MXPA06008053A - An acrylic composition and a curable coating composition including the same - Google Patents

Abstract

An acrylic composition includes the reaction product of an acrylic polymer, a carbamate having anhydride-reactive functionality and carbamate functionality, and a carboxylic acid anhydride that is reactive with the carbamate to form a carboxylic acid carbamate. The acrylic polymer includes the reaction product of a functionalized monomer, a first compound reactive with the functionalized monomer to form a functionalized intermediate, and a highly branched, polyfunctional core molecule reactive with the functionalized intermediate. The first compound includes vinyl functionality reactive with the functionalized monomer and epoxy functionality. The carboxylic acid carbamate has the carbamate functionality and carboxylic acid functionality that is reactive with the acrylic polymer. The acrylic composition is highly-branched and, when used in coating compositions in combination with a suitable cross-linking agent, enhances recoat adhesion and produces cured films that have optimum scratch, mar, and chip performance, and acid etch resistance.

Description

A COMPOSITION OF ACRYLIC AND A COMPOSITION OF CURABLE COATING THAT INCLUDES THE SAME BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates generally to an acrylic composition. More particularly, the present invention relates to an acrylic composition that can be incorporated into a curable coating composition and then used in coating applications, such as an automotive coating application, that produce films that have adequate performance to the tearing, usual wear and peeling paint. 2. Description of the Related Art Acrylic compositions and their use in a wide variety of coating applications are known in the art. In a curable coating composition, acrylic compositions, together with a suitable crosslinking agent, generally produce a film having good film properties, such as tear resistance, usual wear and tear; ' the painting. Curable coating compositions utilizing acrylic compositions usually require solvents that dissolve or otherwise reduce the acrylic composition for processing and application purposes. Solvents are required due mainly to a high molecular weight and a correspondingly high viscosity for the acrylic composition. Although conventional acrylic compositions are generally inexpensive to prepare, these particular compositions with large proportions of non-functional alkyl acrylic monomers provide poor new coating adhesion due to the formation of pendant and non-functional acrylic chains during curing. These acrylic chains migrate to an upper surface of a cured film of a coating composition having the conventional acrylic composition and inhibit the adhesion of the coating compositions that are substantially applied to the cured film. It is also known in the art that other properties of the cured film, including the tear resistance and the usual wear, can be compromised when the coating composition includes the conventional acrylic composition due to the formation of the acrylic chains described above. In addition, conventional acrylic compositions that do not include carbamate functionality for subsequent aminoplast crosslinking exhibit poor resistance to acid attack. As a result, the cured film formed from conventional acrylic compositions is susceptible to damage due to acid rain. * • > It is known that there is a move towards using acrylic compositions having lower molecular weights so that the total amount of the solvents, ie the volatile organic compounds (VOCs), required in the coating composition is reduced. However, it is also known that coating compositions using conventional acrylic compositions with lower molecular weights produce films having poorer film properties as evidenced by reduced performance to tearing, usual wear and peeling of the paint. Highly branched compositions, eg, star, are more frequently used because they offer higher molecular weights although they exhibit low viscosity, when compared to the viscosity of conventional acrylic compositions, ie, acrylic compositions which are not highly branched. These highly branched compositions have been based to date, mainly on polyester. However, some highly branched acrylic compositions have been developed by complex methods such as Atomic Transfer Radical Polymerization (ATRP) and Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT). These methods are complex, and therefore are generally undesirable for a variety of reasons including, but not limited to slow reaction times, poor manufacturing process, use of metal or sulfur containing compounds, and a requirement for the subsequent purification of the acrylic composition . Due to the inadequacy associated with the acrylic polymers of the prior art, especially the highly branched acrylic compositions developed by ATRP and RAFT, it is desirable to provide a novel acrylic composition that is economical and highly branched. It is also advantageous to provide an acrylic composition, and a curable coating composition comprising the acrylic composition, which promotes acid attack resistance, improves the new coating adhesion, and is optimized for crosslinking when used in coating compositions.

SUMMARY OF THE INVENTION AND ADVANTAGES The subject of the invention provides an acrylic composition and a curable coating composition that includes the acrylic composition. The acrylic composition includes an acrylic polymer. The acrylic polymer includes the reaction product of a functionalized monomer, a first compound reactive with the functionalized monomer that forms a functionalized intermediate, and a highly branched polyfunctional core molecule, with the intermediate functionalized to form the acrylic polymer. The first compound includes a functionality of the reactive vinyl with the functionalized monomer and an epoxy functionality. The acrylic polymer is highly branched and cost effective, when compared to conventional acrylic polymers that are highly branched. The acrylic composition further includes a carboxylic acid carbamate. Carboxylic acid carbamate has carbamate functionality and carboxylic acid functionality that is reactive with the functionality of the epoxy of the acrylic polymer. Thus, the final acrylic composition includes a carbamate functionality; The curable coating composition includes the acrylic composition and a crosslinking agent that is reactive with the acrylic composition. When used in the curable coating composition, in combination with the crosslinking agent, the acrylic composition produces films, especially clearcoated films, which have optimum performance to tearing, usual wear and tear of the paint, and resistance to attack. acid. In addition, the acrylic compositions improve the coating adhesion.

