Coating composition having polyolefin network structure

Abstract

An insulating coating system is described herein. The coating system comprises a ring-opening metathesis polymer (ROMP) component and a filler selected to provide sufficient thermal insulation properties, the monomers of the ROMP component being selected to provide optimal Tg, insulating properties and performance characteristics. Methods of making and applying the insulating coating system to a substrate are also described.

Description

Background Art

[0001] Coating compositions are applied to a variety of substrates for a variety of uses and may be used for both protective and aesthetic purposes. Such coatings need to be applied quickly and efficiently.

[0002] Two-component (2K) cross-linked coatings are typically used as protective and / or insulating coatings. The key challenge for such coatings is to balance the curing properties with pot life, open time, working time, etc. This is especially true for high solid coating systems. Coatings used for applications as protective coatings and / or insulating coatings typically require a longer pot life to allow the coating to be applied to the substrate in an effective and practical manner. The viscosity and low solvent content requirements of high solid systems force the selection of resins with low molecular weight and / or lower glass transition temperature (Tg), which will require a larger amount of cross-linking agent. This may also result in a large amount of unreacted by-products in the resin system, resulting in coating performance defects, increased volatile organic content (VOC) and coating toxicity. In general, for high solid systems, it is challenging to achieve a combination of fast drying and optimal performance.

[0003] Ring-opening metathesis polymer (ROMP) polymer systems offer a different approach to achieving a favorable polymer network that can be used in high solids systems while achieving suitable pot life and cure properties. By selecting specific monomers, mixing ratios, and catalyst components, ROMP polymer systems can be used to achieve low viscosity binders for 100% solids coating systems. Currently, ROMP systems have not been widely used to prepare protective and / or insulating coating systems. Proper catalyst selection and sprayability issues have hindered the use of these systems in protective coatings.

[0004] From the foregoing, it should be appreciated that what is needed is a protective and insulating high solids coating system based on a ROMP component that is sprayable, exhibits rapid cure and has optimal performance characteristics. Summary of the invention

[0005] The present description provides a coating composition or coating system for and as a high performance insulating and / or protective coating system. The coating composition is a high solid liquid coating that can be applied to a variety of substrates (including metal and non-metal materials), and the coating is preferably applied by spraying.

[0006] In one embodiment, the insulating and / or protective coating system described herein comprises a ring-opening metathesis polymerization (ROMP) component comprising a combination of a cyclic olefin having one or more polyunsaturated groups and a cyclic olefin having at least one monounsaturated group. The system further comprises at least one metal carbene ROMP catalyst which is a transition metal complex, and further comprises a thermal insulation filler dispersed in the ROMP component.

[0007] The above summary of the invention of the present invention is not intended to describe each disclosed embodiment or each implementation mode of the present invention. The following description more specifically illustrates exemplary embodiments. In several places throughout the application, guidance is provided by lists of examples that can be used in various combinations. In each case, the cited lists are only used as representative groups and should not be interpreted as exclusive enumerations.

[0008] The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.

[0009] Selected Definition

[0010] Unless otherwise indicated, the term "polymer" includes both homopolymers and copolymers (ie, polymers of two or more different monomers).

[0011] As used herein, the term "organic group" means a hydrocarbon group (which has optional elements other than carbon and hydrogen, such as oxygen, nitrogen, sulfur and silicon), which is classified as an aliphatic group, a cyclic group, or a combination of an aliphatic group and a cyclic group (e.g., an alkylaryl group and an aralkyl group). Organic groups as described herein can be monovalent, divalent or polyvalent. The term "aliphatic group" means a saturated or unsaturated straight or branched hydrocarbon group. For example, the term is used to cover alkyl, alkenyl and alkynyl groups. The term "alkyl group" means a saturated straight or branched hydrocarbon group, including, for example, methyl, ethyl, isopropyl, tert-butyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, etc. The term "alkenyl group" means an unsaturated, straight or branched hydrocarbon group with one or more carbon-carbon double bonds, such as a vinyl group.

[0012] The term "alkynyl group" means an unsaturated, straight or branched hydrocarbon group with one or more carbon-carbon triple bonds. The term "cyclic group" means a closed-loop hydrocarbon group, which is classified as an alicyclic group or an aromatic group, both of which may contain heteroatoms. The term "alicyclic group" means a cyclic hydrocarbon group whose characteristics are similar to those of an aliphatic group. The term "Ar" refers to a divalent aryl group (i.e., an arylene group), which refers to a closed aromatic ring or ring system, such as phenylene, naphthylene, biphenylene, fluorenylene and indenyl, and a heteroarylene group (i.e., a closed-loop hydrocarbon in which one or more atoms in the ring are elements other than carbon (e.g., nitrogen, oxygen, sulfur, etc.).

[0013] The terms "alkenyl group" and "alkynyl group" may each independently be referred to as an "unsaturated" group. The term "monounsaturated" as used herein means a group or moiety having one unsaturated group. The term "polyunsaturated" as used herein means a group or moiety that is at least difunctional, i.e., has at least two unsaturated groups, and may contain more than two unsaturated groups.

