CN111386278A

CN111386278A - Ionic liquids

Info

Publication number: CN111386278A
Application number: CN201880076535.3A
Authority: CN
Inventors: S·E·保莱斯; 周宏英; S·斯瓦鲁普; B·A·康奈利; E·纯德利克; J·M·琼斯
Original assignee: PPG Industries Ohio Inc
Current assignee: PPG Industries Ohio Inc
Priority date: 2017-10-10
Filing date: 2018-10-10
Publication date: 2020-07-07
Also published as: WO2019073397A1; EP3694865A1; TW201922765A

Abstract

The present invention relates to a process for preparing alkoxysilane-functional ionic liquids comprising reacting a halogenated compound comprising halogen and active hydrogen functional groups, an isocyanate-functional alkoxy groupSilanes and ionizable compounds capable of forming ionic bonds with halogens to form alkoxysilane-functional ionic liquids. The present invention also relates to alkoxysilane-functional ionic liquids. The present invention also relates to an ionic liquid for use in a coating composition comprising: an ionic liquid comprising a salt group and a first functional group; a film-forming polymer comprising a second functional group; and a curing agent comprising a third functional group, wherein the first functional group is reactive with at least one of the second functional group and the third functional group.

Description

Ionic liquids

Technical Field

The present invention relates to a process for producing ionic liquids and ionic liquids produced thereby as well as coatings and coating compositions comprising ionic liquids.

Background

Ionic liquids are salts with relatively low melting points. Some ionic liquids may be liquids at ambient temperatures or lower. They may also be referred to as liquid electrolytes, ionic melts, ionic fluids, molten salts, liquid salts, or ionic glasses.

Ionic liquids are of interest for many potential applications. Ionic liquids have proven to be effective solvents and useful electrolyte materials due to their conductivity. They are utilized for their catalytic activity, among other uses.

Disclosure of Invention

Disclosed herein is a method of making an alkoxysilane-functional ionic liquid comprising: reacting a halo compound comprising halogen and active hydrogen functional groups, an isocyanate-functional alkoxysilane, and an ionizable compound capable of forming an ionic bond with the halogen to form an alkoxysilane-functional ionic liquid.

Also disclosed herein are alkoxysilane-functional ionic liquids prepared by the process of the present invention.

The present invention also relates to a coating composition comprising: an ionic liquid comprising a salt group and a first functional group; a film-forming polymer comprising a second functional group; and a curing agent comprising a third functional group; wherein the first functional group is reactive with at least one of the second functional group and the third functional group.

The present invention also relates to a coating composition comprising: an ionic liquid comprising a salt group and a first functional group; and a self-curing film-forming polymer comprising a second functional group; wherein the first functional group is reactive with the second functional group.

The present invention further relates to a method of reducing the adhesion of ice to a substrate surface comprising applying the coating composition of the present invention to a substrate surface and at least partially curing the coating composition to form a coating.

The present invention also relates to a coating formed from the coating composition of the present invention in an at least partially cured state.

The invention further relates to a substrate coated with a coating composition according to the invention in an at least partially cured state.

Detailed Description

The present invention relates to a process for preparing alkoxysilane-functional ionic liquids comprising reacting a halo compound comprising halogen and active hydrogen functional groups, an isocyanate-functional alkoxysilane, and an ionizable compound capable of forming an ionic bond with halogen, to form an alkoxysilane-functional ionic liquid.

Ionic liquids are salts that are liquid (i.e., molten) at a temperature of less than or equal to 400 ℃ (such as at a temperature of less than 100 ℃, such as at a temperature of less than or equal to 75 ℃, such as at a temperature of less than or equal to room temperature (i.e., 25 ℃) at atmospheric pressure (101, 325 Pa). The ionic liquid comprises salt groups comprising a cation and an anion. Suitable cations may comprise: for example, imidazolium; pyridinium salts; pyrrolidinium; a phosphonium; ammonium; guanidinium; isouronium; thiouronium; and a sulfonium group. Suitable anions may include: for example, halide anions (i.e., halides), such as fluoride, chloride, bromide, and iodide; tetrafluoroborate radical; hexafluorophosphate radicals; bis (trifluoromethylsulfonyl) imide; tris (pentafluoroethyl) trifluorophosphate (FAP); trifluoromethanesulfonic acid radical; trifluoroacetic acid radical; methyl sulfate radical; octyl sulfate radical; thiocyanate; an organic borate; and p-toluenesulfonate. The salt group may comprise any combination of the above cations and anions, and other suitable cations or anions not listed may be used.

Halogenated compounds include compounds containing at least one halogen atom substituent and at least one active hydrogen functional group. As used herein, the term "halogen" or "halogen atom" refers to an element included in IUPAC group 17 of the periodic table of elements, and includes, for example, fluorine, chlorine, bromine, and iodine. As used herein, the term "active hydrogen functional groups" refers to those groups that are reactive with isocyanates as determined by the Zercwitnoff test as described in juournal OF THE AMERICAN CHEMICAL SOCIETY, volume 49, page 3181 (1927), and may include hydroxyl groups, primary amine groups, secondary amine groups, thiol groups, and combinations thereof.

The halogenated compound may comprise a halohydrin. Halogenated alcohols include alcohols having at least one halogen substituent in a pendant or terminal position. The alcohol may comprise a linear or branched C having a hydroxyl functionality in a pendant or terminal position₁-C₁₂An alkyl chain. The alcohol may comprise ethanol, propanol, butanol, isobutanol, pentanol, hexanol, heptanol (septanol), octanol, nonanol, decanol, undecanol, or dodecanol. The halogen may comprise fluorine, chlorine, bromine, iodine, or combinations thereof. Non-limiting examples of suitable halohydrins include 2-chloroethanol, 3-chloro-1-propanol, 4-chloro-1-butanol, 3-chloro-1-butanol, 5-chloro-1-pentanol, 6-chloro-1-hexanol, and the like, and combinations thereof.

The halogenated compound may comprise a halogenated polymeric compound comprising halogen and active hydrogen functional groups, which may optionally comprise more than one halogen and active hydrogen functional groups per molecule. Halogen polymerizationThe compound may comprise, for example, the reaction product of an epoxy-functional polymeric compound with a haloacid, halohydrin, haloamine, or halothiol, which reaction produces a halogenated polymeric compound comprising halogen and hydroxyl functionality resulting from a ring-opening reaction of the epoxide functionality. The epoxy functional polymeric compound may contain, for example, 1 to 6 epoxy functional groups. The epoxy-functional polymeric compound may comprise: substituted or unsubstituted C₁-C₃₆A mono-or polyglycidyl ether of an alkyl group; substituted or unsubstituted C₆-C₃₆A mono-or polyglycidyl ether of an aromatic group; and substituted or unsubstituted C₃-C₃₆A mono-or polyglycidyl ether of a cycloaliphatic group; number average molecular weight (M)_n) A mono-or polyglycidyl ether of a polyester of greater than 150 g/mol; number average molecular weight (M)_n) A mono-or polyglycidyl ether of a polyether of greater than 200 g/mol; number average molecular weight (M)_n) A mono-or polyglycidyl ether of a polyurethane of greater than 500 g/mol; or number average molecular weight (M)_n) More than 1, 000g/mol of a monoglycidyl ether or polyglycidyl ether of an acrylic resin. The halogenated acid may comprise: carboxy-functional substituted or unsubstituted C further comprising a halogen substituent₁-C₃₆Alkanediyl or C₆-C₃₆A divalent aromatic radical. According to the invention, the divalent aromatic radical may be, for example, a substituted or unsubstituted divalent phenyl radical. The halohydrin may comprise: hydroxy-functional substituted or unsubstituted C further comprising halogen substituents₁-C₃₆Alkanediyl or C₆-C₃₆A divalent aromatic radical. The halogenated amine may comprise: amino-functional substituted or unsubstituted C further comprising halogen substituents₁-C₃₆Alkanediyl or C₆-C₃₆A divalent aromatic radical. The halogenated thiol may comprise: thiol-functional substituted or unsubstituted C further comprising a halogen substituent₁-C₃₆Alkanediyl or C₆-C₃₆A divalent aromatic radical. The halogen substituents may comprise: fluorine, chlorine, bromine, iodine, or combinations thereof. For each of the epoxy-functional compounds which undergo a ring-opening reaction with the acid group of the halogenated acidEpoxy groups, halogenated polymeric compounds comprising the reaction product of an epoxy functional polymeric compound and a haloacid may comprise hydroxyl groups, ether groups, ester groups, and halogen substituents.

The isocyanato-functional alkoxysilane may comprise: an isocyanate-functional monoalkoxysilane, dialkoxysilane or trialkoxysilane. For example, the isocyanate functional alkoxysilane may comprise an isocyanate functional trialkoxysilane according to the following formula (I):

wherein R is₆Is alkanediyl, and R₇Is C₁-C₄An alkyl group. The alkanediyl R6 may contain a straight chain or branched C₁-C₃₆Alkanediyl, straight-chain or branched C₃-C₃₆Cycloaliphatic or straight-chain or branched C₆-C₃₆An aromatic group. C₁-C₄Each alkyl group R7 independently forms an alkoxy group with the oxygen atom to which they are attached, such as, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, or combinations thereof. Non-limiting examples of isocyanato-functional alkoxysilanes can include, but are not limited to, isocyanatopropyltrimethoxysilane, isocyanatobutyltrimethoxysilane, isocyanatopentyltrimethoxysilane, isocyanatohexyltrimethoxysilane, and the like.

The ionizable compound capable of forming an ionic bond with a halogen may comprise: compounds comprising at least one heteroatom, such as nitrogen, phosphorus and/or sulfur, such as, for example, imidazole, pyridine, pyrrolidine, phosphine, ammonia, guanidine, urea, thiourea or thioether. Such compounds may be substituted or unsubstituted. Non-limiting examples of suitable imidazole compounds include N-methylimidazole, 1-ethylimidazole, 2, 4, 5-triphenylimidazole, and the like.

The various reactions and reaction steps described herein may be carried out in the presence of a catalyst. The catalyst may comprise a metal catalyst, such as a tin catalyst. Non-limiting examples of suitable tin catalysts include dibutyltin oxide, dibutyltin octoate, dibutyltin dilaurate, and the like.

According to the invention, the method may comprise: a first step comprising reacting a halo compound and an isocyanate-functional alkoxysilane to form a haloalkoxysilane; and a second step comprising reacting the haloalkoxysilane with an ionizable compound to form an alkoxysilane-functional ionic liquid. In the second step of the process, an ionizable compound replaces the halogen group of the haloalkoxysilane to form a compound containing a cationic group, such as, for example, imidazolium; pyridinium salts; pyrrolidinium; a phosphonium; ammonium; guanidinium; isouronium; thiouronium; or sulfonium, and generates halide anions (i.e., halide ions), such as, for example, fluoride, chloride, bromide, or iodide. The cationic group can form an ionic bond with a halide ion to form an ionic liquid. Non-limiting examples of the first and second steps are provided below in scheme 1 and scheme 2, discussed below and provided in scheme 1-A and scheme 1-B and scheme 2-A and scheme 2-B.

Scheme 1 illustrates the two-step formation of a monomeric ionic liquid according to the present invention.

Scheme 1

Non-limiting examples of a first step comprising reacting a halo compound with an isocyanato-functional alkoxysilane to form a reaction product comprising a haloalkoxysilane are provided below in scheme 1-a. As shown in scheme 1-A, 3-chloro-propanol is reacted with isocyanatopropyltrimethoxysilane to form a reaction product comprising chlorinated urethane trimethoxysilane.

Scheme 1-A

Non-limiting examples of second step reactions comprising reacting a haloalkoxysilane with an ionizable compound to form an alkoxysilane-functional ionic liquid are provided below in scheme 1-B. Reacting a halotrimethoxysilane with N-methylimidazole to form a trimethoxysilane functional ionic liquid.

Scheme 1-B

Scheme 2 illustrates the formation of a monomeric or polymeric ionic liquid according to the present invention, wherein a halogenated compound is first produced by reacting an epoxy-functional compound with a haloacid, wherein n ≧ 1, such as 1 to 6, such as 2 to 6; and R is a monovalent or polyvalent substituted or unsubstituted C₁-C₃₆Chain alkyl, monovalent or polyvalent C₆-C₃₆Aromatic radical, monovalent or polyvalent C₃-C₃₆Alicyclic group, number average molecular weight (M)_n) Monovalent or polyvalent polyester groups of more than 200g/mol, number average molecular weight (M)_n) More than 200g/mol of monovalent or polyvalent polyether groups, monovalent or polyvalent acrylic resins having a number average molecular weight (Mn) of more than 500g/mol or monovalent or polyvalent polyurethane groups having a number average molecular weight (Mn) of more than 500 g/mol.

Scheme 2

Non-limiting examples of a first step comprising reacting a halo compound with an isocyanate-functional alkoxysilane to form a reaction product comprising a haloalkoxysilane are provided below in scheme 2-a. As shown in scheme 2-A, a monomeric (when n ≧ 1) or polymeric (when n ≧ 2, such as 2 to 6) halohydrin is reacted with isocyanatopropyltrimethoxysilane to form a reaction product comprising a monomeric or polymeric chlorinated urethane trimethoxysilane.

Scheme 2-A

Non-limiting examples of reactions for the second step comprising reacting a haloalkoxysilane with an ionizable compound to form an alkoxysilane-functional ionic liquid are provided below in scheme 2-B. Reacting monomeric or polymeric chlorinated urethane trimethoxy silane with N-methylimidazole to form a monomeric or polymeric trimethoxy silane functional ionic liquid.