DETAILED DESCRIPTION OF THE PREFERRED MODALITY The acrylic composition of the present invention is preferably used in curable coating compositions and cured films to improve certain properties of the cured film including, but not limited to, the acid etch resistance and the adhesion of covering. More specifically, the acrylic composition has carbamate functionality that can be crosslinked with a crosslinking agent in the curable coating compositions. As referred to herein, the acrylic composition can include the reaction product of the acrylic polymer and a carboxylic acid carbamate after the reaction of those components. The final acrylic composition formed after the reaction of the above mentioned anion components includes a carbamate functionality. Alternatively, the acrylic composition may include the acrylic polymer and a non-reactive carboxylic acid carbamate. Preferably, the carboxylic acid carbamate includes the reaction product of a carbamate having reactive functionality with anhydride and anhydride carboxylic acid that is reactive with the reactive functionality with carbamate anhydride. Preferably, the reactive functionality with anhydride is at least one of the hydroxyl functionality and the amino functionality. The carboxylic acid carbamate can be formed at any time before crosslinking. Thus, in other embodiments, the acrylic composition may include the acrylic polymer, carbamate, and anhydrous carboxylic acid prior to the reaction between these compounds, or may include the acrylic polymer and the carbamate or the acrylic polymer and the anhydrous carboxylic acid , with the carboxylic acid anhydride or carbamate, respectively, to be added at a last moment before; of crosslinking. The acrylic polymer is also referred to in the art as a star acrylic polymer or a star polymer having a core and a plurality of functionalized acrylate branches (also referred to as chains, arms, appendages and the like). Preferably, the acrylic polymer is formed through a free radical acrylic polymerization method which is further described below. More specifically, the acrylic polymer is the reaction product of a functionalized monomer, a first compound that is reactive with the functionalized monomer that forms a functionalized intermediate, and a highly branched polyfunctional core molecule, reactive with the functionalized intermediate that forms the acrylic polymer. The first compound includes a functionality of the vinyl that is reactive with the monomer. The first compound also includes an epoxy functionality that remains non-reactive in the acrylic polymer. The highly branched polyfunctional core molecule is referred to below simply as the core molecule, which functions as the core of the acrylic polymer. The first compound and the core molecule are further described below. • In one embodiment, the functionalized monomer, hereinafter referred to simply as the monomer, includes a functionality reactive to the hydroxyl and a functionality of the vinyl. The "functionalized" descriptive terminology that precedes the monomers refers to any functionality that can react with the functionality from the core molecule. The vinyl functionality of the monomer is suitable for stopping chain growth during the free radical acrylic polymerization of the monomer and the first compound. Preferably, the hydroxyl-reactive functionality remains non-reactive in the functionalized intermediate, after polymerization between the monomer and the first compound, and is reactive with the functionality of the hydroxyl present in the core molecule. For example, the monomer may include an aliphatic isocyanate functionality, which is reactive with hydroxyl functionality and may also be referred to as isocyanate functionality, if the core molecule includes a polyol, which has hydroxyl functionality. A more preferred monomer is α, α-dimethyl isopropenylbenzyl isocyanate, which has both the functionality of the vinyl and the aliphatic isocyanate functionality as well as the hydroxyl-reactive functionality. The α, α-dimethylisopropenylbenzyl isocyanate is also known in the art as TMI® Unsaturated Aliphatic Isocyanate (Meta) and is commercially available from Cytec Industries. The isocyanate of a, a-dimethyl isopropenylbenzyl is also referred to in the art as isocyanate of 3-isopropenyl-a, a-dimethylbenzyl and isocyanate of a, a-dimethyl meta-isopropenylbenzyl. In addition, although less preferred, the ortho and para forms of the a, a-dimethyl isopropenylbenzyl isocyanate are also feasible. The α, α-dimethyl isopropenylbenzyl isocyanate has the effect of chain stop by limiting the number of -NCO functionality under normal acrylic polymerization conditions. For descriptive purposes, a chemical representation of an isocyanate of a, a-dimethyl isopropenylbenzyl is described below.

Other suitable examples of hydroxyl-reactive functionality of the monomer may include cyano functionality, carboxylic acid halide functionality, melamine functionality and combinations thereof. In other embodiments, the functionality reactive to the hydroxyl can be replaced with a hydroxyl functionality. It will be appreciated that when the functionality of the hydroxyl replaces the reactive functionality to the hydroxyl, the nickel molecule has a reactive functionality to hydroxyl, which will be reacted with the functionality of the hydroxyl of the monomer. One of such preferred TMI monomers that has had the functionality of the isocyanate replaced by the functionality of methylol is modified. Other monomers are suitable for the acrylic composition as long as the monomers are functionalized for subsequent reaction with the core molecule and have either the ability to stop chain growth during free radical acrylic polymerization, or have the ability to disintegrate upon initiation of free radical acrylic polymerization with the first compound. Examples of other suitable monomers that have the ability to stop chain growth include, but are not limited to, functionalized styrene (preferably with substituents at positions 2 and 6), functionalized vinyltoluene, functionalized α-methylstyrene, functionalized diphenylethylene, dinaphthaleethylene functionalized and combinations thereof. In any case, the monomer is preferably present in the acrylic polymer in an amount from 1 to 20, more preferably from 3 to 10 parts by weight based on the total weight of the acrylic polymer. When the monomer including the functionality of the vinyl is used, an initiator is used to initiate free radical acrylic polymerization between the monomer and the first compound. As understood by those skilled in the art, a wide variety of primers can be used. However, it is preferred that the initiator be selected from the group of inorganic persulfates such as ammonium persulfate, (NH4) 2S208, potassium persulfate, K2S208 and sodium persulfate, Na2S20e, dialkyl peroxides such as di-ter-peroxide. butyl and dicumyl peroxide, hydroperoxides such as eumeno hydroperoxides and tert-butyl hydroperoxide, peresters such as tert-butyl peroctoate (TBPO), which is also known as tert-butyl peroxy-2-ethylhexanoate, tert-butyl perbenzoate , tert-butyl perpivalate, tert-butyl per-3, 4, 5-trimethylhexanoate and tert-butyl per-2-ethylhexanoate, azo compounds and combinations thereof. Suitable azo compounds include, but are not limited to Vazo® 52, 64, 67 and the like. Vazo® 52, 64 and 67 are respectively 2, 2 '-azobis (2,4-dimethylpentan-nitrile), 2,2'-azobis (2-methylpropan-nitrile), and 2, 2'-azobis (2-methylbutan) -nitrile). Inorganic peroxodisulfates and ammonium or alkali metal peroxydiphosphates can also be used to initiate the free-radical acrylic polymerization method. More preferably, the initiator is tert-butyl peroctoate. In another embodiment, the monomer includes a radical-forming portion instead of the functionality of the vinyl. The term "radical-forming portion" is defined as any portion of the monomer that disassociates in the presence of a catalyst, up to the application of heat or through any other known method for disassociating the monomer. In addition, the monomer includes-a functionality that can be functional with hydroxyl or a functionality reactive to hydroxyl, depending on the functionality of the core molecule that is used. After the dissociation of the monomer, the radical-forming portion of the monomer has a free radical. Preferably, the monomer includes the radical-forming portion, which preferably includes a peroxide and a hydroxyl functionality. The functionality of the hydroxyl can be reacted with the core molecule which includes a functionality reactive to the hydroxyl. A preferred monomer is Cyclonox®E, which is commercially available from Akzo-Nobel. Cyclonox®E "'is di- (1-hydroxycyclohexyl) peroxide, which is of the formula: The dissociation of di- (l-hydroxycyclohexyl) peroxide results in the cleavage of oxygen-oxygen bond, leaving two radicalized compounds each having the free radical in the oxygen atom that was part of the oxygen-oxygen bond before dissociation , as shown by the following formula: where "*" indicates the free radical. Other monomers that include the radical-forming portion and the functionality of the hydroxy are also suitable. Examples of such other monomers include, but are not limited to, VA-085 and VA-086, which may be characterized by azo compounds having hydroxyl functionality. VA-085 is of the formula: And VA-086 is of the formula: In other embodiments, instead of the functionality of the hydroxyl, the monomer may include a hydroxyl-reactive functionality and a radical-forming portion. The hydroxyl-reactive functionality can react with the core molecule which includes a hydroxyl functionality. A suitable monomer can be formed from Vazo 67 by converting the cyano functionality to an amino or amido functionality. The amino or amido functionality can then be reacted with isocyanate r or aminoplast, respectively. As stated previously, the first compound is reactive with the monomer that forms the functionalized intermediate. When the monomer which includes the functionality of the vinyl is used, the first compound is reactive with the functionality of the vinyl after the initiator initiates free radical acrylic polymerization. When the monomer including the radical-forming portion is used, the first compound is reactive with the radical-forming portion of the monomer. More specifically, it is the functionality of the vinyl of the first compound that is reactive with either the functionality of the vinyl monomer after initiation or the free radical portion of the monomer after dissociation, depending on the monomer used. The first compound having the functionality of the vinyl and the functionality of the epoxy can be any of an acrylate or methacrylate of epoxy functionality. Preferably, the first compound is selected from the group consisting of glycidyl acrylate, glycidyl acrylates and combinations thereof. For descriptive purposes, a chemical representation of glycidyl methacrylate is described below.