[0014] Suitable heteroaryl groups include furanyl, thienyl, pyridinyl, quinolyl, isoquinolyl, indolyl, isoindolyl, triazolyl, pyrrolyl, tetrazolyl, imidazolyl, pyrazolyl, oxazolyl, thiazolyl, benzofuranyl, benzothiophenyl, carbazolyl, benzoxazolyl, pyrimidinyl, benzimidazolyl, quinoxalinyl, benzothiazolyl, naphthyridinyl, isoxazolyl, isothiazolyl, purinyl, quinazolinyl, pyrazinyl, 1-oxopyridinyl, pyridazinyl, triazinyl, tetrazinyl, oxadiazolyl, thiadiazolyl, etc. When such groups are divalent, they are often referred to as "heteroarylene" groups (e.g., furanylene, pyridinylene, etc.).

[0015] It is expected that the organic group of the compounds of this invention is replaced.When the term "group" is used to describe a chemical substituent in this article, the chemical substance described includes an unsubstituted group, and for example, in a chain (such as in an alkoxy group) with an O, N, Si or S atom and a carbonyl group or other conventionally substituted group.For example, the phrase "alkyl group" is intended to include not only pure open-chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, tert-butyl, etc., but also includes an alkyl substituent carrying other substituents as known in the art (such as hydroxyl, alkoxy, alkyl sulfonyl, halogen atom, cyano, nitro, amino, carboxyl, etc.).Therefore, "alkyl group" includes ether groups, haloalkyl, nitroalkyl, carboxyalkyl, hydroxyalkyl, sulfoalkyl, etc.

[0016] The term "crosslinker" refers to a molecule that is capable of forming a covalent bond between polymers or between two different regions of the same polymer. As used herein, the term "crosslinker" is interchangeable with "hardener." The term "curing agent" refers to a component that contains (or can be used as) both a "crosslinker" or "hardener" and a "catalyst" or "catalyst package."

[0017] Unless otherwise indicated, reference to a "(meth)acrylate" compound (where the "meth" is enclosed in parentheses) is intended to include both acrylate and methacrylate compounds.

[0018] Unless otherwise indicated, all parts, ratios and percentages are by weight, and all molecular weights are number average molecular weight (Mn). Molecular weight can be determined by various techniques well known in the art. With respect to the components and / or compositions described herein, molecular weight (whether described as number average (Mn) or weight average (Mw) molecular weight) is preferably determined by gel permeation chromatography (GPC).

[0019] When used in the context of a coating applied to a surface or substrate, the term "on" includes coatings applied directly or indirectly to the surface or substrate. Thus, for example, a coating applied to a primer layer covering a substrate constitutes a coating applied to the substrate.

[0020] The terms "comprises" and variations thereof do not have a limiting meaning when they appear in the description and claims.

[0021] The terms "preferred" and "preferably" refer to embodiments of the present invention that may provide certain benefits in certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. In addition, the description of one or more preferred embodiments does not imply that other embodiments are unusable, and is not intended to exclude other embodiments from the scope of the present invention.

[0022] As used herein, "a", "an", "the", "at least one" and "one or more" are used interchangeably. Thus, for example, a coating composition comprising "an" additive can be interpreted to mean that the coating composition comprises "one or more" additives.

[0023] Also herein, numerical ranges recited by endpoints include all values ​​contained within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.). In addition, disclosure of a range includes disclosure of all subranges included in the broader range (e.g., 1 to 5 discloses 1 to 4, 1.5 to 4.5, 1 to 2, etc.). DETAILED DESCRIPTION

[0024] The present description provides a kind of coating composition or coating system, it is used for and used as high performance insulation and / or protective coating.Coating composition can be applied to a variety of substrates, including but not limited to metallic materials and non-metallic materials.The system comprises ring-opening metathesis polymerization (ROMP) components, and the ring-opening metathesis polymerization components have a combination of cycloolefins containing one or more polyunsaturated groups and cycloolefins containing at least one monounsaturated group.The system also comprises at least one metal carbene ROMP catalyst (it is a transition metal complex), and also comprises a thermal insulation filler dispersed in the ROMP components.

[0025] In at least one embodiment, the insulating and / or protective coating systems described herein feature a ring-opening metathesis polymerization component. "Ring-opening metathesis polymerization" or "ROMP" means a chain growth type polymerization involving a metathesis reaction of cyclic olefins such as norbornene, cyclopentene, etc. The reaction can generally be represented as follows:

[0026]

[0027] Because the reaction involves cyclic olefins, the new olefins produced by ring opening and metathesis remain attached to the catalyst and become part of the growing polymer chain. Without being limited by theory, the reaction is driven by the release of strain in the cyclic olefin and is therefore irreversible. ROMP polymers generally have a very narrow range of molecular weights that are difficult to achieve by standard polymerization methods. The molecular weight distribution is particularly narrow, i.e., the polydispersity index (Mw / Mn) is typically and preferably in the range of 1.03 to 1.10, i.e., monodisperse. ROMP polymers are known in the art and are substantially as described in U.S. Patent Nos. 5,342,909; 6,310,121; 6,515,084; 6,525,125; 6,759,537; 7,329,758, etc.

