage used in this example. A resin of moderate viscosity (150 centipoise at 25°C) was created by dissolving styrene / ethylene / butylene (SEBS) thermoplastic block copolymer (2 phr) in dicyclopentadiene (containing 20-25% tricyclopentadiene) and 2 phr Ethanox® 4702. A resin and catalyst mixture ruthenium [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine) ruthenium(II) (C827, available from Materia, Inc.) (monomer to catalyst in a 30:1 ratio).A 000:1 resin (suspended in paraffin oil) was introduced into the storage area (as shown in Figure 7 and described in Figures 7a-7j) through the entry ports 61a-61(c). The resin reached the exit port 60(a)-60(b) without complete impregnation of the preform. The resin was cured to form a composite laminate, and visual inspection confirmed significant voids and areas of low resin impregnation in the composite laminate.

[0191] Example 5: A moderate viscosity resin (300 centipoise at 25°C) was created by dissolving styrene / ethylene / butylene (SEBS) thermoplastic block copolymer (3.5–4.0 phr) in dicyclopentadiene (containing 20–25% tricyclopentadiene) and 2 phr Ethanox® 4702. The resin and ruthenium [1,3bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine) ruthenium(II) (C827, available from Materia, Inc.) (monomer to catalyst in a 30,000:1 ratio) suspended in paraffin oil mixture was introduced into storage (as shown in Figure 7 and described in Figures 7a–7j) through the inlet ports. 61(a) - 61(c). After the preform was determined Petition 870200096653, dated 03 / 08 / 2020, pages 96 / 112 79 / 84 as being completely impregnated with resin, the resin was cured to form a composite laminate. Visual inspection confirmed the absence of any voids or areas of low resin impregnation in the composite laminate.

[0192] Example 6: The composite laminate in this example was constructed as follows (Figure 8). The bottom layer of the composite laminate consisted of a release-treated and sealed mold surface (10) made of aluminum having dimensions of 36”x36”. Thirty-eight layers of one-way glass fabric reinforcement material (11) having dimensions of 25”x25” were positioned on top of the mold surface (10). A shell layer (12) having dimensions of 33”x27.5” was positioned on top of the one-way glass fabric reinforcement material (11). The resin distribution medium (30) (i.e., Enkafusion Infusion Media) having dimensions of 32”x24” was placed on top of the shell layer (12). A secondary resin distribution medium (14) (i.e., 1 / 4” of a coil) was positioned on top of the resin distribution medium (30) at opposite ends of the composite laminate corresponding to the position of the inlet port (16) and the outlet port (17).A vacuum bag (not shown) was placed over the complete storage. An inlet port (16) and an outlet port (17) were fitted through the vacuum bag (not shown) and positioned on top of the respective secondary resin dispensing medium (14). The vacuum bag (not shown) was affixed to the mold surface using a sealant (i.e., Airtech AT® Yellow tape) and vacuum was applied to the outlet port (17) to evacuate air from the storage. A low viscosity mixture (10-15 centipoise at 25°C) of the resin containing dicyclopentadiene (containing 20-25% tricyclopentadiene), 2 phr Ethanox® 4702 and ruthenium catalyst [1,3-bis-(2,4,6-trimethylphenyl)-2imidazolidinilidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine) ruthenium (II) (C827, available from Materia, Inc.) (monomer to catalyst in a ratio of 30,000:1) suspended in paraffin oil was introduced into the storage at the entrance port (16).The resin reached the exit port (17) without complete impregnation of the preform. The resin was cured to form a composite laminate, and a visual inspection was performed. Petition 870200096653, dated 03 / 08 / 2020, pages 97 / 112 80 / 84 confirmed the regions with significant vacuum and the areas of low resin impregnation in the composite laminate.