As stated above, the functionality of the vinyl is reactive with the monomer. The functionality of the epoxy is non-reactive with the hydroxyl or the reactive functionality of the hydroxyl either of the monomer or of the core molecule under conditions of objective reaction. In other words, the functionality of the epoxy remains non-reactive in the acrylic polymer and is presented to participate in the additional reactions, which will be described in further detail below. The acrylic polymer may further include the reaction product of a second compound that is reactive with the monomer and the first compound to form the functionalized intermediate. The second compound can be included to modify a glass transition temperature Tg of the cured film formed from the curable coating composition, which curable coating composition will be described in further detail below.

In addition, the second compound can also function to modify the equivalent weight and, therefore, the crosslink density in the cured film. Preferably, the second compound is selected from the group of, but is not limited to, acrylates, methacrylates, acrylonitriles, styrenes, alkenes, alkene anhydrides (cyclic or acyclic), and combinations thereof, each of which It has vinyl functionality. The second compound can be functionalized or non-functionalized with an additional functionality different from the functionality of the vinyl. More specifically, the second compound may include additional functionality as long as the additional functionality of the second compound is non-reactive with the functionalities of the monomer, the first compound or the core molecule. Preferably, the second compound is free of functionality different from the functionality of the vinyl. In the preferred embodiment, the first compound, and optionally the second compound, is presented in a total amount from 10 to 99, more preferably from 15 to 90 parts by weight based on the total weight of the acrylic polymer. Preferably, the acrylic polymer has a molecular weight, Mw of 700 to 48,000. For the acrylic polymer having the molecular weight, Mw, within the above range, the functionalized intermediate described below preferably has a molecular weight Mw of about 300 to 12,000, more preferably from 1,000 to 4,000. Of course, higher molecular weights, Mw for the functionalized intermediate, are possible, but such functionalized intermediates are not ideal for curable coating compositions due to excessive resultant viscosity in the acrylic composition. As stated above, the first compound and the monomer react to form the functionalized intermediate. Assuming that the monomer is an isocyanate of a, a-dimethyl isopropenylbenzyl, that is, the monomer has the functionality reactive with hydroxyl and the functionality of the vinyl, with the first compound being glycidyl methacrylate, the functionalized intermediate described below is formed, in where INIT. represents the initiator and m varies from 1 to 80, more preferably from 1-5 to 30.

The functionalized intermediate described above is equivalent to the functionalized acrylate ramifications of the acrylic polymer. That is, this functionalized intermediary functions as the branches for subsequent connection, through condensation, to the core of the acrylic polymer. The functionalized acrylate branches are formed first and the core, i.e., the core molecule, is then condensed with the functionalized acrylate branches. It will be understood that the intermediary functionalized above is simply an example of many different functionalized intermediates that can be formed during the reaction to form the acrylic composition and the subject invention is not necessarily limited to this particular functionalized intermediate and subsequent derivatives thereof. For example, when the monomer is di (1-hydroxycyclohexyl) peroxide, that is, the monomer having the radical forming portion and the functionality of the hydroxyl, and the first compound is glycidyl methacrylate, the functionalized intermediate is formed, where m varies preferably from 1 to 80, more preferably from 15 to 30. The functionalized intermediate is described below. where "*" indicates the free radical. The functionalized intermediate can be terminated, in the free radical, through a number of termination reactions such as through a proton extraction from a solvent reaction with another radicalized compound, the decomposition that forms a double bond at the site. of free radical or any combination of those reactions. Once the functionalized intermediate is formed, the core molecule is introduced to react with the functionalized intermediate that forms the acrylic polymer. The core molecule is selected to provide a functionality that is reactive with the functionality of the monomer that remains non-reactive after polymerization with the first compound. As described above, the core molecule is highly branched and is polyfunctional, that is, it has a functionality greater than or equal to 2. For the purposes of this invention, the term "highly branched" indicates core molecules that initiate with a core and branch into at least two, preferably at least three or more directions. Although excessive branching is not required, it is more preferred that the core molecule, preferably an isocyanate or a polyol, be highly branched to achieve the desired viscosity benefits. The core molecules can also be described as branched compounds having a plurality of functionalities. The functionalities can be primary, secondary and tertiary functions. The. Core molecule is selected from the group of isocyanates, isocyanurates, melamines, polyols, polycarboxylic acid halides and combinations thereof, with the reactive core molecule with the functionalized intermediate to form the acrylic polymer.However, other potential core molecules may be different than those mentioned above. and they could provide a functionality different from those described above For example, the core molecule can also be a melamine-formaldehyde resin.The preferred core molecules when the functionalized intermediate has the hydroxyl-reactive functionality, i.e., wherein the monomer is a, a-dimethyl isopropenylbenzyl isocyanate having the functionality of the aliphatic isocyanate, which includes polyols that are reactive with the functionalized intermediate to form the acrylic polymer Preferably, the polyols are selected from the group of glyl, propylene glycol, erythritol, pentaerythritol , dipentae ritritol, trimethylolethane, trimethylolpropane, dulcitol, threitol and combinations thereof. For descriptive purposes, a chemical representation of pentaerythritol is described below.

