Silicone - acrylic binder for liquid applied thermal insulation coating compositions to resist corrosion under insulation

Abstract

A silicone - acrylic binder is made from a combination of I) a first aqueous emulsion containing a soft acrylic polymer, II) a second aqueous emulsion containing a hard acrylic polymer, and III) an aqueous emulsion of a polyorganosiloxane elastomer. The silicone - acrylic binder can be used to prepare a thermal insulation coating composition that may be applied on a metal (e.g., steel) substrate or primed substrate. A thermal insulation coating prepared by drying the thermal insulation coating composition provides the metal or primed substrate with resistance to corrosion under insulation.

Description

SILICONE - ACRYLIC BINDER FOR LIQUID APPLIED THERMAL INSULATIONCOATING COMPOSITIONS TO RESIST CORROSION UNDER INSULATIONCROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 586,428 filed on 29 September 2023 under 35 U.S.C. §1 19 (e). U.S. Provisional Patent Application Serial No. 63 / 586,428 is hereby incorporated by reference.FIELD

[0002] This invention relates to a silicone - acrylic binder, and a thermal insulation coating composition, and methods for preparation thereof. More particularly, the binder and the thermal insulation coating composition comprise a first (soft) acrylic polymer, a second (hard) acrylic polymer, and a silicone elastomer. The composition can be applied to a metal surface or to a primed substrate and provides a thermal insulation coating with good protection against corrosion under insulation.INTRODUCTION

[0003] Insulation is used to prevent heat transfer from inside an asset (operation or apparatus such as a tank, pipe, vessel, furnace, valve, boiler, etc.) to the outside environment to improve process reliability and provide personnel protection. Mechanical (or physical or bulk) insulation solutions (such as fiberglass, foam wrap, etc., wrapped with metal shrouding, etc.) can be difficult to install on complex geometries, and may act as a sponge if / when exposed to water, exacerbating corrosion under insulation. This can lead to equipment failure and safety concerns.

[0004] Physical insulation is bulky and upon disposal after its useful lifetime and ends up in landfills. Liquid applied organic insulation typically requires long application time and has a poor exterior durability and / or lifetime, resulting in a higher amount of material usage over a given period to protect an asset. Physical insulation often requires metal shrouding with sharp edges and does not enable ease of early failure detection in the event of corrosion under insulation.

[0005] While incumbent liquid-delivered insulation products provide thermal insulation, they require high maintenance costs and downtime for installation and repair. The spray applied solutions are typically applied in 20-50 mil thick coats and require several coats (up to or exceeding 10) to achieve adequate insulation, each of which require a long dry time. In addition, organic -based liquid applied thermal insulation coatings have innate concerns with exterior and / or long-term durability. Corrosion under insulation remains a challenge for both mechanical and liquid insulation solutions.

[0006] CN 102585698A discloses an aqueous based industrial heat insulation coating useful in thermal insulation cover of heat transmitting pipe. The coating includes an aqueous based organic silicon resin, filler, and auxiliary materials.SUMMARY

[0007] A silicone - acrylic binder for a thermal insulation coating composition comprises an aqueous emulsion comprising: A) a first acrylic polymer with Young’s modulus < 50 psi, B) a second acrylic polymer with Young’s modulus > 5,000 psi, and C) a silicone elastomer. The thermal insulation coating composition comprises A) the first acrylic polymer with Young’s modulus < 50 psi, B) the second acrylic polymer with Young’s modulus > 5,000 psi, C) the silicone elastomer, an antifoam, an insulative filler, a metal oxide, and a flash rust inhibitor. Methods for preparation and use of the binder and the thermal insulation coating composition are also disclosed.DETAILED DESCRIPTION

[0008] The binder introduced above may be prepared by a method comprising: i) homogenizing starting materials comprising I) a first aqueous emulsion comprising A) the first acrylic polymer having Young’s modulus < 50 psi, II) a second aqueous emulsion comprising B) the second acrylic polymer having Young’s modulus > 5,000 psi, and III) a third aqueous emulsion comprising C) the silicone elastomer. Step i) may be performed by any convenient means using any convenient equipment. Step i) may comprise combining (e.g., by simple mixing) starting materials comprising I), II), and III). Step i) further comprises homogenizing via applying shear to starting materials comprising I), II), and III), thereby preparing an intermediate. In addition to, or instead of preparing the intermediate, the method may further comprise adding an additional starting material selected from the group consisting of D) an antifoam, E) a coalescing solvent, F) a pH modifier, and a combination of two or more thereof. The starting materials used to prepare the binder are described in detail as follows.Aqueous Acrylic Emulsions

[0009] Starting material I) is a first aqueous emulsion. The first aqueous emulsion comprises starting material A) the first acrylic polymer. The first aqueous emulsion further comprises water and a surfactant. The first acrylic polymer has a Young’s modulus < 50 psi. Alternatively, the first acrylic polymer may have a Young’s modulus up to 45 psi, alternatively up to 40 psi, alternatively up to 35 psi, alternatively up to 30 psi; while at the same time the first acrylic polymer may have a Young’s modulus of at least 5 psi, alternatively at least 6 psi, alternatively at least 17 psi, alternatively at least 20 psi, and alternatively at least 30 psi. Alternatively, the first acrylic polymer may have a Young’s modulus of 6 to < 50 psi,alternatively 6 to 40 psi, and alternatively 20 to 40 psi.

[0010] The first acrylic emulsion may have a particle size, Dv50, of 200 nm to 400 nm, measured according to the test method for Particle Size Measurements described below. Alternatively, the first acrylic emulsion may have a Dv50 of at least 200 nm, alternatively at least 225 nm, alternatively at least 250 nm, alternatively at least 275 nm, alternatively at least 300 nm; while at the same time the first acrylic emulsion may have a Dv50 up to 400 nm, alternatively up to 375 nm, alternatively up to 350 nm, alternatively up to 325 nm, and alternatively up to 300 nm.

[0011] The first acrylic emulsion may comprise 54 % to < 56 % of the first acrylic polymer, 44 % to < 46 % water, 0. 1 % to 0.3 % diphenyl ketone, and 0 to < 0.2 % aqua ammonia. The first aqueous emulsion is commercially available. Suitable examples include RHOPLEX™ EC- 3814 Emulsion Polymer (in which the acrylic polymer has a modulus of 17 psi); RHOPLEX™ 4400 (in which the acrylic polymer has a modulus of 6 psi); RHOPLEX™ EC- 1791 Emulsion Polymer (in which the acrylic polymer has a modulus of 20 psi and a Dv50 with an average value of 350 nm); RHOPLEX™ EC-1791QS (in which the acrylic polymer has a modulus of 20 and a Dv50 with an average value of 350 nm); and RHOPLEX™ 2019RX Water-borne Binder (in which the acrylic polymer has a modulus of 40 psi and a Dv50 with an average value of 250 nm), all of which are commercially available from The Dow Chemical Company of Midland, Michigan USA.

[0012] Starting material II) is a second aqueous emulsion. The second aqueous emulsion comprises B) the second acrylic polymer. The second aqueous emulsion further comprises water and a surfactant. The second acrylic polymer has a Young’s modulus > 5,000 psi. Alternatively, the Young’s modulus of the second acrylic polymer may be > 5,000 psi, alternatively at least 10,000 psi, while at the same time the Young’s modulus of the second acrylic polymer may be up to 15,000 psi. Alternatively, the Young’s modulus of the second acrylic polymer may be > 5,000 psi to 15,000 psi; alternatively 5,800 psi to 14,000 psi; alternatively 5,866 to 13,835; alternatively 10,000 psi to 15,000 psi.

[0013] The second aqueous emulsion may have a particle size, Dv50, of at least 50 nm, alternatively 90 to 300 nm, and alternatively 133 nm to 300 nm, measured according to the test method for Particle Size Measurements described below. Alternatively, the second aqueous emulsion may have a Dv50 of at least 50 nm, alternatively at least 90 nm, alternatively at least 133 nm, alternatively at least 150 nm, alternatively at least 167 nm, alternatively at least 183 nm, alternatively at least 200 nm; while at the same time the second aqueous emulsion may have a Dv50 up to 300 nm, alternatively up to 250 nm, alternatively up to 233 nm, alternatively up to217 nm, and alternatively up to 200 nm.

[0014] The second aqueous emulsion may comprise 44 % to < 51 % of the second acrylic polymer, 49 % to < 56 % of water, 0 to < 1 % diphenyl ketone, and 0 to 0.2 % aqua ammonia. Alternatively, the second aqueous emulsion may comprise 50 % to less than 51 % of the second acrylic polymer, 49 % to less than 50 % of water, and 0 to 0.2 % aqua ammonia. Alternatively, the second aqueous emulsion may comprise 44 % to less than 46 % of the second acrylic polymer, 54 % to < 56 % of water, 0.1 % to < 1.0 % diphenyl ketone, and 0 to 0.2 % aqua ammonia. The second aqueous emulsion is commercially available. Suitable examples include ELASTENE™ 300, MAINCOTE™ PR-71 Emulsion, which contains an acrylic polymer with a modulus of 13,835 psi; and MAINCOTE™ 5045 which contains an acrylic polymer with a modulus 5,866 psi, all of which are commercially available from The Dow Chemical Company of Midland, Michigan USA.