Scheme 2-B

The ratio of isocyanate groups from the isocyanate-functional alkoxysilane to active hydrogen functional groups from the halo compound present in the first step of the process may be at least 1: 3, such as at least 1: 2, such as at least 1: 1.1, such as at least 1: 1, and may be no more than 3: 1, such as no more than 1.5: 1, such as no more than 1.1: 1, such as no more than 1: 1. The ratio of isocyanate groups from the isocyanate-functional alkoxysilane to active hydrogen functional groups from the halo-compound present in the first step of the process may be from 1: 3 to 3: 1, such as from 1: 2 to 1.5: 1, such as from 1: 1.1 to 1.1: 1.

The ratio of halogen substituents from the haloalkoxysilane to molecules of the ionizable compound can be at least 1: 3, such as at least 1: 2, such as at least 1: 1.1, such as at least 1: 1; and may be no more than 3: 1, such as no more than 1.5: 1, such as no more than 1.1: 1, such as no more than 1: 1. The ratio of halogen substituents from the haloalkoxysilane to molecules of the ionizable compound can be from 1: 3 to 3: 1, such as from 1: 2 to 1.5: 1, such as from 1: 1.1 to 1.1: 1.

According to the present invention, the process for preparing alkoxysilane-functional ionic liquids may be initiated by combining a halogenated compound with an optional organic solvent and catalyst in an inert gas atmosphere (e.g., nitrogen atmosphere) and mixing these components. The mixture can be mixed at room temperature or heated to an elevated temperature of 200 ℃ or less, such as, for example, at least 70 ℃. The isocyanato-functional alkoxysilane can be added dropwise over a period of time such as, for example, 30 minutes at elevated temperature. After the addition of the isocyanate functional alkoxysilane, the reaction mixture may be maintained at an elevated temperature for a sufficient time to allow the halo-compound and the isocyanate functional alkoxysilane to react. After the reaction is complete, the ionizable compound may be added dropwise to the reaction mixture over a period of time such as, for example, 10 minutes. After addition, the reaction mixture can be heated to reflux (e.g., 110.6 ℃ if toluene is the organic solvent) for a sufficient period of time to react the haloalkoxysilane with the ionizable compound to form the alkoxysilane-functional ionic liquid. The reaction mixture may then be cooled to a temperature such as, for example, 80 ℃. At said temperature, the stirring can be stopped. After a sufficient period of time, such as, for example, 10 minutes, the reaction mixture may be separated into a two-phase mixture comprising a first phase comprising the ionic liquid and a second phase comprising a solvent other than the ionic liquid and other organic compounds. The solvent-containing phase may be removed by decantation, and additional solvent may be removed by vacuum distillation using a vacuum pump.

The temperature and time period for reacting the halo-compound with the isocyanate-functional alkoxysilane may vary depending on the scale of the reaction, the exact reaction conditions, and the presence or absence of additional ingredients such as, for example, catalysts, but the time period may generally be determined by: the content of the reaction mixture was analyzed by FT-IR spectroscopy until no longer detectable at 2259cm^-1The isocyanate peak at (a), indicating that all of the isocyanate functional groups have been consumed and the reaction is complete and a haloalkoxysilane is formed. A "sufficient period of time" for forming the haloalkoxysilane can be, for example, at least 1 hour, such as at least 3 hours, and can be no more than 10 hours, such as no more than 6 hours, and can range from 1 hour to 10 hours, such as 3 hours to 6 hours.

The temperature and time period for reacting the haloalkoxysilane with the ionizable compound may vary depending on the scale of the reaction, the exact reaction conditions and the presence or absence of additional ingredients such as, for example, catalysts, but the time period may generally be determined by: the presence of unreacted ionizable compound is determined by analyzing the content of the reaction mixture by, for example, Thin Layer Chromatography (TLC) or Gas Chromatography (GC). The "sufficient period of time" for forming the alkoxysilane-functional ionic liquid may be, for example, at least 1 hour, such as at least 4 hours, and may not exceed 20 hours, such as not exceed 6 hours, and may range from 1 hour to 20 hours, such as 4 hours to 6 hours.

According to the invention, the method may comprise: a first step comprising reacting a halogenated compound and an ionizable compound to form an ionic liquid comprising active hydrogen functional groups; and a second step comprising reacting the ionic liquid comprising an active hydrogen functional group with an isocyanate functional alkoxysilane to form an alkoxysilane functional ionic liquid. In a first step of the process, an ionizable compound replaces the halogen group of the halogenated compound to form a compound comprising a cationic group, such as, for example, imidazolium; pyridinium salts; pyrrolidinium; a phosphonium; ammonium; guanidinium; isouronium; thiouronium; or sulfonium, and generates halide anions (i.e., halide ions), such as, for example, fluoride, chloride, bromide, or iodide. The cationic group can form an ionic bond with a halide ion to form an ionic liquid comprising an active hydrogen functional group. Non-limiting examples of the first and second steps are provided below in scheme 3 and scheme 4, and the various steps are discussed below and provided in scheme 3-a and scheme 3-B, and schemes 4-a and 4-B.

Scheme 3 illustrates the formation of monomeric ionic liquids.

Scheme 3

A non-limiting example of a first step of reacting a halogenated compound comprising active hydrogen functional groups with an ionizable compound to form an ionic liquid comprising active hydrogen functional groups is provided below in scheme 3-a. As shown in scheme 3-a, 3-chloro-propanol is reacted with N-methylimidazole to form a reaction product comprising an ionic liquid comprising a hydroxyl functional group.

Scheme 3-A

A non-limiting example of a second step reaction comprising reacting an ionic liquid comprising an active hydrogen functional group with an isocyanate-functional alkoxysilane to form an alkoxysilane-functional ionic liquid is provided below in scheme 3-B. As shown in scheme 3-B, an ionic liquid comprising hydroxyl functional groups is reacted with isocyanatopropyltrimethoxysilane to form a trimethoxysilane functional ionic liquid.

Scheme 3-B

Scheme 4 illustrates the formation of a monomeric or polymeric ionic liquid according to the present invention, wherein a halogenated compound is first produced by reacting an epoxy-functional compound with a haloacid, wherein n ≧ 1, such as 1 to 6, such as 2 to 6; and R is a monovalent or polyvalent substituted or unsubstituted C₁-C₃₆Chain alkyl, monovalent or polyvalent C₆-C₃₆Aromatic radical, monovalent or polyvalent C₃-C₃₆Alicyclic group, number average molecular weight (M)_n) More than 200g/mol of monovalent or polyvalent polyester groups, number-average molecular weight (M)_n) A mono-or polyvalent polyether group of more than 200g/mol, a number average molecular weight (M)_n) A mono-or polyvalent acrylic resin or a number-average molecular weight (M) of more than 500g/mol_n) More than 500g/mol of monovalent or polyvalent polyurethane groups.

Scheme 4

A non-limiting example of a first step of reacting a halogenated compound with an ionizable compound to form an ionic liquid comprising active hydrogen functional groups is provided below in scheme 4-a. As shown in scheme 4-a, monomeric (when N ≧ 1) or polymeric (when N ≧ 2, such as 2 to 6) halohydrins are reacted with N-methylimidazole to form reaction products containing monomeric or polymeric ionic liquids containing hydroxyl functional groups.

Scheme 4-A

A non-limiting example of a second step reaction comprising reacting an ionic liquid comprising an active hydrogen functional group with an isocyanate-functional alkoxysilane to form an alkoxysilane-functional ionic liquid is provided below in scheme 4-B. As shown in scheme 4-B, a monomeric or polymeric ionic liquid comprising hydroxyl functional groups is reacted with isocyanatopropyltrimethoxysilane to form a trimethoxysilane functional ionic liquid.

Scheme 4-B

The ratio of halogen substituents to molecules of the ionizable compound from the halogenated compound containing active hydrogen functional groups may be at least 1: 3, such as at least 1: 2, such as at least 1: 1.1, such as at least 1: 1, and may not exceed 3: 1, such as not exceed 1.5: 1, such as not exceed 1.1: 1, such as not exceed 1: 1. The ratio of halogen substituents to molecules of the ionizable compound from the halogenated compound containing active hydrogen functional groups may be from 1: 3 to 3: 1, such as from 1: 2 to 1.5: 1, such as from 1: 1.1 to 1.1: 1.

The ratio of active hydrogen functional groups from the ionic liquid comprising active hydrogen functional groups to isocyanate groups from the isocyanato-functional alkoxysilane may be at least 1: 3, such as at least 1: 2, such as at least 1: 1.1, such as at least 1: 1, and may not exceed 3: 1, such as not exceed 1.5: 1, such as not exceed 1.1: 1, such as not exceed 1: 1. The ratio of active hydrogen functional groups from the ionic liquid comprising active hydrogen functional groups to isocyanate groups from the isocyanato-functional alkoxysilane may be from 1: 3 to 3: 1, such as from 1: 2 to 1.5: 1, such as from 1: 1.1 to 1.1: 1.

According to the present invention, the process for preparing alkoxysilane-functional ionic liquids may be initiated by combining a halogenated compound comprising an active hydrogen functional group, an ionizable compound, and optionally an organic solvent in an inert gas atmosphere (e.g., a nitrogen atmosphere). The mixture can then be heated to an elevated temperature, such as, for example, the reflux temperature of the organic solvent (e.g., 110.6 ℃ if toluene is the organic solvent), and for a sufficient period of time to react the halohydrin with the ionizable compound to form the hydroxyl-functional ionic liquid. After the reaction was complete, the reaction temperature was cooled to 70 ℃. A catalyst may optionally be added to the reaction mixture and the isocyanato-functional alkoxysilane may be added dropwise over a period of time such as, for example, 30 minutes. After the addition of the isocyanate functional alkoxysilane, the reaction mixture may be maintained at an elevated temperature for a sufficient period of time to react the hydroxyl functional ionic liquid with the isocyanate functional alkoxysilane and form the alkoxysilane functional ionic liquid. The reaction mixture may then be cooled to a temperature such as, for example, 80 ℃. At said temperature, the stirring can be stopped. After a sufficient period of time, such as, for example, 10 minutes, the reaction mixture may be separated into a two-phase mixture comprising a first phase comprising the ionic liquid and a second phase comprising a solvent other than the ionic liquid and other organic compounds. The solvent-containing phase may be removed by decantation, and additional solvent may be removed by vacuum distillation using a vacuum pump.

The temperature and time period for reacting a halogenated compound comprising an active hydrogen functional group (e.g., a halohydrin) with an ionizable compound can vary depending on the scale of the reaction, the exact reaction conditions, and whether additional ingredients, such as catalysts, are present, but the time period can generally be determined by: the presence of unreacted ionizable compound is determined by analyzing the content of the reaction mixture by Thin Layer Chromatography (TLC) or Gas Chromatography (GC). The "sufficient period of time" for forming the ionic liquid comprising active hydrogen functional groups may be, for example, at least 2 hours, such as at least 4 hours, such as at least 8 hours, and may not exceed 24 hours, such as not exceed 18 hours, such as not exceed 12 hours, and may range from 2 hours to 24 hours, such as from 4 hours to 18 hours, such as from 8 hours to 12 hours.

The temperature and time period for reacting an ionic liquid comprising an active hydrogen functional group, e.g., a hydroxyl functional ionic liquid, with an isocyanate functional alkoxysilane may vary depending on the scale of the reaction, the exact reaction conditions, and whether additional ingredients such as, for example, catalysts are present, but the time period may generally be determined by: the content of the reaction mixture was analyzed by FT-IR spectroscopy until no longer detectable at 2259cm^-1The isocyanate peak at (a), indicating that all of the isocyanate functional groups have been consumed and the reaction is complete and an alkoxysilane functional ionic liquid is formed. A "sufficient period of time" for forming the haloalkoxysilane can be, for example, at least 0.5 hour, such as at least 1 hour, such as at least 3 hours, and can be no more than 24 hours, such as no more than 12 hours, such as no more than 8 hours, and can range from 0.5 hours to 24 hours, such as from 1 hour to 12 hours, such as from 3 hours to 8 hours.

The invention also relates to ionic liquids. Ionic liquids may optionally be produced by the process of the invention as described herein. Ionic liquids may comprise monomeric compounds having one salt group per molecule and are referred to as "monomeric ionic liquids". Ionic liquids may comprise compounds (including polymeric compounds) having at least two salt groups per molecule and are referred to as "polymeric ionic liquids". A non-limiting example of the ionic liquid of the present invention may be represented by one of the following formulas (II) to (IV).

According to formula (II) of the present invention, the ionic liquid may comprise a monomeric compound and may comprise or represent:

wherein R is₇Is substituted or unsubstituted C₁-C₃₆Alkanediyl or substituted or unsubstituted C₆-C₃₆A divalent aromatic group; r₂Is hydrogen, substituted or unsubstituted C₁-C₃₆Alkyl or substituted or unsubstituted C₆-C₃₆An aromatic group; r₃Is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group; r₄Is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group; r₅Is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group; r₆Is C₁-C₃₆Alkanediyl, straight-chain or branched C₃-C₃₆Or a linear or branched C₆-C₃₆An aromatic group of (a); and each R7 is independently substituted or unsubstituted C₁-C₄An alkyl group.

Non-limiting examples of suitable ionic liquids according to formula (II) include monomeric compounds represented by formula (III):

according to formula (IV) of the present invention, the ionic liquid may comprise a monomeric (when n ═ 1) compound or a polymeric compound, and may comprise or represent:

wherein n ≧ 1, such as 1 to 6, such as 2 to 6; r is monovalent or polyvalent substituted or unsubstituted C₁-C₃₆Chain alkyl, monovalent or polyvalent C₆-C₃₆Aromatic radical, monovalent or polyvalent C₃-C₃₆Alicyclic group, number average molecular weight (M)_n) Monovalent or polyvalent polyester groups of more than 200g/mol, number average molecular weight (M)_n) A mono-or polyvalent polyether group of more than 200g/mol, a number average molecular weight (M)_n) A mono-or polyvalent acrylic resin of more than 500g/mol, or a number-average molecular weight (M)_n) More than 500g/mol of monovalent or polyvalent polyurethane groups; r₁Is substituted or unsubstituted C₁-C₃₆Alkanediyl, or substituted or unsubstituted C₆-C₃₆An aromatic group; r2 is hydrogen, substituted or unsubstituted C₁-C₃₆Alkyl or substituted or unsubstituted C₆-C₃₆An aromatic group; r₃Is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group; r₄Is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group; r5 is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group; r₆Is C₁-C₃₆Alkanediyl, straight-chain or branched C₃-C₃₆Alicyclic radicals, or straight-chain or branched C₆-C₃₆An aromatic group; and each R7 is independently hydrogen or substituted or unsubstituted C₁-C₄An alkyl group.