The preferred core molecules for reacting with the functionalized intermediate having the functionality of the hydroxyl, ie, wherein the monomer is the peroxide having the functionality of the hydroxyl, which includes isocyanates, isocyanurates, melamines, carboxylic acid halides and combinations of the same ones that are reactive with the functionalized intermediate to form the acrylic polymer. More preferred core molecules for reacting with the functionalized intermediate having hydroxyl functionality include isocyanates. Preferably, isocyanates are selected from the group of trimethylolpropane carbamate with toluene diisocyanate, pentaerythritol carbamate with toluene diisocyanate, and combinations thereof. Other preferred isocyanates include polyisocyanate Desmodur® or Mondur® commercially available from Mobay Corporation of Pittsburgh, PA. For descriptive purposes, a chemical representation of the pentaerythritol carbamate with toluene diisocyanate is described below.

The core molecule is condensed with (the functionalized intermediate, that is, with the functionalized acrylate branches, more specifically, the core molecule and the functionalized intermediate are reacted to form the acrylic polymer.The success of the condensation of the molecule The core and the functionalized intermediate depends on the observation that when the monomer is used to polymerize the first compound, each of the polymer strands formed will have one and only one functionality that originates from the monomer in most cases. of the core molecule present in the reaction must be balanced with the amount of the functionalized intermediate, i.e., the branching of functionalized acrylate, which is formed through the reaction of the monomer, the first compound, and, optionally, the second compound. For this purpose, it is preferred that the molar ratio of the core molecule to functionalized termediary is from 1:20 to 1: 1, more preferably from 1:10 to 1: 3. The core molecule establishes a foundation for the acrylic polymer. Preferably, the core molecule is present in an amount from 0.1 to 20, more preferably from 0.5 to 10, and more preferably from 0.5 to 1.5 parts by weight based on the total weight of the acrylic polymer. When the monomer is a, a-dimethyl isopropenylbenzyl isocyanate, the first compound is glycidyl methacrylate, the second compound is not present, and the core molecule is pentaerythritol, the acrylic polymer is described below, wherein INIT. represents the initiator and m varies from 1 to 80, most preferably from 15 to 30.

When the monomer is di- (l-hydroxycyclohexyl) peroxide, the first compound is glycidyl methacrylate, and the core molecule is pentaerythritol carbamate with toluene diisocyanate, the acrylic polymer is described below, wherein m varies from 1 to 80, more preferably from 15 to 30, and the "*" indicates the free radical, which can be terminated as described above.

Preferably, the acrylic polymer is present in the acrylic composition in an amount of from 10 to 80 parts by weight based on the total weight of the acrylic composition, more preferably from 30 to 60 parts by weight based on the weight total of the acrylic composition. As suggested above, the carboxylic acid carbamate is preferably formed from the carbamate and / or the carboxylic acid anhydride. However, it will be appreciated that any carboxylic acid carbamate may be suitable for the subject invention, and may be formed from components other than the carbamate and the carboxylic acid anhydride. For example, in qfra modality, the carboxylic acid carbamate may include the reaction product of the acidic monomers, such as acrylic acid and methacrylic acid, and esters of the propyl carbamate of those acidic monomers. The acrylic polymer, carbamate and carboxylic acid anhydride are combined together and reacted upon heating at a temperature of about 130 ° C. Reactive functionality with carbamate anhydride and reactive anhydride. The acrylic composition can be combined with the crosslinking agent which is reactive with the acrylic composition to form the curable coating composition. In one embodiment, the carbamate has hydroxyl functionality and carbamate functionality. The carbamate can be described as a hydroxyalkyl carbamate. The hydroxyalkyl carbamate has from 1 to 20 carbon atoms in the alkyl chain. If the carbamate is the hydroxyalkyl carbamate, then it is preferably selected from the group of hydroxymethyl carbamate, hydroxyethyl carbamate, hydroxypropyl carbamate, hydroxybutyl carbamate, and combinations thereof. In general, the hydroxyalkyl carbamates that are suitable for use as the carbamate in the present invention are compounds that include the general structure wherein Ri is CH20H and R is an alkyl or ester having from 1 to 20 carbon atoms. Alternatively, Ri is H and R2 is wherein R3 is an alkyl or an ester having from 1 to 20 carbon atoms. Preferably, the carbamate is hydroxypropyl carbamate. The hydroxypropyl carbamate may include a combination of hydroxypropyl carbamate having a primary hydroxyl functionality and a hydroxypropyl carbamate having a secondary hydroxyl functionality. For descriptive purposes, the chemical representations of the hydroxypropyl carbamate with the functionality of the primary hydroxyl and the hydroxypropyl carbamate with the functionality of the secondary hydroxyl are described respectively after Generally, hydroxyalkyl carbamates are prepared from a compound having an oxirane group. For example, the hydroxypropyl carbamate is prepared from propylene oxide, which is first reacted with C02 to form propylene carbonate. The reaction of propylene carbonate with ammonia produces hydroxypropyl carbamate. Thus, the hydroxyalkyl carbamate can be prepared from any compound containing an oxirane group. An additional compound having an oxirane group that is particularly useful is glycidyl neodecanoate which is commercially available from Millar-Stephenson Chemical Company, Inc., under its CARDURA® product line, as CARDURA E IOS. Volume derivative groups in the hydroxyalkyl carbamates tend to produce lower resin viscosities. It will be appreciated that other compounds having a plurality of hydroxyl functionalities and / or a plurality of carbamate functionalities can also be used as the carbamate. For example, a dihydroxyalkyl carbamate, such as dihydroxybutyl carbamate, can be used as the carbamate. Furthermore, as suggested above, the hydroxyl functionality of the carbamate can be replaced with the amino functionality or any other reactive functionality with anhydride. The carbamate is presented in the acrylic composition in an amount from 1 to 50, preferably from 10 to 30 parts by weight based on the total weight of the acrylic composition. The carboxylic acid anhydride is reactive with the reactive functionality with carbamate anhydride to form the carboxylic acid carbamate having the carbamate functionality and the carboxylic acid functionality. The carbamate and the carboxylic acid anhydride can be reacted in the presence of the acrylic polymer or, alternatively, before being combined with the acrylic polymer. The resulting carboxylic acid carbamate is reactive with the acrylic polymer. The carboxylic acid anhydride can be either an aromatic or non-aromatic cyclic anhydride. Suitable carboxylic acid anhydrides which are suitable for the subject invention are selected from the group of maleic anhydride, hexahydrophthalic anhydride, methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, dodecenylsuccinic anhydride, trimellitic anhydride, glutaric anhydride and combinations thereof. More preferably, the carboxylic acid anhydride is hexahydrophthalic anhydride. For descriptive purposes, a chemical representation of the hexahydrophthalic anhydride is described below.