[0015] Some examples of ethylenically unsaturated monomers that can be used to prepare the first acrylic polymer and the second acrylic polymer described above include alkyl methacrylates having 1-12 carbon atoms such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, propyl methacrylate, phenyl methacrylate, and isobornyl methacrylate; alkyl acrylates having 1-12 carbon atoms in the alkyl group such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, cyclohexyl acrylate, isodecyl acrylate, phenyl acrylate, and isobomyl acrylate; styrene, alkyl substituted styrene such as a-methyl styrene, t-butyl styrene, and vinyl toluene.

[0016] Alternatively, the acrylic polymers may comprise copolymerized ethylenically unsaturated carboxylic acid monomers. When such acid monomers are in their deprotonated form, as at a pH below the pKa of the acid monomers themselves, they can be referred to as anionic monomers. Such monomers may include, for example, an acid-functional group chosen from a phosphorus acid group, a sulfur acid group, salts thereof, and combinations thereof. The phosphorus acid-functional group may be a (di)hydrogen phosphate group, phosphonate group, phosphinate group, alkali metal salt thereof, other salt thereof, or a combination thereof.Suitable phosphorus acid group containing monomers may include, for example, (di)hydrogen phosphate esters of an alcohol containing a polymerizable vinyl or olefinic group, such as phosphates of hydroxyalky l(meth)acrylates including hydroxy ethyl (meth)acrylate. Other suitable such monomers may include, for example, phosphonate functional monomers, like vinyl phosphonic acid. Alternatively, the phosphorus acid monomers may include phosphoethyl(meth)acrylate.

[0017] The aqueous emulsions of the acrylic polymers, starting materials I) and II) are used in amounts to prepare the binder such that the thermal insulation coating composition prepared with the binder will contain a weight ratio of A) the first acrylic polymer : B) the second acrylic polymer (referred to herein as “A):B) ratio”) of greater than 0 : less than 100 (i.e., > 0: <100 to 50:50). Alternatively, A):B) ratio may he 10:90 to 50:50, alternatively A):B) ratio may he 20:80 to 50:50, and alternatively A):B) ratio may be 60:40 to 50:50.

[0018] The aqueous emulsions of the acrylic polymers, starting materials 1) and II), may be selected such that particle size, Dv50, of the discontinuous phase of the first aqueous emulsion is at least 1.5 larger than particle size, Dv50, of the discontinuous phase of the second aqueous emulsion. The ratio of the particle sizes may be calculated as Dv50 of the first aqueous emulsion divided by Dv50 of the second aqueous emulsion, where Dv50 is calculated by the test method for particle size described below. Alternatively, the ratio of the particle sizes may be at least 1.5, alternatively at least 1.75, alternatively at least 2, alternatively at least 2.25, alternatively at least 2.5, alternatively at least 2.75, and alternatively at least 3; while at the same time the ratio of the particle sizes may be up to 4, alternatively up to 3.5, alternatively up to 3.5, alternatively up to 3.25, and alternatively up to 3. Without wishing to be bound by theory, it is thought that when II) the second aqueous emulsion has a smaller particle size than I) the first aqueous emulsion, B) the second acrylic polymer particles will migrate to the surface of the thermal insulation coating prepared with the binder and the thermal insulation coating composition described herein, which may minimize tackiness of the surface of the thermal insulation coating and / or dirt pick up, measured as described below in the EXAMPLES.Ill) Third Aqueous Emulsion

[0019] Starting material III) is a third aqueous emulsion. The third aqueous emulsion comprises C) the silicone elastomer. The third aqueous emulsion further comprises a surfactant and water. The silicone elastomer in the third aqueous emulsion comprises a reaction product of C-l) and C-2) in the presence of C-3) and C-4), whereC-l) is a bis-hydroxyl-terminated polydiorganosiloxane with a viscosity > 5,000 mPa.s to < 500,000 mPa.s;C-2) is a self catalytic crosslinker comprising, on average, more than 2 hydroxylamine groups per molecule;C-3) is a surfactant, andC-4) is water. The third aqueous emulsion further comprises may further comprise C-5) a stabilizer.

[0020] Starting material C-l) is a bis-hydroxyl-terminated polydiorganosiloxane of formula, where each R1is independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, and subscript z is an integer with an average value of 500 to 5,000. In this formula, each R1is a monovalent hydrocarbon group such as an alkyl, alkenyl, or aryl group. Suitable alkyl groups may have 1 to 12 carbon atoms, for example, methyl, ethyl, propyl (including n-propyl and isopropyl), butyl (including n-butyl, t-butyl, isobutyl, and sec-butyl), pentyl, hexyl, heptyl, octyl, nonyl, decyl, and dodecyl, including linear, branched, and cyclic alkyl groups of 5 to 12 carbon atoms. Suitable alkenyl groups may have 2 to 12 carbon atoms and include vinyl, allyl, and hexenyl. Suitable aryl groups may have 6 to 12 carbon atoms and include phenyl, tolyl, xylyl, naphthyl, benzyl, and phenylethyl. Any of the monovalent hydrocarbon groups described above may be halogenated, e.g., by replacing one or more hydrogen atoms with a halogen atom, such as Cl or F, alternatively F. For example, a halogenated alkyl group such as chloromethyl or trifluoropropyl may be used for R1. Alternatively, each R1may be selected from methyl, ethyl, octyl, trifluoropropyl, vinyl, and phenyl groups. Alternatively, each R1may be an alkyl group such as methyl.

[0021] Starting material C-2) is the self catalytic crosslinker comprising more than 2 hydroxylamine groups per molecule. The self catalytic crosslinker may comprise unit formula: (R23SiOi / 2)2(R22SiO2 / 2)a(R2R3SiO2 / 2)b, where each R2is an independently selected alkyl group of 1 to 8 carbon atoms, each R3is an independently selected hydroxyl amine group of formula - ONR22, subscript a is 0 or a positive integer and subscript b > 2. In this unit formula, each R2is an alkyl group of 1 to carbon atoms, for example, methyl, ethyl, propyl (including n-propyl and isopropyl), butyl (including n-butyl, t-butyl, isobutyl, and sec-butyl), pentyl, hexyl, heptyl, and octyl, including linear, branched, and cyclic alkyl groups of 5 to 8 carbon atoms. Alternatively, each R2may be methyl or ethyl, alternatively methyl. Alternatively each R3may be -ON(CH3)2, -ON(CH2CH3)2, -ON(CH2CH2CH3)2. Alternatively, each R3may be -ON(CH2CH3)2. Alternatively, subscript a may be 1 to 10, alternatively 1 to 5, alternatively 2 to 4, and alternatively, subscript a may have an average value of 3. Alternatively, subscript b may be 3 to 10, alternatively 3 to 7, alternatively 4 to 6, and alternatively subscript b may have an average value of 5. The self catalytic crosslinker may be present in an amount of 1 to 5 parts by weightof C-2) self catalytic crosslinker per 100 parts by weight of C-l) the bis-hydroxyl-terminated polydiorganosiloxane.

[0022] Starting material C-3) is the surfactant. The surfactant may be selected from nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, or mixtures of two or more thereof. Suitable surfactants are known in the art and are commercially available. The surfactants disclosed in U.S. Patent 5,944,459 at col. 6, line 15 - col. 9, line 21 , which is hereby incorporated by reference. Alternatively, C-3) the surfactant may be a nonionic surfactant, for example, a branched or linear polyoxyalkylene such as a polyoxyalkylene alkyl ether, a polyoxyalkylene sorbitan ester, a polyoxyalkylene ester, a polyoxyalkylene alkylphenylEther, or a mixture of two or more thereof. The surfactant may be present in an amount of 0.5 to 10 parts by weight per 100 parts by weight of C-l) the bis-hydroxyl-terminated polydiorganosiloxane, alternatively 2 to 10 parts by weight on the same basis.

[0023] Starting material C-4) is water. The water is not generally limited, and may be utilized neat (i.e., absent any carrier vehicles and / or solvents), and / or pure (i.e., free from, or substantially free from, minerals and / or other impurities). For example, the water may be processed or unprocessed prior to use in the methods and compositions described herein.Examples of processes that may be used for purifying the water include distilling, filtering, deionizing, and combinations of two or more thereof, such that the water may be deionized, distilled, and / or filtered. Alternatively, the water may be unprocessed (e.g. may be tap water, i.e., provided by a municipal water system or well water, used without further purification).Alternatively, the water may be purified before use herein. The amount of water in III) the third aqueous emulsion may be 0.5 to 20 parts by weight per 100 parts by weight of C-l) the bis- hydroxyl-terminated polydiorganosiloxane, alternatively 2 to 10 parts by weight on the same basis.

