Polydentate ligands and thiols in curing liquids

Abstract

Compositions, formulations, methods, kits, and processes for curing and hardening of liquids including unsaturated resins, a peroxide, a thiol secondary accelerator, and a chelant capable of chelating at least one transition metal ion through three, four, or five nitrogen atoms, which chelants may each optionally be complexed with one or two transition metal ions, typically iron or manganese ions. Also disclosed are methods and formulations for making associated compositions, compositions resultant from the curing of such liquids, associated kits comprising two or more formulations physically separated from one another, which may be used to provide curable liquids when mixed.

Description

7513-A-WO - PE963282WOPOLYDENTATE LIGANDS AND THIOLS IN CURING LIQUIDSCross-Reference to Related Applications

[0001] None.Technical Field

[0002] The present invention concerns the curing and hardening of liquids comprising unsaturated resins, a peroxide, a thiol secondary accelerator, and a chelant capable of chelating at least one transition metal ion through three, four, or five nitrogen atoms, which chelants may each optionally be complexed with one or two transition metal ions, typically iron or manganese ions. The invention also provides methods and formulations for making associated compositions, compositions resultant from the curing of such liquids, and associated kits comprising two or more formulations physically separated from one another, which may be used to provide curable liquids when mixed.Background of the Invention

[0003] Thermoset resins, including those of the unsaturated polyester and vinyl ester type, are commonly employed in a variety of fabrications and applications, such as casting materials, fibre reinforced materials, and two-component coatings. These resins are typically dissolved in an unsaturated vinyl monomer (often referred to as a reactive diluent), such as styrene, to facilitate crosslinking (curing) and reduce viscosity. Resins are typically cured with a peroxide- or azo-type initiator by means of a free radical co-polymerization mechanism to form a solid article or coating. Accelerators are used to promote the decomposition of peroxides.

[0004] Unsaturated resins are typically cured using peroxide-type initiators. Initiators are typically dissociated using heat, UV light, or at ambient temperature (typically about 18°C to about 25°C) with accelerators to form the free radicals required to initiate polymerization. Accelerators are usually employed with peroxides, with their use not being limited to ambient curing applications: often, peroxides are used in the curing of unsaturated resins at higher temperatures.

[0005] The current state of the art for ambient curing of unsaturated polyester and vinyl ester resins uses peroxides accelerated by the presence of metal compounds, particularly cobalt salts, known as conventional accelerators. Cobalt naphthenate and cobalt octanoate are the most widely used conventional accelerators. The peroxides most commonly used in conjunction with cobalt accelerators are ketone peroxides, hydroperoxides and peresters. The use of methylethylketone peroxide (MEKP) is particularly prevalent. Modified acrylic resins that contain a significant amount of styrene mixed with acrylate monomers can also be cured with MEKP / cobalt system.

[0006] Their ability to activate many different initiators and compatibility with many resin systems accounts for wide use of cobalt accelerators. However, cobalt-containing accelerators have become undesirable because of concerns relating to their impact on health and the environment: cobalt soaps (including cobalt octanoate) may need to be registered as carcinogenic materials. Cobalt accelerators- 1 -55648278-17513-A-WO - PE963282WO also suffer from other technical disadvantages. These include poor reactivity at low temperatures (<15 °C), color imparted to the resin (cobalt octoate and naphthenate are very dark in color) and poor reactivity with acrylic and methacrylic monomers, especially in acrylic resins. Although moulding applications take place at ambient temperatures of more than 15 °C, in winter months in particular, ambient temperature may be significantly lower than 15-40 °C, the typical range of operating temperatures for ambient curing with cobalt accelerators.

[0007] When used as a conventional primary accelerator at a typical concentration of about 0.02 % w / w (based on metal), the color from the cobalt accelerator affects the color of the cure gel coat or moulded composite. Lower cobalt accelerator levels can be used, but with longer gel and peak exotherm times and lower peak exotherm temperatures.

[0008] Unsaturated polyester and vinyl ester type resins have been incorporating low volatile acrylic and methacrylic monomers as one way to meet recent government regulations to restrict styrene emissions in open moulding facilities. However, the amount of styrene substitution is often limited by the poor co-polymerization of most acrylates and methacrylates with maleate and fumarate moieties in the backbone of unsaturated polyesters, as well as, the ability of cobalt-accelerated MEKP systems to effectively form radicals with acrylic monomers. The latter is especially apparent in acrylic resin systems where cobalt-accelerated MEKP systems exhibit little or no reactivity in the absence of styrene.

[0009] Accordingly, there is an ongoing need in connection with the curing of unsaturated resins, particularly those of the unsaturated polyester and vinyl ester type, particularly when producing cure gel coats and moulded composites, for the development of ways to avoid the use of cobalt as an accelerant on the one hand, whilst retaining good curing properties on the other.

[0010] Lastly, unsaturated polyester and vinyl ester type resins have been incorporating metal salts of e.g. manganese or iron and various chelants. Some such approaches further advocate specific formulations suggesting a limited set of organic ligands in combination with transition metals and particular thiol-containing compounds alongside a base. Although these approaches bring to the art accelerators not based on cobalt, it would at least be advantageous to develop alternative additional systems for use in the curing of unsaturated resins, particularly with (liquid) peroxides, partly in view of the desire in the art to seek alternatives for cobalt-based systems. Further, some of these existing approaches, especially those reliant on iron-based formulations with associated organic ligands, may benefit from improvements (reductions in) tackiness, gel-time drift, and other properties. The present invention addresses this.Summary of the Invention

[0011] According to one aspect, the invention provides a liquid curable composition comprising:(i) at least one unsaturated resin;(ii) at least one peroxide;- 2 -55648278-17513-A-WO - PE963282WO(iii) at least one polydentate accelerant ligand selected from the group consisting of bispidon, N4py-type, TACN-type, cyclam and cross-bridged ligands, and trispicen-type ligands, or a mixture thereof;(iv) transition metal ions, which may include, for example, ions of manganese, iron, copper, or vanadium, but may, in preferred embodiments include ions of iron or manganese,(v) at least one thiol secondary accelerator, and(vi) optionally, additional materials, such as at least one reactive diluent; at least one radical inhibitor; at least one pigment dispersant or at least one rheology additive; at least one UV stabilizer; at least one dispersant; at least one surfactant; at least one corrosioninhibitor; at least one filler; at least one antistatic agent; at least one flame-retardant; at least one lubricant; at least one antifoaming agent; at least one antifouling agent; at least one bactericides; at least one fungicide; at least one algaecide; at least one insecticide; at least one extender; at least one antifreezing agent; or at least one thickener.

[0012] In some aspects of the invention, the liquid curable composition is provided in kits of two or more components, wherein each component includes a formulation, and each of the unsaturated resin, peroxide, polydentate accelerant ligand, transition metal ions, thiol secondary accelerator, and optional, additional materials (if present) may be provided in one or more of each formulation. The formulations can be physically separated, such as in separate cartridges, sachets, pouches, tanks, or the like. In some aspects, the invention is embodied in the formulations themselves.

[0013] In further aspects, the invention pertains to methods of use and formation and cured articles and coated articles relating to and / or formed from the above compositions, kits, and formulations.

[0014] These and other aspects of this invention will be evident when viewed in light of the detailed description and appended claims.Detailed Description of the Invention

[0015] Whilst progress has been made to replace the use of toxic cobalt in unsaturated resincontaining composites and coatings, cobalt carboxylates are still unparalleled in their ability to provide coatings or composites with favorable mechanical properties upon curing. BOC, and other catalysts based on transition metal complexes or salts of polydentate nitrogen-donating ligands outperform or match cobalt for curing times, but may still create softer coatings and composites often having an unacceptable tacky feel, which prevents the total replacement of cobalt in all coating and composite applications.

[0016] We have found that transition metal ion-containing compounds, typically comprising iron, manganese, copper or vanadium, often iron or manganese and frequently iron, which comprise specific chelants, capable of chelating at least one such transition metal ion through three, four or five nitrogen atoms (altogether referred to herein as “primary accelerators,” whether complexed together or not forming a complex), are effective as accelerators at relatively low concentrations for curing unsaturated resin(s) in the presence of a peroxide and a thiol compound secondary accelerator.- 3 -55648278-17513-A-WO - PE963282WOWithout being bound by theory, it is believed that the above-mentioned specific chelants (described further below) in combination with transition metal ion-containing compounds but not a thiol secondary accelerator suffer from impaired curing and negative interaction with oxygen at a composite or coating surface (or interface with ambient atmosphere) thereby resulting in tackiness and other unfavorable properties. The addition of a thiol compound secondary accelerator retains bulk hardness and other mechanical properties while improving surface cure and thus reducing tackiness. This permits reduction or avoidance of toxic cobalt accelerators with the resultant compositions exhibiting less color perturbation and lower dependency upon temperature to facilitate curing while retaining other coating and composite mechanical properties relative to cobalt-containing formulations or other formulations that do not include the thiol compound secondary accelerators.

[0017] The invention is particularly applicable to curing media that require reduced amounts of cobalt accelerants whist functioning effectively. Indeed, the present invention permits the avoidance of cobalt accelerants.

[0018] As used herein the term “nitrogen-donor ligand” or “ligand” or “L” or “polydentate accelerant ligand” is an organic structure or molecule which will support coordinating nitrogen atoms. In the present invention, said at least one nitrogen-donor ligand is selected from the group comprising tridentate, tetradentate, pentadentate and hexadentate nitrogen donor ligands.

[0019] Whenever the term “substituted” is used herein, it is meant to indicate that one or more hydrogens on the atom indicated in the expression using “substituted” is replaced with a selection from the indicated group, provided that the indicated atom's normal valency is not exceeded, and that the substitution results in a chemically stable compound, i.e., a compound that is sufficiently robust to survive isolation from a reaction mixture. Where the indicated group is not specified, a person having ordinary skill in the art will be able to select viable substituents that are suitable for the application in question, given the benefit of this disclosure.

[0020] Unless the context clearly indicates otherwise: the word “and” indicates the conjunctive; the word “or” indicates the disjunctive; when the article is phrased in the disjunctive, followed by the words “or both” or “combinations thereof’ both the conjunctive and disjunctive are intended.

[0021] As used in this application, the term “approximately” is within 10% of the stated value, except where noted or context dictates otherwise.

[0022] Throughout the description and claims generic groups are often used, for example alkyl, alkoxy, aryl. Unless otherwise specified, the following are preferred group restrictions that may be applied to generic groups found within compounds disclosed herein.

[0023] As used herein, “alkyl” will mean linear and branched Ci-12-alkyl saturated acyclic hydrocarbon monovalent groups; said alkyl group may further optionally include one or more suitable substituents independently selected from the group consisting of amino, halogen, hydroxy, sulfhydryl, haloalkyl, alkoxy and the like.

[0024] As used herein, “alkenyl” will mean linear and branched C2-12 unsaturated acyclic hydrocarbon monovalent groups; said alkenyl group may further optionally include one or more suitable- 4 -55648278-17513-A-WO - PE963282WO substituents independently selected from the group consisting of amino, halogen, hydroxy, sulfhydryl, haloalkyl, alkoxy and the like.

[0025] Unless otherwise stated, as used herein, “aryl” means selected from homoaromatic compounds having a molecular weight preferably under 300.

[0026] Unless otherwise stated, as used herein, “cycloalkyl” means C3-20 monocyclic saturated hydrocarbon monovalent group, or a C7-20 polycyclic saturated hydrocarbon monovalent group.

[0027] As used herein, the term “gel-time drift” (for a specifically selected period of time, for instance y = 30 or y = 60 days) reflects the phenomenon that when curing is performed at another point of time than at the reference standard moment for curing — for instance, the reference moment may be 24 hours after preparation of the resin in question — the gel time observed is different from the gel time initiated at the point of reference. For unsaturated resins, as can generally be cured under the influence of peroxides, gel time represents the time lapsed in the curing phase of the resin required for the mixture to increase in temperature from 25°C to 35 °C. Normally this corresponds to the time the viscosity of the resin is still in a range where the resin can be handled easily. In closed mould operations, for instance, this time period is very important. The lower the gel-time drift is, the more predictable the behavior of the resin during application (and the resulting properties of the cured material) will be.

[0028] Gel time drift (hereinafter: "Gtd") can be expressed in a formula as in formula (1), below:Gtd=(T25->35°C at y days - T25-35°C after resin preparation) / T25->35°c after resin preparation X 100% (1)

[0029] In this formula, T25->35°c (which also might be represented by Tgei) represents, as mentioned above, the time lapsed during the curing phase of the resin required for an increase in temperature from 25°C to 35°C to occur. T25->35°catydays represents this value when curing is initiated y days after the time curing is initiated forresin preparation. T25->35°c after resin preparation represents the gel time when curing is initiated at some time promptly or shortly after preparing the resin. All polyester resins, by their nature, undergo some changes over time from their production until their actual curing. One of the characteristics where such changes become visible is the gel-time drift. A given gel time and corresponding exotherm curve can be measured according to any suitable method, such as ASTM D7029 - 17 (“Standard Test Method for Determination of Reactivity of Unsaturated Polyesters and Vinyl Esters at 180.0 °F (82.2 °C)”).

[0030] Unless otherwise stated, as used herein, “heteroaryl” means selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl.

[0031] Unless otherwise stated, as used herein, “heterocycloalkyl” means selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1 ,4- piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1 ,4,7-triazacyclononanyl; 1 ,4,8,11- tetraazacyclotetradecanyl; 1 ,4,7,10,13-pentaazacyclopentadecanyl; 1 ,4-diaza-7-thia-cyclononanyl;- 5 -55648278-17513-A-WO - PE963282WO1 ,4-diaza-7-oxa-cyclononanyl; 1 ,4,7,10-tetraazacyclododecanyl; 1 ,4-dioxanyl; 1 ,4,7-trithia- cyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl.

[0032] Unless otherwise stated, as used herein, “carboxylate derivative” means the group --C(O)OR, wherein R is selected from: hydrogen; Ci-Ci2-alkyl; phenyl; Ci-Ce-alkyl-CeHs; Li; Na; K; Cs; Mg; and Ca, carbonyl derivative: the group — C(O)R, wherein R is selected from: hydrogen; Ci-Ci2-alkyl; phenyl;Ci-Ce-alkyl-CeHs and amine (to give an amide) selected from the group: --NR'2, wherein each R' is independently selected from: hydrogen; Ci-Ci2-alkyl; Ci-Ce-alkyl-CeHs; and phenyl, wherein when both R' are Ci-Ci2-alkyl both R' together may form an — NC3 to an — NC5 heterocyclic ring with any remaining alkyl chain forming an alkyl substituent to the heterocyclic ring, sulphonate: the group — S(O)2OR, wherein R is selected from: hydrogen; Ci-Ci2-alkyl; phenyl; Ci-Ce-alkyl-CeHs; Li; Na; K; Cs; Mg; and Ca.

[0033] Unless otherwise specified, the following are more preferred group restrictions that may be applied to groups found within compounds disclosed herein:(a) alkyl: linear and branched Ci-s-alkyl;(b) alkenyl: Cs-s-alkenyl;(c) cycloalkyl: Ce-s-cycloalkyl;(d) aryl: selected from group consisting of: phenyl; biphenyl; naphthalenyl; anthracenyl; and phenanthrenyl;(e) heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; quinolinyl; pyrazolyl; triazolyl; isoquinolinyl; imidazolyl; and oxazolidinyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl; and(f) heterocycloalkyl: selected from the group consisting of: pyrrolidinyl; morpholinyl; piperidinyl; piperidinyl; 1 ,4-piperazinyl; tetrahydrofuranyl; 1 ,4,7-triazacyclononanyl; 1 ,4,8,11-tetraazacyclotetradecanyl; 1 ,4,7,10,13-pentaazacyclopentadecanyl;1 ,4,7,10-tetraazacyclododecanyl; and piperazinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl, carboxylate derivative: the group --C(O)OR, wherein R is selected from hydrogen; Na; K; Mg; Ca; Ci-Ce-alkyl; and benzyl.