[0028] Therefore, in at least one embodiment, composition as described herein is insulating and / or protective coating, preferably also provides the hydrophobic coating of corrosion protection, and comprises the ROMP component of the combination with cycloolefin monomer.The first cycloolefin monomer is polyunsaturated, i.e. cycloolefin is at least difunctional, which means that it has at least two unsaturated groups, preferably more than two unsaturated groups.This type of exemplary polyunsaturated cycloolefin includes but is not limited to dicyclopentadiene (DCPD), tricyclopentadiene (TCPD), cyclopentadiene tetramer, cyclopentadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, octadiene and 5-butenyl-2-norbornene, or their mixture and combination.In a preferred embodiment, polyunsaturated cycloolefin as described herein is dicyclopentadiene.

[0029] The polyunsaturated cyclic olefin monomer is used as part of the ROMP component that constitutes the insulating and / or protective coating compositions described herein. The amount of the first cyclic olefin is not particularly limited and is selected based on the desired Tg and other properties and performance characteristics of the final coating composition described herein. Therefore, in some embodiments, the polyunsaturated cyclic olefin is present as part of the total binder resin in an amount preferably from 15% to 100% by weight and more preferably from 18% to 98% by weight based on the total weight of the coating composition.

[0030] In at least one embodiment, the present description provides an insulating and / or protective coating system comprising a combination of a ROMP component and a cycloolefin monomer. Optionally, the insulating and / or protective coating system described herein may additionally include a monounsaturated cycloolefin monomer, i.e., it has one, and preferably no more than one unsaturated group or part. Exemplary monounsaturated cycloolefins include, but are not limited to, cyclooctene, 5-methylphenyl-2-norbornene, 5-phenyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene and 5-dodecyl-2-norbornene, or a mixture or combination thereof. In a preferred embodiment, the monounsaturated cycloolefin monomer is cyclooctene.

[0031] The monounsaturated cyclic olefin monomer is used as part of the ROMP component that constitutes the insulating and / or protective coating compositions described herein. The amount of the second cyclic olefin is not particularly limited and is selected based on the desired Tg and other properties and performance characteristics of the final coating composition described herein. Therefore, in some embodiments, the monounsaturated cyclic olefin is present as part of the total binder resin in an amount preferably of 0.1% to 15% by weight and more preferably 0.5% to 10% by weight based on the total weight of the coating composition.

[0032] In one aspect, the desired Tg of the ROMP component to be used in the coating compositions described herein is not so limited, but is preferably higher than the Tg typically seen for conventional epoxy / amine 2K coating systems currently in commercial use in the industry. For example, the Tg of the ROMP component used herein is preferably from about 100°C to 200°C, more preferably from about 120°C to 150°C.

[0033] In an embodiment, the coating composition described is an insulating and / or protective coating comprising a combination of a ROMP component with a cycloolefin monomer and a catalyst, the catalyst preferably being a latent catalyst, i.e., a compound that is inactive at ambient temperature but can catalyze a ROMP polymerization reaction when activated. The catalyst is preferably a metal carbene. Without being limited by theory, it is known that the ligand environment of the metal carbene catalyst can affect the polymerization properties of the cycloolefin monomer in the ROMP reaction (e.g., initiation rate, growth rate, polymerization rate, initiation rate constant, growth rate constant (k p ), initiation rate constant / growth rate constant ratio (k i / k p The catalysts described herein are those which initiate the ROMP reaction at a sufficiently slow rate to allow for control of the working time, open time, pot life, etc. By varying the ligands in the metal carbene catalyst, catalysts can be obtained that can be used in the ROMP reaction while allowing for optimal open time, pot life, and cure characteristics.

[0034] In a preferred aspect, the metal carbene catalyst is a transition metal carbene complex, wherein the metal ligand comprises a transition metal of Group 6 or Group 8. The metal carbene catalyst complex has the general structure shown below:

[0035]

[0036] In this general structure,

[0037] ●M is a Group 6 or Group 8 transition metal;

[0038] ● R1 and R2 are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbyl containing heteroatoms, substituted hydrocarbyl containing heteroatoms, and functional groups;

[0039] ●Q is an organic diradical;

[0040] ● X1 and X2 are anionic ligands and may be the same or different;

[0041] L1 is a neutral electron donor ligand, and p is 0 or 1; and

[0042] ●Y is a bond selected from alkylene, substituted alkylene, heteroatom-containing alkylene, substituted heteroatom-containing alkylene, -O-, -S-, -NR9- and -PR9-, wherein R9 is selected from alkyl, substituted alkyl, heteroatom-containing alkyl and substituted heteroatom-containing alkyl, and isomers thereof.