[0024] The third aqueous emulsion may optionally further comprise C-5) a stabilizer. Organic amines and inorganic bases are expected to be useful stabilizers, which may impart heat stability. The stabilizer may have formula (R4)3.XN(H)X, where subscript x is 0, 1, 2, or 3. In this formula, R4may be an alkyl or aryl group. For example, the stabilizer may be an alkylamine such as (CH3)2NH. Alternatively, R4may be an alcohol group such that the stabilizer may be an aminoalcohol such as N(CH2CH2OH)3or HN(CH2CH2OH)2. Alternatively, the stabilizer may comprise an organic amine such as cyclohexylamine, triethylamine, dimethylaminomethylpropanol, diethylaminoethanol, aminomethyl propanol, aminobutanol, monoethanolamine, monoisopropanolamine, dimethylethanolamine, diethanolamine, amino ethylpropanediol, aminomethylpropanediol, diisopropanolamine, morpholine,tris(hydroxymethyl)aminomethane, triisopropanolamine, triethanolamine, aniline, or urea. Inorganic bases such as ammonia and ammonium carbonate may also be used as stabilizers.

[0025] Suitable aqueous emulsions for starting material III) are known in the art and may be made by known methods, such as those described in U.S. Patent 5,944,459, which is hereby incorporated by reference. Suitable aqueous emulsions for starting material III) include DOWSIL™ 8004 Waterborne Resin, which is commercially available from The Dow Chemical Company of Midland, Michigan, USA. Without wishing to be bound by theory, it is thought that including the third aqueous emulsion in the thermal insulation coating composition enables thicker film application capable of drying under ambient conditions without mud cracking than a comparable composition that does not contain starting material III). Without wishing to be bound by theory, it is thought that including the first aqueous emulsion and / or the third aqueous emulsion in the thermal insulation coating composition may enable thicker film application capable of drying under ambient conditions without mud cracking than a comparable composition that does not contain starting materials I) and / or III). Without wishing to be bound by theory, it is thought that the silicone elastomer may improve corrosion resistance and / or provide good weatherability, breathability and / or hydrophobicity to the thermal insulation coating.

[0026] Starting materials I), II), and III) may be used in the method for preparing the binder in amounts of 35 to 92 weight parts of starting material I) the first aqueous emulsion, 3 to 53 weight parts of starting material II) the second acrylic emulsion, and 0. 1 to 30 weight parts of starting material III) the third aqueous emulsion.

[0027] One or more additional starting materials may optionally be used in the method to make the binder. The optional additional starting material may be selected from the group consisting of: D) an antifoam, E) a coalescing solvent, F) a pH modifier, and a combination of two or more thereof.D) Antifoam

[0028] Starting material D) is an antifoam. Without wishing to be bound by theory, it is thought that the antifoam may be added to the binder for the thermal insulation coating composition to during processing to prevent or minimize air entrapment. Suitable antifoams may comprise silica and optionally a polyorganosiloxane compound. Suitable antifoams are commercially available and include DOWSIL™ 107F Additive, DOWSIL™ 8590 Additive, DOWSIL™ 8603 Additive, and DOWSIL™ 8610 Additive, all of which are commercially available from The Dow Chemical Company of Midland, Michigan, USA. The amount of D) the antifoam may be 0 to an amount sufficient to provide 10 ppm of antifoam active (e.g.,polyorganosiloxane and / or silica) to the binder, based on combined weights of starting materials / ), III), and C), and when present II), E) and / or F).F) pH Modifier

[0029] Starting material F) is a pH modifier that may optionally be added, for example, when the pH of starting material I), starting material II), or both is less than 8, alternatively less than 8.5. Without wishing to be bound by theory, it is thought that adding the pH modifier may assist in stabilizing an aerogel in the thermal insulation coating composition. Suitable pH modifiers are commercially available and included bases such as ammonia or ammonium hydroxide, NH4OH. The amount of pH modifier may be 0 to an amount sufficient to adjust pH of a combination of starting materials I) and II), the binder, and / or the thermal insulation coating composition to have a pH > 8, alternatively > 8.5, alternatively 8.5 to 9.Silicone - Acrylic Binder (Binder)

[0030] The binder prepared as described above may comprise: 40 to 93 weight parts of A) the first acrylic polymer, 0.1 to 48 weight parts (alternatively 0.11 to 48 weight parts) of B) the second acrylic polymer, 0.002 to 14 weight parts of C) the silicone elastomer, 0 to 1 weight parts of D) the antifoam, 0 to 5 weight parts of E) the coalescing solvent, > 0 weight parts of F) the pH modifier (0 to 2 weight parts pH modifier), and 0 to 32 weight parts of water, and > 0 weight parts of a surfactant. One skilled in the art would recognize that water and surfactant may be introduced via the aqueous emulsions I), II) and III) used to prepare the binder. The binder has the form of an emulsion or dispersion. Alternatively, the binder may comprise 20 to 53 weight parts of A) the first acrylic polymer, 0.01 to 25 weight parts of B) the second acrylic polymer, 0.002 to 11 weight parts of C) the silicone elastomer, 0 to 1 weight parts of D) the antifoam, 0 to 5 weight parts of E) the coalescing solvent, > 0 weight parts of F) the pH modifier, 27 to 80 weight parts of K) water, and 0.0005 to 7 weight parts of G) the surfactant.Method for Making Thermal Insulation Coating Composition

[0031] The binder described above may be used to make a thermal insulation coating composition. For example, the thermal insulation coating composition may be prepared by combining the binder, described above, with an additional starting material selected from the group consisting of G) a surfactant, H) an insulative filler, I) a metal oxide, J) a flash rust inhibitor, K) water, L) a rheology modifier, and a combination of two or more thereof. Alternatively, the starting materials described above may be used in a method to make a thermal insulation coating, whether or not the binder is made. For example, a method for making the thermal insulation coating composition may comprise:1 ) homogenizing starting materials comprising:I) the first aqueous emulsion comprising A) the first acrylic polymer, a first surfactant, and water;II) the second aqueous emulsion comprising B) the second acrylic polymer, a second surfactant, and water;III) a third aqueous emulsion comprising C) the silicone resin, a third surfactant, and water; optionally 2 ) during and / or after step 1 ), adding an additional starting material selected from the group consisting of D) the antifoam, E) the coalescing solvent, F) the pH modifier, G) an additional surfactant, H) an insulative filler, I) a metal oxide) and a combination of two or more thereof. The first surfactant, the second surfactant, and the third surfactant may be the same or different, and may be as described and exemplified herein for starting material G).

[0032] Alternatively, the method for making the thermal insulation coating composition may comprise:1) practicing the method for making the binder described above, optionally 2) adding G) an additional surfactant during and / or after step 1),3) adding H) an insulative filler to the binder prepared in step 1) or step 2) and homogenizing to prepare a filled intermediate; and4) adding, to the filled intermediate, a slurry comprising I) a metal oxide, and a solution or slurry comprising J) a flash rust inhibitor before, during, or after any one of steps 1) to 3), and homogenizing, optionally 5) adding F) a pH modifier in step 1) when I) the first aqueous emulsion has pH < 8, II) the second aqueous emulsion has pH < 8, or both I) and II) have pH < 8;6) adding D) an antifoam before, during and / or after adding the insulative filler in step 3).The method may optionally further comprise adding an additional starting material selected from the group consisting of D) an additional antifoam, E) a coalescing solvent, and a combination thereof. The method may optionally further comprise adding L) a rheology modifier after step 2). The method may further comprise adding additional K) water.

[0033] Alternatively, and more particularly, the method for making the thermal insulation coating composition introduced above may comprise: optionally i) combining (e.g., by simple mixing) I) the first aqueous emulsion, II) the second aqueous emulsion, and III) the third aqueous emulsion; ii) homogenizing I) the first emulsion, II) the second emulsion, and III) the third aqueous emulsion, thereby preparing the homogeneous intermediate, and thereafteroptionally iii) adding D) the antifoam, optionally iv) adjusting pH by adding F) the pH modifier; thereby forming a pre-mix, v) mixing the pre-mix, optionally vi) adding an additional D) antifoam to the pre-mix, optionally vii) adding E) the coalescing solvent to the pre-mix, viii) adding V) a slurry comprising T) the metal oxide to the pre-mix, ix) adding J) the flash rust inhibitor (either neat or as a dispersion or solution of the flash rust inhibitor in water) to the pre-mix, optionally x) adding IV) a slurry or solution comprising G) an additional surfactant to the premix, optionally xi) adding E) the coalescing solvent to the pre-mix, if the coalescing solvent was not added in step vii), xii) adding H) an insulative filler comprising a hydrophobic aerogel to the pre-mix and mixing until the insulative filler is wet and homogeneously dispersed in the pre-mix, optionally xiii) adding K) water, optionally xiv) adding L) a rheology modifier, and optionally xv) adding additional water. The starting materials 1), II), III), A), B), C), D), E) and F), used in the above method for making the thermal insulation coating composition are described in detail above. The additional starting materials used in making the thermal insulation coating composition are described in detail as follows.G) Surfactant

[0034] Starting material G) is a surfactant that may optionally be added in the thermal insulation coating composition in addition to any surfactants present in starting materials I), II), and III). The surfactant may be nonionic, cationic, anionic, or amphoteric. Alternatively, starting material G) may comprise a nonionic surfactant. Without wishing to be bound by theory, it is thought that adding a surfactant, such as a nonionic surfactant (in addition to any surfactant(s) present in the aqueous emulsions I), II), and III) described above) may facilitate dispersion of H) the insulative filler (e.g., hydrophobic aerogel) in the thermal insulative coating composition and / or improve corrosion prevention of a thermal insulation coating on a metal substrate. The surfactant may be added neat. Alternatively G) the surfactant may be dispersed in water and delivered as IV) a slurry or solution comprising water and G) the surfactant.