The invention also relates to an ionic liquid for use in a coating composition comprising, consisting of or consisting essentially of: an ionic liquid comprising a salt group and a first functional group, a film-forming polymer comprising a second functional group, and a curing agent comprising a third functional group, wherein the first functional group is reactive with at least one of the second functional group and the third functional group.

According to the invention, the composition comprises an ionic liquid. As mentioned above, the ionic liquid may comprise salt groups comprising a cation and an anion. Non-limiting examples of the ionic liquid of the present invention may be represented by formulas (II) to (V). Formulas (II) through (IV) are discussed above.

According to formula (V) of the present invention, the ionic liquid may comprise a monomeric compound and may comprise or represent:

the ionic liquid further can comprise a first functional group. The functional group may comprise, for example, a hydroxyl group or an alkoxysilyl group. The presence of the first functional group enables the ionic liquid to react with other components of the coating composition through a chemical reaction with the first functional group. For example, incorporation of hydroxyl functionality can react the ionic liquid with a compound having a functional group reactive with hydroxyl groups (such as, for example, a compound having an isocyanate group). According to the present invention, the ionic liquid may comprise two or more first functional groups, and the two or more first functional groups may be the same or different functional groups.

The ionic liquid may further comprise a divalent organic group covalently bonding the salt group to the first functional group. The divalent organic group may comprise: substituted or unsubstituted, branched or unbranched alkanediyl, or substituted or unsubstituted, branched or unbranched C₆-C₃₆An aromatic group. The substitution of the alkyl or benzyl ring (if any) may comprise, for example, urethane, urea, ether or thioether functionality, and combinations thereof.

Number average molecular weight (Mn) and weight average molecular weight (M)_w) Can be determined by any technique known in the art, such as, for example, gel permeation chromatography using a Waters 2695 separation module with a Waters 410 differential refractometer (RI detector), polystyrene standards with molecular weights of about 500g/mol to 900,000 g/mol, Tetrahydrofuran (THF) and lithium bromide (LiBr) as eluents (flow rate of 0.5mL/min) and an Asahipak GF-510HQ chromatography column for separation.

When present as a monomeric compound, the ionic liquid may be present in the coating composition in an amount of at least 0.5 wt%, such as at least 2 wt%, such as at least 4 wt%, based on the total weight of the resin solids, and may be present in an amount of no more than 25 wt%, such as no more than 17 wt%, such as no more than 14 wt%, based on the total weight of the resin solids. According to the present invention, when present as a monomeric compound, the ionic liquid may be present in the coating composition in an amount of from 0.5 to 25 wt%, such as from 2 to 17 wt%, such as from 4 to 14 wt%, based on the total weight of resin solids.

When present as a polymeric compound, the ionic liquid may be present in the coating composition in an amount of at least 0.5 wt%, such as at least 10 wt%, such as at least 20 wt%, based on the total weight of resin solids, and may be present in an amount of no more than 50 wt%, such as no more than 40 wt%, such as no more than 35 wt%, based on the total weight of resin solids. According to the present invention, when present as a polymeric compound, the ionic liquid may be present in the coating composition in an amount of from 0.5 to 50 wt%, such as from 10 to 40 wt%, such as from 20 to 35 wt%, based on the total weight of resin solids.

When present as a monomeric or polymeric compound, the ionic liquid may be present in the coating composition in an amount such that the equivalent weight of salt groups in the resulting coating composition is at least 0.001 equivalent weight, such as at least 0.010, such as at least 0.014, such as at least 0.020, per gram of resin solids. When present as monomeric or polymeric compounds, the ionic liquid may be present in the coating composition in an amount such that the equivalent weight of salt groups in the resulting coating composition is from 0.001 to 0.300, such as from 0.010 to 0.250, such as from 0.014 to 0.200, such as from 0.014 to 0.150 per gram of resin solids.

The ionic liquid may be substantially free, essentially free, or completely free of alkali metals and alkaline earth metals. As used herein, "alkali metal" refers to elements included in group I of the periodic table other than hydrogen, including lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr). As used herein, "alkaline earth metal" refers to an element included in group II of the periodic table of elements, including beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra). As used herein, an ionic liquid is "substantially free" of alkali and alkaline earth metals if they are present in the ionic liquid in an amount of less than 5 weight percent, based on the total weight of the salt groups of the ionic liquid. As used herein, an ionic liquid is "essentially free" of alkali and alkaline earth metals if they are present in the ionic liquid in an amount of less than 1 weight percent, based on the total weight of the salt groups of the ionic liquid. As used herein, an ionic liquid is "completely free" of alkali and alkaline earth metals if the alkali and alkaline earth metals are not present in the ionic liquid (i.e., 0%).

According to the present invention, the coating composition may comprise a film-forming polymer. As used herein, the term "polymer" is intended to encompass oligomers and includes, but is not limited to, both homopolymers and copolymers. The film-forming polymer can be selected from, for example, polyol polymers, acrylic polymers, polyester polymers, alkyd polymers, polyurethane polymers, polyamide polymers, polyether polymers, epoxy polymers, polysiloxane polymers, copolymers thereof, and mixtures thereof. In general, these polymers may be any of these types of polymers prepared by any method known to those skilled in the art. Such polymers may be solvent-based or water-dispersible, emulsifiable or of limited water solubility. Suitable mixtures of film-forming polymers may also be used to prepare the compositions of the present invention.

The film-forming polymer may comprise a "second" functional group. The term "second" functional group is intended to distinguish, and not have other meanings, the functional group of the film-forming polymer from the functional group of any other component of the coating composition, such as, for example, the first functional group of an ionic liquid. For example, the term "second" functional group is not intended to refer to a functional group other than a different functional group present on the film-forming polymer. As such, the film-forming polymer may comprise one or more "second" functional groups in the absence of any other functional groups on the film-forming polymer. According to the present invention, the film-forming polymer may be difunctional, trifunctional or multifunctional, wherein the film-forming polymer comprises at least 2, at least 3 or more second functional groups. The second functional group on the film-forming resin can comprise any of a variety of reactive functional groups including, for example, hydroxyl functional groups, epoxy functional groups, thiol functional groups, siloxane functional groups, amino functional groups, or combinations thereof.

The polyol polymer may comprise any suitable polyhydroxyl-functional polymer known in the art. Non-limiting examples include polyester polyols, polyether polyols, polyurethane polyols, alkyd polyols, and acrylic polyols. Suitable mixtures of these polymers may also be used. Some examples of polyol polymers are described in more detail below.

The acrylic polymer may comprise any suitable acrylic polymer known in the art. Suitable acrylic polymers include addition polymers of one or more ethylenically unsaturated monomers, such as alkyl esters of acrylic or methacrylic acid, optionally with one or more other polymerizable ethylenically unsaturated monomers. Useful alkyl esters of acrylic or methacrylic acid include aliphatic alkyl esters containing from 1 to 30 (such as from 4 to 18) carbon atoms in the alkyl group. Non-limiting examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Suitable other copolymerizable ethylenically unsaturated monomers include vinyl aromatic compounds such as styrene and vinyl toluene; nitriles such as acrylonitrile and methacrylonitrile; vinyl and vinylidene halides such as vinyl chloride and vinylidene fluoride; and vinyl esters such as vinyl acetate.

Useful hydroxy-functional monomers include hydroxyalkyl acrylates and methacrylates, typically having 2 to 4 carbon atoms in the hydroxyalkyl group, such as hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, the hydroxy-functional adduct of caprolactone and hydroxyalkyl acrylate, and the corresponding methacrylate, as well as the β -hydroxy ester-functional monomers described below.

β -hydroxy ester functional monomers can be prepared from ethylenically unsaturated epoxy functional monomers and carboxylic acids having from about 2 to about 20 carbon atoms or from ethylenically unsaturated acid functional monomers and epoxy compounds containing at least 5 carbon atoms that are not polymerizable with ethylenically unsaturated acid functional monomers.

Useful ethylenically unsaturated epoxy-functional monomers for preparing β -hydroxy ester-functional monomers include, but are not limited to, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, methallyl glycidyl ether, 1: 1 (mole) adducts of ethylenically unsaturated monoisocyanates with glycidyl esters of hydroxy-functional monoepoxides (such as glycidyl) and polymerizable polycarboxylic acids (such as maleic acid).

Useful ethylenically unsaturated acid-functional monomers for preparing β -hydroxy ester-functional monomers include monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, dicarboxylic acids such as itaconic acid, maleic acid, and fumaric acid, and monoesters of dicarboxylic acids such as monobutyl maleate and monobutyl itaconate ethylenically unsaturated acid-functional monomers and epoxy compounds generally react in a 1: 1 equivalent ratio.epoxy compounds do not contain ethylenic unsaturation that would participate in free radical initiated polymerization reactions with the unsaturated acid-functional monomers.useful epoxy compounds include 1, 2-pentene oxide, styrene oxide, and glycidyl esters or ethers containing 8 to 30 carbon atoms such as butyl glycidyl ether, octyl glycidyl ether, phenyl glycidyl ether, and para (tert-butyl) phenyl glycidyl ether.suitable glycidyl esters of carboxylic acids include versatic acid (VERSATIC ACID)911 and glycidyl ester of acid (CARDURAE), each of which are commercially available from Shell Co.

The polyester polymer may comprise any suitable polyester polymer known in the art. Such polyester polymers may be prepared by condensation of a polyol and a polycarboxylic acid. Suitable polyols include, but are not limited to, ethylene glycol, propylene glycol, butylene glycol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, glycerol, trimethylolpropane, and pentaerythritol. Suitable polycarboxylic acids include, but are not limited to, succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and trimellitic acid. In addition to the polycarboxylic acids described above, functional equivalents of the acids, such as anhydrides or lower alkyl esters of the acids (such as methyl esters) in which they are present, may also be used. Polyesters derived from cyclic esters (such as caprolactone) may also be suitable. The polyester polymer may be linear or branched and may contain hydroxyl, carboxyl, anhydride, epoxy and/or carbamate functional groups.

The polyester polymer may comprise hydroxyl functional groups. For example, the polyester polymer can be prepared by selecting a reactant having an excess of hydroxyl functionality over carboxylic acid functional equivalents such that the resulting polyester polymer comprises hydroxyl functionality and a desired molecular weight.

The polyester polymer may contain epoxy functional groups prepared by art-recognized methods which may include first preparing a hydroxyl functional polyester which is then further reacted with epichlorohydrin.

The polyester polymer may comprise pendant and/or terminal carbamate functional groups prepared by first forming a hydroxyalkyl carbamate that is reactive with the polycarboxylic acid and polyol used to form the polyester. Hydroxyalkyl carbamates can be condensed with acid functional groups on the polyester to provide carbamate functionality. Carbamate functionality can also be incorporated into the polyester by reacting a hydroxy-functional polyester with a low molecular weight carbamate functional material via a transcarbamylation process or reacting isocyanic acid with a hydroxy-functional polyester.

The amide functionality may be incorporated into the polyester polymer by using suitable functional reactants in the preparation of the polymer, or by converting other functional groups to amino groups using techniques known to those skilled in the art. Likewise, other functional groups can be incorporated if desired using suitable functional reactants (if available) or conversion reactions (as desired).

The alkyd polymer may comprise any suitable alkyd polymer known in the art. The alkyd polymer may comprise the residue/reaction product of a polyester resin and an acid. The polyester resin may comprise the residue/reaction product of a diacid and/or anhydride and a polyol. The diacid can comprise phthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, and hexahydrophthalic acid. In addition to the diacids described above, functional equivalents of the diacids, such as the anhydrides in which they are present, including for example phthalic anhydride and maleic anhydride, may also be used. Combinations of diacids and/or anhydrides may also be used. The polyol can comprise ethylene glycol, propylene glycol, butylene glycol, 1, 6-hexanediol, neopentyl glycol, diethylene glycol, glycerol, trimethylolpropane, glycerol, pentaerythritol, and combinations thereof.

The acid may comprise an organic acid, such as a fatty acid. The fatty acid may comprise C₄-C₃₆Suitable unsaturated fatty acids can include, but are not limited to, α -linolenic acid, stearidonic acid, eicosapentaenoic acid, linoleic acid, gamma-linolenic acid, dihomo-gamma-linolenic acid, arachidonic acid, palmitoleic acid, elaidic acid, eicosenoic acid, oleic acid, elaidic acid, macrocephalic acid, crotonic acid, myristoleic acid (myristoleic acid), hexadecenoic acid, eicosadienoic acid, pinolenic acid, eleostearic acid, and midic acid.

The polyurethane polymer may comprise any suitable polyurethane polymer known in the art. Non-limiting examples of suitable polyurethane polymers having pendant and/or terminal hydroxyl functional groups are prepared by: the polyol is reacted with the polyisocyanate such that the OH/NCO (hydroxyl to isocyanate) equivalent ratio is greater than 1: 1, such that free hydroxyl groups are present in the product. Alternatively, isocyanate-functional polyurethanes can be prepared using similar reactants in relative amounts such that the OH/NCO equivalent ratio is less than 1: 1. As known to those skilled in the art, such reactions employ typical conditions (e.g., temperatures of 30 ℃ to 160 ℃ and up to ambient pressure) to form the urethane.