[0043] It is known that the transition metal carbene complexes described herein act as catalysts for olefin metathesis, and therefore can be used as catalysts for ROMP polymerization. Such catalysts, also known as Grubb catalysts, are known in the art and are commercially available. The use of these catalysts in ROMP polymerization reactions reduces the problems of catalyst functional group tolerance, sensitivity to air and moisture, and the degree of polymerization (DP) of macromonomers often seen in the case of conventional catalysts. Suitable catalysts of the type described herein are substantially as described in, for example, U.S. Patent Nos. 5,312,940; 5,342,909; 5,831,108; 5,969,170; 6,111,121; and 6,211,391; U.S. Patent Publication No. 20050261451, and various patents and publications cited therein.

[0044] The amount of the metal carbene catalyst in the ROMP component as described herein is not particularly limited and is selected based on the desired reaction properties, pot life, curing and performance characteristics of the final coating composition. Therefore, in some embodiments, the ROMP catalyst is preferably present in an amount of 0.000001% to 2.5%, preferably 0.0001% to 0.5% by weight based on the total weight of the coating composition. In one aspect, the catalyst is present as a solution in a liquid carrier (such as water or an organic solvent), for example, to dilute the catalyst and also facilitate accurate addition of the catalyst.

[0045] In an embodiment, the insulating and / or protective coatings described herein comprise a ROMP component and at least one insulating filler. As used herein, the term "insulating filler" refers to a material having a relatively low thermal conductivity and reducing or preventing heat transfer. Suitable insulating filler materials for use in the coating systems herein include, for example but not limited to, glass bubbles, polymer spheres (including microspheres, nanospheres, etc.), hollow ceramic spheres, porous glass, expanded perlite, aerogels, ceramic spheres (including microspheres, nanospheres, etc.), other insulating materials known in the art, and mixtures or combinations thereof.

[0046] In one aspect, the thermal insulation filler described herein is dispersed in the coating system, preferably dispersed in the ROMP polymer component. The amount of thermal insulation filler dispersed in the system is not particularly limited and is selected based on the desired thermal insulation properties and performance characteristics of the final coating composition.

[0047] Thus, in some embodiments, the insulating filler is present in an amount preferably of 0.001% to 50%, preferably 0.1% to 35%, by weight, based on the total weight of the coating composition. The density of these fillers is generally very low, so while the loading by weight may be small, the loading by volume is high. Indeed, in some embodiments, at least a portion of the insulating filler loading may be in the form of trapped gas / encapsulated gas, such as, for example, if / when foam is generated and / or trapped by the coating system. That is, the trapped gas / encapsulated gas will have little or no mass, but will provide sufficient volume to obtain the necessary insulating properties.

[0048] Thus, the insulating and / or protective coating systems described herein exhibit low thermal conductivity, preferably at most about 0.2 W / mK, more preferably at most about 0.12 W / mK, even more preferably as high as at most 0.09 W / mK.

[0049] In addition to the thermally insulating filler, in some embodiments, the insulating and / or protective coatings described herein also contain a ROMP component and at least one barrier filler. As used herein, the term "barrier filler" refers to a material used in a coating to form a barrier to moisture and help reduce or inhibit corrosion of the surface or substrate to which the coating is applied. Suitable barrier filler materials for use in the coating systems herein include, for example, but are not limited to, glass flakes, micaceous iron oxides, FTFE flakes, mica, aluminum flakes, barrier filler materials known in the art, and mixtures or combinations thereof. The terms "barrier filler" and "flaky filler" are used interchangeably herein.

[0050] In one aspect, the barrier fillers described herein are dispersed in the coating system together with the thermal insulation fillers, preferably dispersed in the ROMP polymer component. In another aspect, the barrier fillers described herein can be dispersed into the coating system independently of the ROMP polymer component. The amount of barrier filler dispersed in the system is not particularly limited and is selected based on the desired properties and performance characteristics of the final coating composition and the desired end use of the coating system. Therefore, in some embodiments, the barrier filler is present in an amount preferably of 0.1% to 30%, preferably 1% to 25%, by weight based on the total weight of the coating composition.

[0051] Without being limited by theory, it is believed that coating systems having high levels (e.g., preferably greater than about 50% by volume) of fillers result in improved thermal stability, which in turn allows for possible continuous use of the coated substrate or article at temperatures up to about 400F to 450F (approximately 204°C to 232°C). Thus, in one aspect, the total volume of the combination of both thermal insulating fillers and barrier fillers in the insulative and / or protective coating systems described herein is preferably at least 50% by volume, preferably 50% to 60% by volume.

[0052] The use of ROMP components or polymers in the insulative coating systems described herein provides many advantages, especially over conventional coatings in the field. Most conventional coatings currently commercially available are prepared by reacting a first part A with a second part B. Part A is typically an isocyanate and / or an epoxy resin, and part B is typically a polyol and / or an amine. Part A and part B are reacted to form a 2K polyurethane or epoxy coating.