[0035] The surfactant that may be added to the thermal insulation coating composition may be a nonionic surfactant. Some suitable nonionic surfactants which can be used include polyoxyethylene alkyl ethers (such as, lauryl, cetyl, stearyl or octyl), polyoxyethylene alkylphenol ethers, alkylglycosides, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitan monooleates, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, polyethylene glycol (such as polyethylene glycol having 23 ethylene-oxide units), polypropylene glycol, diethylene glycol, ethoxylated trimethylnonanols, tristyrylphenol ethers (TSP’s), distyryl phenol ethers (DSP’s), and polyoxyalkylene glycol modified polysiloxane surfactants.

[0036] Nonionic surfactants which are commercially available include compositions such as (i) 2,6,8-trimethyl-4-nonyloxy polyethylene oxyethanols (6EO) and (10EO) sold under the names TERGITOL™ TMN-6 and TERGITOL™ TMN-10; (ii) the Ci 1-15 secondary alkyl polyoxyethylene ethers (e.g., C11-15 secondary alcohol ethoxylates 7EO, 9EO, and 15EO sold under the names TERGITOL™ 15-S-7, TERGITOL™ 15-S-9, and TERGITOL™ 15-S-15, which has HL value 15.4), other C11-15 secondary alcohol ethoxylates sold under the tradenames ECOSURF™ EH-40 and TERGITOL™ 15-S-12, TERGITOL™ 15-S-30, and TERGITOL™ 15-S-40, by the Dow Chemical Company, of Midland, Michigan, USA; octylphenyl polyoxyethylene (40) ether sold under the name TRITON™ X-405 by the Dow Chemical Company; (iii) nonylphenyl polyoxyethylene (10) ether sold under the name MAKON™ 10 by the Stepan Company; (iv) ethoxylated alcohols sold under the name Trycol 5953 by Henkel Corp. / Emery Group, of Cincinnati, Ohio, USA; (v) ethoxylated alcohols sold under the name BRU™ L23 (with HLB value of 16.9) and BRU™ L4 (with HLB value of 9.7) by Croda Inc. of Edison, New Jersey, USA, (vi) polyoxyethylene 23 lauryl ether (Laureth-23) sold commercially under the trademark BRU™ 23 by ICI Surfactants, Wilmington, Delaware; and RENEX™ 30, a polyoxyethylene ether alcohol sold by ICI Surfactants, Wilmington, Delaware, USA; (vii) alkyloxo alcohol polyglycol ethers such as GENAPOL™ UD 050 (with HLB value of 11.4), and GENAPOL™ UDI 10 (with HLB value of 14.4), (viii) alkyl polyethylene glycol ether based on ClO-Guerbet alcohol and ethylene oxide such as LUTENSOL™ XP 79, and (ix) alkyl polyglycosides, such as those sold under the trade name Glucopon™ by BASF, and alkyl glucosides such as decyl glucoside, lauryl glucoside, and coco-glucoside, which are sold under the trade name EcoSense™ by The Dow Chemical Company of Midland, Michigan, USA.Other commercially available nonionic surfactants include TERGITOL™ 15-S-5, also from The Dow Chemical Company, which has an HLB value of 10.5; Lutensol XP 50 with an HLB value of 10, and Lutensol XP 140 with an HLB value of 16.

[0037] Suitable nonionic surfactants also include poly(oxyethylene)-poly(oxypropylene)- poly(oxyethylene) tri-block cs. Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) triblock copolymers are also commonly known as Poloxamers. They are nonionic triblockcopolymers composed of a central hydrophobic chain of polyoxypropylene (polyi propylene oxide)) flanked by two hydrophilic chains of polyoxyethylene (poly (ethylene oxide)). Poly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) tri-block copolymers are commercially available from BASF of Florham Park, New Jersey, USA, and are sold under the tradename PLURONIC™, such as PLURONIC™ L61, L62, L64, L81, and P84.

[0038] The nonionic surfactant may also be a silicone polyether (SPE). The silicone polyether as a surfactant may have a rake type structure wherein the polyoxyethylene or polyoxyethylene - polyoxypropylene copolymeric units are grafted onto the siloxane backbone, or the SPE can have an ABA block copolymeric structure wherein A represents the polyether portion and B the siloxane portion of an ABA structure. Alternatively, the SPE may have a resinous structure, such as a polyorganosilicate resin having polyether groups bonded to silicon atoms therein. Suitable SPE’s include DOWSIL™ OFX-5329 Fluid from Dow Silicones Corporation of Midland, Michigan, USA. Alternatively, the nonionic surfactant may be selected from polyoxyalkylene-substituted silicones, silicone alkanolamides, silicone esters and silicone glycosides. Such silicone-based surfactants may be used to form such aqueous emulsions and are known in the art, and have been described, for example, in U.S. Patent 4,122,029 to Gee et al., U.S. Patent 5,387,417 to Rentsch, and U.S. Patent 5,811,487 to Schulz et al. Other silicone polyether surfactants are known in the art and are also commercially available, e.g., DOWSIL™ 502W Additive and DOWSIL™ 67 Additive are commercially available from Dow Silicones Corporation of Midland, Michigan, USA.

[0039] Alternatively, the nonionic surfactant may comprise a polyvinyl alcohol compound. Polyvinyl alcohol compounds are known in the art and are disclosed, for example in U.S. Patent Application Publication 2007 / 0099007 at paragraphs

[0172] and

[0173] . Polyvinyl alcohol compounds may be made by saponification of polyvinylacetate, so up to 15 % of polyvinylacetate may remain in the polyvinyl alcohol compound used herein. Alternatively, the polyvinyl alcohol compound may be 88% to 92% polyvinyl alcohol (with the balance being 12% to 8 % polyvinylacetate). The polyvinyl alcohol compound may have a minimum viscosity of 5 cP at 4 % aqueous solution at 20 °C.

[0040] The anionic surfactants include (i) sulfonic acids and their salt derivatives, including alkyl or aralkyl (e.g., alkyl naphthalene or alkyl diphenyl ether) sulfonic acids, and their salts, having at least 6 carbon atoms in the alkyl substituent, such as dodecyl benzene sulfonic acid, and its sodium salt or its amine salt; (ii) alkyl sulfates having at least 6 carbon atoms in the alkyl substituent, such as sodium lauryl sulfate; (iii) the sulfate esters of polyoxyethylene monoalkyl ethers; (iv) long chain carboxylic acid surfactants, such as lauric acid, steric acid, oleic acid, andtheir alkali metal and amine salts. Some other examples of anionic surfactants are alkali metal sulfosuccinates; sulfonated glyceryl esters of fatty acids such as sulfonated monoglycerides of coconut oil acids; salts of sulfonated monovalent alcohol esters such as sodium oleyl isothionate; amides of amino sulfonic acids such as the sodium salt of oleyl methyl tauride; sulfonated products of fatty acid nitriles such as palmitonitrile sulfonate; sulfonated aromatic hydrocarbons such as sodium alpha-naphthalene monosulfonate; condensation products of naphthalene sulfonic acids with formaldehyde; sodium octahydro anthracene sulfonate; alkali metal alkyl sulfates; ether sulfates having alkyl groups of eight or more carbon atoms such as sodium lauryl ether sulfate; and alkylaryl sulfonates having one or more alkyl groups of eight or more carbon atoms such as neutral salts of hexadecylbenzene sulfonic acid and C20 alkylbenzene sulfonic acid.

[0041] Commercial anionic surfactants which can be used include the sodium salt of dodecyl benzene sulfonic acid sold under the trademark SIPONATE™ DS- 10 by Alcolac Inc., Baltimore, Maryland; sodium salt of alkyl alkoxylate sulfate sold under the trademark DOWFAX™ AS-801 by The Dow Chemical Company of Midland, Michigan, USA; sodium n- hexadecyl diphenyloxide disulfonate sold under the trademark DOWFAX™ 8390 by The Dow Chemical Company, Midland, Michigan; the sodium salt of a secondary alkane sulfonate sold under the trademark HOSTAPUR™ SAS 60 by Clariant Corporation, Charlotte, North Carolina; N-acyl taurates such as sodium N-lauroyl methyl taurate sold under the trademark NIKKOL LMT™ by Nikko Chemicals Company, Ltd., Tokyo, Japan; and linear alkyl benzene sulfonic acids sold under the trademark BIO-SOFT™ S-100 by the Stepan Company, Northfield, Illinois. Other suitable surfactants include sodium alkyl sulfonate such as HOSTAPUR™ SAS-30, and triethanolamine dodecyl benzene sulfonate, such as BIO-SOFT™ N 300.