[0193] Example 7: The composite laminate in this example was constructed as follows (Figure 9). The bottom layer of the composite laminate consisted of a release-treated and sealed mold surface (10) made of aluminum having dimensions of 36”x36”. The thirty-eight layers of one-way glass fabric reinforcement material (11) having dimensions of 25”x25” were positioned on top of the mold surface (10). A shell layer (12) having dimensions of 33”x27.5” was positioned on top of the one-way glass fabric reinforcement material (11). The first piece of resin distribution medium (30) (i.e., Enkafusion Infusion Media), having dimensions of 25”x24”, was placed on top of the shell layer (12) so that one end of the resin distribution medium (30) was positioned near one end of the composite laminate and the entry port (16).A second piece of resin distribution medium (31) (i.e., Enkafusion Infusion Media), having dimensions of 3.75”x24”, was placed on top of the shell layer (12) so that one end of the resin distribution medium (31) was positioned near one end of the composite laminate and the exit port (17). The second piece of resin distribution medium (31) was placed so that a physical gap (2”x24”) was created between the first piece of resin distribution medium (30) and the second piece of resin distribution medium (31). A secondary resin distribution medium (14) (i.e., 1 / 4” of a coil) was positioned on top of the resin distribution medium (30, 31) at opposite ends of the composite laminate corresponding to the position of the inlet port (16) and the outlet port (17). A vacuum bag (not shown) was placed over the entire storage.An inlet port (16) and an outlet port (17) were fitted through the vacuum bag (not shown) and positioned on top of the respective secondary resin dispensing medium (14). The vacuum bag (not shown) was affixed to the mold surface using a sealant (i.e., Airtech AT® Yellow tape) and vacuum was applied to the outlet port (17) to evacuate air from the air. Petition 870200096653, dated 03 / 08 / 2020, pp. 98 / 112 81 / 84 Storage. A low viscosity mixture (10-15 centipoise at 25°C) of the resin containing dicyclopentadiene (containing 20-25% tricyclopentadiene), 2 phr Ethanox® 4702 and ruthenium catalyst [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3methyl-2-butenylidene)(tricyclohexylphosphine) ruthenium(II) (C827, available from Materia, Inc.) (monomer to catalyst in a ratio of 30,000:1) suspended in paraffin oil was introduced into the storage at the entry port (16). After the preform was determined to be completely impregnated with the resin, the resin was cured to form a composite laminate. A visual inspection confirmed the absence of any voids or areas of low resin impregnation in the composite laminate.

[0194] Example 8: The composite laminate in this example was constructed as follows (Figure 10). The bottom layer of the composite laminate consisted of a release-treated and sealed mold surface (10) made of aluminum having dimensions of 36”x36”. Thirty-eight layers of one-way glass fabric reinforcement material (11) having dimensions of 25”x25” were positioned on top of the mold surface (10). A shell layer (12) having dimensions of 33”x27.5” was positioned on top of the one-way glass fabric reinforcement material (11). The resin distribution medium (30) (i.e., Enkafusion Infusion Media), having dimensions of 32”x24”, was placed on top of the shell layer (12). The resin flow control structures (20, 21) (Coremat by Lantor; 4 mm thick) having dimensions of 24.5”x2.25” were placed on the upper and lower surfaces of the resin distribution medium (30).A secondary resin distribution medium (14) (i.e., 1 / 4” of a coil) was positioned on top of the resin distribution medium (30) at opposite ends of the composite laminate corresponding to the position of the inlet port (16) and the outlet port (17). A vacuum bag (not shown) was placed over the complete storage. An inlet port (16) and an outlet port (17) were installed through the vacuum bag (not shown) and positioned on top of the respective secondary resin distribution medium (14). The vacuum bag (not shown) was affixed to the mold surface using a sealant (i.e., Airtech AT® Yellow tape) and the... Petition 870200096653, dated 03 / 08 / 2020, pages 99 / 112 82 / 84 vacuum was applied to the outlet port (17) to evacuate air from the storage. A low viscosity mixture (10-15 centipoise at 25°C) of the resin containing dicyclopentadiene (containing 20-25% tricyclopentadiene), 2 phr Ethanox® 4702 and ruthenium catalyst [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro(3-methyl-2-butenylidene)(tricyclohexylphosphine) ruthenium(II) (C827, available from Materia, Inc.) (monomer to catalyst in a ratio of 30,000:1) suspended in paraffin oil was introduced into the storage at the inlet port (16). After the preform was determined to be completely impregnated with the resin, the resin was cured to form a composite laminate. A visual inspection confirmed the absence of any voids or areas of low resin impregnation in the composite laminate.