[0053] In the insulating and / or protective coating systems described herein, parts A and B of conventional coating systems are replaced by olefin monomers, and a polyolefin network is formed with the aid of a transition metal carbene complex as a catalyst. The coatings formed in this manner have similar—and sometimes superior—performance characteristics relative to conventional and currently commercially available 2K polyurethane or epoxy resin coatings. The use of ROMP polymer components reduces the free monomer concentration and thereby reduces or eliminates isocyanates in the coating system. By optimizing various reaction characteristics (monomers, catalysts, the way the components are mixed, etc.), the reaction can be driven to completion and the network formation can be extended. Therefore, the coating systems described herein exhibit properties similar to conventional epoxy / amine 2K coatings, but have longer application life and faster curing at much higher solids content (even 100% solids) at lower VOCs or without VOCs. The coatings described herein also develop hardness faster, so that the substrates to which the coatings are applied can be restored to use faster than in the case of conventional 2K coatings currently commercially available or otherwise known to those skilled in the art.

[0054] The coating compositions described herein can be made by any conventional method or process known in the art. Using ROMP chemistry, various monomers and polymers that are not normally used in coatings can be introduced. By controlling or optimizing the mixing time, amount and type of monomers, catalysts and fillers, and by controlling the exotherm, a coating system with optimal properties can be obtained, which is a low viscosity liquid coating with high solids, preferably 90% to 100% solids, more preferably even 100% solids.

[0055] In the coating systems described herein, the use of ROMP polymer components allows for several desired performance results to be achieved. By carefully selecting the polyunsaturated and monounsaturated monomers in the ROMP component, high Tg values, preferably up to 120°C to 150°C, can be achieved, resulting in coatings that can be used under higher temperature conditions.

[0056] The insulating and / or protective coating systems described herein are hydrophobic systems. Hydrophobicity is measured as a function of the surface contact angle, and therefore, on the one hand, the coating systems described herein have a surface contact angle preferably greater than 90°. On the other hand, the coating systems described herein have low hysteresis. As used herein, the term "hysteresis" refers to a dynamic contact angle hysteresis, which is a measure of the difference between the advancing contact angle and the receding contact angle of a droplet when the droplet wets the surface of the substrate to which it is applied, or as measured when the droplet is immersed in a liquid (i.e., water) and then removed. Therefore, hysteresis provides a useful measure of the uniformity of a surface coated with a hydrophobic coating (i.e., a coating having a surface contact angle greater than 90°). Lower hysteresis (i.e., a smaller difference between the advancing contact angle and the receding contact angle) means a more uniform coating with increased hydrophobicity, so that the coating system described herein can be used as an anti-corrosion coating applied to an aqueous environment or an environment exposed to moisture for a long time. For example, in some embodiments, the increased hydrophobicity of the coating system means that it can be used as a primer composition for reducing corrosion when applied to a metal substrate in a variety of applications. In other embodiments, the coating systems described herein are used as topcoat compositions, or even as direct-to-metal coatings. Preferably, the coating systems described herein form an integral part of a coating applied to a substrate in a variety of end uses.

[0057] In embodiments, due to high hydrophobicity and low hysteresis, the coating systems described herein are ideal candidates for use as corrosion under insulation (CUI) coatings, i.e., coatings that prevent corrosion under insulation, which is a phenomenon involving severe forms of localized, external corrosion that typically occurs on insulating carbon and low alloy steels exposed to corrosive aqueous environments. For example, CUI often occurs on steel substrates in offshore and marine / maritime industries, and particularly at higher temperatures. If left undetected, CUI can lead to catastrophic leaks or explosions, equipment failures, extended downtime for repair or replacement, and safety and environmental issues. The coating systems described herein are highly hydrophobic and can therefore act as barrier coatings to protect substrates from moisture and subsequent corrosion.

[0058] The insulative coating systems described herein also exhibit optimal chemical and corrosion resistance and can therefore be applied to a variety of substrates. Thus, in an embodiment, the coating system described herein is a hydrophobic and chemically resistant tank lining material. In another embodiment, the coating system described herein is an insulative tank lining material.

[0059] In some embodiments, the coating systems described herein can be applied to a variety of substrates. The substrate is preferably, but not exclusively, a metal substrate, including a steel substrate. Suitable substrates to which these coatings can be applied include, for example, but not limited to, utility poles, structures embedded in the ground, above-ground structures, piles of solar panel infrastructure, exteriors of steel water pipes, exteriors of ductile iron pipes, interiors of ductile iron pipes for non-potable liquids or exteriors of tanks, at least a portion of substrate portions for buried services, and the like. Other non-limiting end uses include, for example, fire retardant coatings, roof seals, pool bottoms, reservoirs, secondary containment coatings, submarine insulation, flooring, corrosion resistant primers, and the like.

[0060] In an embodiment, the insulative coating system described herein is a 100% solid system having a viscosity of about 2,000 cps to 70,000 cps (2 Pa-s to 70 Pa-s) as determined by ASTM D2196-20 (Standard Test Methods for Rheological Properties of Non-Newtonian Materials by Rotational Viscometer). At this viscosity, the binder component or ROMP component of the coating can have a higher filler loading and result in a coating having better thermal insulation properties relative to conventional 100% solid systems currently used.

[0061] In an embodiment, the insulating coating system described herein is a coating having a strength of about 0.1 g / cm 3 Up to 1.0g / cm 3 , preferably 0.3 g / cm 3 Up to 0.85g / cm 3 In another aspect, the coating systems described herein have a coefficient of thermal expansion (CTE) of less than 5%.