[0042] Cationic surfactants useful herein include compounds containing quaternary ammonium hydrophilic moieties in the molecule which are positively charged, such as quaternary ammonium salts represented by R8R9R10R11N+X" where R8to R11are alkyl groups containing 1-30 carbon atoms, or alkyl groups derived from tallow, coconut oil, or soy; and X is a halogen, e.g., chlorine or bromine. Alternatively, the quaternary ammonium compounds may be alkyl trimethylammonium and dialkyldimethylammonium halides, or acetates, or hydroxides, having at least 8 carbon atoms in each alkyl substituent. Dialkyl dimethyl ammonium salts can be used and are represented by Rl 2RnN+(CHp2X_where R12and R13are alkyl groups containing 12-30 carbon atoms or alkyl groups derived from tallow, coconut oil, or soy; and X is a halogen as described above. Monoalkyl trimethyl ammonium salts can be used and are represented by R14N+(CH3)3X’_where R14is an alkyl group containing 12-30 carbon atoms oran alkyl group derived from tallow, coconut oil, or soy; and X’ is halogen, acetate, or hydroxide.

[0043] Representative quaternary ammonium halide salts are dodecyltrimethyl ammonium chloride / lauryltrimethyl ammonium chloride (LTAC), cetyltrimethyl ammonium chloride (CTAC), didodecyldimethyl ammonium bromide, dihexadecyldimethyl ammonium chloride, dihexadecyldimethyl ammonium bromide, dioctadecyldimethyl ammonium chloride, dieicosyldimethyl ammonium chloride, and didocosyldimethyl ammonium chloride. These quaternary ammonium salts are commercially available under trademarks such as ADOGEN™ and VARIQUAT™ from Evonik of Essen, Germany, and ARQUAD™ from Nouryon.

[0044] Other suitable cationic surfactants which can be used include fatty acid amines and amides and their salts and derivatives, such as aliphatic fatty amines and their derivatives. AMMONYX™ by the Stepan Company, Northfield, Illinois.H) Insulative Filler

[0045] Starting material H) is an insulative filler that may be used to reduce thermal conductivity, improve hydrophobicity, improve thick-film application, or a combination of forementioned, of the thermal insulation coating prepared from the thermal insulation coating composition. The insulative filler may comprise, alternatively may consist essentially of, alternatively may consist of a hydrophobic aerogel. The term "aerogel" is used to describe a synthetic, highly porous, ultralight-weight material derived from a gel, the liquid components of which have been replaced with a gas (e.g., air). In other words, an aerogel is a gel with the gas as dispersion medium. Historically, the most common method of preparation was by drying a wet sol-gel at temperatures above the critical temperature and at a pressure above the critical pressure. This kind of drying drives off the liquid contained in the gel, e.g., water, and results in a porous structure without damaging the solid matrix structure of the gel. Up to 99.98 % of the volume of aerogels may consist of pores. Thus, e.g., up to 99.98 vol.%, such as 90 to 98.5 vol.% or about 97 vol.%, of an aerogel may be air. Aerogels are micro- or nanoporous open cell solids and dry materials. Typically they comprise a porous solid network, and due to such a structure they are ultralight-weight. The resulting aerogel in addition to low density has thermally insulating properties, i.e., low thermal conductivity. Other methods of manufacture are now used to produce similar products.

[0046] An aerogel may be based on inorganic or organic materials, e.g., silica, magnesia, titania, zirconia, alumina, chromia, tin dioxide, lithium dioxide, ceria and vanadium pentoxide, and combination of any two or more thereof, and organic carbon containing polymers (carbon aerogels) or resorcinol-formaldehyde or melamine-formaldehyde aerogel particles. Suitable hydrophobic aerogel particles are commercially available, and methods for preparing suitablehydrophobic aerogels are known (see, e.g., PCT Patent Application Publications WO 99 / 36355 A2; WO 99 / 36356A2; WO 99 / 36479A1; WO 98 / 45210A2; WO 98 / 45035 Al; WO 98 / 45032A1; WO 96 / 18456A2 and U.S. Patent Application Publication 2021 / 0032499).

[0047] The amount and type of H) the insulative filler typically correlates to thermal conductivity, and the insulative filler selection may directly impact corrosion resistance. The nano-porous (90-95%) structure silica aerogel included has a methylated (hydrophobic) surface treatment and is >90% air (740m2 / g surface). In the present thermal insulation coating composition, the filler specifications may include: pore size 20-60 nm, alternatively 20nm; particle size 0.1-0.7mm; and density 0.12-0.15g / cm3. A suitable silica aerogel has CAS# 102262-30-6. Alternatively, the hydrophobic aerogel may have a particle size of 2 micrometers to 1.2 mm. Suitable hydrophobic aerogels are commercially available, such as ENOVA™ IC- 3100, ENOVA™ IC-3110 and ENOVA™ IC-3120 from Cabot Corporation of Alpharetta, Georgia, USA.

[0048] Alternatively, hollow, non-porous insulative fillers may be used in addition to, or instead of the hydrophobic aerogel described above, in the present thermal insulation coating composition (and the binder described above). The thermal insulation coating composition described herein composition may comprise hollow, non-porous insulative fillers such as SPHERICEL™ hollow glass microspheres from Potters Industries or 3M™ glass bubbles, which are hollow glass spheres with density 0.125-0.6 g / cc; and median particle size 18-65 micron or polymeric bubbles that may be expandable at different temperatures, such as EXPANCEL™ Microspheres available from Nouryon of Amsterdam, Netherlands. Alternatively, Q-CEL™ hollow inorganic microspheres or EXTENDOSPHERES™ (from Sphere One of Chattanooga, Tennessee, USA) are low density, high strength hollow ceramic cenospheres may be used. Hollow, non-porous insulative fillers, the hydrophobic aerogel, and I) the metal oxide are distinct from one another.I) Metal Oxide

[0049] The metal oxide may be added to the thermal insulation coating composition to provide barrier properties, provide color (i.e. white), improve corrosion resistance, improve hydrophobicity, improve adhesion, provide temperature resistance, act as an opacifying agent, and / or reflect UV. The metal oxide is exemplified by titanium dioxide, zirconium dioxide, iron oxides (including micaceous iron oxide), zirconium silicates, manganese oxides, and combinations thereof. Alternatively, the metal oxide may comprise titanium dioxide. Suitable metal oxides are known in the art and are commercially available, and are described, for example, as IR opacifiers in U.S. Patent Application Publication 2021 / 0269359 paragraph|0017|.J) Flash Rust Inhibitor

[0050] Starting material J) is a flash rust inhibitor that may be added to the thermal insulation coating composition to inhibit rust formation when the thermal insulation coating composition, which can be in the form of an aqueous emulsion, is applied to a metal substrate, particularly before the water is removed, as described below. Suitable flash rust inhibitors are known, for example, from U.S. Patent Application Publication 2021 / 0380840 Al paragraph

[0031] . The flash rust inhibitor may be selected from zinc phosphate tetrahydrate, zinc orthophosphate, zinc phosphate, aluminum dihydrogen phosphate, polyaniline / zinc / cerium nitrate, zinc tannate, magnesium tannate, zinc phosphate aluminum tripolyphosphate (ZnAPC ) 2@A1HTP30IO), aluminum tripolyphosphate ( AflUPsOio- 2H2O), zinc oxide or a combination thereof.

[0051] Alternatively, the flash rust inhibitor may comprise sodium nitrite. Sodium nitrite can prevent flash rust in direct-to-metal (DTM) application. Sodium nitrite may be delivered in a carrier. For example, sodium nitrite may be delivered as a dispersion in water, such as 15% NaNC and 85% water.K) Water

[0052] Starting material K) is water. Water is present in the binder and the thermal insulation coating composition. Water may be incorporated via delivery of starting materials A), B), and C), which are provided in aqueous emulsions starting materials I), II). and III), respectively. Alternatively, additional water may be added during the method for making the binder and / or the thermal insulation coating composition in a separate additional step. The water is not generally limited, and may be utilized neat (i.e., absent any carrier vehicles and / or solvents), and / or pure (i.e., free from, or substantially free from, minerals and / or other impurities). For example, the water may be processed or unprocessed prior to use in the methods and compositions described herein. Examples of processes that may be used for purifying the water include distilling, filtering, deionizing, and combinations of two or more thereof, such that the water may be deionized, distilled, and / or filtered. Alternatively, the water may be unprocessed (e.g. may be tap water, i.e., provided by a municipal water system or well water, used without further purification). Alternatively, the water may be purified before use herein.L) Rheology Modifier

[0053] The rheology modifier(s) may be used to stabilize H) the hydrophobic aerogel insulative filler in the (waterborne) thermal insulation coating composition; e.g., to provide sag resistance, improve stability of dispersed insulative filler, and / or to provide buildability (thick film application). Suitable rheology modifiers may comprise a polyurethane resin, a polyacrylicacid, a copolymer of methacrylic acid and acrylate ester, or a fumed silica. Alternatively, the rheology modifier may comprise a polyurethane resin (in an amount of 17 to 25%, alternatively 17 to 18 %, and alternatively 22 to 25%), gluconic acid (in an amount of 0 to 5%, alternatively 3 to 5%), enzymatically modified starch (in an amount of 0 to 5%, alternatively 4 to 5%), and water (in an amount of 75 to 80 %, alternatively 78 to 80%, alternatively 75 to 78%). Suitable rheology modifiers are commercially available, such as ACRYSOL™ TT-615 Thickener, ACRYSOL™ RM-12W, RM-8W, and RM-995 all from The Dow Chemical Company of Midland, Michigan, USA.Optional Starting Materials

[0054] The thermal insulation coating composition may optionally contain one or more additional starting materials. For example, the thermal insulation coating composition may optionally further comprise a colorant such as calcium carbonate or a (non-metal) oxide, such as a mica (e.g., muscovite or phlogopite).