[0195] It is to be understood that while the invention has been described in conjunction with specific embodiments thereof, the above description and the examples that follow are intended to be illustrative and not limiting of the scope of the invention. Other aspects and modifications within the scope of the invention will be apparent to a person skilled in the art to which the invention pertains. The contents of all patents and patent applications cited in this disclosure are incorporated herein by reference. DESIGNS Figure 1 Legend: caption 1: resin delivery medium 2: reinforcement layers 3: mold surface 4: lead-lag 5: vacuum Figure 2 10: mold surface 11: fibrous reinforcement (preform) 12: canvas drop 14: secondary resin delivery medium 15: vacuum bag 16: resin inlet 17: vacuum outlet 18: watertight cavity 20: Resin flow control structure (above) Petition 870200096653, dated 03 / 08 / 2020, pages 100 / 112 83 / 84 21: Resin flow control structure (below) 30: resin delivery medium Figure 3 10: mold surface 11: fibrous reinforcement (preform) 12: canvas fall 14: secondary resin delivery medium 16: resin entrance door 17: Vacuum outlet port 18: watertight cavity (not shown) 20: Resin flow control structure (above) 21: Resin flow control structure (below) 30: resin delivery medium Figure 4 20, 21: resin flow control structures 30: resin delivery medium Figure 5 20, 21, 22: resin flow control structures 30, 31: resin distribution medium Figure 8 10: mold surface 11: fibrous reinforcement (preform) 12: canvas fall 14: secondary resin delivery medium 16: resin entrance door 17: Vacuum outlet port 18: watertight cavity (not shown) 30: resin delivery medium Figure 9 10: mold surface 11: fibrous reinforcement (preform) 12: canvas fall 14: secondary resin delivery medium 16: resin entrance door 17: Vacuum outlet port 18: airtight cavity / vacuum bag (not shown) 30: resin delivery medium 31: resin delivery medium Figure 10 10: mold surface 11: fibrous reinforcement (preform) 12: canvas fall 14: secondary resin delivery medium 16: resin entrance door 17: Vacuum outlet port 18: airtight cavity / vacuum bag (not shown) 20: Resin flow control structure (above) 21: Resin flow control structure (below) Petition 870200096653, dated 03 / 08 / 2020, pages 101 / 112 84 / 84 30: resin delivery medium Petition 870200096653, dated 03 / 08 / 2020, pages 102 / 112

Claims

1 / 10 CLAIMS 1. Method for controlling the flow of low viscosity resins in vacuum assisted resin transfer molding to form a laminated material, the method CHARACTERIZED in that it comprises: providing a vacuum assisted resin transfer mold assembly comprising a mold having a first mold surface (10) and a second mold surface (15) arranged so as to enclose a laminated assembly within a space between the first and second mold surfaces (10, 15) when the laminated assembly is placed on the first mold surface (10);provide a laminated assembly comprising at least one laminated preform (11), at least one shell layer (12), and at least one resin distribution means (30) prior to the flow of a resin, the laminated assembly having first and second surfaces, the first surface of the laminated assembly positioned to be in contact with the first mold surface (10), the second surface of the laminated assembly positioned to be in contact with the second mold surface (15), the shell layer (12) positioned so that the second surface of the laminated preform (11) is in contact with the shell layer (12), and the resin distribution means (30) positioned to be contained within the first and second mold surfaces (10, 15);position at least one resin flow control structure (20, 21) to modify the resin flow within at least one distribution medium (30), wherein said at least one resin flow control structure (20, 21) decreases the resin flow rate in the resin distribution medium (30); provide at least one inlet (16) and at least one outlet (17) in the laminated assembly such that resin can be introduced into the laminated assembly through at least one inlet (16); arrange and seal the second mold surface (15) to enclose the laminated assembly within the space between the first and second mold surfaces (10, 15) such that a vacuum can be drawn into the laminated assembly contained within the space between the first and second mold surfaces (10, 15); apply a vacuum to the mold assembly;allow the resin to flow into the laminated assembly through at least one inlet (16) such that the resin flows into at least one resin distribution medium (30); allow the resin to flow out of the laminated assembly through at least one outlet (17); and allow the resin to cure in the laminated assembly to form the laminated material, wherein at least one resin flow control structure (20, 21) is a grouped material, wherein the low viscosity resin has a viscosity less than 200 cp at 25°C or less than 100 cp at 40°C.