[0062] Relative to other polyolefin coating systems, the insulating coating systems described herein exhibit excellent adhesion to substrates. On the one hand, this is due to the special pretreatment applied to the surface of a given metal substrate. By modifying the functional groups on the monomers used in the ROMP component, the coating can be coupled to the substrate surface instead of other polyolefin networks. Therefore, on the one hand, the coating system described herein is recoatable, that is, it can be recoated without adhesion failure. Where necessary, such as, for example, for specific substrates that pose adhesion challenges, the coating system described herein may include other additives to further improve adhesion.

[0063] In an embodiment, the insulating and / or protective coating system described herein is sprayable. On the one hand, the coating system described herein is applied with a dry film thickness of about 10 mils to 40 mils (about 250 μm to 1000 μm). Conventionally, high solid polyolefin systems designed using ROMP polymers are not sprayable due to higher viscosities. Surprisingly, the coating system described herein has a lower viscosity of about 2,000 cps to 70,000 cps (2 Pa-s to 70 Pa-s) even at 100% solids, allowing the coating to be easily sprayed on a variety of substrates, including metal substrates, preferably steel substrates. Before applying the coating composition described herein, the substrate can be directly applied to the metal (DTM), or applied to an untreated surface, a pretreated surface, a modified surface, or even a primed surface.

[0064] In embodiments, coating systems as described herein are applied to substrate surfaces to form insulating and / or protective films. The dry film thickness (DFT) of these coatings is not particularly limited, and is selected based on the desired properties and performance characteristics of the final coating composition and the desired end use of the coating system. Therefore, in some embodiments, the coating system has a dry film thickness (DFT) of about 1 mil to 7000 mils (about 25.4 μm to 177.8 mm). On the one hand, in the case where the described coating is used as a CUI coating, DFT is preferably about 5 mils to 100 mils (about 127 μm to 2.54 mm). On the other hand, the coating has a dry film thickness (DFT) of about 10 mils to 40 mils (about 254 μm to 1.02 mm), wherein the coating is used as a tank lining. On the other hand, in the case where the coating is used as an insulating tank lining, the coating has a dry film thickness (DFT) of about 20 mils to 7000 mils (about 508 μm to 177.8 mm).

[0065] Various additives may be included in the coating compositions described herein. Materials that provide desired effects to the final coating system may be included, such as additives that improve application, adhesion, curing, or final performance or appearance. Examples include, but are not limited to, reactive diluents, non-reactive diluents, pigments, fillers, curing catalysts, antioxidants, color stabilizers, anti-corrosion additives, degassing additives, flow control agents, adhesion promoters, toughening agents, toughening agents, etc., and mixtures or combinations thereof.

[0066] The coating compositions and methods described herein can be used with a variety of substrates and / or for a variety of applications or end uses. Typically and preferably, the coating compositions described herein are used to coat metal substrates, including but not limited to unprimed metals, clean blasted metals, and pretreated metals, including plated substrates and electrophoretic coating treated metal substrates. The metal substrates to which the coating is applied can be used in a variety of applications, including but not limited to external tank linings, insulating (internal) tank linings, external and internal pipe linings, insulating coatings, corrosion under insulation (CUI) coatings, fire retardant coatings, roof seals, pool bottoms, reservoirs, secondary containment coatings, submarine insulation, flooring, corrosion resistant primers, etc.

[0067] Example

[0068] The present invention is illustrated by the following examples. It should be understood that the specific examples, materials, amounts and procedures are to be interpreted broadly in accordance with the scope and spirit of the present invention as described herein. Unless otherwise indicated, all parts, ratios and percentages are by weight and all molecular weights are number average molecular weights (M). n ). The exemplary coating compositions described herein may include additional materials at varying concentrations. For example, the composition may also include one or more fillers, wet and dry leveling agents, adhesion promoters, rheological additives, degassing agents, and combinations thereof. Unless otherwise indicated, all chemicals used are commercially available from, for example, Sigma-Aldrich (St. Louis, Missouri).

[0069] Test Method

[0070] Unless otherwise indicated, the following test methods were utilized in the following examples.

[0071] A. Thermal conductivity test

[0072] The thermal conductivity properties of the coating compositions described herein were evaluated using the standard test ASTM C518 (Standard Test Method for Steady-State Thermal Transmission Properties by Means of the Heat Flow Meter Apparatus). Briefly, the test measures the rate at which heat flows through a flat coupon mounted on either side of a guarded hot plate. Results for thermal conductivity are reported in W / mK, and low values ​​are characteristic of insulative coatings.

[0073] B. Corrosion under insulation test

[0074] The corrosion resistance of coatings under insulation (CUI) as described herein was determined using the industry standard test method AMPP TM21442 (Standard Practice for Evaluating Protective Coatings for Use Under Insulation). The test samples were coated with CUI coating, followed by conventional insulation (e.g., mineral wool), and then cladding. The samples were then placed in a tank and cycled through different temperatures with and without the presence of water. The corrosion was monitored over a period of 6 months using electrochemical methods.