[0055] When selecting starting materials for the thermal insulation coating composition described herein, there may be overlap between types of starting materials because certain starting materials described herein may have more than one function. For example, calcium carbonate may be used as a colorant and / or opacifier. When adding additional starting materials to the composition, the additional starting materials are distinct from one another.Thermal Insulation Coating Composition

[0056] The thermal insulation coating composition may be prepared by the method described above using the starting materials described above. The thermal insulation coating composition may comprise: 33% to 78% of A) the first acrylic polymer, 0.1% to 43% of B) the second acrylic polymer, 0.005% to 11% of C) the silicone elastomer, 0 to 1% of D) the antifoam, 0 to 5% of E) the coalescing solvent, 0 to 1% of F) the pH modifier, 0 to 7% of G) the surfactant, 2 to 30% of H) the insulative filler (e.g., the hydrophobic aerogel), 2.5 to 10% of I) the metal oxide, 0.1 to 1.2% of J) the flash rust inhibitor, 0 to 28% of K) the water, and 0 to 5% of L) the rheology modifier. Alternatively, the thermal insulation coating composition may comprise: 17% to 45% of A) the first acrylic polymer, 0.004% to 25% of B) the second acrylic polymer, 0.003% to 11% of C) the silicone elastomer, 0 to 1% of D) the antifoam, 0 to 5% of E) the coalescing solvent, 0 to 1% of F) the pH modifier, > 0.00008 to 10% of G) the surfactant, 2 to 30% of H) the insulative filler, 2.5 to 10% of I) the metal oxide, 0.1 to 1.2% of J) the flash rust inhibitor, 27 to 80% of K) the water, and 0 to 5% of L) the rheology modifier.Method of Use of the Composition

[0057] The thermal insulation coating composition described above can be applied to asurface of an asset to be insulated by various means. The composition can be spray, brush, or roll applied in a single coat, multiple coats, injected, or poured into a mold and casted to achieve adequate thermal insulation. The asset to be insulated may be, for example, a tank, pipe, vessel, furnace, valve, boiler, oven, liquefied gas container, or cooling unit. The surface of the asset to be insulated may comprise metal, e.g., steel as its material of construction.

[0058] A method for insulating an apparatus may comprise: i) applying the thermal insulation coating composition described above in a layer on a surface of the apparatus, and ii) removing water from the thermal insulation coating composition, thereby forming a thermal insulation coating on the surface of the apparatus. The thermal insulation coating composition may be applied in step 1) in an amount sufficient to provide a thermal insulation coating with a thickness of at least 390 mils, alternatively 390 to 400 mils, in a single coat on a horizontal surface or at least 250 mils, alternatively 250 mils to 260 mils on a vertical surface in a single coat. The method may optionally further comprise repeating steps i) and ii) one or more times to increase thickness of the thermal insulation coating. The method may optionally further comprise applying a primer to the surface before step i). However, a primer is not required, and the thermal insulation coating composition may be applied directly to the metal surface to form a thermal insulation coating that adheres to the metal surface and that provides corrosion resistance. The method may optionally further comprise applying a top coat over the thermal insulation coating prepared as described above. However, a topcoat is not required.EXAMPLES

[0059] The following examples are provided to illustrate the invention to one skilled in the art and are not to be construed as limiting the scope of the invention set forth in the appended claims. The starting materials used in these examples are summarized in Table 1.Table 1 - Starting Materials

[0060] In this Inventive Example 1 , a thermal insulation coating composition was prepared as follows: First, a binder was prepared by loading RHOPLEX™ EC-1791 (432.00 g; 59.11 wt%), MAINCOTE™ PR-71 (108.00 g: 14.78 wt%), DOWSIL™ 8004 Waterborne Resin (56.10 g; 7.68wt%), and De-ionized water (133.00 g: 18.19wt%) to a container and stirring with a propeller blade on a Lightning II mixer at 250 rpm. Next, DOWSIL™ 8590 Additive (1.79 g: 0.24 wt%) was loaded into the container, and the contents continued to stir with a propeller blade on the Lightning II mixer at 250 rpm until the resulting mixture was uniform (40 min in this example).

[0061] The thermal insulation coating composition was prepared using the binder (described above) as follows: 730.89g of the binder prepared as described above (77.43 wt%) and UCAR™ Filmer IBT (8.10 g: 0.86 wt%) were added to the binder, and the resulting mixture was stirred with a propeller blade on a Lightning II mixer at 250 rpm. Ti Pure™ R-741 Titanium Dioxide Slurry (52.81 g: 5.60 wt%) was added, and then 15 wt% Sodium Nitrite solution in water (8.33 g: 0.89 wt%) was added, and mixing continued. Next, a solution of 25 % Pluronic P84 solution in water (28.89 g: 3.06 wt%) was added. The container was covered, and the contents continued mixing at 250 rpm for 40 minutes until the resulting composition was uniform. Mixing speed was then increased to 400 rpm. The insulative filler, Enova IC-3110 Aerogel (108.00 g: 11.44wt%) portion was added slowly, increasing the rpm to 800 as needed tomaintain a vortex in the binder. Next, ACRYSOL™ RM-12W Rheology Modifier (5.71 g: 0.60 wt%) was loaded dropwise and ACRYSOL™ RM-8W Rheology Modifier (1.18 g: 0.12 wt%) was loaded drop wise, then mixed for 10 minutes at 800 rpm.

[0062] In this Inventive Example 2, a thermal insulation coating composition was prepared as described in Inventive Example 1, except RHOPLEX™ EC-1791 was replaced with RHOPLEX™ 2019RX, and different amounts of some starting materials were used, as shown below in Table 2.

[0063] In this Comparative Example 1, RHOPLEX™ EL2000 (350 g: 80.46 wt%) and UCAR™ Filmer IBT (5.25 g: 1.21 wt%) were combined and stir with a propeller blade on a Lightning II mixer at 250 rpm. Next, DOWSIL™ 8590 Additive (1.05 g: 0.24 wt%) was loaded into the container, and the contents continued to stir with a propeller blade on the Lightning II mixer at 250 rpm until the resulting mixture was uniform. Next Ti Pure™ R-741 Titanium Dioxide Slurry (31.01 g: 7.13 wt%) was added, and then 15 wt% Sodium Nitrite solution in water (3.84 g: 0.88 wt%) was added, and mixing continued. A solution of 25 wt% PLURONIC™ P84 in water (5.46 g: 1.25 wt%) was added. The container was covered, and mixing continued at 250 rpm for 40 minutes until the binder blend was uniform. Mixing speed was then increased to 400rpm.

[0064] Next, ENOVA™ IC-3110 Aerogel (35.56 g: 8.18 wt%) was added portion wise slowly, increasing the rpm to 800 as needed to maintain a vortex in the binder blend. ACRYSOL™ RM-12W Rheology Modifier (1.88 g: 0.43 wt%) was added dropwise, and ACRYSOL™ RM-8W Rheology Modifier (0.94 g: 0.22 wt%) was added dropwise, then the contents of the container were mixed for 10 minutes at 800 rpm.In this Comparative Example 2, RHOPLEX™ EC-3814 (350.00 g; 75.57 wt%) and DOWSIL™ 6694 (28.00 g; 6.05 wt%) were added to a container and stirred with a propeller blade on a Lightning II mixer at 250 rpm. DOWSIL™ 8590 Additive (1.13 g: 0.25 wt%) was added. Ammonium hydroxide (3.67 g; 0.79 wt%) was added. The container contents were stirred with a propeller blade on a Lightning II mixer at 250 rpm until the mixture was uniform (40 min in this example). Next, UCAR™ Filmer IBT (5.25 g: 1.13 wt%) was added, and the resulting mixture was stirred with a propeller blade on a Lightning II mixer at 250 rpm.