[0034] As used herein, and unless otherwise stated, the term “arylalkyl” refers to an aliphatic saturated hydrocarbon monovalent group onto which an aryl group (such as defined above) is attached, and wherein the said aliphatic or aryl groups may be optionally substituted with one or more substituents independently selected from the group consisting of halogen, amino, hydroxyl, sulfhydryl, alkyl, haloalkyl and nitro. Specific examples of the arylalkyl groups are those having 7 to 40 carbon- 6 -55648278-17513-A-WO - PE963282WO atoms wherein the alkyl group may be straight-chain or branched, such as benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl and phenylhexyl groups.

[0035] As used herein, and unless otherwise stated, the term “alkylaryl” refers to an aryl group (such as defined above) onto which an aliphatic saturated hydrocarbon monovalent group is attached, and wherein the said aliphatic or aryl groups may be optionally substituted with one or more substituents independently selected from the group consisting of halogen, amino, hydroxyl, sulfhydryl, alkyl, trifluoromethyl and nitro. Specific non-limiting examples of the unsubstituted or alkyl-substituted aryl groups are the aryl groups having 6 to 18 carbon atoms such as phenyl, diphenyl and naphthyl groups, and alkylaryl groups having 7 to 40 carbon atoms wherein the alkyl group may be straightchain or branched and may be bonded to any position on the aryl group, such as tolyl, xylyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, diethylphenyl, dibutylphenyl and dioctylphenyl groups. The alkylaryl groups may additionally have substituents including functional groups such as alkoxy, hydroxy, cyano, nitro, halides, carboxylic acids, etc.

[0036] As used herein, “Deca-Co-10”, means cobalt neodecanoate, a prevalent cobalt-based prior art accelerator, as illustrated below.

[0037] Where percentages by weight are referred to herein (e.g. % w / w, wt % or % by weight), these mean, unless a text or context clearly dictates to the contrary, percentages by weight with respect to the total weight of curable components within the formulation or compositions, which curable components are typically unsaturated resin(s) and optionally reactive diluent(s) if present. For example, where a composition comprising unsaturated resin, peroxide, chelant, transition metal ion, and thiol secondary accelerator comprises 0.00005 % w / w of chelant, this is with respect to the weight of the curable components of the composition (i.e. the weight of the unsaturated resin(s), including the weight of any reactive diluent present). If the example composition comprised 95 grams of unsaturated resin and 5 grams of reactive diluent, it would comprise 0.00005 grams of chelant.

[0038] By a “well-defined complex” is meant herein (as the term is used customarily in the art) a complex that has been isolated such that it is susceptible to characterization (i.e. definition) and analysis (e.g. to determine its structure and degree of purity). In contrast, a complex that is “not well- defined” is one that is prepared without isolation from the medium (e.g. reaction medium) in which it is prepared. Well-defined complexes often consist of a single active component, whereas complexes that are not well-defined often, but not necessarily, comprise more than one active component. For example, a mixture of mononuclear and dinuclear species may exist or a mixture of different ancillary ligands may be present.- 7 -55648278-17513-A-WO - PE963282WO

[0039] As summarized above, the present invention is based, in part, on the recognition that complexes of transition metal ions (particularly, although not necessarily, of iron or manganese ions and often, although again not necessarily, of iron ions) and a polydentate accelerant ligand or chelant are effective for accelerating the curing of unsaturated resins with peroxides. Such complexes or their components whether complexed or not complexed are referred to together herein as primary accelerators. Such primary accelerators are particularly effective in the presence of thiol compound secondary accelerators.

[0040] The present invention thus relates to primary accelerators with added thiol secondary accelerators for curing unsaturated polyester resins, vinyl ester resins (including acrylic and methacrylic (= (meth)acrylic) resins) (altogether referred to as “unsaturated resins” herein) in conjunction with peroxide type initiators. Also disclosed are curable resin compositions including the forgoing primary accelerators and thiol secondary accelerators and a curing process for employing these accelerators. These resin compositions show good curing properties and do not require the presence of cobalt accelerators. The present invention further relates to gel coats and moulded composites prepared from such unsaturated polyester, vinyl ester, and (meth)acrylic resins.UNSATURATED RESIN

[0041] The unsaturated resin present in the compositions and other relevant aspects and embodiments of the invention, is typically an unsaturated polyester resin or vinyl ester resin as are well known in the art. It will be understood that more than one type of resin (e.g. mixtures of resins) may be used in accordance with the present invention. The resin may comprise a reactive diluent that serves to crosslink. Unsaturated polyester resins and vinyl ester resins useful in accordance with the present invention are often subdivided in the art into different categories as described below.

[0042] Ortho resins: these are based on phthalic anhydride, maleic anhydride, or fumaric acid and glycols, such as ethylene glycol, diethylene glycol, triethylene glycol, 1 ,2-propylene glycol, 1 ,3- propylene glycol, dipropylene glycol, tripopylene glycol, neopentyl glycol, or hydrogenated bis-phenol A. Commonly, those derived from 1 ,2-propylene glycol are used in combination with a reactive diluent such as styrene.

[0043] Iso-resins: these are usually prepared from isophthalic acid, maleic anhydride or fumaric acid, and a glycol. These resins typically contain a higher level of reactive diluent than the ortho resins.

[0044] Bisphenol-A-fumarates: these are based on ethoxylated bisphenol-A and fumaric acid.

[0045] Chlorendics: are resins prepared from chlorine / bromine containing anhydrides or phenols in the preparation of unsaturated polyester resins.

[0046] Vinyl ester resins: these are often used because of their hydrolytic resistance and excellent mechanical properties; they have unsaturated sites only in the terminal position, introduced by reactions of epoxy resins with (meth)acrylic acid. Typical types of epoxy resins include bisphenol-A, novalac, tetraphenyloethane, cycloaliphatic, tetrabromobisphenol-A, etc. A common type of vinyl ester resin is acrylic resin, described in greater detail below.- 8 -55648278-17513-A-WO - PE963282WO

[0047] Similar to iso resins and ortho resins are unsaturated polyester resins containing terephthalic acid. Besides these classes of resins so-called dicyclopentadiene (DCPD) resins can also be regarded as unsaturated polyester resins. As used herein, a vinyl ester resin may be a (meth)acrylate functional resin. Also, the class of vinyl ester urethane resins (also referred to urethane methacyclate resins) are to be regarded as vinyl ester resins. Preferably, the vinyl ester resin used in the present invention is a resin that is obtained by the esterification of an epoxy resin with a (meth)acrylic acid or a (meth)acrylamide.

[0048] All of these resins, as can be used in the context of the present invention, may be modified according to methods known in the art, e.g. for achieving lower acid number, hydroxyl number or anhydride number, or for becoming more flexible due to insertion of flexible units in the backbone, etc.

[0049] Also, other reactive groups curable by reaction with peroxides may be present in the resins, for instance reactive groups derived from itaconic acid, citraconic acid and allylic groups, etc. Compositions and formulations comprising unsaturated resins referred to herein in accordance with the present invention, typically the polyester resins or vinyl ester resins described above, may contain solvents. The solvents may be inert to the resin system or they may be reactive therewith during the curing step. The latter type are known as reactive diluents and their use is noteworthy in the context of the present invention. Accordingly, the unsaturated resin used in accordance with the various aspects of the invention is often present in a composition or formulation further comprising a reactive diluent. Examples of suitable reactive diluents are styrene, vinyl toluene, divinyl benzene, methyl methacrylate, diallyl phthalate, a-methyl styrene, triallyl cyanurate, (meth)acrylates, N- vinylpyrrolidone, and N-vinylcaprolactam. Mixtures of the reactive diluents, particularly mixtures comprising styrene, may be employed. The amount of styrene and / or other reactive diluent may be as large as 60 % w / w but is typically between 25 % w / w and 35 % w / w (with % w / w being expressed as weight reactive diluent in relation to the weight of unsaturated resin).

[0050] The unsaturated polyester resins and vinyl ester resins useful in accordance with the present invention may be any type of such resins, but are typically chosen from the group consisting of DCPD resins, iso-phthalic resins, ortho-phthalic resins and vinyl ester resins, or blends of any of the foregoing.

[0051] The composition according to the invention typically has an acid value in the range of from 0.001-300 mg KOH / g of resin composition. As used herein, the acid value of a resin composition is determined titrimetrically according to ISO 2114-2000. Typically, the molecular weight of the unsaturated polyester resin is in the range of from 500 to 200,000 g / mol. As used herein, the molecular weight of the resin is determined using gel permeation chromatography according to ISO 13885-1.

[0052] In some embodiments, compositions according to the invention comprising unsaturated resin, peroxide, chelant, transition metal ion, and thiol secondary accelerator generally contain less than 5 % w / w of water.

[0053] In other embodiments, the unsaturated resin may be considered a waterborne resin.- 9 -55648278-17513-A-WO - PE963282WO

[0054] Acrylic resins useful according to the present invention may be selected, for example, from thermoset acrylic resins or acrylic modified resins as are well known in the art. Examples of acrylic resins or acrylic modified resins are listed below.

[0055] Acrylic resins: based on acrylic monomers that typically contain either acrylate functionality or methacrylate functionality of the general structures:O OCH2=CH-C-O-R CH2=C-C-O-R CH3wherein R can be hydrogen, linear, branched or cyclic aliphatic groups and / or aromatic groups.

[0056] Acrylic monomers, also known as acrylic ester and methacrylic ester monomers, are typically synthesized from acrylic acid or methacrylic acid and alcohols. In addition to the standard side-chains, special functionality can be added to (meth)acrylic ester monomers by the use of the appropriate functional alcohol. Examples include glycidyl methacrylate, t-butylaminoethyl methacrylate, dimethylaminoethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, N- hydroxymethy acryliamide, N-hydroxymethyl methacrylamide, etc., as well as, hydroxy (meth)acrylates made from glycidyl esters of carboxylic acids.

[0057] Also included as vinyl monomers are functional monomers related to methacrylic acid, acrylic acid, and itiaconic acid, such as the multifunctional monomers 1 ,4-butylene dimethacrylate, ethyleneglycol dimethacrylate, 1 ,6-hexandiol dimethacrylate, diethyleneglycol dimethacrylate, bisphenol-A dimethacrylate, ethoxylated bisphenol-A dimethacrylate, trimethylol propane tricarylate, trimethylol propane methacrylate and ethoxylated trimethylolpropane trimethacrylate.

[0058] Acrylic resins can also incorporate oligomeric acrylates, which are acrylated urethanes, epoxies, polyesters, polyethers, and acrylics. The oligomeric acrylates are formed by reacting acrylate functional monomers with primary or secondary functional groups on the oligomomer. The acrylate functional monomers can be added directly to the oligomer or attached to the oligomer using a secondary difunctional monomer. For instance, ureathane acrylate oligomers are formed by reacting polyester or polyether polyol oligomers with diisocyanates (aliphatic or aromatic) and hydroxy (meth)acrylates. Epoxy acrylate oligomers are formed by reacting epoxy resins with carboxyl functional (meth)acrylates. Polyether oligomers can also be reacted with carboxy functional (meth)acrylates to form polyethylene glycol dimethacrylate, as an example.

[0059] Additionally, acrylic resins can use pre-reacted polymer-in-monomer syrups made by polymerizing an acrylic monomer or co-polymerizing a mixture of different acrylic monomers to a specific degree of polymerization, typically 10-60 %. The polymerization is typically carried out at SO- 110°C using a small amount of polymerization initiator and an optional chain transfer agent. The reaction proceeds to a predetermined viscosity, approximation of polymerization degree, and is then cooled to room temperature. Optionally, the reaction is quench-cooled by the addition of cold monomer containing a polymerization inhibitor.- 10 -55648278-17513-A-WO - PE963282WO

[0060] Acrylic modified resins are a broad category of resins that are similar to oligomeric acrylates, with the exception that acrylic modified resins use a base resin of sufficient molecular weight so as not to be considered an oligomer. Examples of base resins include polyols, unsaturated polyols, polyesters, unsaturated polyesters, unsaturated dicyclopentadiene-based polyesters, polyisocyantes (chain extended and / or multifunctional), epoxies (Bisphenol-A, novalac, and chain extended) and polyacids, which are typically the products of polyols and polycarboxylic acids or anhydrides. Acrylic modified resins are formed by reacting a base resin’s primary and secondary functional groups directly with functional acrylic monomers to create primary and / or secondary (meth)acrylic double bonds on the base resin. Base resin modification with (meth)acrylic double bonds may also be achieved indirectly by initially reacting the resin’s primary and / or secondary functional groups with other difunctional or polyfunctional compounds such as isocyanates, acids, or anhydrides. Additionally, acrylic resins may be further modified by reacting secondary functional groups formed during the initial modification. Methods for the preparation of acrylic modified resins are well known to those skilled in the art.

[0061] Acrylic modified resins useful in accordance with the present invention may comprise solvents. The solvents may be inert to the resin system or they may be reactive therewith during the curing step (i.e reactive diluents). Reactive diluents are particularly preferred. Acrylic monomers and / or oligomeric acrylates, discussed above, are examples of reactive diluent typically used with acrylic modified resins. Alternately, acrylic monomers can be copolymerized with styrene, vinyl toluene, divinyl benzene, acrylonitrile, vinyl acetate, and vinyl esters of carboxylic acids, etc. in both acrylic and acrylic modified resin.

[0062] The use of acrylic monomers and / or oligomeric acrylates as reactive diluents for curing or crosslinking further extends the definition of acrylic modified resins to include resins modified by allylic functional groups, where the allylic functionality is introduced to the base resin by allyl glycidyl ether, trimethylol propanediallyl ether, allyl pentaerythritol, and related derivatives.

[0063] The compositions and formulations according to the invention or otherwise described herein that comprise an unsaturated resin typically, though not necessarily, further comprise one or more reactive diluents, often in an amount of at least 5 % w / w (reactive diluent weight on unsaturated resin weight). As mentioned earlier, amounts of up to 60% w / w may be used although amounts of between 25% w / w and 35% w / w are typical. Such reactive diluents are useful for reducing the viscosity of the unsaturated resin in order to improve handling properties, particularly for being used in techniques like vacuum injection, spraying, etc. However, it will be understood that the amount of reactive diluents in the compositions and formulations according to the invention or otherwise described herein is not critical and useful amounts can be arrived at without undue burden by the skilled person. Typically, the reactive diluent is a methacrylate and / or styrene.PRIMARY A CCELERA TOR

[0064] The primary accelerator, as referred to herein, refers to a polydentate accelerant ligand or chelant and a transition metal ion compound whether complexed (well defined or not-we Il-defined), not complexed, together in one solution or dispersion, or in physically separate formulations. Primary- 11 -55648278-17513-A-WO - PE963282WO accelerators comprising one or more of these chelants and one or more suitable transition metal ions, in particular, ions of iron, manganese, vanadium and copper, more typically ions of iron and manganese, more typically ions of iron, accelerate the curing of unsaturated resins with peroxide, which acceleration is absent in the absence of suitable transition metal ions.

[0065] The polydentate accelerant ligand, e.g., a tetradentate, pentadentate or hexadentate nitrogen donor ligand, may be built up within any organic structure which will support coordinating nitrogen atoms. For example, one can take a ligand such as 1 ,4,7-triazacyclononane (TACN), optionally substituted with further nitrogen coordinating groups, e.g., -CH2-CH2-NH2, -CH2-Py (Py = pyridyl, typically 2-pyridyl), covalently bound to one or more of the nitrogen atoms within the tridentate ligand (e.g., TACN) or aliphatic groups (e.g. one or more of the ethylene diradicals in TACN).

[0066] If present, iron ions may be selected from Fe(ll) and / or Fe(lll); manganese ions may be selected from Mn(ll), Mn(lll), and Mn(IV), or vanadium ions selected from V(l I) , V(lll), (III), (IV) and (V), or mixtures thereof. According to some embodiments, the primary accelerator comprises the polydentate accelerant ligand that is a mono- or bidentate complex of one of the foregoing ions, or a mixture thereof.

[0067] The polydentate accelerant ligand (L) may be provided, for example, in complexes of one or more of the formulae: [MnLCh]; [FeLCh]; [Fel_CI]CI; [FeL(H2O)](PF6)2; [Fel_]CI2, [FeLCI]PF6and [FeL(H2O)](BF4)2 as well as in complexes with iron carboxylates, e.g., iron neodecanoate. It will be understood that the counteranions shown in the complexes may coordinate to other transition metal ions if desired, e.g. of vanadium or copper.