[0075] C. Thermal expansion

[0076] This is a test that measures the dimensional response to thermal energy, i.e., the test measures the expansion of the coating as the temperature increases. The coefficient of thermal expansion (CTE) of the coatings described herein is typically determined under tension on a rheometer or rheological instrument (such as a TA Instruments RSA G2 analyzer) with a 10 g force heated at 3°C / min.

[0077] D. Water absorption

[0078] For the coatings described herein, the ability to draw or absorb as little water as possible after extended exposure indicates an effective insulating and protective coating. To test, samples are immersed in water at an elevated temperature of about 120F for 24 hours, and the results are reported as the percent weight change of the sample. Test samples that exhibit little weight change after immersion are considered resistant to water absorption.

[0079] E. Viscosity

[0080] The viscosity of the coating compositions described herein is determined by the standard method as described in ASTM D2196-20 (Standard Test Method for Rheological Properties of Non-Newtonian Materials by Rotational Viscometer) using a Brookfield DV-1 Viscometer on RV Spindle 7 at 50 rpm at 25°C.

[0081] Example 1. Preparation of insulating coating composition

[0082] Exemplary coating compositions #1 to #5 as described herein were prepared by mixing together the components in the amounts (percent by weight based on the total weight of the composition) as shown in Table 1. The compositions were then applied to test panels and / or free films and evaluated for various performance characteristics, including corrosion resistance and thermal conductivity. Commercially available acrylic insulating coatings were also tested for comparison. The results are shown in Table 2.

[0083] Table 1. Preparation of insulating coating compositions

[0084] Components #1 #2 #3 #4 <![CDATA[#5 1 ]]> Commercial coatings Cyclic olefins <![CDATA[97.7 a ]]> <![CDATA[59.7 a ]]> <![CDATA[98 a ]]> <![CDATA[77.3 b ]]> <![CDATA[67.7 c ]]> Low TC filler 1 0.9 Low TC Filler 2 <![CDATA[39.2 2 ]]> Low TC filler 3 21.2 Flake filler 27.0 Other additives 3.3 Catalyst solution 2.0 1.1 2.0 1.5 2.0

[0085] a Proxima R6400 (EXP1961-NI) cyclic olefin obtained from Materia Inc., Pasadena, CA

[0086] b Proxima R6200 (EXP1992-NI) cyclic olefin obtained from Materials Corporation, Pasadena, CA

[0087] c Proxima R6400 / R6200 cyclic olefins obtained from Materials Inc., Pasadena, CA

[0088] Table 2. Performance characteristics of insulating coatings

[0089]

[0090] Example 2. Preparation of coating for corrosion under insulation

[0091] The coating for corrosion under insulation was prepared by mixing together the components in the amounts (percent by weight based on the total weight of the composition) as shown in Table 3. The composition was then applied to the test panel by spraying. The composition met the standards required by AMPP TM 21442 (data not shown).

[0092] Table 3. Coatings for corrosion under insulation

[0093]

[0094] The complete disclosures of all patents, patent applications and publications cited herein and electronically available materials are incorporated by reference. The aforementioned detailed description and examples are given only for the purpose of clear understanding. It should be understood that there are no unnecessary restrictions. The present invention is not limited to the exact details shown and described, and changes obvious to those skilled in the art will be included in the present invention defined by the claims. In some embodiments, in the absence of any element not specifically disclosed herein, the illustrative disclosed invention of this paper can be appropriately practiced.

Claims

1. An insulating coating system, comprising: a ring-opening metathesis polymerization (ROMP) component comprising at least one cyclic olefin having one or more polyunsaturated groups; Optionally, at least one cyclic olefin having at least one monounsaturated group; and at least one metal carbene ROMP catalyst, wherein the catalyst is a transition metal complex; and A thermally insulating filler is dispersed in the ROMP component.

2. An insulating coating system, comprising: A ring-opening metathesis polymerization (ROMP) component comprising At least one cycloolefin having one or more polyunsaturated groups, wherein the cycloolefin is selected from dicyclopentadiene, tricyclopentadiene, cyclopentadiene tetramer, cyclopentadiene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-isopropenyl-2-norbornene, 5-propenyl-2-norbornene, octadiene and 5-butenyl-2-norbornene or a combination thereof; Optionally, at least one cyclic olefin having at least one monounsaturated group, wherein the cyclic olefin is selected from cyclooctene, 5-tolyl-2-norbornene, 5-phenyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene and 5-dodecyl-2-norbornene, or combinations thereof; and at least one metal carbene ROMP catalyst, wherein the catalyst is a transition metal complex; and At least one thermally insulating filler is dispersed within the system.

3. An insulating coating system, comprising: a ring-opening metathesis polymerization (ROMP) component comprising at least one cyclic olefin having at least one monounsaturated group, wherein the cyclic olefin is selected from cyclooctene, 5-tolyl-2-norbornene, 5-phenyl-2-norbornene, 5-butyl-2-norbornene, 5-hexyl-2-norbornene, 5-octyl-2-norbornene, 5-decyl-2-norbornene and 5-dodecyl-2-norbornene, or a combination thereof; and Optionally, at least one metal carbene ROMP catalyst, wherein the catalyst is a transition metal complex; and At least one thermally insulating filler is dispersed within the system.