[0065] Next, Ti Pure™ R-741 Titanium Dioxide Slurry (33.49 g: 7.23 wt%) was loaded into the container, and then 15 wt% Sodium Nitrite solution in water (4.32 g: 0.93 wt%) was loaded, and mixing continued. A solution of 25 wt% PLURONIC™ P84 in water (5.46 g: 1.18 wt%) was added, the container was covered, and mixing continued at 250 rpm for 40 minutes until the binder blend was uniform. Mixing speed was increased to 400rpm. Next, ENOVA™ IC-3110Aerogel (29.00 g: 6.26 wt%) was added portion wise slowly, increasing the rpm to 800 as needed to maintain a vortex in the binder blend. Next, ACRYSOL™ RM-12W Rheology Modifier (1.88 g: 0.41 wt%) was added dropwise, and ACRYSOL™ RM-8W Rheology Modifier (0.94 g: 0.20 wt%) was added dropwise, then the resulting mixture was mixed for 10 minutes at 800 rpm.

[0066] in this Comparative Example 3 FORMASHIELD™ 12 (325.00 g; 70.92 wt%) and DOWSIL™ IE-6683 (64.15 g; 14.00 wt%) were loaded to a container and stirred with a propeller blade on a Lightning II mixer at 250 rpm. DOWSIL™ 8590 Additive (1.17 g: 0.25 wt%) was added to the container. Stirring continued with a propeller blade on a Lightning II mixer at 250 rpm until the mixture was uniform (40 min in this example). UCAR™ Filmer IBT (4.87 g: 1.06 wt%) was added, and the mixture was stirred with a propeller blade on a Lightning II mixer at 250 rpm.

[0067] Next, Ti Pure™ R-741 Titanium Dioxide Slurry (27.58 g: 6.02wt%) and 15 wt% Sodium Nitrite solution in water (4.29 g: 0.94 wt%) were added, and mixing continued. A solution of 25 wt% PLURONIC™ P84 in water (5.07 g: 1.11 wt%) was added, and the container was covered. Mixing continued at 250 rpm for 40 minutes until the binder blend was uniform. Mixing speed was increased to 400 rpm.

[0068] ENOVA™ IC-3110 Aerogel (23.50 g: 5.13 wt%) was added portion wise slowly, increasing the rpm to 800 as needed to maintain a vortex in the binder blend. ACRYSOL™ RM-12W Rheology Modifier (1.75 g: 0.38 wt%) was added dropwise, and ACRYSOL™ RM- 8W Rheology Modifier (0.87 g: 0.19 wt%) was added dropwise. The resulting mixture was mixed for 10 minutes at 800 rpm.

[0069] In this Comparative Example 4 FORMASHIELD™ 12 (375.00 g; 77.70 wt%) and DOWSIL™ 8004 Waterborne Resin (34.81 g; 7.21 wt%) were loaded to a container and stirred with a propeller blade on a Lightning II mixer at 250 rpm. DOWSIL™ 8590 Additive (1.23g: 0.25 wt%) was added to the container. Stirring continued with a propeller blade on a Lightning II mixer at 250 rpm until the mixture was uniform (40 min in this example). UCAR Filmer IBT (5.62 g: 1.17 wt%) was added, and the mixture was stirred with a propeller blade on a Lightning II mixer at 250 rpm.

[0070] Next, Ti Pure™ R-741 Titanium Dioxide Slurry (29.05 g: 6.02 wt%) and 15 wt% Sodium Nitrite solution in water (4.54 g: 0.94 wt%) were added, and mixing continued. A solution of 25 wt% Pluronic P84 in water (5.85 g: 1.21 wt%) was added, and the container was covered. Mixing continued at 250 rpm for 40 minutes until the binder blend was uniform. Mixing speed was increased to 400 rpm.

[0071] Enova IC-3110 Aerogel (23.5 g: 4.87 wt%) was added portion wise slowly, increasing the rpm to 800 as needed to maintain a vortex in the binder blend. ACRYSOL™ RM-12W Rheology Modifier (2.01 g: 0.42 wt%) was added dropwise, and ACRYSOL™ RM-8W Rheology Modifier (1.01 g: 0.21 wt%) was added dropwise. The resulting mixture was mixed for 10 minutes at 800 rpm.

[0072] Tn this Comparative Example 5 RHOPLEX™ EC-1791 (600.00 g; 71.16 wt%) and DOWSIL™ 8004 Waterborne Resin (63.50 g; 7.53 wt%) were loaded to a container and stirred with a propeller blade on a Lightning II mixer at 250 rpm. DOWSIL™ 8590 Additive (1.99 g: 0.24 wt%) was added to the container. Stirring continued with a propeller blade on a Lightning II mixer at 250 rpm until the mixture was uniform (40 min in this example). UCAR Filmer IBT (9.00 g: 1.07 wt%) was added, and the mixture was stirred with a propeller blade on a Lightning II mixer at 250 rpm.

[0073] Next, Ti Pure™ R-741 Titanium Dioxide Slurry (58.78 g: 6.97 wt%) and 15 wt% Sodium Nitrite solution in water (7.59 g: 0.90 wt%) were added, and mixing continued. A solution of 25 wt% Pluronic P84 in water (20.33 g: 2.41 wt%) was added, and the container was covered. Mixing continued at 250 rpm for 40 minutes until the binder blend was uniform. Mixing speed was increased to 400 rpm.

[0074] ENOVA™ IC-3110 Aerogel (76.00 g: 9.01 wt%) was added portion wise slowly, increasing the rpm to 800 as needed to maintain a vortex in the binder blend. ACRYSOL™ RM-12W Rheology Modifier (4.02 g: 0.48 wt%) was added dropwise, and ACRYSOL™ RM- 8W Rheology Modifier (2.01 g: 0.24 wt%) was added dropwise. The resulting mixture was mixed for 10 minutes at 800 rpm.

[0075] Corrosion rating and dirt pick up (DPU) were evaluated according to the test methods below. Results are shown below in Table 2.Table 2

[0076] In Table 2, 10 indicates best corrosion rating, i.e., least corroded sample, and 0 indicates worst corrosion rating (most corroded sample); and +++ indicates best performance (best DPU rating), ++ denotes second best, + denotes third best, and — indicates worst performance, - denotes next to worst, and - denotes performance less than + and better than -. Table 2 shows that the samples containing A) a first acrylic polymer with a modulus < 50 psi, a second acrylic polymer with a modulus > 5,000 psi, and C) a silicone elastomer produced thermal insulation coatings with superior corrosion resistance under the conditions tested.

[0077] In this Reference Example 3, samples of thermal insulation coating compositions were prepared as follows: First, a binder was prepared by loading RHOPLEX™ EC-1791 (300.00 g; 46.6 wt%), and MAINCOTE™ PR-71 (200.00 g; 31.0 wt%) to a container and stirring with a propeller blade on a Lightning II mixer at 250 rpm. Next, Dowsil 8590 Additive (1.50 g: 0.2 wt%) was loaded into the container, and the contents continued to stir with a propeller blade on the Lightning II mixer at 250 rpm until the resulting mixture was uniform (40 min in this example).

[0078] Next, a thermal insulation coating was prepared as follows: 501.50 g of the binder prepared as described above (77.8 wt%) and UCAR™ Filmer IBT (7.50 g: 1.2 wt%) were combined and stirred with a propeller blade on a Lightning II mixer at 250 rpm. Next, Ti Pure™ R-741 Titanium Dioxide Slurry (44.30 g: 6.9 wt%) was added, and then 15 wt% Sodium Nitrite solution in water (5.68 g: 0.1 wt%) was added, and mixing continued. A solution of 25 wt% Pluronic P84 in water (7.80 g: 1.2 wt%) was added, the container was covered, and mixing continued at 250 rpm for 40 minutes until the mixture was uniform. Mixing speed was increased to 400 rpm. Enova IC-31 10 Aerogel (56.54 g: 8.8 wt%) was added portion wise slowly, increasing the rpm to 800 as needed to maintain a vortex in the mixture. ACRYSOL™ RM- 12W Rheology Modifier (2.69 g: 0.4 wt%) was added dropwise, and ACRYSOL™ RM-8W Rheology Modifier (1.34 g: 0.2 wt%) was added dropwise, then the mixture was mixed for 10 minutes at 800 rpm.

[0079] The samples were evaluated for corrosion and dirt pick up resistance according to the test methods below. The results are in Table 3.

[0080] The data in Tables 2 and 3 show that a combination of the first acrylic polymer with modulus< 50 psi and the second acrylic polymer with modulus > 5,000 psi provided better performance that samples with only one of the two acrylic polymers. However, samples thatcontained a silicone resin in addition to the first acrylic polymer with modulus < 50 psi and the second acrylic polymer with modulus > 5,000 psi produced a thermal insulation coating with both good corrosion rating and good dirt pick up resistance as shown by, for example, Inventive example 2, which contained DOWSIL™ 8004 and had better corrosion resistance than the comparative example in Table 3, which contained the same two acrylic polymers but without the silicone elastomer. And, Inventive Example 1 had the same two acrylic polymers a comparative example in Table 3, however, the data in Table 2 indicate that Inventive Example 1 had better corrosion resistance and better dirt pick up resistance than the comparative example in Table 3 that used the same two acrylic polymers, but without the silicone elastomer.Industrial Applicability

[0081] The examples above demonstrate that the binder and thermal insulation coating composition of the present invention provide the unexpected benefit of both good corrosion resistance (10 or 9) corrosion rating according to the corrosion test method herein and good dirt pick up resistance (DPU) rating according to the test method herein. Furthermore, thermal insulation coatings can be prepared from the silicone - acrylic binder and the thermal insulation coating composition described herein with low thermal conductivity. For example, without wishing to be bound by theory it is thought that a thermal insulation coating with a thermal conductivity of > 0.045 W / mK. The single coat thickness of the thermal insulation coating may be up to 400 mil on a horizontal surface or up to 250 mil on a vertical surface. Alternatively, the single coat thickness may be 20-400 mil; alternatively 80-400 mil on a horizontal surface.Alternatively, the single coat thickness may be 20-250 mil; alternatively 80-250 mil on a vertical surface.Test Methods

[0082] The following test methods were used to measure properties herein, unless otherwise indicated. Samples were coated on metal substrates, dried, and corroded according to ASTM B- 117. The corrosion was measured according to ASTM Standard D1654 - 08 Standard Test Method for Evaluation of Painted or Coated Specimens Subjected to Corrosive Environments.