[0068] Complexes comprising a chelant may, for example, be of the generic formula (2):[MaLkXn]Ym (2) in which:M represents an ion selected those of iron, manganese, vanadium and copper; each X independently represents a coordinating species selected from any mono-, bi-, or tricharged anions and any neutral molecule able to coordinate a metal ion M in a mono-, bi- or tridentate manner; each Y is independently a non-coordinating counterion; a represents an integer from 1 to 10; k represents an integer from 1 to 10; n represents an integer from 1 to 10; m represents an integer from 0 to 20; andL represents a chelant as described further herein, or a hydrate thereof.- 12 -55648278-17513-A-WO - PE963282WO

[0069] In some embodiments, M in formula (2) represents a transition metal ion selected from Fe(ll), Fe(lll), Fe(IV), Fe(V), Mn(ll), Mn(lll), Mn(IV) and Mn(V).

[0070] According to particular embodiments of formula (2), including those embodiments in which M represents a transition metal ion selected from Fe(ll), Fe(lll), Fe(IV), Fe(V), Mn(ll), Mn(lll), Mn(IV) and Mn(V) alone or in combination (where the context permits):M represents a metal ion selected from Fe(ll), Fe(lll), Mn(ll), Mn(lll), and Mn(IV);X represents a coordinating species selected from O2[R6BC>2]2R6COO; [R6CONR6]; OH-,Y represents a counterion selected from CIO CF3SO3 [B(R6) ] [FeCk] PFe R6COO; NCF , R6O; N+R6R7R8R9, Ch, Br, I; F; S2O62OCN; SCN; H2O, BF4SO42;R6, R7, R8and R9each independently represents hydrogen, optionally substituted alkyl or optionally substituted aryl; a represents an integer from 1 to 4; k represents an integer from 1 to 10; n represents an integer from 1 to 4; and m represents an integer from 1 to 8.

[0071] The nature of the counterion(s) Y are not of great importance. The choice of these may be affected by the solubility of the complex of metal ions and chelant in a given formulation or composition. For example, counterion(s) Y such as chloride, sulfate or acetate may serve to provide a readily water-soluble complex. When using solvent-based (i.e. non-aqueous) compositions, it may be desirable to use larger, less polar counterions such as 2-ethylhexanoate. Suitable counterion(s) Y (and coordinating species X) may be selected without difficulty by the skilled person.

[0072] According to particular embodiments, X and Y may be independently selected from the group consisting of bromide, iodide, nitrate, sulfate, methoxide, ethoxide, formate, acetate, propionate, 2- ethylhexanoate, octanoate, neodecanoate (3,3,5,5-tetramethylhexanoate), naphthenate, oxide, and hydroxide. An example of a neutral molecule able to coordinate the metal is acetonitrile, for example, to afford a complex of the formula [ML(CH3CN)2]Cl2.

[0073] It will be understood that counterions Y serve to balance the charge resultant from the complex formed by the metal ion(s) M, coordinating species X and chelant(s) L. Thus, if the charge on the complex is positive, there will be one or more anions Y. Conversely, there will be one or more cations Y if the charge on the complex is negative.

[0074] Below are described classes of polydentate accelerant ligands that may form iron, manganese, vanadium, or copper complexes of tetrad entate, pentadentate or hexadentate nitrogen donor ligands. The below ligands most commonly form such complexes with iron and manganese transition metal ions.- 13 -55648278-17513-A-WO - PE963282WO

[0075] If unspecified, the length of an alkyl chain is C1-C12 alkyl and preferably is linear. If unspecified, the length of an alkenyl or alkynyl chain is C2-C12 and preferably is linear. If unspecified an aryl group is a phenyl group.CHELANTS (OR “POLYDENTATE ACCELERANT LIGANDS”)

[0076] A characteristic feature of the various aspects of the present invention is the use of a chelant (also referred to herein as a polydentate accelerant ligand) of one of the below forms or classes. It will be understood that more than one such chelant may be used in accordance with the various aspects of the invention. Also, one or more of these chelants may be used in combination with a chelant described elsewhere, such as those described in WO 2011 / 083309 A1 . Typically, however, only one type of chelant will be used.

[0077] By a chelant capable of chelating at least one transition metal ion through (as an example) three nitrogen atoms is meant a polydentate chelant capable of chelating one or more transition metal ions by the formation of coordinate bonds between three nitrogen atoms of the chelant and a common transition metal ion. Thus, in this example, chelation herein and as the term is customarily used in the art requires that three of the nitrogen atoms of the chelant coordinate to the same transition metal ion, generally (but not necessarily) an iron or manganese ion. The chelants useful in connection with the present invention are at least tridentate. Some of these chelants may have a denticity of greater than three, however. For example, some of the chelants described herein, which are capable of chelating at least one transition metal ion through three nitrogen atoms, are hexadentate or heptadentate, capable of coordinating through six or seven nitrogen atoms. With these chelants, however, chelation is nevertheless still achieved by the formation of coordinate bonds between three nitrogen atoms and a common transition metal ion: for example, three of the six or seven nitrogen atoms in these hexadentate or heptadentate chelants can chelate to a first transition metal ion and the three or four other donor nitrogen atoms can chelate to a second transition metal ion. This is generally achieved by such polydentate chelants having two portions of their structure giving rise to two separate regions of chelation, often separated by a bridge.

[0078] For the avoidance of doubt, whilst the chelants described herein may have an overall denticity of greater than three to five, the phrase “chelant capable of chelating at least one transition ion through three nitrogen atoms” does not permit chelation through four (or more) or two (or fewer) nitrogen atoms with respect to a single transition metal ion. Likewise, the phrase “chelant capable of chelating at least one transition ion through four nitrogen atoms” does not permit chelation through five (or more) or three (or fewer) nitrogen atoms.

[0079] Often, the chelant or polydentate accelerant ligand is present in the curable liquid compositions of the invention at a concentration of from about 0.00005 to about 0.5 % w / w, more typically from about 0.0001 to about 0.1 % w / w, more typically from 0.001 to 0.1 % w / w, more typically from 0.002 to 0.05 % w / w, even more typically from 0.005 to 0.05 % w / w.

[0080] In embodiments in which the polydentate accelerant ligand is present in a formulation with the unsaturated resin prior to combination with a separate formulation, the polydentate accelerant ligand- 14 -55648278-17513-A-WO - PE963282WO is present in the formulation with the unsaturated resin at a concentration of from about 0.00005 to about 0.5 % w / w, more typically from about 0.0001 to about 0.1 % w / w, more typically from 0.001 to 0.1 % w / w, more typically from 0.002 to 0.05 % w / w, even more typically from 0.005 to 0.05 % w / w.

[0081] In embodiments in which the polydentate accelerant ligand is present in a formulation that is physically separated from unsaturated resin prior to combination with a separate formulation containing unsaturated resin, the polydentate accelerant ligand is present in the formulation at a concentration of from about 0.0005 to about 10 % w / w, more typically from about 0.001 to about 2 % w / w, more typically from 0.01 to 1 % w / w, more typically from 0.02 to 1 % w / w, even more typically from 0.05 to 0.5 % w / w.

[0082] BISPIDON

[0083] The bispidon class are typically in the form of an iron transition metal catalyst. The bispidon ligand is preferably of Formula I or Formula l-A:wherein:- 15 -55648278-17513-A-WO - PE963282WO each R in is independently selected from the group consisting of hydrogen, F, Cl, Br, Formula (I) hydroxyl, Ci-4-alkylO-, -NH-CO-H, -NH-CO-Ci-4alkyl, -NH2, -NH-Ci-4.alkyl, and Ci— 4-alkyl;R1 and R2areindependently selected from the group consisting of Ci— 24-alkyl, Ce-io-aryl, and a group containing one or two heteroatoms (e.g. N, O or S) capable of coordinating to a transition metal;R3 and R4 are independently selected from the group consisting of hydrogen, Ci- s-alkyl, Ci-8-alkyl-O-Ci-8-alkyl, Ci-s alkyl-O-Ce-io aryl, Ce-io-aryl, Ci-s-hydroxyalkyl and - (CH2)nC(O)OR5 wherein R5 is independently selected from hydrogen, C1- 12-alkyl, and Ci-4-alkyl-O-Ci-4-alkyl and n is from 0 to 4;X is selected from the group consisting of C=O, -[C(R6)2]y- wherein y is from 0 to3; each R6 is independently selected from the group consisting of hydrogen, hydroxyl, Ci-4.alkoxy and Ci— 4-alkyl; and each D in is independently selected from the group consisting of thiazol-2-yl and Formula (l-A) thiazol-4-yl.

[0084] Often R3 = R4 and is selected from -C(O) -O-CH3, -C(O) -O-CH2CH3, -C(O)-O-CH2CeH5 and CH2OH. Often the heteroatom capable of coordinating to a transition metal is provided by pyridin—2-ylmethyl optionally substituted by Ci-4alkyl or an aliphatic amine optionally substituted by C1-8- alkyl. Often X is C=O or C(OH)2.

[0085] Typical groups for -R1 and -R2 are -CH3, -C2H5, -C3H7, -benzyl, -C Hg, -CeHia, -CsH , -C12H25, and -C18H37 and -pyridin-2-yl. An example of a class of bispidon is one in which at least one of R1 or R2 is pyridin-2-ylmethyl or benzyl or optionally alkyl-substituted amino-ethyl, e.g., pyridin-2- ylmethyl or / V, / V-dimethylamino-ethyl.

[0086] Two examples of bispidons are dimethyl 2,4-di-(2-pyridyl)-3-methyl-7-(pyridin-2-ylmethyl)-3,7- diaza-bicyclo[3.3.1]nonan-9-one-1 ,5-dicarboxylate (N2py3o-C1) and dimethyl 2,4-di-(2-pyridyl)-3- methyl-7-(N,N-dimethyl-amino-ethyl)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1 ,5-dicarboxylate and the corresponding iron complexes thereof. FeN2py3o-C1 may be prepared as described in WO 02 / 48301 . Other examples of bispidons are those which, instead of having a methyl group at the3-position, have longer alkyl chains (e.g. C4-Ci8-alkyl or Ce-Cis-alkyl chains) such as / sobutyl, (n- hexyl) C6, (n-octyl) C8, (n-dodecyl) C12, (n-tetradecyl) C14, (n-octadecyl) C18; these may be prepared in an analogous manner.

[0087] As used in this application, BOC is iron(1 +), chloro[dimethyl 9,9-dihydroxy-3-methyl-2,4-di(2- pyridinyl-kN)-7-[(2-pyridinyl-kN)methyl]-3,7-diazabicyclo[3.3.1]nonane-1 ,4-dicarboxylate-kN3,kN7]-, chloride(1 :1) illustrated below.- 16 -55648278-17513-A-WO - PE963282WO

[0088] N4py type

[0089] The N4py type ligands are typically in the form of an iron transition metal catalyst. The N4py type ligands are typically of the formula (II): wherein: each R1 and R2 independently represents -R4-R5;R3 represents hydrogen, Ci-s-alkyl, aryl selected from homoaromatic compounds having a molecular weight under 300, or C7-4o-arylalkyl, or -R4-R5, each R4 independently represents a single bond or a linear or branched Ci-s-alkyl- substituted-C2-6-alkylene, C2-6-alkenylene, C2-6-oxyalkylene, C2-6-aminoalkylene, C2-6-alkenyl ether, C2-6-carboxylic ester or C2-6-carboxylic amide, and each R5 independently represents an optionally N-alkyl-substituted aminoalkyl group or an optionally alkyl-substituted heteroaryl: selected from the group consisting of pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl;- 17 -55648278-17513-A-WO - PE963282WO1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl.

[0090] According to some embodiments R1 or R2 represents pyridin-2-yl; or R2 or R1 represents 2- amino-ethyl, 2-(N-(m)ethyl)amino-ethyl or 2-(N,N-di(m)ethyl)amino-ethyl. If substituted, R5 often represents 3-methyl pyridin-2-yl. R3 preferably represents hydrogen, benzyl or methyl.

[0091] Examples of N4Py ligands include N4Py itself ( / .e. N, N-bis(pyridin-2-yl-methyl)-bis(pyridin-2- yl)methylamine which is described in WO 95 / 34628); and MeN4py ( / .e. N,N-bis(pyridin-2-yl-methyl-1 , 1 -bis(pyridin-2-yl)-1 -aminoethane) and BzN4py (N,N-bis(pyridin-2-yl-methyl-1 , 1 -bis(pyrid in-2-yl)-2- phenyl-1 -aminoethane) which are described in EP 0909809.

[0092] TACN -type

[0093] The TACN-Nx are preferably in the form of an iron or manganese transition metal catalyst. These ligands are based on a 1 ,4,7-triazacyclononane (TACN) structure but have one or more pendent nitrogen groups that serve to complex with the transition metal to provide a tetradentate, pentadentate or hexadentate ligand. According to some embodiments of the TACN-Nx type of ligand, the TACN scaffold has two pendent nitrogen-containing groups that complex with the transition metal (TACN-N2). TACN-Nx ligands are typically of the formula (III): wherein each R20 is independently selected from: Ci-s-alkyl, Cs-s-cycloalkyl, heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1 ,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1 ,4,7-triazacyclononanyl; 1 ,4,8,11-tetraazacyclotetradecanyl;1 ,4,7,10,13-pentaazacyclopentadecanyl; 1 ,4-diaza-7-thia-cyclononanyl; 1 ,4-diaza-7- oxa-cyclononanyl; 1 ,4,7,10-tetraazacyclododecanyl; 1 ,4-dioxanyl; 1 ,4,7-trithia- cyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl; heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-triazinyl; quinolinyl; isoquinolinyl;- 18 -55648278-17513-A-WO - PE963282WO quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, aryl selected from homoaromatic compounds having a molecular weight under 300, or C7-4o-arylalkyl group optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulfonate, amine, alkylamine and N+(R21)3,R21 is selected from hydrogen, Ci-s-alkyl , C2-6-alkenyl, C7-4o-arylalkyl, arylalkenyl, Ci-s-oxyalkyl, C2-6-oxyalkenyl, Ci-s-aminoalkyl, C2-6-aminoalkenyl, Ci-s-alkyl ether, C2-6-alkenyl ether, and -CY2-R22,Y is independently selected from H, CH3, C2H5, C3H7 andR22 is independently selected from Ci-8-alkyl-substituted heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl; and wherein at least one of R20 is a -CY2-R22.

[0094] R22 is typically selected from optionally alkyl-substituted pyridin-2-yl, imidazol-4-yl, pyrazol-1- yl, quinolin-2-yl groups. R22 is often either a pyridin-2-yl or a quinolin-2-yl.

[0095] As used herein, TMTACN is 1 ,4,7-trimethyl-1 ,4,7-triazonane illustrated below.

[0096] As used herein, Borchi® Dragon is a product from Borchers containing manganese neodecanoate and TMTACN.- 19 -55648278-17513-A-WO - PE963282WO

[0097] CYCLAM and Cross-Bridged Ligands

[0098] The cyclam and cross-bridged ligands are preferably in the form of a manganese transition metal catalyst. The cyclam ligand is typically of the formula (IV):wherein:Q is independently selected from andR2CR3R4CR5R6 ] p is 4;R is independently selected from: hydrogen, Ci-6-alkyl,CH2CH2OH, pyridin-2-ylmethyl, and CH2COOH, or one of R is linked to the N of another Q via an ethylene bridge; and R1R2R3R4R5 ANC| R6are independently selected from: H, Ci-4-alkyl, andCi-4-alkylhydroxy.