4. The coating system according to any one of the preceding claims, wherein the coating is sprayable.

5. The coating system according to any one of the preceding claims, wherein the catalyst is a Group 8 transition metal complex.

6. The coating system according to any one of the preceding claims, wherein the catalyst is a Group 6 transition metal complex.

7. The coating system according to any one of the above claims, wherein the at least one cyclic olefin having one or more polyunsaturated groups is present in an amount of about 18 wt% to 98 wt% based on the total weight of the coating.

8. The coating system according to any one of the preceding claims, wherein the at least one cyclic olefin having at least one monounsaturated group is present in an amount of about 0.5 wt% to 10 wt%, based on the total weight of the coating.

9. The coating system of any one of the above claims, wherein the metal carbene ROMP catalyst is present in an amount of about 0.0001 wt% to 1 wt% based on the total weight of the coating.

10. The coating system of any of the above claims, wherein the thermally insulating filler is present in an amount of about 0.001 wt% to 35 wt% based on the total weight of the coating.

11. The coating system according to any one of the preceding claims, further comprising one or more non-reactive diluents.

12. The coating system of any of the above claims, wherein the coating is about 90% to 100% solids.

13. The coating system of any one of the above claims, wherein the coating has a viscosity of about 2 Pa-s to 70 Pa-s.

14. The coating system of any of the above claims, wherein the coating exhibits a water absorption of up to about 2.0 wt. % with a receding contact angle greater than 50°.

15. The coating system of any of the above claims, wherein the coating has a dry film thickness (DFT) of about 1 mil to 7000 mils (about 25.4 μm to 177.8 mm).

16. The coating system of any of the above claims, wherein the coating has a dry film thickness (DFT) of about 2 mils to 10 mils (about 50.8 μm to 254 μm).

17. The coating system of any one of the above claims, wherein the coating has a thermal conductivity of at most about 0.12 W / mK.

18. The coating system of any one of the preceding claims, wherein the coating is recoatable.

19. The coating system of any one of the preceding claims, wherein the coating has a coefficient of thermal expansion (CTE) of less than 5%.

20. The coating system of any one of the preceding claims, wherein the coating has a surface contact angle greater than 90°.

21. The coating system of any one of the preceding claims, wherein the coating has a receding contact angle greater than 50° after immersion.

22. The coating system of any one of the preceding claims, wherein the coating has a density of 0.18 g / cm3 to 0.84 g / cm3.

23. The coating system of any one of the preceding claims, wherein the coating can be applied directly to a substrate with or without a primer.

24. The coating system of any one of the preceding claims, wherein the coating is a corrosion under insulation coating.

25. The coating of any of the above claims, further comprising a barrier filler material selected from glass flakes, micaceous iron oxide, FTFE flakes, mica, aluminum flakes, or combinations thereof.

26. The coating system of any one of the preceding claims, wherein the coating is a tank lining.

27. The coating system of any one of the preceding claims, wherein the coating is an insulating tank lining.

28. A coated article, comprising: Base material; and A coating system according to any one of the preceding claims, said coating system being disposed on at least one surface of said substrate.

29. The coated article of claim 28, wherein the coating is a corrosion under insulation coating, a tank lining, or an insulative tank lining.

30. A method of coating a substrate, the method comprising: Providing a substrate; contacting at least one surface of the substrate with a coating system according to any one of the preceding claims; as well as The surface of a substrate contacted with the coating system according to any one of the preceding claims is subjected to conditions effective to promote the ROMP reaction in the presence of a ROMP catalyst to form a ROMP matrix as a coating on the substrate surface.

31. A coated article formed by the method of claim 30.

32. The method of claim 30, wherein the substrate forms at least a portion of a utility pole.

33. The method of claim 30, wherein the substrate forms at least a portion of a pile on a solar panel infrastructure.

34. The method of claim 30, wherein the substrate forms at least a portion of a metal structure embedded in the ground.

35. The coating system of any of the above claims, wherein the coating is applied to a substrate as a direct to metal coating.

36. The coating system of any of the above claims, wherein the coating is applied to a substrate as part of a primer-topcoat system.

37. The coating system of any of the above claims, wherein the coating is applied to both above-ground and below-ground portions of the substrate.

38. A coating system according to any one of the preceding claims, wherein the coating is applied to a substrate for buried service.

39. The coating system of claim 38, wherein the substrate for buried service is selected from the group consisting of a steel water pipe exterior, a ductile iron pipe exterior, a ductile iron pipe interior for non-potable liquids, or a storage tank exterior.

40. The coating system according to any of the above claims, wherein the thermally insulating filler is selected from glass bubbles, polymer spheres, aerogels, hollow ceramic spheres, porous glass, expanded perlite, or combinations thereof.

41. The coating system of any of the preceding claims, wherein a portion of the insulating filler loading is in the form of trapped or encapsulated gas in the coating system.

42. The coating system according to any of the preceding claims, wherein a mixture of fillers from claims 25, 40 and 41 can be utilized.

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