2. Method for controlling the flow of low viscosity resins in vacuum-assisted resin transfer molding to form a laminated material, according to claim 1, CHARACTERIZED in that said second mold surface (15) is a vacuum bag.

3. Method for controlling the flow of low viscosity resins in vacuum-assisted resin transfer molding to form a laminated material, according to claim 1, CHARACTERIZED in that said at least one resin flow control structure (20, 21) reduces the lead-lag in the laminated preform (11).

4. Method for controlling the flow of low viscosity resins in vacuum-assisted resin transfer molding to form a laminated material, according to claim 1, CHARACTERIZED in that said at least one resin flow control structure (20, 21) modifies the direction of resin flow. Petition 870260055030, dated 08 / 06 / 2026, page 9 / 27 3 / 10 5. Method for controlling the flow of low viscosity resins in vacuum-assisted resin transfer molding to form a laminated material, according to claim 1, CHARACTERIZED in that said at least one resin flow control structure (20, 21) is permeable to gases.

6. Method for controlling the flow of low viscosity resins in vacuum-assisted resin transfer molding to form a laminated material, according to claim 1, CHARACTERIZED in that the resin comprises a cyclic olefin selected from stretched cyclic olefins, unstretched cyclic olefins, dienes, and unsaturated polymers, or combinations thereof, wherein the cyclic olefin may contain a functional group, or be substituted with a group selected from halogen, hydroxyl, hydrocarbyl, alkoxy, alkenyloxy, alkynyloxy, aryloxy, aralkyloxy, alkaryloxy, acyl, acyloxy, alkoxycarbonyl, alkylcarbonate, arylcarbonate, carboxy, carboxylate, carbamoyl, alkyl-substituted carbamoyl, haloalkyl-substituted carbamoyl, aryl-substituted carbamoyl, thiocarbamoyl substituted with thiocarbamoyl alkyl, thiocarbamoyl substituted with aryl, carbamide, cyano, cyanate, thiocyanate, formyl, thioformyl, amino,amino substituted with alkyl, amino substituted with aryl, alkylamido, arylamido, imino, alkylimino, arylimino, nitro, nitroso, sulfo, sulfonate, alkylsulfanila, arylsulfanila, alkylsulfinila, arylsulfinila, alkylsulfonyla, alkylaminosulfonyla, arylsulfonyla, borila, borono, boronate, phosphono, phosphonate, phosphinate, phospho, phosphine, or a combination thereof.

7. A method for controlling the flow of low viscosity resins in vacuum-assisted resin transfer molding to form a laminated material, according to claim 6, CHARACTERIZED in that the cyclic olefin is selected from cyclobutene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclooctadiene, cyclononadiene, cyclododecatriene, norbornene, dicyclopentadiene, tricyclopentadiene, tetracyclododecene, tetracyclododecadiene, substituted norbornenes, substituted dicyclopentadienes, or combinations thereof.