The carboxylic acid anhydride provides an acid functionality. That is, the functionality of the carboxylic acid in the carboxylic acid carbamate originates in the carboxylic acid anhydride. The carboxylic acid anhydride is present in an amount from 1 to 60, preferably from 10 to 40, and more preferably from 15 to 30, parts by weight based on the total weight of the acrylic composition. Also, the effective equivalents of the carbamate to the carboxylic acid anhydride are from 0.5: 3 to 3: 0.5. More specifically, in the preferred embodiment, the molar ratio of the carbamate, ie, hydroxypropyl carbamate to the carboxylic acid anhydride, i.e., hexahydrophthalic anhydride, is 1: 1. For descriptive purposes, a chemical representation of the carboxylic acid carbamate formed by the reaction of one mole of hydroxypropyl carbamate and one mole of hexahydrophthalic anhydride is described below. The carboxylic acid carbamate that is formed by the reaction of the hydroxypropyl carbamate having the primary hydroxyl functionality is first described Next, the carboxylic acid carbamate which is formed by the reaction of the hydroxypropyl carbamate having the secondary hydroxyl functionality is described.

As described above, any of the above carboxylic acid carbamates, formed with the preferred reagents, have a carboxylic acid functionality and a carbamate functionality. The preferred carboxylic acid carbamate is usually a combination of the two structures described above. The carboxylic acid functionality of the carboxylic acid carbamate is formed when the anhydride ring of the hexahydrophthalic anhydride is opened and forms ester connections with the hydroxyl functionality of the hydroxypropyl carbamate. The hydrogen atom from the hydroxyl functionality of the hydroxypropyl carbamate and the oxygen atom originally from the reactive anhydride ring to form the carboxylic acid functionality. The chemical representations of the carboxylic acid carbamate described above are merely illustrative of the subject invention. The carboxylic acid carbamate described above has a carboxylic acid functionality and a carbamate functionality which are derived from the structures of the carbamate, preferably hydroxypropyl carbamate, and from the carboxylic acid anhydride, preferably hexahydrophthalic anhydride. It will be understood that if the alternative compounds are selected for the carbamate and for the carboxylic acid anhydride, then the carboxylic acid carbamate may be different from that described above, and may have multiple carboxylic acid functionalities and multiple hydroxyl functionalities. The carboxylic acid functionality of the carboxylic acid carbamate is reactive with the epoxy functionality of the acrylic polymer. In a preferred embodiment of the subject invention, the carbamate includes hydroxypropyl carbamate, the carboxylic acid anhydride includes hexahydrophthalic anhydride, and the acrylic polymer is any of the two structures shown above which are the reaction product of either isocyanate of a, α-dimethyl isopropenyl, glycidyl methacrylate and pentaerythritol or the reaction product of di- (1-hydroxycyclohexyl) peroxide, glycidyl methacrylate and pentaerythritol carbamate with toluene diisocyanate. However, it will be appreciated that other acrylic polymers may also be suitable for the subject invention. For descriptive purposes, a chemical representation of a portion of the acrylic compositions described above is shown below.

As illustrated, the carboxylic acid functionality of the carboxylic acid carbamate has reacted with the epoxy functionality of the acrylic polymer through a ring-opening reaction, which results in the formation of the hydroxyl functionality and the binding of the carbamate of carboxylic acid to the acrylic polymer, thereby imparting the functionality of carbamate to the acrylic polymer. The above chemical representation is valid for any of the two preferred embodiments as described above, wherein the label "Acrylic Polymer" corresponds to the structure of the respective modality of the acrylic polymer, R corresponds to both the initiator and the free radical, depending of the monomer used and m is from 1 to 80, more preferably from 15 to 30.

As suggested above, the curable coating composition that includes the acrylic composition also includes the crosslinking agent that is reactive with the acrylic composition. Preferably, the crosslinking agent is reactive with the carbamate functionality of the acrylic composition. Additionally, the crosslinking agent can be reactive with the hydroxyl functionality that is formed as a result of the reaction between the epoxy functionality of the acrylic polymer and the carboxylic acid functionality of the carboxylic acid carbamate. Suitable crosslinking agents are selected from the group of, but not limited to, polyisocyanates, polyisocyanurates, melamine-formaldehyde resins, polycarboxylic acid halides and combinations thereof. Also suitable for the crosslinking agent are aminoplast resins which are reactive with the functionality of the carbamate. As understood by those skilled in the art, an aminoplast resin is formed by the reaction product of a formaldehyde and an amine wherein the preferred amine is a urea or a melamine. In other words, the aminoplast resin may include urea resins and melamine-formaldehyde resins. The melamine-formaldehyde resins of the preferred embodiment include either a methylol functionality, an alkoxymethyl functionality or both. The functionality of the alkoxymethyl is of the general formula -CH2OR ?, wherein Ri is an alkyl chain having from 1 to 20 carbon atoms. As understood by those skilled in the art, the functionality of the methylol and the functionality of the alkoxymethyl are reactive with the carbamate functionality of the acrylic composition. The functionalities of methylol and alkoxymethyl are preferably reactive with the functionality of the carbamate, when opposed to any functionality of the hydroxyl, for Yeticular 'the curable coating composition until cure. Examples of suitable aminoplast resins include, but are not limited to, monomeric or polymeric melamine-formaldehyde resins, including melamine resins that are partially or fully alkylated using alcohols preferably having one to six, more preferably one to four carbon atoms, such as melamine methylated with hexametoxy; urea formaldehyde resins including methylol ureas and siloxy ureas such as a butylated urea formaldehyde resin, alkylated benzoguanimines, guanyl ureas, guanidines, biguanidines, polyiguanidines and the like. Although urea and melamine are the preferred amines, other amines such as triazines, triazoles, diazines, guanidines or guanamines can also be used to prepare the aminoplast resins. In addition, although formaldehyde is preferred to form the aminoplast resin, other aldehydes, such as acetaldehyde, crotonaldehyde and benzaldehyde may also be used. The monomeric melamine-formaldehyde resins are particularly preferred. The melamine-formaldehyde resin includes hexametoxymethylmelamine (HMMM). The HMMM is commercially available from Solutia under its Amino Resimene Retinulant Resins. HMMM is shown in the following chemical representation.