Organic polyisocyanates useful in preparing the polyurethane polymer include one or more aliphatic diisocyanates or higher polyisocyanates.

Examples of suitable aliphatic diisocyanates include linear aliphatic diisocyanates such as 1, 6-hexamethylene diisocyanate. Likewise, cycloaliphatic diisocyanates may be employed. Examples include isophorone diisocyanate and 4, 4' -methylene-bis- (cyclohexyl isocyanate). Examples of suitable higher polyisocyanates include 1, 2, 4-benzene triisocyanate and polymethylene polyphenyl isocyanates.

Terminal and/or pendant carbamate functional groups can be incorporated into the polyurethane by reacting a polyisocyanate with a polyol containing terminal/pendant carbamate groups. Alternatively, the carbamate functionality may be incorporated into the polyurethane by reacting the polyisocyanate with the polyol and the hydroxyalkyl carbamate or the isocyanate as separate reactants. Carbamate functionality can also be incorporated into the polyurethane by reacting a hydroxyl functional polyurethane with a low molecular weight carbamate functionality via a transcarbamylation process. Additionally, the isocyanate functional polyurethane may be reacted with a hydroxyalkyl carbamate to produce a carbamate functional polyurethane.

The amide functionality can be incorporated into the polyurethane polymer by using suitable functional reactants in the preparation of the polymer, or by converting other functional groups to amino groups using techniques known to those skilled in the art. Likewise, other functional groups can be incorporated if desired using suitable functional reactants (if available) or conversion reactions (as desired).

The polyamide polymer may comprise any suitable polyamide polymer known in the art. Non-limiting examples of polyamide polymers include condensation products of polyamines with oligomeric fatty acids. The polyamine may be diethylenetriamine, triethylenetetramine, tetraethylenepentamine and generally of the formula H (HNR)_nNH₂Those polyamines represented by wherein R is an alkanediyl group having 2 to 6 carbon atoms and n is an integer of 1 to 6. Oligomeric fatty acids may be those derived from the polymerization of dry or semi-dry oils or their free acids, or simple aliphatic alcohol esters of these acids, particularly from sources rich in linoleic acid. Simple dry or semi-dry oils include soybean oil, linseed oil, tung oil, perilla oil, cottonseed oil, corn oil, sunflower oil, safflower oil and dehydrated castor oil. Suitable fatty acids can also be obtained from tall oil, soap stock and other similar materials. Sufficient bis-during the preparation of the oligomeric fatty acidThe bond functionality of the fatty acids is most likely to combine by a Diels-Alder (Diels-Alder) mechanism to provide a mixture of binary and oligomeric fatty acids. These acids are referred to as dimers, trimers, etc. The term "oligomerized fatty acid" as used herein is intended to include any single oligomerized fatty acid as well as mixtures of oligomerized fatty acids, the latter generally comprising a major portion of dimer acid, a minor amount of trimer and higher polymerized fatty acids, and some residual monomer. If desired, oligomeric fatty acids which comprise predominantly the dimeric form of the acid and some residual monomers as well as small amounts of trimers and higher polymeric fatty acids can be hydrogenated and the hydrogenated products employed to form polyamides. In addition, the oligomerized fatty acid can be distilled to provide a relatively high dimer content of the acid.

The polyamine and oligomeric fatty acid condense at elevated temperatures to form polyamides. An excess of polyamine can be used to obtain an amine functional (such as amine terminated) polyamide, wherein the amine functional group is at a terminal position of the polyamide. Excess means that the ratio of equivalents of amine to equivalents of carboxyl groups is greater than 1. The amine number of the reaction product may be in the range of 50 to 80, as measured by any suitable technique known in the art.

The polyamide may be combined with an epoxidized olefin. The epoxidized olefin and polyamide are mixed and heated to a temperature of from 100 ℃ to 225 ℃ to form the product. The weight ratio of polyamide to epoxidized olefin may be (10-40) to (90-60). The reaction time varies depending on the temperature, but is usually 30 minutes to 3 hours.

The polyether polymer may comprise any suitable polyether polymer known in the art. For example, the polyether polymer may comprise polyether polyols formed from the alkoxylation of various polyols, for example, diols such as ethylene glycol, 1, 6-hexanediol, bisphenol a, and the like, or other higher polyols such as trimethylolpropane, pentaerythritol, and the like. Higher functionality polyols may be utilized, which, as noted, may be prepared, for example, by alkoxylation of compounds such as sucrose or sorbitol. One commonly used alkoxylation process is to react a polyol with an alkylene oxide, such as propylene oxide or ethylene oxide, in the presence of an acidic or basic catalyst. Specific polyethers include those sold under the tradenames TERATHANE and TERACOL available from DuPont, E.I. Du Pont de Nemours and company, Inc., and POLYMEG available from Q O Chemicals, Inc., a subsidiary of Great Lakes Chemicals (Great Lakes Chemical Corp.).

The polyether polymer may also comprise a polyetheramine. Polyetheramines are understood to mean compounds having one or more amine functions attached to the polyether backbone, such as a compound characterized by repeating units of propylene oxide, ethylene oxide or a mixture of propylene oxide and ethylene oxide in their respective structures, such as, for example, one of the Jeffamine series of products. Examples of such polyetheramines include aminated propoxylated pentaerythritol (such as Jeffamine XTJ-616) and those represented by formulas (VI) to (VIII).

According to formula (VI), the polyetheramine may comprise:

wherein y is 0-39 and x + z is 1-68.

Suitable polyetheramines represented by formula (VI) include, but are not limited to, amine-terminated polyethylene glycols, such as those commercially available from Hensman Corporation (Huntsman Corporation) in its JEFFAMINE ED series, such as JEFFAMINE HK-511, JEFFAMINE ED-600, JEFFAMINE ED-900, and JEFFAMINE ED-2003; and amine terminated polypropylene glycols such as the JEFFAMINE D series thereof, such as JEFFAMINE D-230, JEFFAMINE D-400, JEFFAMINE D-2000, and JEFFAMINE D-4000.

According to formula (VII), the polyetheramine may comprise:

wherein each p is independently 2 or 3.

Suitable polyetheramines represented by formula (VII) include, but are not limited to, amine-terminated polyethylene glycol-based diamines, such as the JEFFAMINE EDR series of Hensman, such as JEFFAMINE EDR-148 and JEFFAMINE EDR-176.

According to formula (VIII), the polyetheramine may comprise:

wherein R is₈Is H or C₂H₅M is 0 or 1, a + b + c is 5-85.

Suitable polyetheramines represented by formula (VIII) include, but are not limited to, amine terminated propoxylated trimethylolpropane or glycerol, such as the JEFFAMINE T series of Hensman, such as JEFFAMINE T-403, JEFFAMINE T-3000, and JEFFAMINE T-5000.

The polysiloxane polymer may comprise any suitable polysiloxane polymer known in the art. The polysiloxane can have a weight average molecular weight (M) of 200g/mol to 100,000 g/mol, such as 500g/mol to 100,000 g/mol, such as 1, 000g/mol to 75,000 g/mol, such as 2,000 g/mol to 50,000 g/mol_w). Suitable polysiloxanes include polymeric polysiloxanes such as Polydimethylsiloxane (PDMS). The polysiloxane can have at least one functional group that reacts with a functional group on at least one other component of the coating composition, such as an ionic liquid or a curing agent. For example, the polysiloxane may have at least one hydroxyl and/or amine functional group, such as PDMS having at least two amine functional groups, such that it reacts with a curing agent having isocyanate functional groups. Suitable silicone polymers also include those as prepared in U.S. patent No. 5,275,645 and U.S. patent No. 5,618,860, which are incorporated by reference in their entirety, such as PSX 700, which is commercially available from the PPG Industries group (PPG Industries). Examples of other commercially available polysiloxanes include: WACKER FLUID NH 130D from Wacke chemical GmbH (WACKER Chemie AG); Shin-Etsu KF-6003 commercially available from Shin-Etsu chemical Co., Ltd (Shin-Etsu); MCR-C18, MCR-C62, and DMS-531 commercially available from Gelest, Inc.; and DC 200-1000 commercially available from Dow corning.

The epoxy polymer may comprise any suitable epoxy polymer known in the art. For example, epoxy polymers can be prepared by reacting a polyepoxide and a polyol selected from alcoholic hydroxyl group-containing materials and phenolic hydroxyl group-containing materials to extend the chain or increase the molecular weight of the polyepoxide. Chain extended polyepoxides are generally prepared as follows: the polyepoxide and polyol are reacted "neat" together or in the presence of inert organic solvents such as ketones (including methyl isobutyl ketone and methyl amyl ketone), aromatic compounds such as toluene and xylene, and alcohol ethers such as the dimethyl ether of diethylene glycol. The reaction is typically carried out at a temperature of 80 ℃ to 160 ℃ for 30 to 180 minutes until an epoxy polymer reaction product is obtained. The equivalent ratio of reactants (i.e., epoxy: polyol) can be in the range of 1.00: 0.50 to 1.00: 2.00. As will be appreciated by those skilled in the art, the epoxy polymer may contain epoxy functional groups and/or hydroxyl functional groups depending on the proportions of the reactants.

Polyepoxides typically have at least two 1, 2-epoxy groups. The polyepoxides may be saturated or unsaturated, cyclic or acyclic, aliphatic, cycloaliphatic, aromatic or heterocyclic. In addition, the polyepoxides may contain substituents such as halogen, hydroxyl, and ether groups. Examples of polyepoxides are those having a1, 2-epoxy equivalent of greater than 1 and/or 2; i.e., polyepoxides having an average of at least two epoxy groups per molecule. Suitable polyepoxides include the polyglycidyl ethers of polyhydric alcohols such as cyclic polyols and polyglycidyl ethers of polyhydric phenols such as bisphenol A. These polyepoxides can be produced by etherification of a polyhydric phenol with an epihalohydrin or dihalohydrin such as epichlorohydrin or dichlorohydrin (dichlorohydrin) in the presence of a base. In addition to the polyhydric phenols, other cyclic polyols may also be used to prepare polyglycidyl ethers of cyclic polyols. Examples of other cyclic polyols include cycloaliphatic polyols, particularly cycloaliphatic polyols, such as hydrogenated bisphenol a, 1, 2-cyclohexanediol and 1, 2-bis (hydroxymethyl) cyclohexane. Epoxy group-containing acrylic polymers are also useful in the present invention.

Examples of polyols used to chain extend the polyepoxide or increase the molecular weight of the polyepoxide (i.e., via a hydroxyl-epoxy reaction) include alcoholic hydroxyl group-containing materials and phenolic hydroxyl group-containing materials. Examples of alcoholic hydroxyl group-containing materials are simple polyols such as neopentyl glycol; and polyester polyols such as those described in U.S. patent No. 4,148,772; polyether polyols such as those described in U.S. patent No. 4,468,307; and urethane diols such as those described in U.S. patent No. 4,931,157. Examples of phenolic hydroxyl group-containing substances are polyhydric phenols (such as bisphenol a), phloroglucinol, catechol, and resorcinol. Mixtures of alcoholic hydroxyl group-containing substances and phenolic hydroxyl group-containing substances can also be used.

When used in combination with a monomeric ionic liquid, the film-forming polymer may be present in the coating composition in an amount of at least 20 wt%, such as at least 40 wt%, such as at least 50 wt%, and may be present in an amount of no more than 90 wt%, such as no more than 85 wt%, such as no more than 77 wt%, based on the total weight of resin solids. The film-forming polymer may be present in an amount of 20 to 90 weight percent, such as 40 to 85 weight percent, such as 50 to 77 weight percent, based on the total weight of resin solids.

It is also possible that the ionic liquid itself is included as part or all of the film-forming polymer. For example, the ionic liquids described above can be incorporated into polymers to form polymeric ionic liquids for use as film-forming polymers. Such film-forming polymers may be reacted with an appropriately selected curing agent. The curing agent may be selected from any curing agent known in the art that crosslinks with functional groups on the polymer. Suitable curing agents are described more fully below. In addition, the film-forming polymer may also be self-curing and may cure without the need for a curing agent. Thus, when used in combination with a polymeric ionic liquid, additional film-forming polymers are optional.

When the ionic liquid is in the form of a polymeric ionic liquid, the film-forming polymer may be present in the coating composition in an amount of at least 0.5 wt%, such as at least 10 wt%, such as at least 30 wt%, and may be present in an amount of no more than 80 wt%, such as no more than 70 wt%, such as no more than 65 wt%, based on the total weight of resin solids. The film-forming polymer may be present in the coating composition in an amount of from 0.5 to 80 weight percent, such as from 10 to 70 weight percent, such as from 30 to 65 weight percent, based on the total weight of resin solids.

According to the present invention, the coating composition may optionally comprise a curing agent. The curing agent may comprise any curing agent known in the art that crosslinks with functional groups on the film-forming polymer. Thus, the curing agent comprises a third functional group that reacts with the second functional group of the film-forming polymer. The term "third" functional group is intended to distinguish the functional group of the curing agent from the functional group of any other component of the coating composition (such as the first functional group of the ionic liquid or the second functional group of the film-forming polymer) and has no other meaning. For clarity, the term "third" functional group is not intended to refer to a functional group other than a different functional group present on the curing agent. As such, the curing agent may comprise two or more "third" functional groups, with or without any other functional groups present on the curing agent. One skilled in the art can select a suitable curing agent from known curing agents such as, for example, melamine, phenolic resins, carbodiimides, hydroxyalkylamides, isocyanates, blocked isocyanates, benzoguanamines, epoxy resins, oxazolines, aminosilanes, and the like, based on the functionality of the film-forming polymer. Thus, the third functional group may comprise an amino group, a hydroxyl group, an isocyanate group, an epoxy group, a siloxane, or a combination thereof.