[0099] Examples of non-cross-bridged ligands are 1 ,4,8,11-tetraazacyclotetradecane (cyclam), 1 ,4,8,11 -tetramethyl- 1 ,4,8,11-tetraazacyclotetradecane (Me4cyclam),1 ,4,7,10-tetraazacyclododecane (cyclen), 1 ,4,7,10-tetramethyl-1 ,4,7,10-tetraazacyclododecane (Me4cyclen), and 1 ,4,7,10-tetrakis(pyridine-2ylmethyl)-1 ,4,7,10-tetraazacyclododecane (Py4cyclen). With Py4cyclen the iron complex is preferred.- 20 -55648278-17513-A-WO - PE963282WO

[0100] A preferred cross-bridged ligand is of the formula (V):whereinR1is independently selected from H, Ci-20-alkyl, C7-4o-alkylaryl, C2-6-alkenyl or C2-6-alkynyl.

[0101] All nitrogen atoms in the macropolycyclic rings may be coordinated with a transition metal. In formula (VI), each R1may be the same. Where each R1is Me, this provides the ligand5.12-dimethyl-1 ,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane (L) of which the complex [Mn(L)Ch] may be synthesised according to WO98 / 39098. Where each R1 = benzyl, this is the ligand 5,12-dibenzyl-1 .5.8.12-tetraaza-bicyclo[6.6.2]hexadecane (!_’) of which the complex [Mn(L’)Cl2] may be synthesised as described in WO 98 / 39098. Further suitable crossed-bridged ligands are described in WO98 / 39098.

[0102] TRISPICEN-type

[0103] The trispicens are preferably in the form of an iron transition metal catalyst. The trispicen type ligands are preferably of the formula (VI):R17R17N-X-NR17R17 (VI), wherein:X is selected from -CH2CH2-, -CH2CH2CH2-, -CH2C(OH)HCH2-; each R17 independently represents a group selected from: R17, Ci-s-alkyl, Cs-s-cycloalkyl, heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1 ,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1 ,4,7-triazacyclononanyl; 1 ,4,8,11- tetraazacyclotetradecanyl; 1 ,4,7,10,13-pentaazacyclopentadecanyl; 1 ,4-diaza- 7-thia-cyclononanyl; 1 ,4-diaza-7-oxa-cyclononanyl; 1 ,4,7,10- tetraazacyclododecanyl; 1 ,4-dioxanyl; 1 ,4,7-trithia-cyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl; heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl;- 21 -55648278-17513-A-WO - PE963282WO oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, aryl selected from homoaromatic compounds having a molecular weight under 300, and C7-40 arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulfonate, amine, alkylamine and N+(R19)3 , whereinR19 is selected from hydrogen, Ci-s-alkyl, C2-6-alkenyl, C7-4o-arylalkyl,C7-4o-arylalkenyl, Ci-s-oxyalkyl, C2-6-oxyalkenyl, Ci-s-aminoalkyl, C2-6-aminoalkenyl, Ci-s-alkyl ether, C2-6-alkenyl ether, and -CY2-RI8, in which each Y is independently selected from H, CH3, C2H5, C3H7 and R18 is independently selected from an optionally substituted heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl; and at least two of R17 are -CY2-RI8.

[0104] The heteroatom donor group is preferably pyridinyl, e.g. 2-pyridinyl, optionally substituted by -Ci-C4-alkyl.

[0105] Other preferred heteroatom donor groups are imidazol-2-yl, 1-methyl-imidazol-2-yl, 4-methyl- imidazol-2-yl, imidazol-4-yl, 2-methyl-imidazol-4-yl, 1-methyl-imidazol-4-yl, benzimidazol-2-yl and 1-methyl-benzimidazol-2-yl. Preferably three of R17 are CY2-RI8.

[0106] The ligand Tpen (N, N, N’, N’-tetra(pyridin-2-yl-methyl)ethylenediamine) is disclosed in WO 97 / 48787. Other suitable trispicens are described in WO 02 / 077145 and EP 1001009A.

[0107] Preferably, the ligand is selected from dimethyl 2,4-di-(2-pyridyl)-3-methyl-7-(pyridin-2- ylmethyl)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1 ,5-dicarboxylate, dimethyl 2,4-di-(2-pyridyl)-3-methyl- 7-(N,N-dimethyl-amino-ethyl)-3,7-diaza-bicyclo[3.3.1]nonan-9-one-1 ,5-dicarboxylate, 5,12-dimethyl- 1 ,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane, 5,12-dibenzyl-1 ,5,8,12-tetraaza- bicyclo[6.6.2]hexadecane, N,N-bis(pyridin-2-yl-methyl-1 , 1 -bis(pyridin-2-yl)-1 -aminoethane, and N,N- bis(pyridin-2-yl-methyl-1 , 1 -bis(pyridin-2-yl)-2-phenyl-1 -aminoethane.

[0108] OTHER LIGANDS

[0109] Other polydentate accelerant ligands known to those in the art may also be used, and these are discussed below. Typically, these ligands may be used in pre-formed transition metal complexes, which comprise the polydentate accelerant ligand.

[0110] Firstly, the polydentate accelerant ligand may be a bidentate nitrogen donor ligand, such as 2,2’-bipyridine or 1 ,10-phenanthroline, both of which are used known in the art as polydentate accelerant ligands in siccative metal driers. Often 2,2’-bipyridine or 1 ,10-phenanthroline are provided- 22 -55648278-17513-A-WO - PE963282WO as ligands in manganese- or iron-containing complexes. Other bidentate polydentate accelerant ligands include bidentate amine-containing ligands. 2-aminomethylpyridine, ethylenediamine, tetramethylethylene-diamine, diaminopropane, and 1 ,2-diaminocyclohexane.

[0111] A variety of bi- to hexadentate oxygen donor-containing ligands, including mixed oxygen- and nitrogen-containing donor ligands, are also known. For example, WO 03 / 029371 A1 describes tetradentate diimines of the formula:RI-C(AI-O)=N-R2-N=C(A2-O)-R3wherein:Ai and A2 both are aromatic residues;R1 and R3 are covalently bonded groups, for example hydrogen or an organic group; andR2 is a divalent organic radical.

[0112] The use of 1 ,3-diketones as polydentate accelerant ligands is described in both EP 1382648 A1 and WO 00 / 11090 A1 , EP 1382648 also describing the use of complexes comprising 1 ,3-diketones (or 1 ,3-diimines) and bidentate diamines, including bipyridine and phenanthroline.

[0113] A variety of metal driers are described in US 2005 / 0245639, including vanadium, manganese, iron, cobalt, cerium and lead complexes, including those containing imidazoles and pyrazoles such as those described in WO 00 / 11090, and aromatic and aliphatic amines.

[0114] Of the non-bispidon type siccatives the following are most preferred: 5,12-dimethyl-1 ,5,8,12- tetraaza-bicyclo[6.6.2]hexadecane, 5,12-dibenzyl-1 ,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane, 1 ,4,8,11-tetraazacyclotetradecane, 1 ,4,8,11 -tetramethyl- 1 ,4,8,11-tetraazacyclotetradecane,1 .4.7.10-tetraazacyclododecane, 1 ,4,7,10-tetramethyl-1 ,4,7,10-tetraazacyclododecane, and1 .4.7.10-tetrakis(pyridine-2ylmethyl)-1 ,4,7,10-tetraazacyclododecane, N,N-bis(pyridin-2-yl-methyl)- bis(pyridin-2-yl)methylamine, N,N-bis(pyridin-2-yl-methyl-1 , 1 -bis(pyridin-2-yl)-1 -aminoethane, N,N-bis(pyridin-2-yl-methyl-1 ,1-bis(pyridin-2-yl)-2-phenyl-1-aminoethane and 1 ,4,7-trimethyl-1 ,4,7- triazacyclononane.

[0115] In some embodiments, the polydentate accelerant ligand is a bispidon ligand. In some exemplary embodiments, the bispidon ligand is BOC.

[0116] In some embodiments, the polydentate accelerant ligand is a TACN-type ligand. In some exemplary embodiments, the TACN-type ligand is Borchi® Dragon.TRANSITION METAL IONS

[0117] Transition metal ions to which the polydentate accelerant ligands may coordinate to provide complexes (primary accelerators that can accelerate curing of the unsaturated resin with peroxide in formulations and compositions of the invention) may be, according to particular embodiments, iron, manganese, vanadium, or copper (preferably iron or manganese) ions, or mixtures of any these metal - 23 -55648278-17513-A-WO - PE963282WO ions. The valency of the metal ions may range from +1 to +6, often from +2 to +5. Examples include metal ions selected from the group consisting of Fe(ll), Fe(lll), Fe(IV), Fe(V), Mn(ll), Mn(lll), Mn(IV), and Mn(V), for example metal ions selected from the group consisting of Fe(ll), Fe(lll), Mn(ll), Mn(lll), and Mn(IV).

[0118] In complexes comprising a chelant, the number of metal ions per chelant molecule may be either 1 or 2. Since the disclosed chelants may contain two tridentate, tetradentate or pentadentate nitrogen donor moieties, each tridentate, tetradentate or pentadentate nitrogen donor moiety may bind to one transition metal (e.g. iron or manganese) ion. Thus, one may obtain a molar ratio of the chelant to metal ion of 1 :2. Also one may obtain complexes or species in which one chelant containing two tridentate, tetradentate or pentadentate nitrogen donor moieties binds to only one metal ion, for example if a molar excess of chelant is employed. In this way, there are provided complexes having a molar ratio of the chelant to metal ion of 1 :1 , in which one of the tridentate, tetradentate or pentadentate nitrogen donor moieties will not coordinate to a manganese or iron ion.

[0119] An appropriate quantity of suitable transition metal cations (e.g. ions of one or more of iron, manganese, vanadium and copper) can be added to the compositions and formulations of the invention, for example when introducing other components to form an oxidatively curable medium.

[0120] The typical molar ratio between transition metal ions and the chelant is between about 0.1 :1 and about 10:1 , often between about 0.3:1 and about 3:1 . Often, the molar ratio between chelant and transition metal ions will be approximately between 1 :2 and 1 :1. However, this need not necessarily be the case. Without being bound to theory, an excess of transition metal ions may be beneficial in allowing a curing behaviour following a different mechanism to that in which a well-defined or not well- defined transition metal complex is involved. Conversely, a stoichiometric excess of chelant may be beneficial to improve regeneration of catalytically active species during curing, which can lead to improved curing performance despite using a lower quantity of transition metal ions. Using a stoichiometric excess of chelant can also be advantageous by reducing the intensity of colored metal ions and / or complexes.

[0121] Often, the transition metal ions are present in the curable liquid compositions of the invention at a concentration of between about 0.00005 % w / w and about 0.1 % w / w, in further embodiments, about 0.0001 % w / w to about 0.05 % w / w, in still further embodiments, between about 0.0001 % w / w and about 0.02 % w / w, and in yet still further embodiments, between about 0.005 % w / w and about 0.01 % of the suitable transition metal ion.

[0122] In embodiments in which the transition metal ions are present in a formulation with the unsaturated resin prior to combination with a separate formulation, the transition metal ions are present in the formulation with the unsaturated resin at a concentration of from about 0.00005 % w / w to about 0.1 % w / w, in further embodiments, about 0.0001 % w / w to about 0.05 % w / w, in still further embodiments, between about 0.0001 % w / w and about 0.02 % w / w, and in yet still further embodiments, between about 0.005 % w / w and about 0.01 % of the suitable transition metal ion. In some of these embodiments, the separate formulation can if desired comprise less than 0.00001 % by weight of each of at least iron, manganese, cobalt vanadium and copper ions, in further- 24 -55648278-17513-A-WO - PE963282WO embodiments, less than 0.00005 % by weight, in further embodiments, less than 0.0001 % by weight, and in still further embodiments, less than 0.001 % by weight. Ideally, embodiments of the composition of the invention with concentrations of specific transition metal ions of less than 0.001 % w / w, 0.0001 % w / w, 0.00005 % w / w, or 0.00001 % w / w are absent any of the transition metal ions specified. This may be, in practice, impossible to achieve, however. Accordingly, these are preferably absent the transition metal ions specified to the greatest extent practicable.

[0123] In embodiments in which the transition metal ions are present in a formulation that is physically separated from unsaturated resin prior to combination with a separate formulation containing unsaturated resin, the transition metal ions are present in formulation at a concentration of from about 0.0005 % w / w to about 1 .0 % w / w, in further embodiments, about 0.001 % w / w to about 0.5 % w / w, in still further embodiments, between about 0.001 % w / w and about 0.4 % w / w, and in yet still further embodiments, between about 0.01 % w / w and about 0.1 % of the suitable transition metal ion. In some of these embodiments, the separate formulation containing unsaturated resin can if desired comprise less than 0.00001 % by weight of each of at least iron, manganese, cobalt vanadium and copper ions, in further embodiments, less than 0.00005 % by weight, in further embodiments, less than 0.0001 % by weight, and in still further embodiments, less than 0.001 % by weight. Ideally, embodiments of the composition of the invention with concentrations of specific transition metal ions of less than 0.001 % w / w, 0.0001 % w / w, 0.00005 % w / w, or 0.00001 % w / w are absent any of the transition metal ions specified. This may, in practice, be impossible to achieve. Accordingly, these are preferably absent the transition metal ions specified to the greatest extent practicable. In particular, formulations of the invention comprising a chelant and a peroxide will generally be absent the transition metal ions specified above to the greatest extent practicable, in view of possibility safety issues.THIOL SECONDARY ACCELERATOR (Crosslinker)

[0124] A further characteristic feature of the various aspects of the present invention is the use of a thiol secondary accelerator of one of the below forms or classes. The sulfur analogs of alcohols may be called thiols. Traditionally, thiols are referred to as mercaptans. The functional group of a thiol is an -SH end group bonded to a carbon atom. A thiol or thiol derivative is any organosulfur compound of the form R-SH, where R represents an alkyl or other organic substituent. The -SH functional group itself is referred to as either a thiol group or a sulfhydryl group, or a sulfanyl group.

[0125] Without being bound by theory, it is believed that the thiol secondary accelerators of the disclosed invention, in combination with the other components of the disclosed invention, may act as an accelerator (accelerating decomposition and action of the peroxide initiator), a crosslinker (making linkages between different parts of the same or different molecules of an unsaturated resin), or both. Thus, while thiol or polythiol “secondary accelerator” is used in various places throughout the present disclosure, no functional limitation as to the mechanism of action in the inventive formulations and compositions is intended, nor should such a limitation be implied.

[0126] In a more generic form, the thiol and / or polythiol secondary accelerator may be represented as follows in formula (VII):- 25 -55648278-17513-A-WO - PE963282WOwhereinZ is a covalently bonding bridging moiety;R30is independently selected from the group consisting of a C1-30 branched or straight chain alkyl; C1-30 branched or straight chain alkenyl, C5-45-cycloalkyl, C5-45-cycloalkenyl, Ce- 45-aryl, Ce-45-arylalkyl, Ce-45-alkylaryl, Ci-s-oxyalkyl, C2-6-oxyalkenyl, Ci-8-aminoalkyl, C2-6-aminoalkenyl, Ci-s-alkyl ether, C2-6-alkenyl ether, and -CY2-RI 8, in which each Y is independently selected from H, CH3, C2H5, C3H7 and R18 is independently selected from an optionally substituted heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl; and further wherein R30or Z are heteroatoms based on O, N, S, or P; e.g., an epoxy group; or a siloxane or polysiloxane group such as dimethylsiloxane, branched or linear equivalents, that can also contain additional functionality such as an acrylate, unsaturated carbon-carbon bonds, alcohol or acid groups, the crosslinker can for example be silicone-thiol resin; R30or Z groups can be an alcohol functionality - the thiol crosslinker may consist of acrylic or polyacrylic groups that may have comonomers or monomers with functionality such as free allyl groups, free thiol groups, unsaturated carbon-carbon-bonds such as the use of ethylene glycol dimethacrylate, or alcohol groups incorporated by use of hydroxyethylmethacrylate, or acids for example from acrylic acid, or epoxy groups; polymeric crosslinkers can also be made from polyurethanes, polyesters, and other polymers known;R32and R33are selected from the group identified for R30; m, n, and 0 are independently 0 or 1 ; and p is an integral value from 1 to 10; and wherein the siloxane or polysiloxane is linear or branched polymer or derivatized polymer with acetoxy, oxime, amine, or alkoxy substituents having a weight average (Mw) molecular weight of between 200 - 50,000, more preferably 500 - 10,000, and55648278-17513-A-WO - PE963282WO most preferably 1 ,000 - 5,000, and may further comprise a copolymers thereof including copolymers of polypropylene oxide and polyethylene oxide:and whereinR34to R40are independently selected from the group for R30above; and a, b, and c are independently selected from 0 to 3,000 inclusive.