Until the addition of the crosslinking agent to the acrylic composition, the functionality of the alkoxymethyl of the HMMM, specifically the CH2OCH3 group and the functionality of the carbamate of the acrylic polymer reacts to establish urethane (-H-CO-O-) connections. The urethane connection between the acrylic composition and the crosslinking agent is from the carbamate-melamine reaction and is ideal for environmental acid etch resistance. Because the acrylic composition of the present invention has functionality of the terminal carbamate and because the aminoplast is reactive with the functionality of the carbamate, the ether connections resulting from a hydroxyl-aminoplast cure functionality, and the which are particularly susceptible to acid attack, can be avoided as the primary crosslinking mechanism. To achieve this, the amount of the crosslinking agent, ie, the aminoplast resin, '- in the preferred embodiment, is limited so that the crosslinking agent reacts only with the functionality of the available carbamate in the acrylic composition. That is, in the preferred embodiment, the aminoplast crosslinking agent preferably reacts with a carbamate functionality available prior to any substance reaction with the hydroxyl functionality that occurs in the acrylic composition. It is therefore possible to control the amount of ether connections that are formed when the acrylic composition and the crosslinking agent are crosslinked. The amount of the crosslinking agent can be increased if crosslinking with hydroxyl functionality is desired for any reason. Although not necessarily preferred, an alternative crosslinking agent for use in the subject invention is the polyisocyanate crosslinking agent. The most preferred polyisocyanate crosslinking agent is a triisocyanurate. The polyisocyanate crosslinking agent can be an aliphatic polyisocyanate including a cycloaliphatic polyisocyanate or an aromatic polyisocyanate. The term "polyisocyanate" as used herein refers to any compound having a plurality of isocyanate functionalities on average per molecule. The polyisocyanates include, for example, monomeric polyisocyanates including monomeric diisocyanates, biurets and isocyanurates of monomeric polyisocyanates, extended polyfunctional isocyanates formed by reacting one mole of a diol with two moles of a mole diisocyanate of a triol with three moles of a diisocyanate and the like. Useful examples of suitable polyisocyanate crosslinking agents include, without limitation, ethylene diisocyanate, 1,2-diisocyanatopropane, 1,3-diisocyanatopropane, 1,4-butylene diisocyanate, lysine diisocyanate, 1,4-methylene bis (isocyanate of cyclohexyl), isophorone diisocyanate, toluene diisocyanate, toluene diisocyanate isocyanurate, 4,4 '-diphenylmethanol diisocyanate, 4,4'-isocyanurate-diphenylmethane diisocyanate, methylenebis-4, -isocyanatocyclohexane, diisocyanate isophorone, isocyanurate of isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 1,6-hexamethylene diisocyanate isocyanurate, 1,4-cyclohexane diisocyanate, p-phenylene diisocyanate, 4,4 '-4"- Triphenylmethane triisocyanate, tetra ethyl hexylene diisocyanate, metaxylene diisocyanate and combinations thereof Aliphatic polyisocyanates are preferred when the curable coating composition is used as a finishing composition. final automotive Generally, the acrylic composition is presented in an amount of from 65 to 90, preferably from 75 to 90 parts by weight based on the total weight of the curable coating composition and the crosslinking agent is presented in an amount from 1 to 35, preferably from 5 to 25, and more preferably from 7 to 15 parts by weight based on 100 parts by weight of the curable coating composition. The ratio of the effective equivalents of the acrylic composition to the crosslinking agent is from 3: 1 to 1: 3. The curable coating composition may also include an additive or a combination of additives. Such additives include, but are not limited to solvents, catalysts, hindered amine light stabilizers (HALs), ultraviolet absorbers (UVAs), rheology control agents, anti-yellowing agents, adhesion promoting agents and the like. Specific examples of some of the above additives include n-methyl pyrrolidone and oxo-hexyl acetate as solvents for affecting such characteristics as launch and release resistance, and polybutyl acrylate, fumed silica and silicone as rheology control agents. A method for preparing the acrylic composition can include the steps for reacting the monomer with the first compound to form the functionalized intermediate, and reacting the highly branched polyfunctional core molecule with the functionalized intermediate to form the acrylic polymer. The carbamate having the reactive functionality with anhydride and the functionality of the carbamate is reacted with the carboxylic acid anhydride to form the carboxylic acid carbamate having the carbamate functionality and the carboxylic acid functionality. The carbamate and the carboxylic acid anhydride can be reacted either in the presence or absence of the acrylic polymer. Once formed, the carboxylic acid carbamate is reacted with the epoxy functionality of the acrylic polymer to form the acrylic composition having the carbamate functionality. The following examples illustrating the formation and use of the acrylic composition of the present invention, as presented herein, are intended to illustrate and not limit the invention.

EXAMPLES In the Examples, Polymer A Acrylic was prepared by adding and reacting the following components, in parts by weight based on the total weight of the acrylic composition, unless otherwise indicated.

Table 1 To form Acrylic Polymer A, 75.0 grams of Solvesso® 100 (also referred to as Aromatic 100) were added into a reactor, and the reactor was heated through a conventional heat supply at a temperature of 150 ° C. Once the reactor reached 150 ° C, a mixture of the Functionalized Monomer, the First Compound, the Second Compound A, the Second Compound B, and the Initiator were added to the reactor for about 3 hours to form the functionalized intermediate. Once the functionalized intermediate was formed, the temperature was decreased until the temperature of the functionalized intermediate reached approximately 100-110 ° C. Then, Nucleus A Molecule was added to the reactor along with an additional 11 grams of Solvesso® 100. One drop of DBTDL was added. The reaction was maintained until 100 ° C until the measured% of NCO was less than 0.1 meq in solids. Polymer B Acrylic was prepared by adding and reacting the following components, in parts by weight based on the total weight of the acrylic composition, unless otherwise indicated.

Table 2 To form the acrylic polymer, 75.0 grams of Solvesso® 100 (also referred to as Aroma-tic 100) would be added into a reactor, and the reactor would be heated through a conventional heat supply at a temperature of 121 ° C. Once the reactor reached 121 ° C, a mixture of the Functionalized Monomer, the First Compound, the Second Compound A and the Second Compound B according to Table 2 would be added to the reactor for about 3 hours to form the functionalized intermediate. Once the functionalized intermediate is formed, the temperature will be lowered until the temperature of the functionalized intermediate reaches approximately 100-110 ° C. Then, the core molecule will be added to the reactor along with an additional 11 grams of Solvesso® 100. A drop of DBTDL will also be added and the reaction will be maintained at 100 ° C until the% of NCO measurements is less than 0.02 meq. solid Acrylic Composition A is prepared and Acrylic Composition B would be prepared by adding and reacting the following components, in parts by weight based on the total weight of the acrylic composition, unless otherwise indicated.