The curing agent may comprise one or more polyisocyanates such as diisocyanates, triisocyanates and higher functional isocyanates and may comprise biurets and isocyanurates the diisocyanates may comprise, for example, toluene diisocyanate, 4,4 '-methylene-bis- (cyclohexyl isocyanate), isophorone diisocyanate, isomeric mixtures of 2, 2, 4-trimethylhexamethylene diisocyanate and 2, 4, 4-trimethylhexamethylene diisocyanate, 1, 6-hexamethylene diisocyanate, tetramethylxylylene diisocyanate and/or 4, 4' -diphenylmethylene diisocyanate.

Trifunctional isocyanates may also be used as curing agents, such as, for example, isophorone diisocyanate, hexamethylene diisocyanate, triisocyanatononane, triphenylmethane triisocyanate, 1, 3, 5-benzene triisocyanate, trimers of 2, 4, 6-toluene triisocyanate, the adduct of trimethylol and tetramethylxylene diisocyanate sold under the trade name cyclothane 3160 by the cyanogen industry (CYTEC Industries) and DESMODUR N3300 available from CovestroAG as the isocyanurate of hexamethylene diisocyanate.

The polyisocyanate may also be one of those disclosed above, chain extended with one or more polyamines and/or polyols using suitable materials and techniques known to those skilled in the art to form a polyurethane prepolymer having isocyanate functional groups. Exemplary polyisocyanates are described in U.S. patent application publication No. 2013/0344253A1, which is incorporated herein by reference, paragraphs [0012] - [0033 ].

The curing agent may be present in the coating composition in an amount of at least 10 weight percent, such as at least 12 weight percent, such as at least 14 weight percent, and may be present in an amount of no more than 80 weight percent, such as no more than 50 weight percent, such as no more than 40 weight percent, based on the total weight of resin solids. The curing agent may be present in the coating composition in an amount of 10 to 80 weight percent, such as 12 to 50 weight percent, such as 14 to 40 weight percent, based on the total weight of resin solids.

According to the invention, the film-forming polymer may also be self-curing or self-condensing, i.e. self-crosslinking, and cure without the need for the presence of a curing agent. Thus, the coating composition may be substantially free, essentially free, or completely free of curing agents. As used herein, a coating composition is "substantially free" of curing agent if the curing agent is present in an amount less than 5 weight percent, based on the total weight of resin solids. As used herein, a coating composition is "essentially free" of curing agent if the curing agent is present in an amount less than 1 weight percent, based on the total weight of resin solids. As used herein, a coating composition is "completely free" of curing agent if the curing agent is not present in the coating composition, i.e., 0 weight percent. As described above, examples of self-curing film-forming polymers include polysiloxane polymers having alkoxysilane groups. Thus, the self-curing film-forming polymer may comprise a second functional group comprising, for example, an alkoxysilyl group. Suitable self-curing polysiloxane polymers are described in U.S. patent No. 5,275,645 and U.S. patent No. 5,618,860, each of which is incorporated herein by reference.

When used in combination with a monomeric ionic liquid, the self-curing film-forming polymer may be present in the coating composition in an amount of at least 75 wt%, such as at least 85 wt%, such as at least 88 wt%, and may be present in an amount of no more than 99.5 wt%, such as no more than 97 wt%, such as no more than 95 wt%, based on the total weight of resin solids. The self-curing film-forming polymer can be present in the coating composition in an amount of from 75 wt% to 99.5 wt%, such as from 85 wt% to 97 wt%, such as from 88 wt% to 95 wt%, based on the total weight of resin solids.

When used in combination with a polymeric ionic liquid, the self-curing film-forming polymer may be present in the coating composition in an amount of at least 50 weight percent, such as at least 60 weight percent, such as at least 65 weight percent, and may be present in an amount of no more than 99.5 weight percent, such as no more than 90 weight percent, such as no more than 80 weight percent, based on the total weight of resin solids. The self-curing film-forming polymer may be present in the coating composition in an amount of 50 to 99.5 weight percent, such as 60 to 90 weight percent, such as 65 to 80 weight percent, based on the total weight of resin solids.

According to the present invention, the coating composition may optionally further comprise a solvent. Any suitable solvent used in the art that is compatible with the components of the coating composition may be used. Non-limiting examples of suitable organic solvents include aliphatic hydrocarbons, aromatic hydrocarbons, ketones, and esters. Non-limiting examples of suitable aliphatic hydrocarbons include hexane, heptane, octane, and the like. Non-limiting examples of suitable aromatic hydrocarbons include benzene, toluene, xylene, and the like. Non-limiting examples of suitable ketones include methyl isobutyl ketone, diisobutyl ketone, methyl ethyl ketone, methyl hexyl ketone, ethyl butyl ketone, and the like. Non-limiting examples of suitable esters include ethyl acetate, isobutyl acetate, amyl acetate, 2-ethylhexyl acetate, and the like. Mixtures of solvents may also be used.

The amount of solvent present in the coating composition will depend on the desired end use of the coating composition, such as whether the coating composition is applied by spraying, brushing, or other suitable method. For example, the solvent may be present in the coating composition in an amount of at least 0.1 wt.%, such as at least 12 wt.%, such as at least 20 wt.%, and may be present in an amount of no more than 30 wt.%, such as no more than 28 wt.%, such as no more than 26 wt.%, based on the total weight of the coating composition. The solvent may be present in the coating composition in an amount of 0.1 to 30 weight percent, such as 12 to 28 weight percent, 20 to 26 weight percent, based on the total weight of the coating composition.

According to the present invention, the first functional group of the ionic liquid reacts with at least one of the second functional group of the film-forming polymer or the third functional group of the curing agent. The first functional group of the ionic liquid can react with both the second functional group of the film-forming polymer and the third functional group of the curing agent. The reactivity of the first functional group of the ionic liquid with the second functional group of the film-forming polymer and/or the third functional group of the curing agent enables the ionic liquid to react with and be incorporated into the polymer backbone of the polymer matrix formed during curing of the coating composition.

According to the present invention, when the film-forming polymer is self-curing, the first functional group of the ionic liquid may react with the second functional group of the film-forming polymer. Thus, the ionic liquid reacts with and is incorporated into the polymer backbone of the polymer matrix formed during curing of the self-curing coating composition.

Without being bound by any theory, it is believed that by incorporating the ionic liquid into the polymer backbone of the cured coating, the coating retains the ionic liquid comprising the salt groups over its lifetime. It is further believed that the presence of salt group functional groups on the coating surface may achieve good ice adhesion properties, such as reduced surface energy, reduced average maximum load required to remove ice from the coating surface, and reduced average maximum stress required to remove ice from the coating surface, and may result in a reduction in the freezing point of water on the coating surface. These "anti-icing" characteristics can mitigate the accumulation of ice on the surface of the coated substrate without the need for anti-icing treatments currently used in the art.

The average maximum load required to remove ice from the coating surface and the average maximum stress required to remove ice from the coating surface can be measured according to the ice adhesion test described more fully in the examples below.

According to the present invention, the average maximum load of ice adhesion as measured according to the ice adhesion test may be reduced by at least 50%, such as at least 60%, such as at least 70%, such as at least 75%, and may be reduced by 50% to 90%, such as 60% to 90%, such as 70% to 90%, for a coating formed from a coating composition comprising 5% by weight of the above-described ionic liquid, based on the total weight of resin solids, as compared to a coating formed from a control coating composition not comprising the ionic liquid.

According to the present invention, the average maximum load of ice adhesion as measured according to the ice adhesion test may be reduced by at least 50%, such as at least 60%, such as at least 70%, such as at least 75%, such as at least 80%, and may be reduced by 50% to 90%, such as 60% to 90%, such as 70% to 90%, for a coating formed from a coating composition comprising 10 wt% of the above-described ionic liquid, based on the total weight of resin solids, as compared to a coating formed from a control coating composition not comprising the ionic liquid.

According to the present invention, the average maximum stress of ice adhesion as measured according to the ice adhesion test may be reduced by at least 50%, such as at least 70%, such as at least 75%, such as at least 80%, and may be reduced by 50% to 90%, such as 70% to 90%, such as 75% to 90%, such as 80% to 90%, based on the total weight of resin solids, for a coating formed from a coating composition comprising 5% by weight of the above-described ionic liquid, as compared to a coating formed from a control coating composition that does not include the ionic liquid.

According to the present invention, the average maximum stress of ice adhesion as measured according to the ice adhesion test may be reduced by at least 50%, such as at least 70%, such as at least 75%, such as at least 80%, and may be reduced by 50% to 90%, such as 70% to 90%, such as 75% to 90%, such as 80% to 90%, for a coating formed from a coating composition comprising 10 wt% of the above-described ionic liquid, based on the total weight of resin solids, as compared to a coating formed from a control coating composition not comprising the ionic liquid.

According to the present invention, the coating composition may optionally comprise a silicone additive. The silicone additive may comprise any suitable silicone additive known in the art. For example, the silicone additive may comprise a silicone-modified polymer comprising (i) pendant functional groups reactive with isocyanate functional groups and (ii) polysiloxane side chains. Alternatively, the silicone-modified polymer may contain alkoxysilyl groups in addition to the polysiloxane side chains so that the silicone additive can react with the self-crosslinking film-forming polymer described above. Such polymers may comprise a plurality of polysiloxane side chains along the polymer backbone, as well as a plurality of pendant and/or terminal functional groups that react with isocyanate-based functional groups. The pendant and/or terminal functional groups can comprise, for example, hydroxyl functional groups. The silicone-modified polymer may comprise a polyol polymer, an acrylic polymer, a polyester polymer, an alkyd polymer, a polyurethane polymer, a polyamide polymer, a polyether polymer, an epoxy polymer, a polysiloxane polymer, copolymers thereof, and mixtures thereof.

The silicone-modified polymer may comprise a hydroxy-functional silicone-modified acrylic polymer. The hydroxy-functional silicone-modified acrylic polymer may exhibit a hydroxyl number of 5 to 100mg KOH/g polymer, such as 10 to 80mg KOH/g polymer, such as 20 to 60mg KOH/g polymer. The silicone-modified acrylic polymer can have a weight average molecular weight (Mw) of 3,000 to 100,000 g/mol, such as 4,000 to 80,000 g/mol, such as 5,000 to 60,000 g/mol. The hydroxyl number may be determined by any suitable technique known in the art, such as, for example, ASTM E222. Suitable silicone-modified acrylic polymers are disclosed in U.S. patent No. 7,122,599, column 2, line 35 to column 7, line 40, which is incorporated herein by reference. Commercially available silicone modified acrylic polymers include BYK-Silclean3700, a 25% solids resin clear solution in 1-methoxy-2-propanol acetate with a hydroxyl number of 30mg KOH/g and a weight average molecular weight of 15,000 g/mol based on solid resin available from Bekkaides and Instruments (BYKAdditives and Instruments).

The silicone additive may be present in the coating composition in an amount of at least 1 weight percent, such as at least 2 weight percent, such as at least 4 weight percent, and may be present in an amount of no more than 15 weight percent, such as no more than 10 weight percent, such as no more than 8 weight percent, based on the total weight of resin solids. The silicone additive may be present in an amount of 1 to 15 weight percent, such as 2 to 10 weight percent, such as 4 to 8 weight percent, based on the total weight of resin solids.

It has surprisingly been found that in the coating composition of the present invention, the combination of ionic liquid and silicone additive produces a synergistic effect on the ice adhesion properties of the cured coating. Incorporation of the ionic liquid and silicone additive in the amounts provided above can result in: the reduction in average maximum load and average maximum stress is greater than the reduction in coatings that include only the ionic liquid or silicone additive. For example, the average maximum load as measured according to the ice adhesion test may be reduced by at least 75%, such as at least 80%, such as at least 85%, and may be reduced by 75% to 95%, such as 85% to 95%; and the average maximum stress as measured according to the ice adhesion test may be reduced by at least 75%, such as at least 80%, such as at least 85%, and may be reduced by 75% to 95%, such as 85% to 95%.

According to the present invention, the coating composition may optionally comprise a catalyst. The catalyst may promote the reaction of the film-forming polymer and the curing agent. In addition, self-curing film-forming polymers can be combined with catalysts to promote hydrolysis and polycondensation of the polysiloxane polymer to effect curing. The catalyst may comprise any suitable catalyst known in the art that is compatible with the other components of the coating composition. Non-limiting examples of suitable catalysts include tertiary amine catalysts, nitrogen-containing heteroaromatic catalysts, metal compound catalysts, guanidine catalysts, or combinations of catalysts to achieve a desired cure rate. Suitable tertiary amine catalysts include, but are not limited to, triethylamine, N-methylmorpholine, triethylenediamine, and the like. Suitable nitrogen-containing heteroaromatic catalysts include pyridine, picoline, and the like. Suitable metal compound catalysts include, but are not limited to, compounds based on lead, zinc, cobalt, titanates, iron, copper, and tin, such as lead 2-ethylhexanoate, zinc 2-ethylhexanoate, cobalt naphthenate, tetraisopropyl titanate, iron naphthenate, copper naphthenate, dibutyltin diacetate, dibutyltin dioctoate, dibutyltin dilaurate, and the like. Suitable guanidine catalysts include those described in U.S. patent No. 7,842,762, column 1, line 53 through column 3, line 45, the cited portions of which are incorporated herein by reference. These catalysts may be used alone or in combination.

The catalyst may be present in the coating composition in an amount of at least 0.01 wt%, such as at least 0.5 wt%, such as at least 1 wt%, and may be present in an amount of no more than 5 wt%, such as no more than 3 wt%, such as no more than 2 wt%, based on the total weight of resin solids. The catalyst may be present in the coating composition in an amount of 0.01 to 5 wt%, such as 0.5 to 3 wt%, such as 1 to 2 wt%, based on the total weight of resin solids.