[0127] Examples of suitable thiol secondary accelerators include, but are not limited to, the esters of thioglycolic acid, 2-mercapto-propionic acid or 3-mercaptopropionic acid with polyols, such as glycols, pentaerythritol, di-pentaerythritol and trimethylolpropane, and optionally a fatty acid, such as oleic acid, stearic acid, isononanoic acid or sunflower fatty acid. Specific examples of suitable thiol secondary accelerators are ethylene glycol bis (thioglycolate), ethylene glycol bis (2- mercaptopropionate), ethylene glycol bis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (2-mercaptopropionate), pentaerythritol tetrakis (3- mercaptopropionate), trimethylolpropane tris(2-mercaptopropionate), trimethylolpropane tris(3- mercaptopropionate), and the condensation product of di-trimethylolpropane, 2,2-dimethylolpropionic acid, stearic acid, and 3-mercaptopropionic acid. An example of a commercial silicone-thiol can be, for example, Silmer SH Q20 (i.e., silicon thiol resin with very high cross-link density - Silmer SH Q20 contains no dimethyl silicone groups to maximize the hardness of the materials cured from it - Appearance: Clear to slightly hazy liquid; Viscosity: cPs 15,000; Active Content: % 100; SH content: % 14.2; Odor: Distinctive but mild) or Silmer SH 208-30Q (i.e., silicon thiol resin with very high crosslink density - Silmer SH 208-30Q contains no dimethyl silicone groups to maximize the hardness of- 27 -55648278-17513-A-WO - PE963282WO the materials cured from it - Appearance: Clear to slightly hazy liquid; Viscosity: cPs 3,000; Active Content: % 100; SH content: % 14.6; Odor: Distinctive but mild).

[0128] Preferably, compositions of the present invention comprise 0.01 to 20 % w / w of thiol secondary accelerator, in further embodiments, 0.02 to 10 % w / w of thiol compounds, in still further embodiments, 0.05 to 7 % w / w, in still further embodiments 0.1 to 5 % w / w, and in yet still further embodiments, 0.5 to 3 % w / w. The thiols may for example have a weight average (Mw) molecular weight of ~200 — 50,000 inclusive, more preferably ~1 ,000 — 10,000 inclusive, and most preferably ~500 — 5,000 inclusive and preferred ~750 - ~2000.

[0129] Any of the above compounds compound having at least one (preferably two or more) thiol (— SH) functional groups may be advantageously used as a thiol secondary accelerator in the compositions of the present invention. For example, the thiol secondary accelerator may contain three or more thiol groups, four or more thiol groups or five or more thiol groups. A thiol secondary accelerator could be a branched or a hyperbranched polymer, containing a range of thiol groups from 2 to 100.

[0130] Suitable (poly)thiols for use in the present invention may also be characterized with respect to their thiol equivalent weight (calculated by dividing the molecular weight of the (poly)thiol by the number of thiol functional groups per molecule). In various embodiments of the invention, the thiol secondary accelerator has a thiol equivalent weight of at least 80 Daltons, at least 90 Daltons, at least 95 Daltons or at least 100 Daltons and / or a thiol equivalent weight of not more than 450 Daltons, not more than 400 Daltons, not more than 350 Daltons, not more than 300 Daltons, not more than 250 Daltons or not more than 200 Daltons. For example, the thiol equivalent weight of the thiol secondary accelerator may be from 80 Daltons to 450 Daltons, from 90 Daltons to 400 Daltons or from 100 Daltons to 200 Daltons.

[0131] Additionally, it will generally be desirable to select a thiol secondary accelerator or combination of thiol secondary accelerator having low odor. For example, the (poly)thiol(s) may be sufficiently low in odor that the coating or sealant composition containing the (poly)thiol(s) does not have any sulfur odor discernable to a human olfactory system when the composition is spread as a layer on a substrate surface at 25°C. In other embodiments, the thiol secondary accelerator(s) used has a relatively high flash point, e.g., a flash point of at least 100°C, as measured by ASTM D92-12b.

[0132] According to various embodiments of the invention, the thiol secondary accelerator may be a monomer, an oligomer or a polymer (i.e., the backbone or skeleton of the polythiol secondary accelerator may be monomeric, oligomeric or polymeric in character). Each thiol group may be attached to the skeleton or backbone of a polythiol compound either directly or via a linking moiety.

[0133] In certain embodiments of the present invention, the thiol secondary accelerator is a thiol- functionalized ester of a polyalcohol (a compound containing two or more alcohol functional groups).

[0134] The following may be mentioned by way of example as polyalcohols suitable for esterifying with a thiol-functionalized carboxylic acid to provide a thiol secondary accelerator: alkanediols, such as butanediol, pentanediol, hexanediol, alkylene glycols, such as ethylene glycol, propylene glycol- 28 -55648278-17513-A-WO - PE963282WO and polypropylene glycol, glycerin, 2-(hydroxyl methyl)propane-1 ,3-diol, 1 ,1 ,1 ,- tris(hydroxymethyl)ethane, 1 ,1 ,1 -trimethylolpropane, di(trimethylolpropane), tricyclodecane dimethylol, 2,2,4-trimethyl-1 ,3-pentanediol, bisphenol A, cyclohexane dimethanol, alkoxylated and / or ethoxylated and / or propoxylated derivatives of neopentyl glycol, tetraethylene glycol cyclohexanedimethanol, hexanediol, 2-(hydroxymethyl)propane-1 ,3-diol, 1 ,1 ,1-tris(hydroxymethyl)ethane, 1 ,1 ,1- trimethylolpropane and castor oil, pentaerythritol, sugars, sugar alcohols or mixtures thereof.

[0135] Suitable thiol secondary accelerators include esters of a-thioacetic acid (2-mercaptoacetic acid), p-thiopropionic acid (3-mercaptopropionic acid) and 3-thiobutyric acid (3-mercaptobutyric acid), wherein such acids are esterified with diols, triols, tetraols, pentaols or other polyols, such as 2-hydroxy-3-mercaptopropyl derivatives of diols, triols, tetraols, pentaols or other polyols. Mixtures of alcohols may also be used as a basis for the thiol-functionalized compound.

[0136] Examples of suitable thiol secondary accelerators which may be mentioned are: glycol-bis(2- mercaptoacetate), glycol-bis(3-mercaptopropionate), 1 ,2-propylene glycol-bis(2-mercaptoacetate),1 .2-propylene glycol-bis(3-mercaptopropionate), 1 ,3-propylene glycol-bis(2-mercaptoacetate),1 .3-propylene glycol-bis(3-mercaptopropionate), tris(hydroxymethyl)methane-tris(2-mercaptoacetate), tris(hydroxymethyl)methane-tris(3-mercaptopropionate), 1 ,1 ,1-tris(hydroxymethyl)ethane-tris(2- mercaptoacetate), 1 ,1 ,1-tris(hydroxymethyl)ethane-tris(3-mercaptopropionate),1 ,1 ,1-trimethylolpropane-tris(2-mercaptoacetate), ethoxylated 1 ,1 ,1-trimethylolpropane-tris(2- mercaptoacetate), propoxylated 1 ,1 ,1-trimethylolpropane-tris(2-mercaptoacetate), 1 ,1 ,1 -trimethylol propane-tris(3-mercaptopropionate), ethoxylated 1 ,1 ,1-trimethylolpropane-tris(3-mercaptopropionate), propoxylated trimethylolpropane-tris(3-mercaptopropionate), 1 ,1 ,1-trimethylolpropane-tris(3- mercaptobutyrate), pentaerythritol-tris(2-mercaptoacetate), pentaerythritol-tetrakis(2- mercaptoacetate), pentaerythritol-tris(3-mercaptopropionate), pentaerythritol-tetrakis(3- mercaptopropionate), pentaerythritol-tris(3-mercaptobutyrate), pentaerythritol-tetrakis(3- mercaptobutyrate), Capcure® 3-800 (Gabriel Performance Products, LLC), GPM-800 (Gabriel Performance Products LLC), Capcure® LOF (Gabriel Performance Products, LLC) (Low odor and low skinning uncatalyzed polymercaptan, Color, Gardner < 2.0, Mercaptan value > 3.0 meg / g, Viscosity @25°C, Brookfield 100 - 200 poise. Specific gravity @25°C 1.15), GPM-800LO (Gabriel Performance Products LLC) (GABEPROTM GPM-800 curing agent is a mercaptan (-SH) terminated liquid curing agent), KarenzMT PE-1 (Showa Denko) (i.e., Pentaerythritol tetrakis(3-mercaptobutylate), 2- ethylhexylthioglycolate, iso-octylthioglycolate, di(n-butyl)thiodiglycolate, glycol-di-3- mercaptopropionate, 1 ,6-hexanedithiol, ethylene glycol-bis(2-mercaptoacetate) and tetra(ethylene glycol)dithiol).

[0137] Such thiol secondary accelerators may be prepared by any method known in the art or obtained from commercial sources, such as the polythiols sold under the trade name "Thiocure®" in Table A by Bruno Bock.

[0138] The thiol secondary accelerator may be used alone or as a combination of two or more different thiol secondary accelerators.

[0139] Some exemplary thiol secondary accelerators are provided below in Table A.- 29 -55648278-17513-A-WO - PE963282WOTable A - Exemplary Thiols-30-55648278-17513-A-WO - PE963282WO55648278-17513-A-WO - PE963282WO-32-55648278-17513-A-WO - PE963282WO

[0140] The above Thiocure® polythiols are synthesized by esterification of mercaptocarboxylic acids and polyfunctional alcohols and commercially available from Bruno Bock Chemische Fabrik GmbH &Co. KG.Table B - Other Secondary Accelerator Types55648278-17513-A-WO - PE963282WOPEROXIDE

[0141] The various aspects of the invention further include a peroxide initiator compound. Any peroxide known to the skilled person can be used for curing the unsaturated resins described herein. Such peroxides include organic and inorganic peroxides, which may be either solids or liquids.Hydrogen peroxide may also be used. Examples of suitable peroxides include those comprising the functional groups -OCOO- (peroxy carbonates), -C(O)OO- (peroxy esters), -C(O)OOC(O)- (dialkylperoxides), -OO- (dialkylperoxides) and the like. These peroxides can also be oligomeric or polymeric of nature. An extensive list of suitable peroxide compounds can be found, amongst others, in US 2002 / 0091214 A1 , paragraph

[0018] ,- 34 -55648278-17513-A-WO - PE963282WO

[0142] Often, the peroxide is an organic peroxide. Examples of suitable peroxides are tertiary alkylhydroperoxides (such as t-butyl-hydroperoxide), other hydroperoxides (such as cumylhydroperoxide), ketone peroxides (such as formed by mixing ketones with hydrogen peroxide, like acetylacetone peroxide or methylethylketone peroxide), peroxyesters, or peracids (such as t-butyl peresters, benzoyl peroxide, peracetates, perbenzoates, laurylperoxide, peroxy diethylether. Other useful hydroperoxides include 1 ,1 ,3,3-tetramethylbutyl hydroperoxide, isopropylcumylhydroperoxide, t-amylhydroperoxide, 2,5-dimethyl-2,5-dihydroperoxide, pinanehydroperoxide, pinene hydroperoxide. Other preferred ketone peroxides include methylisopropyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide and acetylacetone peroxide. Often the organic peroxides used as curing agent are tertiary peresters or tertiary hydroperoxides, i.e. peroxy moieties having the tertiary carbon directly bound to the OO-acyl or OOH group. Also, mixtures of various peroxy compounds may be applied.

[0143] It is preferred to use a liquid peroxyester, a liquid hydroperoxide or a liquid mixture of hydroperoxides. Handling of liquid peroxides is generally easier: mixing is easier and the rate of dissolution into the resin to be cured is higher. Most preferred is to use a liquid ketone peroxide, specifically methyl ethyl ketone peroxide (MEKP) or a liquid alkyl hydroperoxide, especially cumyl hydroperoxide.

[0144] The level of peroxide optimally employed varies depending on the type of peroxide, unsaturated resin used and the intended application. The skilled person in the art is able to optimize the level and type of peroxide in conjunction with the unsaturated resin and metal chelant mixture or complex being used. The level of peroxide is from 0.001 to 10 % w / w, more preferably from 0.01 to 8 % w / w, still more preferably from 0.1 to 6 % w / w or even more preferably from 0.3 to 4 % w / w, and most preferably from 0.5 to 2 % w / w, where % w / w is expressed here as peroxide weight relative to the weight of curable components of the relevant composition (unsaturated resin and any reactive diluent).COATING AND COMPOSITE COMPOSITIONS, FORMULATIONS, KITS, AND METHODS

[0145] In some embodiments, the invention is directed to a liquid curable composition that includes:(i) at least one unsaturated resin;(ii) at least one peroxide;(iii) at least one polydentate accelerant ligand selected from the group consisting of bispidon, N4py-type, TACN-type, cyclam and cross-bridged ligands, and trispicen-type ligands, or a mixture thereof;(iv) transition metal ions, which may include, for example, ions of manganese, iron, copper, or vanadium, but may, in preferred embodiments include ions of iron or manganese,(v) at least one thiol secondary accelerator, and(vi) optionally, additional materials, such as at least one reactive diluent; at least one radical inhibitor; at least one pigment dispersant or at least one rheology additive; at least one UV stabilizer; at least one dispersant; at least one surfactant; at least one corrosioninhibitor; at least one filler; at least one antistatic agent; at least one flame-retardant; at- 35 -55648278-17513-A-WO - PE963282WO least one lubricant; at least one antifoaming agent; at least one antifouling agent; at least one biocide; at least one fungicide; at least one algaecide; at least one insecticide; at least one extender; at least one antifreezing agent; or at least one thickener.

[0146] If present, one or more radical inhibitors are typically selected from phenolic compounds, stable radicals, like galvinoxyl, N-oxyl based compounds, chatechols and / or phenothiazines. Suitable examples of radical inhibitors that can be used are 2-methoxyphenol, 4-methoxyphenol, 2,6-dibutyl-4- methylphenol, 2,6-dibutylphenol, 2,4,6-trimethyl-phenol, 2,4,6-trimethyl-phenol, 2,4,6-tris- dimethylaminomethyl-phenol, 4,4’-thio-bis(3-methyl-6-t-butylphenol), 4,4’-isopropylidine diphenol, 2,4- di-t-butylphenol, 6,6’-di-t-butyl-2,2’-methylene-di-p-cresol, hydroquinone, 2-methyl-hydroquinone, 2,5- di-t-butyl-hydroquinone, 2,6-di-t-butyl-hydroquinone, 2,6-dimethylhydroquinone, 2,3,5- trimethylhydroquinone, catechol, 4-t-butylcatechol, 4,6-di-t-butylcatechol, benzoquinone, 2, 3,5,6- tetrachloro-1 ,4-benzoquinone, methylbenzoquinone, 2,6-dimethylbenzoquinone, naphthaquinone, 1- oxyl-2,2,6,6-tetramethylpiperidine (TEMPO), 1-oxyl-2,2,6,6-tetramethylpiperidine-4-ol (TEMPOL), 1- oxyl-2,2,6,6-tetramethylpiperidine-4-one (TEMPON), 1-oxyl-2,2,6,6-tetramethyl-4carboxyl-piperidine (4-carboxy-TEMPO), 1-oxyl-2,2,5,5-tetramethylpyrrolidine, 1-oxyl-2,2,5,5-tetramethyl-3- carboxypyrrolidine, aluminium-N-nitrosophenyl hydroxylamine, diethylhydroxylamine, phenothiazine and / or derivatives or combinations of any of these radical inhibitors.

[0147] If present, the amount of radical inhibitor used may vary depending on the desired cure time. Often the radical inhibitor, e.g. a phenolic inhibitor, is dosed in the range from 0.0001 to 10 wt%. More preferably, the amount of radical inhibitor is in the resin composition is in the range of from 0.001 to 1 wt%.