Table 3 For Table 3 above, 23.8 grams of HPC, 30.8 grams of HHPa, and 20 grams of amyl acetate were added to a reaction flask. The reaction flask, including HPC and HHPA, was heated with a conventional heat supply at a temperature of about 110 ° C to form the carboxylic acid carbamate. In this example, the reaction to form the carboxylic acid carbamate took about 8 hours. After the IR spectroscopy verification to confirm that the majority (> 95%) of the HHPA was reacted, 140 grams of the Acrylic Polymer A and 50 grams of toluene were charged to the reaction flask. Alternatively, when Acrylic Composition B was made, 120 grams of Acrylic Polymer B would be loaded at this point in place of Acrylic Polymer A. The contents of the reaction flask were heated and maintained within the temperature range from 140 to 150 ° C. IR spectroscopy verified that all the functionality of epoxy (from Polymer A Acrylic) had reacted, that is, the absence of epoxide peak, the reaction mixture was cooled to approximately 60 to 65 ° C, and 10 grams of amyl acetate and 10 grams of isobutanol to completely disperse Polymer A Acrylic. Polymer A Acrylic reacted with the reaction mixture that has HPC and HHPA in 2 hours. Acrylic Composition A had a non-volatile% from 40 to 50% by weight. The final acrylic composition has a carbamate functionality and, optionally, a hydroxyl functionality, which will be available for reaction with various crosslinking agents, which have been previously established, for coating purposes. The invention has been described in an illustrative manner, and it will be understood that the terminology which has been used is intended to be in the nature of the words of the description rather than limitation. Obviously, many modifications and variations of the present invention are possible in light of the above teachings, and the invention may be practiced otherwise than as specifically described.

Claims (50)