The coating composition may additionally include a variety of other optional ingredients and/or additives (depending in part on the particular application of the coating composition), such as other catalysts, pigments, colorants, fillers, reinforcing agents, thixotropic agents, accelerators, surfactants, plasticizers, extenders, stabilizers, corrosion inhibitors, diluents, hindered amine light stabilizers, ultraviolet light absorbers, and antioxidants.

According to the present invention, the coating composition may comprise a two-component or "2K" composition. In a two-component coating composition, the resin component (e.g., film-forming polymer) and the curing agent component of the coating composition are maintained separately immediately prior to application of the coating composition. For example, immediately prior to application, the resin components of the polyurethane coating composition (e.g., the film-forming polymer (e.g., polyol polymer)) and the ionic liquid, as well as the isocyanate curing agent, can be maintained separately. After coating, the isocyanate curing agent and polyol polymer and ionic liquid react at ambient temperature to form a cured coating.

According to the invention, the coating composition may be a one-component or "1K" composition. In a one-component coating composition, all components, including the film-forming polymer and the curing agent, are maintained in the same dispersion. The curing agent may be a latent curing agent such that the curing agent does not react with the film-forming polymer during storage at ambient temperatures. For example, the latent curing agent may comprise a blocked polyisocyanate that is unreactive without the application of an external energy source such as heat or UV radiation.

According to the invention, the coating composition may be a varnish. A varnish is understood to be a substantially transparent or translucent coating. Thus, the varnish may have a degree of color as long as it does not significantly opacify the varnish or otherwise affect the ability to see the underlying substrate. The varnish of the invention can be used, for example, in combination with pigmented paints. The varnish may be formulated as known in the coatings art.

The present invention also relates to a method of reducing the adhesion of ice to a surface of a substrate, the method comprising applying the above-described coating composition to a substrate and at least partially curing the coating composition to form a coating. The substrate that can be coated by the method of the present invention is not limited. Suitable substrates in the method of the present invention include rigid metal substrates such as ferrous metal, aluminum alloys, copper, and other metal and alloy substrates. Ferrous metal substrates used in the practice of the present invention may include iron, steel and alloys thereof. Non-limiting examples of useful steel materials include cold rolled steel, galvanized (galvanized) steel, electrogalvanized steel, stainless steel, pickled steel, zinc-iron alloys (such as GALVANNEAL), and combinations thereof. Combinations or composites of ferrous and non-ferrous metals may also be used. Aluminum alloys of the 2XXX, 5XXX, 6XXX or 7XXX series, as well as clad aluminum alloys of the A356 series and cast aluminum alloys may also be used as substrates. Magnesium alloys of AZ31B, AZ91C, AM60B or EV31A series may also be used as the substrate. The substrate used in the present invention may also comprise titanium and/or a titanium alloy. Other suitable non-ferrous metals include copper and magnesium, and alloys of these materials. Suitable metal substrates for use in the present invention include those used in the assembly of vehicle bodies (such as, but not limited to, doors, body panels, trunk lids, roof panels, hoods, roofs and/or side rails, rivets, landing gear components, and/or skins used on aircraft), vehicle frames, vehicle parts, motorcycles, wheels, and industrial structures and components. As used herein, "vehicle" or variations thereof include, but are not limited to, civil aircraft, commercial aircraft, and military aircraft and/or land vehicles, such as automobiles, motorcycles, and/or trucks. The metal substrate may also be in the form of a sheet of metal or a fabricated part, for example. It is also understood that the substrate may be pretreated with a pretreatment solution comprising a zinc phosphate pretreatment solution (such as, for example, those described in U.S. Pat. nos. 4,793,867 and 5,588,989) or a zirconium-containing pretreatment solution (such as, for example, those described in U.S. Pat. nos. 7,749,368 and 8,673,091). The substrate may comprise a composite material, such as a plastic or fiberglass composite material. The substrate may be a glass fibre and/or carbon fibre composite material in the form of a wind blade. The methods disclosed herein are also applicable to mitigating ice build-up on substrates used in turbines and aircraft parts (such as wings, flanks, stabilizers, rudders, ailerons, engine inlets, propellers, rotors, fuselages, etc.) and other substrates that may be subject to ice-cold conditions.

It is common, but not necessary, to remove foreign matter from a surface by thoroughly cleaning and degreasing the surface before depositing any coating composition on the surface of the substrate. Such cleaning is typically performed after the substrate is formed (stamped, welded, etc.) into the final use shape. The substrate surface may be cleaned/degreased by physical and/or chemical means, such as mechanically abrading the surface or with commercially available alkaline or acidic cleaners (such as sodium metasilicate and/or sodium hydroxide) well known to those skilled in the art. A non-limiting example of a cleaning agent is CHEMKLEEN 163, which is an alkaline cleaner commercially available from PPG industries group.

After the cleaning step, the substrate may be rinsed with an aqueous solution of deionized water, solvent, or rinsing agent to remove any residue. The substrate may be air dried, for example, by using an air knife, by flashing water by briefly exposing the substrate to elevated temperatures, or by passing the substrate between squeeze rollers.

The substrate may be a bare, clean surface; it may be oily, pretreated with one or more pretreatment compositions, and/or may be precoated with one or more coating compositions, primers, paints, topcoats, and the like, applied by any method including, but not limited to, electrodeposition, spray coating, dip coating, roll coating, curtain coating, and the like.

In the method of the present invention, the above-described coating composition may be applied to at least a portion of one surface of a substrate and may be at least partially cured. The substrate may have one continuous surface, or two or more surfaces, such as two opposing surfaces. In general, the surface to be coated is any surface that can be expected to be exposed to conditions prone to ice build-up, but the coating composition can be applied to any substrate. The coating composition can be applied to the substrate by one or more of a variety of methods including spraying, dipping/immersion, brushing, or flow coating. After forming a film of the coating composition on the substrate, the coating composition can be cured by allowing it to stand at ambient temperature (e.g., 72 ° F, 22 ℃), or curing and baking in combination with ambient temperature, or simply baking. The composition may be cured at ambient temperature, typically over a period of about 24 hours to about 36 hours. If ambient temperature and baking are used in combination, the composition is typically allowed to stand for about 5 hours to about 24 hours and then baked at a temperature of up to about 140 ° F (60 ℃) for a period of about 20 minutes to about 1 hour. The coating may also be cured by baking the substrate at an elevated temperature of 60 ℃ to 260 ℃ for a period of 1 minute to 40 minutes. The coating formed from the coating composition can have a dry film thickness of 1 to 25 mils (25.4 to 635 micrometers), such as 5 to 25 mils (127 to 635 micrometers).

The present invention also relates to coatings formed from the coating compositions of the present invention in an at least partially cured state.

The invention also relates to a coated substrate coated with the coating composition of the invention in an at least partially cured state.

As used herein, the term "reactive" with respect to a functional group refers to a functional group that is capable of chemically reacting with another functional group under typical curing conditions, such as, for example, reacting spontaneously when the components are mixed or upon application of an external energy source or in the presence of a catalyst or by any other means known to those skilled in the art.

As used herein, the terms "cure," "cured," or similar terms, used in connection with the coating compositions described herein, refer to the crosslinking of at least a portion of the components forming the coating composition to form a coating. Additionally, curing of the coating composition refers to subjecting the composition to curing conditions such as those described above, thereby causing the reactive functional groups of the components of the coating composition to react and causing the components of the composition to crosslink and form a cured coating. The coating composition may be subjected to curing conditions until it is at least partially cured. As used herein, the term "at least partially cured" refers to subjecting a coating composition to curing conditions to form a coating layer in which at least a portion of the reactive groups of the components of the coating composition are reacted. The coating composition may also be subjected to curing conditions such that substantially complete curing is achieved, and wherein further curing does not result in a significant further improvement in coating properties (such as, for example, hardness).

As used herein, "resin solids" include ionic liquids, film-forming polymers, curing agents, any resins used to prepare the pigment paste (if present), and any additional non-pigmented components.

For the purposes of this detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

Additionally, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges between (and including 1 and 10) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.

In this application, the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. For example, although reference is made herein to "a" halogenated compound, "an" isocyanate-functional alkoxysilane, "an" imidazole, "a" metal catalyst, "an" ionic liquid, "a" film-forming polymer, "a" curing agent, or "a" functional group, combinations (i.e., pluralities) of these components may be used. In addition, in this application, the use of "or" means "and/or" unless specifically stated otherwise, even though "and/or" may be explicitly used in some cases.

As used herein, in the context of this application, "comprising," "including," and similar terms are to be understood as being synonymous with "comprising," and thus open-ended, and do not preclude the presence of additional unrecited or unrecited elements, materials, ingredients, or method steps. As used herein, in the context of the present application, "consisting of … …" is understood to exclude the presence of any unspecified element, ingredient or method step. As used herein, in the context of the present application, "consisting essentially of … …" is to be understood as including the named elements, materials, ingredients, or method steps "as well as those elements, materials, ingredients, or method steps that do not materially affect the basic and novel characteristics of the described solution.

As used herein, the terms "on … …", "onto … …", "coated on … …", "coated onto … …", "formed on … …", "deposited on … …", "deposited on … …" refer to being formed, covered, deposited, or provided on, but not necessarily in contact with, a surface. For example, a coating composition "deposited onto" a substrate does not preclude the presence of one or more other intermediate coating layers of the same or different composition located between the coating composition and the substrate.

While specific aspects of the invention have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. Accordingly, the particular arrangements disclosed are meant to be illustrative only and not limiting as to the scope of the invention which is to be given the full breadth of the claims appended and any and all equivalents thereof.

Aspect(s)

Aspects of the invention include, but are not limited to, the following:

1. a method of preparing an alkoxysilane-functional ionic liquid comprising:

reacting a halo compound comprising halogen and active hydrogen functional groups, an isocyanate-functional alkoxysilane, and an ionizable compound capable of forming an ionic bond with the halogen to form the alkoxysilane-functional ionic liquid.

2. The method of aspect 1, wherein the method comprises:

a first step comprising reacting the halo compound with the isocyanate-functional alkoxysilane to form a haloalkoxysilane, and

a second step comprising reacting the haloalkoxysilane with the ionizable compound to form the alkoxysilane-functional ionic liquid.

3. The method of aspect 1, wherein the method comprises:

a first step comprising reacting the halogenated compound with the ionizable compound to form an ionic liquid comprising active hydrogen functional groups, and

a second step comprising reacting the ionic liquid comprising an active hydrogen functional group with the isocyanate functional alkoxysilane to form the alkoxysilane functional ionic liquid.

4. The process according to any one of the preceding aspects, wherein the halogenated compound comprises a halohydrin, wherein the halohydrin preferably comprises 3-chloropropanol.

5. The method of any one of the preceding aspects, wherein the isocyanate-functional alkoxysilane comprises an isocyanate-functional trialkoxysilane represented by formula (I):

wherein R is₆Is C₁-C₃₆Alkanediyl, straight-chain or branched C₃-C₃₆Cycloaliphatic or straight-chain or branched C₆-C₃₆An aromatic group; and R is₇Is C₁-C₄An alkyl group, wherein the isocyanate functional trialkoxysilane preferably comprises isocyanatopropyltrimethoxysilane.

6. The method according to any of the preceding aspects, wherein the ionizable compound comprises an imidazole, wherein the imidazole preferably comprises N-methylimidazole.

7. The method according to any one of the preceding aspects, wherein the reaction takes place in the presence of a metal catalyst, wherein the metal catalyst preferably comprises a tin catalyst.

8. An alkoxysilane-functional ionic liquid prepared according to the method of any one of the preceding aspects.

9. The alkoxysilane-functional ionic liquid according to aspect 8 represented by formula (II):

wherein R is₁Is substituted or unsubstituted C₁-C₃₆Alkanediyl or substituted or unsubstituted C₆-C₃₆A divalent aromatic group;

R₂is hydrogen, substituted or unsubstituted C₁-C₃₆Alkyl or substituted or unsubstituted C₆-C₃₆An aromatic group;

R₃is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₄is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₅is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₆is C₁-C₃₆Alkanediyl, straight-chain or branched C₃-C₃₆Cycloaliphatic or straight-chain or branched C₆-C₃₆An aromatic group; and is

R₇Is substituted or unsubstituted C₁-C₄An alkyl group.

10. The alkoxysilane-functional ionic liquid according to aspect 8 represented by formula (III):

11. the alkoxysilane-functional ionic liquid according to aspect 8 represented by formula (IV):

wherein n is more than or equal to 1;

r is monovalent or polyvalent substituted or unsubstituted C₁-C₃₆Alkyl, monovalent or polyvalent substituted or unsubstituted C₆-C₃₆Aromatic radicals or monovalent or polyvalent substituted or unsubstituted C₃-C₃₆A cycloaliphatic group;

R₁is substituted or unsubstituted C₁-C₃₆Alkanediyl or substituted or unsubstituted C₆-C₃₆A divalent aromatic group;

R₃is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₄is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₅is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₇Is substituted or unsubstituted C₁-C₄An alkyl group.

12. The alkoxysilane-functional ionic liquid according to aspect 8 represented by formula (IV):

wherein n is more than or equal to 1;

r is the number average molecular weight (M)_n) More than 200g/mol of monovalent or polyvalent polyester groups;

R₃is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₄is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₅is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₇Is substituted or unsubstituted C₁-C₄An alkyl group.

13. The alkoxysilane-functional ionic liquid according to aspect 8 represented by formula (IV):

wherein n is more than or equal to 1;

r is the number average molecular weight (M)_n) More than 200g/mol of monovalent or polyvalent polyether groups;

R₃is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₄is hydrogen or substituted or notSubstituted C₁-C₃₆An alkyl group;

R₅is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₇Is substituted or unsubstituted C₁-C₄An alkyl group.