[0148] Alternatively, it may be advantageous for a formulation to be provided, for example by the producer of an unsaturated resin, which comprises unsaturated resin, chelant that is bound to a suitable transition-metal ion, often selected from those of iron, manganese, vanadium or copper, more often iron or manganese, and thiol secondary accelerator, i.e. in which such formulations lack the peroxide present in the compositions of the invention. The complex of the chelant bound to such a transition metal ion or ions may or may not be a well-defined complex. In other embodiments, the transition metal ion and / or thiol secondary accelerator may also be absent or substantially absent from such formulations with the understanding that these components may be added with alternative formulations, with or without the peroxide. In still further embodiments, one or both of the transition metal ion and thiol secondary accelerator may be included in both the unsaturated resin formulation and a formulation including the peroxide or a separate formulation.

[0149] A benefit in omitting the peroxide is that, for a producer of finished products, e.g. anyone wishing to produce cured product on demand, will be that the curing of the unsaturated resin can be deferred until peroxide is added to such formulations (whereby to provide a composition of the present invention) to initiate curing. With the benefit of this disclosure, the producer of the unsaturated resin can determine the optimal level of chelant, transition metal ion, and thiol secondary accelerator to include in such formulations, with the chelant and transition metal ion provided as a complex that is not well defined, as a well-defined complex, or in separate formulations that provide a complex on- 36 -55648278-17513-A-WO - PE963282WO mixing. The entity wishing to produce a cured product will just need to add the optimal amount of peroxide to a given formulation to obtain the desired curing, and can be instructed in this regard by the manufacturer of the formulations.

[0150] By substantially absent peroxide is meant herein that there is less than about 0.001 % w / w peroxide (i.e. with respect to curable components of the formulation concerned), often less than about 0.01 % w / w, would often still less than about 0.1 % w / w peroxide.

[0151] It will also be appreciated in view of the considerations outlined above, that the invention contemplates a series of kits made up of physically separated (for instance in separate cartridges, sachets, pouches, tanks, or the like) formulations including at least those described below, though other kits and combinations will be possible in accordance with the present invention and the principles enumerated in this disclosure.

[0152] A first kit according to the invention includes a two-component or 2k system. In a first component, a first formulation includes unsaturated resin, a complex (well defined or not well defined) of chelant and transition metal ion, and a thiol secondary accelerator. In a second component, a second formulation includes a peroxide.

[0153] A second kit according to the invention includes a two-component or 2k system. In a first component, a first formulation includes unsaturated resin and a complex (well defined or not well defined) of chelant and transition metal ion. In a second component, a second formulation includes a peroxide and a thiol secondary accelerator.

[0154] A third kit according to the invention includes a two-component or 2k system. In a first component, a first formulation includes unsaturated resin, a chelant, and a thiol secondary accelerator. In a second component, a second formulation includes a peroxide and a transition metal ion.

[0155] A fourth kit according to the invention includes a two-component or 2k system. In a first component, a first formulation includes unsaturated resin and a chelant. In a second component, a second formulation includes a peroxide, a transition metal ion, and a thiol secondary accelerator.

[0156] A fifth kit according to the invention includes a two-component or 2k system. In a first component, a first formulation includes unsaturated resin and a transition metal ion. In a second component, a second formulation includes a peroxide, a chelant, and a thiol secondary accelerator.

[0157] A sixth kit according to the invention includes a two-component or 2k system. In a first component, a first formulation includes unsaturated resin, a transition metal ion, and a thiol secondary accelerator. In a second component, a second formulation includes a peroxide and a chelant.

[0158] A seventh kit according to the invention includes a three-component or 3k system. In a first component, a first formulation includes unsaturated resin and a complex (well defined or not well defined) of chelant and transition metal ion. In a second component, a second formulation includes a peroxide. In a third component, a third formulation includes a thiol secondary accelerator.- 37 -55648278-17513-A-WO - PE963282WO

[0159] An eighth kit according to the invention includes a three-component or 3k system. In a first component, a first formulation includes unsaturated resin and a thiol secondary accelerator. In a second component, a second formulation includes a peroxide. In a third component, a third formulation includes a complex (well defined or not well defined) of chelant and transition metal ion.

[0160] A ninth kit according to the invention includes a three-component or 3k system. In a first component, a first formulation includes unsaturated resin. In a second component, a second formulation includes a peroxide. In a third component, a third formulation includes a complex (well defined or not well defined) of chelant and transition metal ion and a thiol secondary accelerator.

[0161] In each of the various formulations of the different kits, optional additional materials can be included. Typically, if present, such optional additional materials will be, but need not necessarily be, included in a formulation with the unsaturated resin. Some optional additional materials may only be appropriate in certain formulations with certain other materials, as will be appreciated by a person of ordinary skill in the art (for example the formulations comprising unsaturated resin(s) may also comprise a reactive diluent(s)).

[0162] The components of such kits are generally combined with one another, whereby to provide a composition of the invention, which may cure to provide a cured coating or composite composition or a cured article or coated article in accordance with the invention.

[0163] Formulations of the invention that are essentially or substantially absent transition metal ions, including at least iron, manganese, cobalt vanadium and copper ions comprise less than 0.0001 % by weight of at least ions of each of iron, manganese, cobalt, vanadium and copper. By this is meant that such a composition of the invention is absent 0.0001% by weight manganese ions, absent 0.0001% by weight iron ions, absent 0.0001 % by weight cobalt ions, absent 0.0001 % by weight vanadium ions and absent 0.0001% by weight copper ions. An appropriate quantity of suitable transition metal cations (e.g. ions of one or more of iron, manganese, vanadium and copper) can be added after preparation of such a composition or in a separate formulation, for example when introducing optional additional materials to form an oxidatively curable medium. Particular compositions and formulations of the invention can if desired comprise less than 0.001 % w / w, less than 0.0001 % w / w, less than 0.00005 % w / w, or less than 0.00001 % w / w by weight of each of at least iron, manganese, cobalt vanadium and copper ions.

[0164] Some embodiments are directed to a method of contacting the various formulations of a given inventive kit. There is no particular order in which the contacting of the methods need be carried out. For example, unsaturated resin may be mixed with thiol secondary accelerator and chelant (in which the chelant is optionally being part of a transition metal ion complex) with the peroxide added afterwards. Alternatively, peroxide may be mixed with thiol secondary accelerator and chelant (but with the chelant generally not being part of a transition metal ion complex, for the reasons discussed herein) with the unsaturated resin added afterwards; or unsaturated resin may be mixed with peroxide with the chelant and thiol secondary accelerator added afterwards.- 38 -55648278-17513-A-WO - PE963282WO

[0165] In some embodiments of the methods of the invention, the chelant is not part of a transition metal ion-containing complex, in which case a source of transition metal ions may, if wished, be added afterwards (or indeed the transition metal ions may have been formulated together with an unsaturated resin before the resultant mixture is contacted with a chelant so as to form a complex comprising the chelant in situ (i.e. within the formulation comprising the unsaturated resin and optionally a peroxide (if it has yet to be added))). It will be understood that such a complex is to be regarded as not well-defined.

[0166] Often, the metal salt used will be an iron or manganese salt, typically of a divalent or trivalent redox state. Upon contacting the iron or manganese (or other transition metal ion) salt with the chelant, formation of iron- or manganese chelant complexes (or other transition metal chelant complexes) takes place.

[0167] It will be understood that there is no particular limitation as to the source of the transition metal ions. Typically, however, where the transition metal ions are manganese or iron salts, salts are selected from the group consisting of optionally hydrated MnCh, FeCh, FeCh, MnBr2, Mn(NC>3)2, Fe(NOs)3, MnSC , FeSC , (Fe)2(SC>4)3, Mn(acetylacetonate)2, Fe(acetylacetonate)2, Mn(acetylacetonate)3 Fe(acetylacetonate)3, Mn(R4COO)3 (including Mn (acetate^), Fe(R4COO)3, Mn(R4COO)2 (including Mn (acetate^) and Fe(R4COO)2 (including Fe(acetate)2, wherein R4 is selected from a Ci-24alkyl. Where the salt comprises two R4 groups, these can be the same or different. The alkyl moieties, by which is meant saturated hydrocarbyl radicals, may be straight-chain or comprise branched and / or cyclic portions. Indeed, throughout the specification, where reference is made to alkyl, unless the context dictates to the contrary, this means a Ci-24alkyl, which may be straight-chain or branched and may be cycloalkyl or comprise a cyclic portion (e.g. alkyl may be cyclohexylmethyl), for example O-ioalkyl or Ci-salkyl, e.g. methyl.

[0168] The chelant may be dissolved in an organic solvent described above (or emulsified in a waterbased liquid), as described above. The chelant may be added to a formulation comprising the unsaturated resin either just after its production, immediately prior to curing with peroxide or any time in between. The chelant may be added as a pure material to the unsaturated resin(s), or as a solution. Adding the chelant as a solution can be advantageous in permitting improved and / or easier mixing with the (solution of) resin(s). It may be beneficial to dilute chelant in a suitable solvent before adding to the binder if it is wished to introduce a very small amount of chelant, so greater accuracy of dosing can be achieved. Depending on the properties of the chelant and the desired resin-chelant formulation, suitable solvents include aliphatic hydrocarbons, such as heptanes, water, alcohols, such as ethanol, isopropylalcohol, ethyleneglycol or propylene glycol, or mixtures thereof. The skilled person will be able to easily formulate such solutions, generally using a solvent such as those described above.

[0169] The kits of the invention may optionally comprise instructions or other guidance as to methods according to which the various may be contacted. In this way, the manufacture of cured thermoset resin materials, such as casting materials, fibre-reinforcement materials and coatings, can, for example, after optimising the nature of the source of transition metal ions by the preparation of a- 39 -55648278-17513-A-WO - PE963282WO particular solution of a particular transition metal ions salt, optimize the manner in which formulations containing transition metal complexes and / or thiol secondary accelerator can be prepared. The preparation of an activated resin composition may be by the manufacturer of said cured thermoset materials who can contact a source of transition metal ions with an otherwise fully formulated activated resin composition. In this way, the manufacture of the unsaturated resins can provide guidance to the producer of cured thermoset resin materials as to which peroxide(s) and which optimal dosing can be used. Likewise, the manufacture of the peroxide can provide guidance to the producer of cured thermoset resin materials as to which unsaturated resin(s) and which optimal dosing can be used.

[0170] The embodiments of the invention can be applied in all applications typical for such types of resins. In particular, they can be suitably used in closed mould applications, but they can also be used in open mould applications. For closed mould applications it is especially important that the manufacturer of the closed mould products reliably can use favourable properties of the resins according to the invention. End segments where the various embodiments of the invention can be applied include marine applications, chemical anchoring, construction, industrial wood, relining, roofing, flooring, windmill blades, containers, tanks, pipes, automotive parts, corrosion, electrical, transportation, etc.

[0171] The present invention also relates to all cured gel coats and moulded composites as are being obtained when curing an unsaturated resin (typically an unsaturated polyester resin, vinyl ester resin (e.g. acrylic resin) according to the invention, where gel coat includes pigmented or nonpigmented gel coats, as well as in-mould coatings, often for application in marine, sanitary, or automotive settings, typically having film thickness of up to 0.75 mm and appropriate weather resistance, hydrolytic stability, and mechanical properties. Moulded composites are considered to have a thickness of at least 0.5 mm and appropriate mechanical properties, preferably as reinforced composite products, and used in the field of chemical anchoring, construction, roofing, flooring, marine applications, windmill blades, containers, tanks, pipes, boats, corrosion, electrical, transportation, aerospace, etc.

[0172] Thus, the invention also provides a method comprising applying to a substrate a composition according to, or obtainable according to the invention, to a substrate. The thus applied composition may then be allowed to cure.

[0173] Any known method can be used to apply the coating compositions of the invention to a substrate. In an exemplary embodiment, gel coating compositions of the present invention are applied via airless spray of a two- or three-component coating or kit to combine each formulation of the coating or kit at the point of application to a substrate. Alternatively, each formulation in a two- or three-component coating or kit may be mixed in a vessel near the place of application and then applied to the intended substrate during a working window (also referred to in the art as “pot life”) prior to curing of the resulting mixture.

[0174] The gel coating compositions of the present invention can be applied and fully cured at ambient temperature conditions in the range of from about -10°C. to 50°C. Curing of said polymer - 40 -55648278-17513-A-WO - PE963282WO composition according to the invention typically can proceed very rapidly, and in general can take place at a temperature within the range of from -10°C. to +50°C., in particular from 0°C. to 40°C., more in particular from 3°C to 25°C. However, compositions of the present invention may be cured by additional heating. The gel coating compositions of the present invention can also be cured via a bake cure. With the benefit of this disclosure, one having ordinary skill in the art would be able to select the appropriate temperatures for a bake cure (these would generally be higher than the ranges referenced above for ambient curing).

[0175] The coating compositions of the present invention may be used as a single coating, a top coating, a base coating in a two-layered system, or one or more layers of a multi-layered system including a clear top coating composition, colorant layer and base coating composition, or as a primer layer. A typical opaque system may comprise: 1 or 2 layers of primer and 1 or 2 layers of top coat (a total of 3 layers). Alternative opaque systems may comprise: 1 primer layer, 1 layer of mid coat and 1 layer top coat. Examples of transparent systems may comprise 1 layer of impregnant and 3 layers of top coats or 3 layers of top coat for maintenance work.

[0176] The present invention further relates to a process for radically curing an unsaturated resin, for example by providing a composition and / or formulations in accordance with the invention, or by practising a method of the invention and allowing the composition to cure, for example by mixing the formulations of the kits of the invention with one another and allowing the resultant compositions to cure. It has been found that thiol secondary accelerators and transition metal ion complexes (especially those of iron or manganese ions) of the chelants described herein accelerate the radical curing of unsaturated polyester resins, vinyl ester resins, and acrylic resins. Generally the curing takes place at a temperature between -20 and +200 °C, preferably in the range between -20 and +100 °C, and most preferably in the range from -10 to +60 °C (so-called cold curing).

[0177] A particular advantage of the compositions, formulations, and methods of the present invention is the maintenance of bulk material mechanical properties while providing enhanced surface curing. In the context of 2- and 3-component gel coating compositions (and kits therefore) comprising unsaturated resin, transition metal ion, chelant, thiol secondary accelerator, and peroxide, such enhanced surface curing provides reduced tackiness upon curing relative to compositions that do not include one of the thiol secondary accelerators or chelants.

[0178] As discussed above, the compositions and formulations of the present invention may include various optional, additional materials. In certain embodiments relating to gel coats, the gel coat compositions of the present invention comprise at least one colorant. The colorant component of the coating composition may comprise one or more inorganic or organic, transparent or non-transparent pigments. Non-limiting examples of such pigments are titanium dioxide, iron oxides, mixed metal oxides, bismuth vanadate, chromium oxide green, ultramarine blue, carbon black, lampblack, monoazo and diazo pigments, anthraquinones, isoindolinones, isoindolines, quinophthalones, phthalocyanine blues and greens, dioxazines, quinacridones and diketo-pyrrolopyrroles; and extender pigments including ground and crystalline silica, barium sulfate, magnesium silicate, calcium silicate, mica, micaceous iron oxide, calcium carbonate, zinc oxide, aluminum hydroxide, aluminum silicate- 41 -55648278-17513-A-WO - PE963282WO and aluminum silicate, gypsum, feldspar, talcum, kaolin, and the like. The amount of pigment that is used to form the coating composition is understood to vary, depending on the composition application, and can be zero when a clear composition is desired.

[0179] Embodiments relating to gel coats may further be used as a clear varnish.