1. CLAIMS 1. An acrylic composition, comprising the reaction product of: A) an acrylic polymer comprising the reaction product of; i) a functionalized monomer; ii) a first compound reactive with such functionalized monomer to form a functionalized intermediate, the first compound comprises a functionality of the vinyl reactive with the functionalized monomer and an epoxy functionality; and iii) a highly branched polyfunctional core molecule reactive with the functionalized intermediate to form the acrylic polymer; and B) a carboxylic acid compound comprising a carboxylic acid functionality that is reactive with • a, such functionality of the epoxy of the acrylic polymer to form an acrylic composition. The acrylic composition as set forth in claim 1, wherein the carboxylic acid carbamate comprises the reactive product of a carbamate having reactive functionality with anhydride and a carboxylic acid anhydride reactive with the reactive functionality with carbamate anhydride. 3. The acrylic composition as set forth in claim 2, wherein the reactive functionality with anhydride is further defined as at least one hydroxyl functionality and one amino functionality. 4. The acrylic composition, as set forth in claim 3, wherein the carbamate comprises hydroxyalkyl carbamate. 5. The acrylic composition as set forth in claim 4, wherein the hydroxyalkyl carbamate has from 1 to 20 carbon atoms in the alkyl chain. The acrylic composition as set forth in claim 2, wherein the carboxylic acid anhydride is selected from the group of maleic anhydride, hexahydrophthalic anhydride, methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, dodecenylsuccinic anhydride , trimellitic anhydride, glutaric anhydride and combinations thereof. The acrylic composition as set forth in claim 2, wherein the ratio of the effective equivalents of the carbamate to the carboxylic acid anhydride is from 0.5: 3 to 3: 0.5. The acrylic composition as set forth in claim 1, wherein the functionalized monomer comprises a hydroxyl-reactive functionality and a vinyl functionality. 9. The acrylic composition as set forth in claim 8, wherein the hydroxyl-reactive functionality comprises an aliphatic isocyanate functionality. The acrylic composition as set forth in claim 9, wherein the functionalized monomer comprises a, a-dimethyl isopropenylbenzyl isocyanate. 11. The acrylic composition as set forth in claim 8, wherein the first compound is selected from the group of glycidyl acrylate, glycidyl acrylates and combinations thereof. The acrylic composition as set forth in claim 8, wherein the core molecule comprises a polyol reactive with the intermediate functionalized to form the acrylic polymer. 13. The acrylic composition as set forth in claim 12, wherein the polyol is selected from the group of glycerol, propylene glycol, erythritol, pentaerythritol, dipentaerythritol, trimethylolethane, trimethylolpropane, dulcitol, threitol and combinations thereof. The acrylic composition as set forth in claim 8, wherein the acrylic polymer further comprises the reaction product of an initiator selected from the group of inorganic persulfates, dialkyl peroxides, hydroxyperoxides, peresters, azo compounds and combinations of the same. 15. The acrylic composition as set forth in claim 1, wherein the functionalized monomer comprises a hydroxyl functionality and a vinyl functionality. 16. The acrylic composition as set forth in claim 15, wherein the core molecule is selected from the group of isocyanates, isocyanurates, melamines, carboxylic acid halides and combinations t thereof with the core molecule reactive with the functionalized intermediate to form the acrylic polymer. The acrylic composition as set forth in claim 1, wherein the functionalized monomer comprises a radical-forming moiety and a hydroxyl functionality. 18. The acrylic composition as set forth in claim 17, wherein the functionalized monomer comprises di- (1-hydroxycyclohexyl) peroxide. 19. The acrylic composition as set forth in claim 17, wherein the first compound is selected from the group of glycidyl acrylate, glycidyl acrylates and combinations thereof. The acrylic composition as set forth in claim 17, wherein the core molecule is selected from the group of isocyanates, isocyanurates, melamines, carboxylic acid halides and combinations thereof with the core molecule reactive with the functionalized intermediate to form the acrylic polymer. 21. The acrylic composition as set forth in claim 1, wherein the functionalized monomer comprises a radical-forming portion and a hydroxyl-reactive functionality. 22. The acrylic composition as set forth in claim 19, wherein the functionalized monomer is selected from the group of isocyanates, isocyanurates, melamines, carboxylic acid halides and combinations thereof. 23. The acrylic composition as set forth in claim 19, wherein the first compound is selected from the group of glycidyl acrylate, glycidyl acrylates and combinations thereof. The acrylic composition as set forth in claim 19, wherein the core molecule comprises a polyol reactive with the intermediate functionalized to form the acrylic polymer. 25. The acrylic composition as set forth in claim 1, wherein the acrylic polymer further comprises the reaction product of a second compound comprising vinyl functionality and is reactive with the functionalized monomer and the first compound to form the intermediate. functionalized 26. The acrylic composition as set forth in claim 23, wherein the second compound is selected from the group of acrylates, methacrylates, acrylonitriles, styrenes, alkenes, cyclic alkene anhydrides, acyclic alkene anhydrides and combinations thereof. 27. The acrylic composition as set forth in claim 2, wherein the functionalized monomer comprises a, a-dimethyl isopropenylbenzyl isocyanate, the first compound comprises glycidyl acrylate or glycidyl methacrylate, the core molecule comprises pentaerythritol, the carbamate comprises carbamate, - Hydroxypropyl and the carboxylic acid anhydride comprises hexahydrophthalic anhydride. The acrylic composition as set forth in claim 2, wherein the functionalized monomer comprises di (1-hydroxycyclohexyl) peroxide, the first compound comprises glycidyl acrylate or glycidyl methacrylate, the core molecule comprises trimethylolpropane carbamate with diisocyanate of toluene or pentaerythritol carbamate with toluene diisocyanate, the carbamate comprises hydroxypropyl carbamate, and the carboxylic acid anhydride comprises hexahydrophthalic anhydride. 29. A curable coating composition, comprising: (A) an acrylic composition comprising the reaction product of: i) an acrylic polymer comprising the reaction product of; a) a functionalized monomer; »* B) a first compound reactive with such functionalized monomer to form a functionalized intermediate, the first compound comprising a functionality of the vinyl reactive with the functionalized monomer and an epoxy functionality; and c) a highly branched polyfunctional core molecule reactive with the functionalized intermediate to form the acrylic polymer; and ii) a carboxylic acid carbamate having a carbamate functionality and a carboxylic acid functionality that is reactive with the epoxy functionality of the acrylic polymer; and (B) a reactive crosslinking agent with the acrylic composition. 30. The curable coating composition as set forth in claim 29, wherein the carboxylic acid carbamate comprises the reaction product of a carbamate having an reactive functionality with anhydride and a functionality of carbamate and a carboxylic acid anhydride reactive with reactive functionality with carbamate anhydride. 31. The curable coating composition as set forth in claim 30, wherein the carbamate comprises a hydroxyalkyl carbamate. 32. The curable coating composition com: * is set forth in claim 31, wherein the carbamate comprises hydroxypropyl carbamate. 33. The curable coating composition as set forth in claim 30, wherein the carboxylic acid anhydride is selected from the group of maleic anhydride, hexahydrophthalic anhydride, ethyl hexahydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, dodecenylsuccinic anhydride, trimellitic anhydride, glutaric anhydride and combinations thereof. 34. The curable coating composition as set forth in claim 29, wherein the first compound is selected from the group of glycidyl acrylate, glycidyl acrylates and combinations thereof. 35. The curable coating composition as set forth in claim 34, wherein the functionalized monomer comprises a, a-dimethyl isopropenylbenzyl isocyanate. 36. The curable coating composition as set forth in claim 35, wherein the core molecule is selected from the group of glycerol, propylene glycol, erythritol, pentaerythritol, dipentaerythritol, trimethylolethane, trimethylolpropane, dulcitol, threitol and combinations thereof with the molecule reactive nucleus with the functionalized intermediate to form the acrylic polymer. • * 37. The curable coating composition as set forth in claim 29, wherein the functionalized monomer comprises di- (l-hydroxycyclohexyl) peroxide. 38. The curable coating composition as set forth in claim 37, wherein the core molecule is selected from the group of isocyanates, isocyanurates, melamines, carboxylic acid halides and combinations thereof with the core molecule reactive with the functionalized intermediate for form the acrylic polymer. 39. The curable coating composition as set forth in claim 29, wherein the crosslinking agent is selected from the group of polyisocyanates, polyisocyanurates, melamine-formaldehyde resins, polycarboxylic acid halides and combinations thereof. 40. The curable coating composition as set forth in claim 29, wherein the crosslinking agent comprises an aminoplast resin reactive with the carbamate functionality. 41. The curable coating composition as set forth in claim 40, wherein the aminoplast resin is selected from the group of melamine-formaldehyde resins having methylol functionality, alkoxymethyl functionality and combinations of the misits, which are reactive with the carbamate functionality. 42. The curable coating composition as set forth in claim 29, wherein the ratio of effective equivalents of the acrylic composition to the crosslinking agent is from 3: 1 to 1: 3. 43. The curable coating composition as set forth in claim 29, further comprising at least one additive selected from the group of solvents, catalysts, hindered amine light stabilizers, ultraviolet absorbers, rheology control agents, anti-yellowing agents. , adhesion promotion agents and combinations thereof. 44. An acrylic composition, comprising: '' A) an acrylic polymer comprising the reaction product of: i) a functionalized monomer; ii) a first compound reactive with the functionalized monomer to form a functionalized intermediate, the first compound comprises a functionality of vinyl reactive with the functionalized monomer and an epoxy functionality; and iii) a highly branched polyfunctional core molecule reactive with the functionalized intermediate to form the acrylic polymer; and B) a carbamate having a reactive functionality with anhydride and a carbamate functionality. 45. The acrylic composition as set forth in claim 44, further comprising a carboxylic acid anhydride reactive with the carbamate anhydride reactive functionality to form a carboxylic acid carbamate having the carbamate functionality and the carboxylic acid functionality which is reactive with the epoxy functionality of the acrylic polymer. 46. The acrylic composition as set forth in claim 45, wherein the carboxylic acid anhydride is selected from the group of maleic anhydride, hexahydrophthalic anhydride, methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, dodecenylsuccinic anhydride, anhydride trimellitic, glutaric anhydride and combinations thereof. 47. The acrylic composition as set forth in claim 45, wherein the functionalized monomer comprises a, a-dimethyl isopropenylbenzyl isocyanate, the first compound comprises glycidyl acrylate or glycidyl methacrylate, the core molecule comprises pentaerythritol, the carbamate it comprises hydroxypropyl carbamate, and the carboxylic acid anhydride comprises hexahydrophthalic anhydride. 48. The acrylic composition as set forth in claim 45, wherein the functionalized monomer comprises di- (1-hydroxycyclohexyl) peroxide, the first compound comprises glycidyl acrylate or glycidyl methacrylate, the core molecule comprises trimethylolpropane carbamate with toluene diisocyanate or pentaerythritol carbamate with toluene diisocyanate, the carbamate comprises hydroxypropyl carbamate, and the carboxylic acid anhydride comprises hexahydrophthalic anhydride. 49. An acrylic composition, comprising: A) an acrylic polymer comprising the reaction product of: i) a functionalized monomer; ii) a first compound reactive with the functionalized monomer to form a functionalized intermediate, the first compound comprises a functionality of vinyl reactive with the functionalized monomer and an epoxy functionality; and iii) a highly branched polyfunctional core molecule reactive with the functionalized intermediate to form the acrylic polymer; and B) a carboxylic acid anhydride. 50. The acrylic composition as set forth in claim 49, wherein the carboxylic acid anhydride is selected from the group of maleic anhydride, hexahydrophthalic anhydride, methyl-hexahydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, succinic anhydride, dodecenylsuccinic anhydride, anhydride trimellitic, glutaric anhydride and combinations thereof.