14. The alkoxysilane-functional ionic liquid according to aspect 8 represented by formula (IV):

wherein n is more than or equal to 1;

r is the number average molecular weight (M)_n) More than 500g/mol of a mono-or polyvalent acrylic resin;

R₃is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₄is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₅is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₇Is substituted or unsubstituted C₁-C₄An alkyl group.

15. The alkoxysilane-functional ionic liquid according to aspect 8 represented by formula (IV):

wherein n is more than or equal to 1;

r is the number average molecular weight (M)_n) More than 500g/mol of monovalent or polyvalent polyurethane groups;

R₃is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₄is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₅is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₇Is substituted or unsubstituted C₁-C₄An alkyl group.

16. A coating composition comprising:

an ionic liquid comprising a salt group and a first functional group;

a film-forming polymer comprising a second functional group; and

a curing agent comprising a third functional group;

wherein the first functional group is reactive with at least one of the second functional group and the third functional group.

17. The coating composition of aspect 16, wherein the salt group comprises a pyridinium, pyrrolidinium, imidazolium, ammonium, guanidinium, phosphonium, isouronium, thiouronium, or sulfonium.

18. The coating composition of aspect 16 or 17, wherein the salt group comprises a halide, a dicyanamide, a tetrafluoroborate, a hydrogensulfate, a methylsulfate, an octylsulfate, a hexafluorophosphate, a bis (trifluoromethylsulfonyl) imide, a tris (pentafluoroethyl) trifluorophosphate, a triflate, a trifluoroacetate, a thiocyanate, an organic borate, and a p-toluenesulfonate.

19. The coating composition of any one of aspects 16-18, wherein the ionic liquid comprises a salt group comprising imidazolium and chloride.

20. The coating composition of any one of aspects 16 to 19, wherein the ionic liquid comprises a structure according to formula (V):

21. the coating composition of any one of aspects 16 to 19, wherein the ionic liquid comprises a structure according to formula (II):

R₃is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₄is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₅is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₆is substituted or unsubstituted C₁-C₃₆Alkanediyl, straight-chain or branched C₃-C₃₆Cycloaliphatic or straight-chain or branched C₆-C₃₆An aromatic group; and is

R₇Is substituted or unsubstituted C₁-C₄An alkyl group.

22. The coating composition of any one of aspects 16 to 19, wherein the ionic liquid comprises a structure according to formula (III):

23. the coating composition of any one of aspects 16 to 19, wherein the ionic liquid comprises a structure according to formula (IV):

wherein n is more than or equal to 1;

r comprises monovalent or polyvalent substituted or unsubstituted C₁-C₃₆Chain alkyl, monovalent or polyvalent C₆-C₃₆Aromatic radical, monovalent or polyvalent C₃-C₃₆Alicyclic group, number average molecular weight (M)_n) Monovalent or polyvalent polyester groups of more than 200g/mol, number average molecular weight (M)_n) A mono-or polyvalent polyether group of more than 200g/mol, a number average molecular weight (M)_n) A mono-or polyvalent acrylic resin of more than 500g/mol, or a number-average molecular weight (M)_n) More than 500g/mol of monovalent or polyvalent polyurethane groups;

R₃is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₄is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₅is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₇Is substituted or unsubstituted C₁-C₄An alkyl group.

24. The coating composition of any one of aspects 16 to 23, wherein the ionic liquid is substantially free of alkali and alkaline earth metals.

25. The coating composition of any one of aspects 16-24, wherein the first functional group comprises a hydroxyl or an alkoxysilyl group.

26. The coating composition of any one of aspects 16-25, wherein the second functional group comprises a hydroxyl group, an epoxy group, a siloxane group, or a combination thereof.

27. The coating composition of any one of aspects 16 to 26, wherein the film-forming polymer comprises at least two of the second functional groups per molecule.

28. The coating composition of any one of aspects 16-27, wherein the third functional group comprises an isocyanate group, an amino group, or a combination thereof.

29. The coating composition of any one of aspects 16-28, wherein the curing agent comprises at least two of the third functional groups per molecule.

30. The coating composition of any one of aspects 16-29, further comprising a silicone additive.

31. The coating composition of any of aspects 16 to 30, wherein the average maximum load of an at least partially cured coating formed from the coating composition of any of aspects 16 to 30 comprising 5 wt% ionic liquid is reduced by at least 50%, based on the total weight of resin solids, compared to an at least partially cured coating formed from a coating composition that does not comprise the ionic liquid, as measured according to the ice adhesion test.

32. The coating composition of any of aspects 16 to 30, wherein an average maximum stress of an at least partially cured coating formed from the coating composition of any of aspects 16 to 30 comprising 5 wt% ionic liquid is reduced by at least 50%, based on the total weight of the resin solids, compared to an at least partially cured coating formed from a coating composition that does not include the ionic liquid, as measured according to the ice adhesion test.

33. A coating composition comprising:

an ionic liquid comprising a salt group and a first functional group; and

a self-curing film-forming polymer comprising a second functional group;

wherein the first functional group is reactive with the second functional group.

34. A method of reducing ice adhesion to a substrate surface comprising applying the coating composition of any one of aspects 16 to 33 onto the substrate surface and at least partially curing the coating composition to form a coating. Herein, the ice adhesion on the coated substrate surface is reduced compared to an uncoated substrate surface and preferably compared to a substrate coated with a substantially identical coating except for the ionic liquid.

35. A coating formed from the coating composition of any one of aspects 16 to 33 in an at least partially cured state.

36. A substrate coated with the coating composition according to any one of aspects 16 to 33 in an at least partially cured state.

The following examples illustrate the invention, however, the following examples should not be construed as limiting the invention to the details thereof. Unless otherwise indicated, all parts and percentages in the following examples, as well as throughout the specification, are by weight.

Examples

Ionic liquid synthesisExamples

Example A

Synthesis of alkoxysilane-functional methylimidazolium chloride Ionic liquids: a500 mL 4-neck kettle equipped with a stirrer, condenser, nitrogen inlet, and thermocouple was charged in a heating mantle with 3-chloro-1-propanol (46.23g, 0.489mol, commercially available from Aldrich), toluene (110mL), and dibutyltin dilaurate (0.028g, available from Air products, Inc.)&Chemicals) commercially available). Agitation was started by a pneumatic motor and a nitrogen flow of 0.2scft/min through the nitrogen inlet. The reaction mixture was heated to 70 ℃. Isocyanatopropyltrimethoxysilane (109.2g, 0.533mol, commercially available from mayian group (Momentive)) was added dropwise to the reaction mixture over 30 minutes at 70 ℃ via an addition funnel. The addition funnel was then rinsed with toluene (11 mL). The reaction mixture was held until 2259cm were no longer detectable by Thermo scientific Nicolet iS5 FT-IR spectrometer^-1Isocyanate peak at (c). After the reaction was complete (about 3 hours), N-methylimidazole (39.75g, 0.484mol, commercially available from odrich) was added dropwise to the reaction mixture over 10 minutes. After addition, the reaction mixture was heated to reflux and held for 4 hours. The reaction mixture was then cooled to 80 ℃ and the stirring was stopped. After 10 minutes, the reaction mixture separated into two phases. The solvent phase was removed by decantation. Additional toluene remaining in the aqueous phase was removed by vacuum distillation. An orange oil was obtained.

Example B

Synthesis of hydroxy-functional methylimidazolium chloride Ionic liquids: a500 mL 4-neck kettle equipped with a stirrer, condenser, nitrogen inlet, and thermocouple was charged with 3-chloro-1-propanol (72.55g, 0.7674mol, commercially available from Odrich), N-methylimidazole (60g, 0.7308mol, commercially available from Odrich), and toluene (120mL) in a heating mantle. Agitation was started by a pneumatic motor and a nitrogen flow of 0.2 scft/min. The reaction mixture was heated to reflux for 4 hours. The reaction mixture was cooled to 70 ℃ and the stirring was stopped. After 10 minutes, the reaction mixture separated into two phases. The solvent phase was removed by decantation. Additional toluene remaining in the aqueous phase was removed by vacuum distillation. An orange oil was obtained.

Example C

Synthesis of polymeric alkoxysilane-functional ionic liquids: a500 mL four-necked kettle equipped with a stirrer, condenser, nitrogen inlet, and thermocouple was charged with Eponex in a heating mantle^TM1510(115.10g, bisphenol A type epoxy resin commercially available from Vast Specialty Chemicals, Hexion Specialty Chemicals), toluene (107.20mL), 2-chloroacetic acid (45.77g, commercially available from Sigma Aldrich) and ethyltriphenylphosphonium iodide (ETPPI, 0.20g, commercially available from Dow Chemical Co.). Agitation was started by a pneumatic motor and a nitrogen flow of 0.2scft/min through the nitrogen inlet. The reaction mixture was gradually heated to 130 ℃. The reaction was held at 130 ℃ for 13 hours until the acid number was less than 2. The acid number was determined by titration using Metrohm 888Titrando and 0.1N KOH in methanol as titrant. The reaction mixture was then cooled to 70 ℃. When the reaction temperature reached 70 ℃, dibutyltin dilaurate (0.046g, commercially available from air chemical company) was added to the reaction mixture. Isocyanatopropyltrimethoxysilane (99.25g, commercially available from mei group) was then added dropwise to the reaction mixture over 30 minutes via an addition funnel. The addition funnel was then rinsed with toluene (10 mL). The reaction mixture was held at 70 ℃ for 6 hours and the equivalent weight of the isocyanate was determined by reacting a sample of the isocyanate with a known excess of dibutylamine in N-methyl-2-pyrrolidone and measuring the excess dibutylamine by potentiometric titration using 888 tirrando and 0.2N hydrochloric acid in isopropanol. The equivalent weight of the isocyanate was determined to be 3, 038 g/eq. After calculation based on isocyanate equivalents, chloropropanol (8.0g, commercially available from sigma aldrich) was added to the reaction mixture. The reaction mixture was held until 2259cm were no longer detectable by Thermo scientific Nicolet iS5 FT-IR spectrometer^-1Up to the isocyanate peak at (c). After completion of the reaction (about 1 hour), N-methylimidazole (39.75g, 0.484mol, commercially available from aldrich) was added dropwise over 10 minutes to the reaction mixture. After addition, the reaction mixture was heated to reflux and held for 5 hours. After holding, the reaction mixture was cooled toAnd the stirring was stopped at 80 ℃. After 10 minutes, the reaction mixture separated into two phases. The solvent phase was removed by decantation. The residual solvent was removed by vacuum distillation. An orange oil was obtained.

Example D

Synthesis of hydroxy-functional methylimidazolium chloride Ionic liquids: a500 mL 4-neck kettle equipped with a stirrer, condenser, nitrogen inlet, and thermocouple was charged with 3-chloro-1-propanol (48.06g, 0.5084mol, commercially available from Odrich), N-methylimidazole (39.75g, 0.4842mol, commercially available from Odrich), and toluene (79.50mL) in a heating mantle. Agitation was started by a pneumatic motor and a nitrogen flow of 0.2 scft/min. The reaction mixture was heated to reflux for 5 hours. The reaction mixture was cooled to 70 ℃ and the progress of the reaction was monitored using TLC plates. Dibutyltin dilaurate (0.029g, commercially available from air chemicals) was then added to the reaction mixture, and isocyanatopropyltrimethoxysilane (99.25g, 0.384mol, commercially available from Meiji corporation) was added dropwise to the reaction mixture over 30 minutes. The addition funnel was then rinsed with butyl acetate (10 mL). After addition, the reaction mixture was held until 2259cm were no longer detectable by Thermo Scientific Nicolet iS5 FT-IR spectrometer^-1Up to the isocyanate peak at (c). The reaction mixture was then cooled to 40 ℃ and the stirring was stopped. After 10 minutes, the reaction mixture separated into two phases. The solvent-containing phase was removed by decantation. The residual solvent was removed by vacuum distillation. An orange oil was obtained.

Paint coating examples

An aluminum panel having a polished surface was used as the test substrate the panel was 0.25 "× 4" × 12 ". The two component epoxy amine primer CA 7502 (available from PPG industries group) was hand sprayed onto one side of the panel with a 2.0 tipped DeVilbiss GTI spray gun at a pressure of 40 pounds per square inch (psi). the primer coating was applied at a dry film thickness (" DFT ") (+ -0.2 mil) of 1.0 mil and allowed to dry at room temperature (about 25℃.) for four hours.

Example 1

The alkoxysilane-functional methylimidazolium chloride ionic liquid of example a was added to a two-component polyurethane topcoat coating composition to form an experimental coating composition. A control polyurethane coating composition without ionic liquid was also used. The two-component polyurethane finish coating composition is

CA 8800 (available from PPG industries). The polyol base material was combined with the solvent according to the manufacturer's instructions. For the experimental coating compositions, 5 wt% or 10 wt% of the ionic liquid of example a (yielding 4.76 wt% and 9.09 wt% of ionic liquid, respectively, based on total resin solids) based on the total weight of base resin and crosslinker, was added to the premixed polyol base material and solvent under agitation using a high lift blade Fawcett pneumatic motor (model # 103A). After the ionic liquid addition was complete, low speed stirring was continued for five minutes. The stirring was then stopped and the mixture allowed to equilibrate for about twenty minutes. The crosslinker was then added to the mixture and the mixture was shaken by hand for about two minutes until the mixture appeared to be consistent. After mixing the components, the coating composition was filtered through a Gerson Elite paint filter having a mesh size of 260 microns into a spray gun as described below. The components of the coating compositions evaluated are shown in table IA below.

TABLE 1A

The control and experimental topcoat coating compositions were hand sprayed onto one side of the primed panel at 40psi using a DeVilbiss GTI spray gun with a 2.0 tip. The topcoat coating composition was applied at a dry film thickness of 2.0 mils (+ -0.2 mils) and allowed to dry at room temperature (about 25 ℃) for four hours. The topcoat coating composition was applied to the other side of the panel in the same manner and allowed to dry at room temperature (about 25 ℃) for four hours. The panels were then cured at room temperature (about 25 ℃ and 40% relative humidity) for seven days before testing.