[0180] Coating compositions and formulations may furthermore contain optional, additional materials including one or more additives such as UV stabilisers, cosolvents, dispersants, surfactants, inhibitors, fillers, anti-static agents, flame-retardant agents, lubricants, anti-foaming agents, extenders, plasticisers, anti-freezing agents, waxes, thickeners, thixotropic agents, etc. Furthermore, the coating compositions and formulations according to the invention may optionally comprise various antioxidants and anti-skinning agents known in the art of the formulation of coating compositions, for example: phenol derivatives, e.g. pyrogallol, 2, 6-di-tert. butylhydroxytoluene, hydroquinone, octadecyl- 3-(3,5-di-tert.butyl-4-hydroxyphenyl)propionate - Irganox® 1076 (available from Ciba SC), bis(2- mercapto-ethyl)-(3-(3,5-di-tert.butyl-4-hydroxyphenyl)propionate) sulphide - Irganox® 1035 (available from Ciba SC), monomethyl ether of hydroquinone, propenyl phenol, 4-acetoxystyrene, iso-eugenol, lauryl gallate; sulphides, e.g. phenothiazine, dodecylsulphide, di(dodecyl)thiodipropionate; phosphines, e.g. trimethylphosphine, tri-n. octylphosphine, triphenylphosphine; phosphites, e.g. trimethylphosphite, triphenylphosphite, tris(nonylphenyl)phosphite, ethyl-bis(2,4-di-tert.butyl-6- methylphenyl)phosphite - lrgafos®38 (available from Ciba SC), tris(2,4-di-tert.butylphenyl)phosphite - lrgafos® 168 (available from Ciba SC), bis(2,4-di-tert.butylphenyl)pentadiphosphite - Ultranox®626 (available from General Electric); phosphonites, e.g. tetrakis(2,4-di-tert. butylphenyl)(1 , 1 -biphenyl)- 4,4'-diylbisphosphonite - Irgafos® P-EPQ (available from Ciba SC); dioxo-compounds, e.g. 2,4- pentanedione, dibenzoylmethane, 2,4-hexanedione, 1 ,3-cyclohexanedione, oxopropionic acid, 2- methyl-3-oxosuccinic acid diethyl ester, oxalacetic acid; oximes, e.g. butanone oxime, butyraldehyde oxime, cyclohexanone oxime; hydroxyacetone, diethylhydroxylamine, 3,5-dimethylpyrazole, ascorbic acid, Hindered Amine Light Stabilisers (HALS), e.g. Tinuvin® 123 (i.e., Bis(1-octyloxy-2, 2,6,6- tetramethyl-4-piperidyl)sebacate) and Tinuvin® 292c (i.e., a blend of Bis (1 , 2, 2, 6, 6-pentamethyl-4- piperidyl) sebacate & Methyl 1 , 2, 2, 6, 6- pentamethyl-4-piperidyl sebacate) available from Ciba SC, 2,3-butenediol, dibenzoyloxybutene, dibenzylthiocarbamic acid zinc salt, Vitamin E, Vitamin E acetate, hypophosphorous acid, 2-butylbenzofuran, 3,4-dihydro-2-ethoxy-2H-pyran, dodecylmercaptane, dicyclopentadiene.

[0181] Various additional materials and applications as enumerated in W02020008203A1 may further be useful in the context of the present invention as will be recognized by one or ordinary skill in the art in light of the present disclosure.

[0182] Each and every patent and non-patent reference referred to herein is hereby incorporated by reference in its entirety, as if the entire content of each reference was set forth herein in its entirety.- 42 -55648278-17513-A-WO - PE963282WO

[0183] The invention may be further understood with reference to the following non-nonlimiting clauses:Clause 1 . A composition comprising:(i) from 40 to 100 % w / w of an unsaturated resin;(ii) from 0.001 to 10 % w / w of a peroxide;(iii) from 0.00005 to 0.5 % w / w of a chelant selected from the group consisting of bispidon, N4py-type, TACN-type, cyclam and cross-bridged ligands, and trispicen-type ligands, or a mixture thereof; and(iv) from 0.01 to 20 % w / w of thiol secondary accelerator, wherein % w / w is calculated as percentage of the weight of unsaturated resin and any reactive diluent, if present.Clause 2. The composition of clause 1 , wherein the chelant is a bispidon ligand of Formula (I) or Formula (l-A):wherein:- 43 -55648278-17513-A-WO - PE963282WO each R in is independently selected from the group consisting of hydrogen, F, Cl, Br, Formula (I) hydroxyl, Ci-4-alkylO-, -NH-CO-H, -NH-CO-C1-4 alkyl, -NH2, -NH-C1-4 alkyl, and C1-4 alkyl;R1 and R2areindependently selected from the group consisting of C 1—24-al ky I, Ce-io-aryl, and a group containing one or two heteroatoms (e.g. N, O or S) capable of coordinating to a transition metal;R3 and R4 are independently selected from the group consisting of hydrogen, Ci- s-alkyl, Ci-8-alkyl-O-Ci-8-alkyl, Ci-s alkyl-O-Ce-io aryl, Ce-io-aryl, Ci-s-hydroxyalkyl and - (CH2)nC(O)OR5 wherein R5 is independently selected from hydrogen, C1- 12-alkyl, and Ci-4-alkyl-O-Ci-4-alkyl and n is from 0 to 4;X is selected from the group consisting of C=O, -[C(R6)2]y- wherein y is from 0 to3; each R6 is independently selected from the group consisting of hydrogen, hydroxyl, C1-4 alkoxy and C1-4 alkyl; and each D in is independently selected from the group consisting of thiazol-2-yl and Formula (l-A) thiazol-4-yl, or the chelant is a N4py-type ligand of Formula (II):wherein: each R1 and R2 independently represents -R4-R5;R3 represents hydrogen, Ci-s-alkyl , aryl selected from homoaromatic compounds having a molecular weight under 300, or C7-4o arylalkyl, or -R4-R5, each R4 independently represents a single bond or a linear or branched Ci-s-alkyl- substituted-C2-6-alkylene, C2-6-alkenylene, C2-6-oxyalkylene, C2-6-aminoalkylene, C2-6-alkenyl ether, C2-6-carboxylic ester or C2-6-carboxylic amide, and each R5 independently represents an optionally N-alkyl-substituted aminoalkyl group or an optionally alkyl-substituted heteroaryl: selected from the group consisting of pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-- 44 -55648278-17513-A-WO - PE963282WO triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, or the chelant is a TACN-type ligand of Formula (III)wherein each R20 is independently selected from: Ci-s-alkyl, Cs-s-cycloalkyl, heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1 ,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1 ,4,7-triazacyclononanyl; 1 ,4,8,11-tetraazacyclotetradecanyl; 1 ,4,7,10,13-pentaazacyclopentadecanyl; 1 ,4-diaza-7-thia-cyclononanyl;1 ,4-diaza-7-oxa-cyclononanyl; 1 ,4,7,10-tetraazacyclododecanyl; 1 ,4-dioxanyl;1 ,4,7-trithia-cyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl; heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, aryl selected from homoaromatic compounds having a molecular weight under 300, or C7-4o-arylalkyl group optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulfonate, amine, alkylamine and N+(R21)3,R21 is selected from hydrogen, Ci-s-alkyl , C2-6-alkenyl, C7-4o-arylalkyl, arylalkenyl, Ci-s-oxyalkyl, C2-6-oxyalkenyl, Ci-s-aminoalkyl, C2-6-aminoalkenyl, Ci-s-alkyl ether, C2-6-alkenyl ether, and -CY2-R22,Y is independently selected from H, CHs, C2H5, C3H7 and- 45 -55648278-17513-A-WO - PE963282WOR22 is independently selected from Ci-a-alkyl-substituted heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl;1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl; and wherein at least one of R20 is a -CY2-R22, or the chelant is a cyclam or cross-bridged ligand of Formula (IV):wherein:Q is independently selected fromR- N - [ CR1CR2CR3R4] - andp is 4;R is independently selected from: hydrogen, Ci-6-alkyl,CH2CH2OH, pyridin-2-ylmethyl, and CH2COOH, or one of R is linked to the N of another Q via an ethylene bridge; and R1R2R3R4R5 ANC| R6are independently selected from: H, Ci-4-alkyl, andCi-4-alkylhydroxy, or the chelant is a cross-bridged ligand of the Formula (V):- 46 -55648278-17513-A-WO - PE963282WOwhereinR1is independently selected from H, C1-20 alkyl, C7-4o-alkylaryl, C2-6-alkenyl or C2-6-alkynyl, or the chelant is a trispicen-type ligand of formula (VI):R17R17N-X-NR17R17 (VI), wherein:X is selected from -CH2CH2-, -CH2CH2CH2-, -CH2C(OH)HCH2-; each R17 independently represents a group selected from: R17, Ci-s-alkyl, C3-8-cycloalkyl, heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1 ,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl;1 .4.7-triazacyclononanyl; 1 ,4,8,11-tetraazacyclotetradecanyl;1 ,4,7,10,13-pentaazacyclopentadecanyl; 1 ,4-diaza-7-thia-cyclononanyl;1 ,4-diaza-7-oxa-cyclononanyl; 1 ,4,7,10-tetraazacyclododecanyl; 1 ,4-dioxanyl;1 .4.7-trithia-cyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl; heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, aryl selected from homoaromatic compounds having a molecular weight under 300, and C7-4o-arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulfonate, amine, alkylamine and N+(R19)3 , whereinR19 is selected from hydrogen, Ci-s-alkyl, C2-6-alkenyl, C7-4o-arylalkyl, C7-4o-arylalkenyl, Ci-s-oxyalkyl, C2-6-oxyalkenyl, Ci-s-aminoalkyl, C2-6-aminoalkenyl, Ci-s-alkyl ether, C2-6-alkenyl ether, and -CY2-RI 8, in which55648278-17513-A-WO - PE963282WO each Y is independently selected from H, CH3, C2H5, C3H7; andR18 is independently selected from an optionally substituted heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl; and at least two of R17 are -CY2-R18.Clause 3. The composition of any preceding clause, wherein the chelant is is iron(1 +), chloro[dimethyl 9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-kN)-7-[(2-pyridinyl-kN)methyl]-3,7- diazabicyclo[3.3.1]nonane-1 ,4-dicarboxylate-kN3,kN7]-, chloride(1 :1)Clause 4. The composition of clause 1 or clause 2, wherein the chelant is 1 ,4,7-trimethyl- 1 ,4,7-triazononane (TMTACN).Clause 5. The composition of any preceding clause, wherein the chelant is capable of chelating at least one transition metal ion through four donor nitrogen atoms.Clause 6. The composition of any preceding clause, wherein the chelant is present in the composition at a concentration of between about 0.00005 and about 0.2 % w / w with respect to unsaturated resin and any reactive diluent if present.55648278-17513-A-WO - PE963282WOClause 7. The composition of the immediately preceding clause, wherein the chelant is present in the composition at a concentration of between about 0.0001 and about 0.1 % w / w with respect to unsaturated resin and any reactive diluent if present.Clause 8. The composition of any preceding clause, wherein the peroxide is present at a concentration of between about 0.01 and about 8 % w / w with respect to unsaturated resin.Clause 9. The composition of the immediately preceding clause, wherein the peroxide is present at a concentration of between about 0.1 and about 6 % w / w with respect to unsaturated resin.Clause 10. The composition of the immediately preceding clause, wherein the peroxide is present at a concentration of between about 0.3 and about 4 % w / w with respect to unsaturated resin.Clause 11. The composition of the immediately preceding clause, wherein the peroxide is present at a concentration of between about 0.5 and about 2 % w / w with respect to unsaturated resin.Clause 12. The composition of any preceding clause, wherein the peroxide is an organic peroxide, for example a hydroperoxide or a ketone peroxide.Clause 13. The composition of the immediately preceding clause, wherein the peroxide is selected from the group consisting of cumyl hydroperoxide, 1 ,1 ,3,3-tetramethylbutyl hydroperoxide, t- butylhydroperoxide, isopropylcumylhydroperoxide, t-amylhydroperoxide, 2,5-dimethyl-2,5- dihydroperoxide, pinanehydroperoxide and pinene hydroperoxide.Clause 14. The composition of clause 12, wherein the peroxide is selected from methylethylketone peroxide, methylisopropylketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, acetylacetone peroxide.Clause 15. The composition of any preceding clause, wherein the thiol secondary accelerator is is of Formula (VI I):whereinZ is a covalently bonding bridging moiety;R30is independently selected from the group consisting of a C1-30 branched or straight chain alkyl; C1-30 branched or straight chain alkenyl, C5-45 cycloalkyl, C5-45-cycloalkenyl, Ce-45-aryl, Ce-45-arylalkyl, Ce-45-alkylaryl, Ci-s-oxyalkyl, C2-6-oxyalkenyl,- 49 -55648278-17513-A-WO - PE963282WOCi-8-aminoalkyl, C2-6-aminoalkenyl, Ci-s-alkyl ether, C2-6-alkenyl ether, and -CY2-RI 8, in which each Y is independently selected from H, CH3, C2H5, C3H7 andR30or Z may comprise a heteroatom link based on O, N, S, P or terminal groups based on those heteroatoms and further wherein the heteroatom link may contain an epoxy group or a siloxane or a polysiloxane group including branched or linear equivalents, that can also contain additional functionality which includes an acrylate, unsaturated carbon-carbon bonds, alcohol or acid groups, and still further wherein the crosslinker can be a silicone-thiol resin and wherein R30or Z groups can be an alcohol functionality and further wherein the thiol or polythiol may further comprise an acrylic or polyacrylic groups that may have comonomers or monomers with functionality comprising free allyl groups, free thiol groups, unsaturated carbon-carbon-bonds including the use of ethylene glycol dimethacrylate, or alcohol groups incorporated by the use of hydroxyethylmethacrylate, or acids from acrylic acid, or epoxy groups further comprising polymeric crosslinkers derived from polyurethanes and polyesters,R32and R33are selected from the group identified for R30; m, n, and 0 are independently 0 or 1 ; and p is an integral value from 1 to 10, preferably is an integral value from 3 to 6; and wherein the siloxane or polysiloxane is linear or branched polymer or derivatized polymer with acetoxy, oxime, amine, or alkoxy substituents having a weight average (Mw) molecular weight of between 200 and 50,000 inclusive, and may further comprise a copolymers thereof including copolymers of polypropylene oxide and polyethylene oxide:55648278-17513-A-WO - PE963282WO and whereinR34to R40are independently selected from the group for R30above; and a, b, and c are independently selected from 0 to 3,000 inclusive.Clause 16. The composition of any of clauses 1 to 14, wherein the thiol secondary accelerator is selected from the group consisting of:(A) ethylene bis(thioglycolate)(B) trimethylolpropane tris(3-mercaptopropionate)(C) pentaerythritol tetrakis(3-mercaptopropionate)55648278-17513-A-WO - PE963282WO(D) dipentaerythritol hexakis(3-mercaptopropionate)wherein the molecular weight of segments for I + m + n being adjusted so that the weight average (Mw) MW totals to ~500-2000 and wherein I + m + n independently total to a range between ~ 10-40.Clause 17. The composition of any preceding clause, wherein the thiol secondary accelerator includes at least 15 wt. % thiol group content or more preferably, at least 25 wt. % thiol group content, wherein wt. % thiol group content is the average number of thiol groups per thiol secondary accelerator molecule times the molecular weight of a thiol group (atomic weight of sulfur plus atomic weight of hydrogen) divided by the molecular weight of the thiol secondary accelerator (number average molecular weight, where the thiol secondary accelerator is a polymer).- 52 -55648278-17513-A-WO - PE963282WOClause 18. The composition of any preceding clause, wherein the thiol secondary accelerator has a thiol equivalent weight (calculated by dividing the molecular weight of the thiol secondary accelerator by the number of thiol functional groups per molecule) of at least 80 Daltons, at least 90 Daltons, at least 95 Daltons or at least 100 Daltons and / or a thiol equivalent weight of not more than 450 Daltons, not more than 400 Daltons, not more than 350 Daltons, not more than 300 Daltons, not more than 250 Daltons or not more than 200 Daltons.Clause 19. The composition of any preceding clause, wherein the thiol secondary accelerator is present at a concentration of at least about 0.02 % w / w, at least about 0.05 % w / w, at least about 0.1 % w / w, at least about 0.5 % w / w, or at least about 1 .0 % w / w and / or wherein the thiol secondary accelerator is present at a concentration of at most about 10 % w / w, at most about 7 % w / w, at most about 5 % w / w, at most about 4 % w / w, or at most about 3 % w / w.Clause 20. The composition of any one preceding clause, wherein the unsaturated resin is an unsaturated polyester resin or a vinyl ester resin.Clause 21. The composition of the immediately preceding clause, wherein the vinyl ester resin is a (meth)acrylic resin.Clause 22. The composition of any preceding clause, wherein the composition comprises a reactive diluent.Clause 23. The composition of the immediately preceding clause, wherein the reactive diluent is selected from styrene, vinyl toluene, divinyl benzene, methyl methacrylate, diallyl phthalate, a- methyl styrene, triallyl cyanurate, (meth)acrylates, N-vinylpyrrolidone, and N-vinylcaprolactam.Clause 24. The composition of any preceding clause, which comprises a complex comprising the chelant and a transition metal ion selected from the group consisting of ions of iron, manganese, vanadium and copper.Clause 25. The composition of the immediately preceding clause, which comprises a complex comprising the chelant and a transition metal ion selected from the group consisting of ions of iron and manganese.Clause 26. The composition of the immediately preceding clause, which comprises a complex comprising the chelant and an iron ion.Clause 27. The composition of any of clauses 24 to 26, wherein the complex is not well- defined.Clause 28. The composition of any one of clauses 1 to 23, which composition comprises less than 0.0001 % by weight of ions of each of iron, manganese, cobalt, vanadium and copper.- 53 -55648278-17513-A-WO - PE963282WOClause 29. A method of preparing a composition as defined in any preceding clause, the method comprising contacting a first formulation comprising a peroxide as defined in any preceding clause, a second formulation comprising a chelant as defined in any preceding clause; and a third formulation comprising an unsaturated resin as defined in any preceding clause.Clause 30. The method of clause 29 wherein the composition is as defined in clause 28.Clause 31. The method of the immediately preceding clause further comprising contacting the composition with a source of transition metal ions.Clause 32. The method of any one of clauses 29 to 30, wherein the peroxide and the unsaturated resin are contained in the same formulation, which is contacted with the second formulation and a source of transition metal ions.Clause 33. The method of clause 29, wherein the chelant and the peroxide are contained in the same formulation, which comprises less than 0.00001 % by weight, less than 0.00005 % by weight, less than 0.0001 % by weight, or less than 0.001 % by weight of ions of each of iron, manganese, vanadium, cobalt and copper, which formulation is contacted with the third formulation and a source of transition metal ions.Clause 34. The method of clause 29, wherein the chelant and the unsaturated resin are contained in the same formulation, which further comprises a source of transition metal ions, which formulation is contacted with the first formulation.Clause 35. The method of any one of clauses 30 to 34, wherein the transition metal ions are iron, manganese, vanadium or copper ions.Clause 36. The method of any one of clauses 30 to 35, wherein the transition metal ions are in a solution.Clause 37. The method of any one of clauses 30 to 36, wherein the transition metal ions are iron or manganese ions.Clause 38. The method of the immediately preceding clause, wherein the source of transition metal ions is an optionally hydrated salt selected from the group consisting of MnCh, FeCh, FeCh, MnBr2, Mn(NC>3)2, Fe(NC>3)3, MnSC , FeSC , (Fe)2(SC>4)3, Mn(acetylacetonate)2, Fe(acetylacetonate)2, Mn(acetylacetonate)3, Fe(acetylacetonate)3, Mn(R4COO)3, Fe(R4COO)3, Mn(R4COO)2 and Fe(R4COO)2, wherein each R4 is a C1-C24 alkyl.Clause 39. The method of any one of clauses 30 to 38, wherein the transition metal ions are iron ions.Clause 40. The method of the immediately preceding clause, wherein the source of the transition metal ions is an optionally hydrated salt selected from the group consisting of FeCh, FeCh,- 54 -55648278-17513-A-WO - PE963282WOFe(NOs)3, FeSC , (Fe)2(SC>4)3, Fe(acetylacetonate)2, Fe(acetylacetonate)3, Fe(acetate)2, Fe(acetate)3, Fe(octanoate)2, Fe(2-ethylhexanoate)2, Fe(naphthenate)2 and Fe(neodecanoate)2.Clause 41. The method of clause 29, wherein the second formulation comprises a mixture of the chelant and a salt of a transition metal ion selected from the group consisting of ions of iron, manganese, vanadium and copper.Clause 42. The method of the immediately preceding clause, wherein the second formulation comprises an iron salt or a manganese salt.Clause 43. The method of any of clauses 41 to 42, wherein the second formulation comprises a complex as defined in clause 11 .Clause 44. The method of any of clauses 29 to 43, wherein the first formulation further comprises a thiol secondary accelerator as described in any of clauses 1 and 15 to 19.Clause 45. The method of any of clauses 29 to 43, wherein the second formulation further comprises a thiol secondary accelerator as described in any of clauses 1 and 15 to 19.Clause 46. The method of any of clauses 29 to 43, wherein the third formulation further comprises a thiol secondary accelerator as described in any of clauses 1 and 15 to 19.Clause 47. A composition resultant from curing of a composition as defined in any one of clauses 24 to 27.Clause 48. A formulation comprising a chelant as defined in any one of clauses 1 to 28 and a thiol secondary accelerator as defined in any one of clauses 1 to 28 and either an unsaturated resin or a peroxide.Clause 49. The formulation of the immediately preceding clause, which comprises a complex comprising the chelant and a transition metal ion selected from the group consisting of ions of iron, manganese, vanadium and copper.Clause 50. The formulation of the immediately preceding clause, which comprises a complex comprising the chelant and a transition metal ion selected from the group consisting of ions of iron and manganese.Clause 51 . The formulation of clause 49 or clause 50, which comprises a complex comprising the chelant and an iron ion.Clause 52. The formulation of any one of clauses 49 to 51 , wherein the complex is not well- defined.- 55 -55648278-17513-A-WO - PE963282WOClause 53. The formulation of any one of clauses 48 to 52, which comprises an unsaturated resin, for example an unsaturated polyester resin or a vinyl ester resin, and optionally a reactive diluent, for example a reactive diluent as defined in any of clauses 22 or 23.Clause 54. The formulation of clause 48, wherein the formulation comprises an unsaturated resin and optionally a reactive diluent, and the formulation comprises less than 0.00001 % by weight, less than 0.00005 % by weight, less than 0.0001 % by weight, or less than 0.001 % by weight of ions of each of iron, manganese, cobalt, vanadium and copper.Clause 55. A method of preparing a composition as defined in any of clauses 1 to 28, the method comprising contacting a first formulation comprising an unsaturated resin as defined in any of clauses 1 to 28 and a second formulation comprising a peroxide as defined in any of clauses 1 to 28.Clause 56. The method of clause 54 wherein the composition is as defined in clause 28.Clause 57. The method of the immediately preceding clause further comprising contacting the composition with a source of transition metal ions.Clause 58. The method of any one of clauses 55 to 56, wherein either the first or the second formulation includes a source of transition metal ions.Clause 59. The method of clause 55, wherein the first formulation further comprises a source of transition metal ions and a chelant, which formulation is contacted with the second formulation.Clause 60. The method of any one of clauses 56 to 59, wherein the transition metal ions are iron, manganese, vanadium or copper ions.Clause 61 . The method of any one of clauses 56 to 60, wherein the transition metal ions are in a solution.Clause 62. The method of any one of clauses 56 to 61 , wherein the transition metal ions are iron or manganese ions.Clause 63. The method of the immediately preceding clause, wherein the source of transition metal ions is an optionally hydrated salt selected from the group consisting of MnCh, FeCh, FeCh, MnBr2, Mn(NC>3)2, Fe(NC>3)3, MnSC , FeSC , (Fe)2(SC>4)3, Mn(acetylacetonate)2, Fe(acetylacetonate)2, Mn(acetylacetonate)3, Fe(acetylacetonate)3, Mn(R4COO)3, Fe(R4COO)3, Mn(R4COO)2 and Fe(R4COO)2, wherein each R4 is a C1-C24 alkyl.Clause 64. The method of any one of clauses 56 to 63, wherein the transition metal ions are iron ions.Clause 65. The method of the immediately preceding clause, wherein the source of the transition metal ions is an optionally hydrated salt selected from the group consisting of FeCh, FeCh,- 56 -55648278-17513-A-WO - PE963282WOFe(NOs)3, FeSC , (Fe)2(SC>4)3, Fe(acetylacetonate)2, Fe(acetylacetonate)3, Fe(acetate)2, Fe(acetate)3, Fe(octanoate)2, Fe(2-ethylhexanoate)2, Fe(naphthenate)2 and Fe(neodecanoate)2.Clause 66. The method of clause 55, wherein the second formulation comprises a mixture of the chelant and a salt of a transition metal ion selected from the group consisting of ions of iron, manganese, vanadium and copper.Clause 67. The method of the immediately preceding clause, wherein the second formulation comprises an iron salt or a manganese salt.Clause 68. The method of any of clauses 66 to 67, wherein the second formulation comprises a complex as defined in clause 11 .Clause 69. The method of any of clauses 55 to 68, wherein the first formulation further comprises a thiol secondary accelerator as described in any of clauses 1 and 15 to 19.Clause 70. The method of any of clauses 55 to 68, wherein the second formulation further comprises a thiol secondary accelerator as described in any of clauses 1 and 15 to 19.Clause 71 . A kit comprising a first formulation, which is a composition as defined in clause 28 and, separately, a second formulation comprising transition metal ions selected from the group consisting of iron, manganese, vanadium and copper ions.Clause 72. A kit comprising a first formulation which comprises an unsaturated resin, a chelant as defined in any one of clauses 1 to 27, a thiol secondary accelerator as defined in any one of clauses 1 to 27, and transition metal ions selected from the group consisting of iron, manganese, vanadium and copper ions and, separately, a second formulation comprising a peroxide.Clause 73. A kit comprising:(i) a first formulation comprising an unsaturated resin and a thiol secondary accelerator as defined in any one of clauses 1 to 27;(ii) a second formulation comprising a complex comprising one or two transition metal ions selected from the group consisting of iron, manganese, vanadium and copper ions and a chelant as defined in any one of clauses 1 to 27; and(iii) a third formulation comprising a peroxide.Clause 74. A kit comprising:(i) a first formulation comprising an unsaturated resin;(ii) a second formulation comprising a thiol secondary accelerator as defined in any one of clauses 1 to 27 and a complex comprising one or two transition metal ions selected from the group consisting of iron, manganese, vanadium and copper ions and a chelant as defined in any one of clauses 1 to 27; and- 57 -55648278-17513-A-WO - PE963282WO(iii) a third formulation comprising a peroxide.Clause 75. The kit of any of clauses 71 to 74, wherein the unsaturated resin is an unsaturated polyester resin or a vinyl ester resinClause 76. The kit of the immediately preceding clause, wherein the vinyl ester resin is a (meth)acrylic resin.Clause 77. The kit of any one of clauses 71 to 76 wherein the first formulation further comprises a reactive diluent.Clause 78. The kit of the immediately preceding clause, wherein the reactive diluent is selected from styrene, vinyl toluene, divinyl benzene, methyl methacrylate, diallyl phthalate, a-methyl styrene, triallyl cyanurate, (meth)acrylates, N-vinylpyrrolidone, and N-vinylcaprolactam.Clause 79. The kit of any of clauses 71 to 78, wherein the transition metal ions are iron or manganese ions.Clause 80. The kit of the immediately preceding clause, wherein the transition metal ions are iron ions.Clause 81 . The kit of any of clauses 71 to 80, wherein the kit is used for a gel coat formulation.Clause 82. A method of use for a gel coating formulation, the method of use including a step of combinging the formulations of any of the kits of clauses 71 to 81 in an airless spray directed toward a substrate.Clause 83. A method of use for a gel coating formulation, the method of use including a first step of mixing the formulations of any of the kits of clauses 71 to 81 to form an active mixture and a second step of applying the active mixture to a substrate and allowing the active mixture to cure.Clause 84. A gel coat formulation as described in any of clauses 81 to 83, wherein the gel coat formulation exhibits reduced surface tack or tackiness relative to gel coat formulations that do not contain one of either the thiol secondary accelerator as defined in any of clauses 1 to 28 or the chelant as defined in any of clauses 1 to 28.Clause 85. A gel coat formulation as described in any of clauses 81 to 84, wherein the gel coat formulation exhibits improved gel time drift relative to gel coat formulations that do not contain one of either the thiol secondary accelerator as defined in any of clauses 1 to 28 or the chelant as defined in any of clauses 1 to 28.