8. Method for controlling the flow of low viscosity resins in vacuum-assisted resin transfer molding to form a laminated material, according to claim 1, CHARACTERIZED in that the resin comprises a catalyst selected from a Group 8 transition metal complex having the structure wherein, M is a Group 8 transition metal; L1, L2 and L3 are independently selected from neutral electron-donating ligands; n is 0 or 1, such that L3 may or may not be present; m is 0, 1, or 2; k is 0 or 1; X1 and X2 are independently selected from anionic ligands; R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups;wherein one or both R1 and R2 may have the structure -(W)n-U+V, in which W is selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene; U is a positively charged substituted Group 15 or Group 16 element with hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, or substituted heteroatom-containing hydrocarbyl; V is a negatively charged counter-ion; en is zero or 1, wherein any two or more of X1, X2, L1, L2, L3, R1, and R2 may be taken together to form one or more cyclic groups, and further wherein any one or Petition 870260055030, dated 08 / 06 / 2026, p. 11 / 27 5 / 10 plus X1, X2, L1, L2, L3, R1, and R2 can be attached to a bracket.

9. Method for controlling the flow of low viscosity resins in vacuum-assisted resin transfer molding to form a laminated material, according to claim 8, CHARACTERIZED in that at least one of L1, L2, and L3 is an N-heterocyclic carbene binder.

10. Method for controlling the flow of low viscosity resins in vacuum-assisted resin transfer molding to form a laminated material, according to claim 1, CHARACTERIZED in that the catalyst has the structure in which, M is a Group 8 transition metal; n is zero or 1; m is 0, 1, or 2; k is 0 or 1; X1 and X2 are independently selected from anionic ligands; L2 and L3 are independently selected from neutral electron-donating ligands; or they can be taken together to form a single neutral bidentate electron-donating ligand; R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, or may be taken together to form Petition 870260055030, dated 08 / 06 / 2026, page 12 / 27 6 / 10 an indenylidene fraction;X and Y are selected independently of C, N, O, S, and P; p is zero when X is O or S, ep is 1 when X is N or P; q is zero when Y is O or S, eq is 1 when Y is N or P; Q1, Q2, Q3, and Q4 are selected independently of hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, and -(CO)-, and further wherein two or more substituents on adjacent atoms within Q may be attached to form an additional cyclic group; w, x, y, and z are independently zero or 1;and R3, R3A, R4, and R4A are independently selected from hydrogen, hydrocarbonyl, substituted hydrocarbonyl, heteroatom-containing hydrocarbonyl, and substituted heteroatom-containing hydrocarbonyl, wherein any two or more of X1, X2, L2, L3, R1, R2, Q1, Q2, Q3, Q4, R3, R3A, R4, and R4A may be taken together to form a cyclic group, and further wherein any one or more of X1, X2, L2, L3, Q1, Q2, Q3, Q4, R1, R2, R3, R3A, R4, and R4A may be attached to a support.

11. Method for controlling the flow of low viscosity resins in vacuum-assisted resin transfer molding to form a laminated material, according to claim 10, CHARACTERIZED in that M is ruthenium, w, x, y, and z are zero, X and Y are N, and R3A and R4A are linked to form -Q-, such that the complex has the structure Petition 870260055030, dated 08 / 06 / 2026, page 13 / 27 7 / 10 wherein Q is a hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene linker, and further wherein two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group.

12. Method for controlling the flow of low viscosity resins in vacuum-assisted resin transfer molding to form a laminated material, according to claim 11, CHARACTERIZED in that: X1 and X2 are halides; Q is -CR11R12-CR13R14- or -CR11=CR13-, wherein R11, R12, R13, and R14 are independently selected from hydrogen, hydrocarbonyl, substituted hydrocarbonyl, heteroatom-containing hydrocarbonyl, substituted heteroatom-containing hydrocarbonyl, and functional groups, or wherein any two of R11, R12, R13, and R14 can be linked together to form a substituted or unsubstituted, saturated or unsaturated ring; and R3 and R4 are aromatics.