[0083] Dirt pick-up resistance test method was performed as follows:1. Prepare panels. Draw-down emulsion or blend of emulsions at 4mil wet thickness on 3x6” chromate pre-treated aluminum Q-panel with drawdown bar. Allow to ambiently dry for 7 days.2. Prepare dirt mixture. Weigh 10g KMI Industrial Minerals MIOX™ Sub Micro 5 FezCh + 35g DI water into MAX 60 dental cup. Dental speed mix at 2,000rpm for 2min.3. Soil panel. Pipette 0.2g drop wise onto panel (5 drops with pipettes used for this test). Spread dirt mixture onto panel with small foam paint brush, horizontally on the same path 10 times.4. Rinse panel. Hold soiled part of panel under cold sink water for lOsec. Pat dry.5. Compare & rate all panels side-by-side.

[0084] Modulus Measurements of the acrylic polymers were performed as follows: Films for Young’s modulus measurements were prepared by adding 15-20 g of emulsions as received to 2.5" x 3" Teflon molds clamped on top of release liners. The films were dried at room temperature for 7 days. The dried films were cut into a dog-bone shape using a DIN S2 die. Strain-stress curves were collected on an MTS Alliance RT-5 at 20.0 in / min using a 100 N load cell. Young's Modulus was automatically calculated using the instrument software based on the slope at the low-strain section of the strain-stress curve. Measurements were made with 4 dog-bones per material.

[0085] Particle Size Measurements were made as follows: A sample was prepared by diluting 0.1 g of an emulsion (corresponding to any of starting materials I), II), or III) described herein) in 20 mL of water. Particle size was measured using a Mastersizer™ 3000 laser diffraction particle size analyzer from Malvern Instruments. The average particle size expressed as volume- averaged median diameter, Dv50, is used to address the particle size of the first (soft) acrylic polymer and second (hard) acrylic polymer. Particle size ratio may be calculated by Dv50 of the first acrylic polymer divided by Dv50 of the second acrylic polymer.Definitions and Usage of Terms

[0086] All amounts, ratios, and percentages herein are by weight, unless otherwise indicated by the context of the specification. The articles ‘a’, ‘an’, and ‘the’ each refer to one or more, unless otherwise indicated by the context of specification. The singular includes the plural unless otherwise indicated by the context of the specification. The SUMMARY and ABSTRACT are hereby incorporated by reference. The amounts of all starting materials in a composition total 100%. The transitional phrases “comprising”, “consisting essentially of”, and “consisting of” are used as described in the Manual of Patent Examining Procedure Ninth Edition, Revision 08.2017, Last Revised January 2018 at section §2111.03 I., IL, and III. Any feature or aspect of the invention may be used in combination with any other feature or aspect recited herein. The abbreviations used herein have the definitions in Table 5.Table 5 - Abbreviations

Claims

CLAIMS:

1. A binder comprising:A) a first acrylic polymer with a Young’s modulus < 50 psi,B) a second acrylic polymer with a Young’s modulus > 5,000 psi,C) a silicone elastomer prepared by reacting starting materials comprising a bis-hydroxyl terminated polydiorganosiloxane and a self catalytic crosslinker,G) a surfactant,K) water, optionally D) an antifoam, optionally E) a coalescing solvent, and optionally F) a pH modifier.

2. The binder of claim 1 , wherein the first acrylic polymer has a modulus of 6 psi to 40 psi.

3. The binder of claim 1 or claim 2, wherein the second acrylic polymer has a modulus of 5,800 to 14,000 psi.

4. The binder of any one of claims 1 to 3, where bis-hydroxyl-terminated polydiorganosiloxane comprises formulaeach R1is independently selected from the group consisting of monovalent hydrocarbon groups and monovalent halogenated hydrocarbon groups, and subscript z is an integer with an average value of 500 to 5,000.

5. The binder of any one of claims 1 to 4, where the self catalytic crosslinker comprises unit formula: (R23SiOi / 2h(R22SiO2 / 2) (R2R3SiO2 / 2)b, where each R2is an independently selected alkyl group of 1 to 8 carbon atoms, each R3is an independently selected hydroxyl amine group of formula -ONR22, subscript a is 0 or a positive integer, andsubscript b > 2.

6. The composition of any one of claims 1 to 5, where the binder comprises:20 to 53 weight parts of A) the first acrylic polymer,0.01 to 25 weight parts of B) the second acrylic polymer,0.002 to 1 1 weight parts of C) the silicone elastomer,0 to 1 weight parts of D) the antifoam,0 to 5 weight parts of E) the coalescing solvent,> 0 weight parts of F) the pH modifier,27 to 80 weight parts of K) water, and 0.0005-7 weight parts of G) the surfactant.

7. A method for preparing the binder of any one of claims 1 to 6, wherein the method comprises:1) homogenizing starting materials comprising:I) a first aqueous emulsion comprisingA) the first acrylic polymer, a first surfactant, and water;II) a second aqueous emulsion comprisingB) the second acrylic polymer, a second surfactant, and water;III) a third aqueous emulsion comprisingC) a polyorganosiloxane elastomer comprising a reaction product ofC-l) the bis-hydroxyl terminated polydimethylsiloxane, C-2) the self catalytic crosslinker, a third surfactant, and water; optionally 2 ) during and / or after step ), adding an additional starting material selected from the group consisting of the antifoam, the coalescing solvent, the pH modifier, and a combination of two or more thereof.

8. A thermal insulation coating composition comprising:A) a first acrylic polymer with a modulus < 50 psi,B) a second acrylic polymer with a modulus > 5,000 psi,C) a silicone elastomer,D) a surfactant,K) water,G) an antifoam,H) an insulative filler,J) a flash rust inhibitor, optionally I) a metal oxide, optionally F) a pH modifier, optionally E) a coalescing solvent, and optionally L) a rheology modifier.

9. The thermal insulation coating composition of claim 8, where the composition comprises:17 weight% to 45 weight% of A) the first acrylic polymer,0.004 weight% to 25 weight% of B) the second acrylic polymer,0.003 weight% to 11 weight% of C) the silicone elastomer,0 to 1 weight% of D) the antifoam,0 to 5 weight% of E) the coalescing solvent,0 to 1 weight% of F) the pH modifier,> 0.00008 weight% to 10 weight% of G) the surfactant,2 weight% to 30 weight% of H) the insulative filler,2.5 weight% to 10 weight% of I) the metal oxide,0. 1 weight% to 1.2 weight% of J) the flash rust inhibitor,27 to 80% of K) the water, and0 to 5% of L) the rheology modifier.

10. The composition of claim 8 or claim 9, where H) the insulative filler comprises a hydrophobic aerogel.

11. A method for making a thermal insulation coating composition, wherein the method comprises:I) practicing the method of claim 7, thereby preparing the binder, optionally 2) adding G) a surfactant during and / or after step 1),3) adding H) an insulative filler to the binder prepared in step 1) or step 2) andhomogenizing to prepare a filled intermediate; and4) adding, to the filled intermediate, a slurry comprising I) a metal oxide, and a solution or slurry comprising J) a flash rust inhibitor before, during, or after any one of steps 1) to 3), and homogenizing, optionally 5) adding F) a pH modifier in step 1) when I) the first aqueous emulsion has pH < 8, II) the second aqueous emulsion has pH < 8, or both I) and II) have pH < 8;6) adding D) an antifoam before adding the hydrophobic aerogel insulative filler in step 3).

12. The method of claim 11, further comprising adding an additional starting material selected from the group consisting of an additional antifoam, E) a coalescing solvent, additional water, and a combination thereof.

13. The method of claim 11 or claim 12, further comprising adding a rheology modifier after step 2).

14. The method of any one of claims 11 to 13, where H) the insulative filler comprises a hydrophobic aerogel.

15. A method for insulating an apparatus, wherein the method comprises: optionally putting a primer on a metal surface of an apparatus; i) applying the thermal insulation coating composition of any one of claims 8 to 10 in a layer on the metal surface of the apparatus, and ii) removing water, thereby forming a thermal insulation coating on the metal surface of the apparatus; and optionally iii) repeating steps i) and ii) one or more times to increase thickness of the thermal insulation coating.

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