The contact angle and surface energy of the cured coating were measured using a Kraus Drop Shape Analyzer (Kr ü ss Drop Shape Analyzer) DSA 100. A faceplate was mounted on a sample stage, then a 2 μ L Drop of water was deposited on the coating. an automatic baseline was determined by measuring the position of the intersection of the three phases of solid, liquid, and gas, and the contact angle of the Drop of water with the coating was measured.

The ice adhesion was measured according to the "ice adhesion test" defined as having the procedure of cutting each coated panel into five strips of 1 "× 4" and placing in a CREEL fixture and securing in the fixture with 2 "duct tape from the top 1/2" on each side of the fixture, thereby forming a1 "water tight cavity, filling the cavity up to the top with chilled deionized water that has been placed in a refrigerator set at-15 ℃ to-20 ℃ for about 60 minutes, then placing the filled CREEL fixture in a refrigerator at-20 ℃ overnight to freeze the panels thoroughly in ice, then measuring the average maximum load and average maximum stress of the ice adhesion of each of the five panels using an Instron5567 equipped with an environmental chamber set at-20 ℃, mounting the test fixture such that the fixed end of the tensile tester is connected to the test fixture and the movable panel is connected to the test jaw, this test jaw setting produces relative motion between the test strip and the ice formed by the water, removing the tape holding the water in place, then using a constant pull force, recording the average maximum stress required for each panel and the maximum stress reported in the test B.

TABLE 1B

As shown in table 1B, inclusion of 5 wt.% and 10 wt.% of the ionic liquid resulted in cured coatings having reduced surface energy for ice release, as well as reduced average maximum load and average maximum stress, compared to a control coating that did not include the ionic liquid.

Example 2

The alkoxysilane-functional methylimidazolium chloride ionic liquid of example a was added to a two-component polysiloxane topcoat coating composition to form an experimental coating composition. A control silicone coating composition without ionic liquid was also used. The two-component polysiloxane topcoat coating composition used was PSX 700 (available from PPG industries). For the experimental coating compositions, 5 wt% or 10 wt% of the ionic liquid of example a (yielding 6.53 wt% and 12.27 wt% of ionic liquid, respectively, based on total resin solids) based on the total weight of base resin and crosslinker, was added to the polysiloxane base component with agitation using a high lift blade Fawcett air motor (model # 103A). After the ionic liquid addition was complete, low speed stirring was continued for five minutes. The stirring was then stopped and the mixture allowed to equilibrate for about twenty minutes. The crosslinker was then added to the mixture and the mixture was shaken by hand for about two minutes until the mixture appeared to be consistent. After mixing the components, the coating composition was filtered through a Gerson Elite paint filter having a mesh size of 260 microns into a spray gun as described below. The components of the coating compositions evaluated are shown in table 2A below.

TABLE 2A

The control and experimental topcoat coating compositions were hand sprayed onto one side of the primed panel at 40psi using a DeVilbiss GTI spray gun with a 2.0 tip. The topcoat coating composition was applied at a dry film thickness ("DFT") of 2.0 mils (+ -0.2 mils) and allowed to dry at room temperature (about 25℃.) for four hours. The topcoat coating composition was applied to the other side of the panel in the same manner and allowed to dry at room temperature (about 25 ℃) for four hours. The panels were then cured at room temperature (about 25 ℃ and 40% relative humidity) for seven days before testing.

The contact angle, surface energy and ice adhesion properties of the cured coatings were measured as described in example 1 above. The results of the testing are included in table 2B below.

TABLE 2B

As shown in table 2B, inclusion of 5 wt% and 10 wt% ionic liquid resulted in a cured coating with reduced surface energy for ice release, as well as reduced average maximum load and average maximum stress compared to a control coating that did not include ionic liquid.

Example 3

The hydroxy-functional methylimidazolium chloride ionic liquid of example B and the silicone additive were added to a two-component polyurethane topcoat coating composition to form an experimental coating composition. A control polyurethane coating composition without ionic liquid or silica was also used. The two-component polyurethane finish coating composition is

CA 8925 (available from PPG industries). The polyol base material was combined with the solvent according to the manufacturer's instructions. For the experimental coating compositions, 7 wt% of the ionic liquid of example B and 5.8 wt% of the silicone additive (BYK-Silclean 3700, available from birk aids and instruments) based on the total weight of base resin and crosslinker (yielding 7.39 wt% of the ionic liquid and 6.27 wt% of the silicone additive based on total resin solids) were added to the premixed polyol base material and solvent under agitation using a high lift blade Fawcett pneumatic motor (model # 103A). After the ionic liquid and the organic silicon additive are added, low-speed stirring is continued for five minutes. The stirring was then stopped and the mixture allowed to equilibrate for about twenty minutes. The crosslinker was then added to the mixture and the mixture was shaken by hand for about two minutes until the mixture appeared to be consistent. After mixing the components, the coating composition was filtered through a Gerson Elite paint filter having a mesh size of 260 microns into a spray gun as described below. The components of the coating compositions evaluated are shown in table 3A below.

TABLE 3A

¹Available from birk aids and instruments; contains 25.00% of nonvolatiles.

The contact angle, surface energy and ice adhesion properties of the cured coatings were measured as described in example 1 above. The results of this test are included in table 3B below.

TABLE 3B

As shown in table 3B, inclusion of 7 wt% ionic liquid and 5.8 wt% silicone additive resulted in a cured coating with reduced surface energy for ice release, as well as reduced average maximum load and average maximum stress compared to a control coating that did not include ionic liquid.

Example 4

The hydroxy-functional methylimidazolium chloride ionic liquid of example B was added to a two-component polyurethane topcoat coating composition to form an experimental coating composition. A control polyurethane coating composition without ionic liquid was also used. The two-component polyurethane topcoat coating composition used was CA 8800 (available from PPG industries). The polyol base material was combined with the solvent according to the manufacturer's instructions. For the experimental coating compositions, 5 wt% or 10 wt% of the ionic liquid of example B (yielding 4.76 wt% and 9.09 wt% of the ionic liquid, respectively, based on total resin solids) based on the total weight of base resin and crosslinker, was added to the premixed polyol base material and solvent under agitation using a high lift blade Fawcett pneumatic motor (model # 103A). After the ionic liquid addition was complete, low speed stirring was continued for five minutes. The stirring was then stopped and the mixture allowed to equilibrate for about twenty minutes. The crosslinker was then added to the mixture and the mixture was shaken by hand for about two minutes until the mixture appeared to be consistent. After mixing the components, the coating composition was filtered through a Gerson Elite paint filter having a mesh size of 260 microns into a spray gun as described below. The components of the coating compositions evaluated are shown in table 4A below.

TABLE 4A

The contact angle, surface energy and ice adhesion properties of the cured coatings were measured as described in example 1 above. The results of this test are included in table 4B below.

TABLE 4B

As shown in table 4B, inclusion of 5 wt% and 10 wt% ionic liquid resulted in a cured coating with reduced surface energy for ice release, as well as reduced average maximum load and average maximum stress compared to a control coating that did not include ionic liquid.

Example 5

The polymeric alkoxysilane-functional ionic liquid of example C was added to a two-component polysiloxane topcoat coating composition to form an experimental coating composition. A control silicone coating composition without ionic liquid was also used. The two-component polysiloxane topcoat coating composition used was PSX 700 (available from PPG industries). For the experimental coating compositions, 21 wt% or 29 wt% of the ionic liquid of example C (yielding 21.55 wt% and 29.17 wt% of the ionic liquid, respectively, based on total resin solids) based on the total weight of base resin and crosslinker, was added to the polysiloxane base component with agitation using a high lift blade Fawcett air motor (model # 103A). After the ionic liquid addition was complete, low speed stirring was continued for five minutes. The stirring was then stopped and the mixture allowed to equilibrate for about twenty minutes. The crosslinker was then added to the mixture and the mixture was shaken by hand for about two minutes until the mixture appeared to be consistent. After mixing the components, the coating composition was filtered through a Gerson Elite paint filter having a mesh size of 260 microns into a spray gun as described below. The components of the coating compositions evaluated are shown in table 5A below.

TABLE 5A

The control and experimental topcoat coating compositions were hand sprayed onto one side of the primed panel at 20psi using a DeVilbiss GTI spray gun with a 2.0 tip. The topcoat coating composition was applied at a dry film thickness ("DFT") of 2.0 mils (+ -0.2 mils) and allowed to dry at room temperature (about 25℃.) for four hours. The topcoat coating composition was applied to the other side of the panel in the same manner and allowed to dry at room temperature (about 25 ℃) for four hours. The panels were then cured at room temperature (about 25 ℃ and 40% relative humidity) for seven days before testing.

The contact angle, surface energy and ice adhesion properties of the cured coatings were measured as described in example 1 above. The results of the testing are included in table 5B below.

TABLE 5B

As shown in table 5B, inclusion of 21 wt% and 30 wt% of the polymeric ionic liquid resulted in cured coatings having reduced average maximum load and average maximum stress for ice release compared to control coatings that did not include the polymeric ionic liquid.

It will be appreciated by those skilled in the art, in view of the foregoing disclosure, that numerous modifications and variations can be made without departing from the broad inventive concept described and illustrated herein. Accordingly, it should be understood that the foregoing disclosure is only illustrative of various exemplary aspects of the present application and that numerous changes and modifications within the spirit and scope of the present application and appended claims may be readily made by those skilled in the art.

Claims

1. A method of preparing an alkoxysilane-functional ionic liquid comprising:

2. The method of claim 1, wherein the method comprises:

reacting the halogenated compound with the isocyanate-functional alkoxysilane to form a haloalkoxysilane, and

reacting the haloalkoxysilane with the ionizable compound to form the alkoxysilane-functional ionic liquid.

3. The method of claim 1, wherein the method comprises:

reacting the halogenated compound with the ionizable compound to form an ionic liquid comprising active hydrogen functional groups, and

reacting the ionic liquid comprising an active hydrogen functional group with the isocyanate functional alkoxysilane to form the alkoxysilane functional ionic liquid.

4. The method of claim 1, wherein the ionizable compound comprises a heteroatom.

5. The method of claim 1, wherein the isocyanate-functional alkoxysilane comprises an isocyanate-functional trialkoxysilane represented by formula (I):

wherein R is₆Is C₁-C₃₆Alkanediyl, straight-chain or branched C₃-C₃₆Cycloaliphatic or straight-chain or branched C₆-C₃₆An aromatic group; and R is₇Is C₁-C₄An alkyl group.

6. The method of claim 1, wherein the reaction occurs in the presence of a metal catalyst.

7. An alkoxysilane-functional ionic liquid prepared according to the process of claim 1.

8. The alkoxysilane-functional liquid of claim 7 represented by formula (II):

R₃is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₄is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₅is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₇Is substituted or unsubstituted C₁-C₄An alkyl group.

9. The alkoxysilane-functional liquid of claim 7 represented by formula (III):

10. the alkoxysilane functional liquid of claim 7 represented by formula (IV):

wherein n is more than or equal to 1;

R₃is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₄is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₅is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₇Is substituted or unsubstituted C₁-C₄An alkyl group.

11. A coating composition comprising:

an ionic liquid comprising a salt group and a first functional group;

a film-forming polymer comprising a second functional group; and

a curing agent comprising a third functional group;

12. The coating composition of claim 11, wherein the ionic liquid comprises a structure according to formula (II):

R₃is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₄is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₅is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₇Is substituted or unsubstituted C₁-C₄An alkyl group.

13. The coating composition of claim 11, wherein the ionic liquid comprises a structure according to formula (III):

14. the coating composition of claim 11, wherein the ionic liquid comprises a structure according to formula (IV):

wherein n is more than or equal to 1;

R₃is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₄is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₅is hydrogen or substituted or unsubstituted C₁-C₃₆An alkyl group;

R₇Is substituted or unsubstituted C₁-C₄An alkyl group.

15. The coating composition of claim 11, wherein the ionic liquid comprises a structure according to formula (V):

16. the coating composition of claim 11, wherein the ionic liquid is substantially free of alkali metals and alkaline earth metals.

17. The coating composition of claim 11, wherein the first functional group comprises a hydroxyl group or an alkoxysilyl group, wherein the second functional group comprises a hydroxyl group, an epoxy group, a siloxane group, or a combination thereof, and/or wherein the third functional group comprises an isocyanate group, an amino group, or a combination thereof.

18. The coating composition of claim 11, further comprising a silicone additive.

19. A coated substrate, wherein the coated substrate is at least partially coated with the composition of claim 11.

20. The substrate of claim 19, wherein the average maximum load of the at least partially cured coating is reduced by at least 50% as compared to an at least partially cured coating formed from a coating composition that does not include the ionic liquid, as measured according to the ice adhesion test.

21. The substrate of claim 19, wherein the at least partially cured coating has an average maximum stress that is reduced by at least 50% as compared to an at least partially cured coating formed from a coating composition that does not include the ionic liquid, as measured according to conducting an ice adhesion test.

22. A part at least partially coated with the composition of claim 11.

23. A vehicle comprising the part of claim 22.

24. The vehicle of claim 23, wherein the vehicle comprises an aircraft.

25. A vehicle at least partially coated with the composition of claim 11.

26. The vehicle of claim 25, wherein the vehicle comprises an aircraft.

27. A coating composition comprising:

an ionic liquid comprising a salt group and a first functional group; and

a self-curing film-forming polymer comprising a second functional group;

28. A method of reducing ice adhesion to a substrate surface comprising applying the coating composition of claim 11 onto at least a portion of the substrate surface and at least partially curing the coating composition.