13. Method for controlling the flow of low viscosity resins in vacuum-assisted resin transfer molding to form a laminated material, according to claim 1, CHARACTERIZED in that the catalyst has the structure Petition 870260055030, dated 08 / 06 / 2026, page 14 / 27 8 / 10 L1 R5 R wherein, M is a Group 8 transition metal; X1 and X2 are independently selected from anionic ligands; L1 is selected from neutral electron-donating ligands; Y is a heteroatom selected from N, O, S, and P;R5, R6, R7, and R8 are each independently selected from the groups consisting of hydrogen, halogen, alkyl, alkenyl, alkynyl, aryl, heteroalkyl, heteroatom-containing alkenyl, heteroalkenyl, heteroaryl, alkoxy, alkenyloxy, aryloxy, alkoxycarbonyl, carbonyl, alkylamino, alkylthio, aminosulfonyl, monoalkylaminosulfonyl, dialkylaminosulfonyl, alkylsulfonyl, nitrile, nitro, alkylsulfinyl, trihaloalkyl, perfluoroalkyl, carboxylic acid, ketone, aldehyde, nitrate, cyano, isocyanate, thioisocyanate, cyanate, thiocyanate, hydroxyl, ester, ether, amine, imine, amide, substituted halogen amide, trifluoramide, sulfide, disulfide, sulfonate, carbamate, silane, siloxane, phosphine, phosphate, or borate; and any combination of R5, R6, R7, and R8 that can be linked to form one or more cyclic groups; n is 1 or 2, so that n is 1 for divalent O or S heteroatoms, and n is 2 for trivalent N or P heteroatoms;and Z is a group selected from hydrogen, alkyl, aryl, functionalized alkyl, functionalized aryl where the functional group(s) may independently be one or more of the following: alkoxy, aryloxy, halogen, carboxylic acid, ketone, aldehyde, Petition 870260055030, dated 08 / 06 / 2026, page 15 / 27 9 / 10 nitrate, cyano, isocyanate, thioisocyanate, cyanate, thiocyanate, hydroxyl, ester, ether, amine, imine, amide, trifluoramide, sulfide, disulfide, carbamate, silane, siloxane, phosphine, phosphate, or borate; methyl, isopropyl, sec-butyl, t-butyl, neopentyl, benzyl, phenyl, and trimethylsilyl; and in which any combination or combinations of X1, X2, L1, Y, Z, R5, R6, R7, and R8 can be connected to a support.

14. Method for controlling the flow of low viscosity resins in vacuum-assisted resin transfer molding to form a laminated material, according to claim 1, CHARACTERIZED in that the grouped material is a nonwoven synthetic embedded with microspheres.

15. Vacuum-assisted resin transfer molding apparatus for forming a laminated material for carrying out the method as defined in claim 1, CHARACTERIZED in that the apparatus comprises: a VART™ mold assembly comprising a mold having a first mold surface (10) and a second mold surface (15) arranged so as to enclose a laminated assembly within a space between the first and second mold surfaces (10, 15) when the laminated assembly is placed on the first mold surface (10);a laminated assembly comprising at least one laminated preform (11), at least one shell layer (12), at least one resin distribution means (30) prior to resin flow, at least one inlet port (16), and at least one outlet port (17), the laminated assembly having first and second surfaces, with the first surface of the laminated assembly in contact with the first mold surface (10), the second surface of the laminated assembly in contact with the second mold surface (15), the shell layer positioned so that the second surface of the laminated preform (11) is in contact with the shell layer (12), and the resin distribution means (30) positioned to be contained within the first and second mold surfaces (10, 15);at least one resin flow control structure (20, 21) for modifying the flow of resin within at least one resin distribution medium (30), wherein said at least one resin flow control structure (20, 21) decreases the flow rate of resin in the resin distribution medium (30); means for extracting a vacuum in the mold assembly; and means for allowing resin to flow into the laminate assembly through at least one inlet port (16) such that the resin flows into at least one resin distribution medium (30), wherein the at least one resin flow control structure (20, 21) is a grouped material, wherein the resin has a viscosity less than 200 cp at 25°C or less than 100 cp at 40°C.

16. Apparatus, according to claim 15, CHARACTERIZED in that the bonded material is a nonwoven synthetic material incorporating microspheres.

17. Manufactured article CHARACTERIZED by the fact that it is made using the method as defined in claim 1. Petition 870260055030, dated 08 / 06 / 2026, page 17 / 27

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