[0184] The invention will be more readily understood by reference to examples, which are included merely for purpose of illustration of certain aspects and embodiments of the present invention and are not intended to limit the invention.- 58 -55648278-17513-A-WO - PE963282WO

[0185] Examples

[0186] Unless otherwise stated, all the values in formulation Tables refer to mass in parts by weight and percents are provided as weight percent of a total mixture weight.Table C - Examples Material Glossary- 59 -55648278-17513-A-WO - PE963282WO

[0187] Samples were made by manually mixing the materials in the amounts (provided in parts by sample weight) provided below in Table 1 . Each sample includes an unsaturated polyester resin, a peroxide, solvent (note, solvent may not be explicitly called out as a separate component in Table 1), and an accelerator, and some samples further include a secondary accelerator.

[0188] Table 1.- 60 -55648278-17513-A-WO - PE963282WO

[0189] Promptly after mixing, samples 1-A through 6-A and 1-B through 6- B were tested fortheir gel time according to China standard GB / T 7193.6 : 1987, “Unsaturated polyester resin--Determination of gel time at 25 Centigrade (English Version),” Standardization Adminstration of China, January 12, 2013 Gel times are reported below in Table 2 in minutes and seconds (min:sec).

[0190] Table 2.

[0191] Samples 4-A through 6-A and 4-B through 6-B make a significant reduction in gel time relative to samples 1-A through 3-A and 1-B through 3-B, respectively. Samples 1-A through 3-A and 1-B through 3-B do not contain a secondary accelerator.

[0192] Duplicates of samples 1-A through 6-A and 1-B through 6-B were prepared and tackiness observed at 30 minutes following mixing. To assess tackiness, the observer, wearing a latex glove, touches an upper surface of each mixed sample once, briefly, and with light pressure. Any perceptible sticking results in a rating of “tacky” (“T”), while no perceptible sticking results in a rating of “not tacky” (“NT”). Results are reported below in Table 3.

[0193] Table s.

[0194] Samples 4-A through 6-A show favorable reduction in early tackiness relative to cobalt- containing systems not including the secondary accelerator. Samples 4-B through 6-B show favorable reduction in early tackiness relative to one of the cobalt-containing samples and the BOC-containing - 61 -55648278-17513-A-WO - PE963282WO sample that does not contain a secondary accelerator.

[0195] Each of samples 1-A through 6-A and 1-B through 6-B was visually observed for its color after 60 minutes of curing. Each of samples 1-A, 2-A, 1-B, and 2-B (containing a cobalt accelerator) began (promptly after mixing) with a translucent, dark yellow color with a reddish tint. Each such sample cured to a translucent red or pink color. Each of samples 3-A through 6-A and 3-B through 6-B began (promptly after mixing) with a translucent, yellow or light yellow color and cured to a comparable or slightly lighter yellow color, indicating that secondary accelerant imparts no unfavorable color characteristics either before or after cure.

[0196] Preferred embodiments of the subject matter of this application are described herein. Variations of those preferred embodiments may become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventors expect skilled artisans to employ such variations as appropriate, and the inventors intend for the subject matter described herein to be practiced otherwise than as specifically described herein. Accordingly, this disclosure includes all modifications and equivalents of the subject matterrecited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the present disclosure unless otherwise indicated herein or otherwise clearly contradicted by context.- 62 -55648278-1

Claims

1. 7513-A-WO - PE963282WOWhat is Claimed is:1 . A composition comprising:(i) from 40 to 99.99 % w / w of an unsaturated resin;(ii) from 0.001 to 10 % w / w of a peroxide;(iii) from 0.00005 to 0.5 % w / w of a chelant selected from the group consisting of Bispidon,N4py-type, TACN-type, cyclam and cross-bridged ligands, and trispicen-type ligands, or a mixture thereof;(iv) from 0.00005 to 0.1 % w / w of a transition metal ion selected from the group consisting of ions of iron, manganese, vanadium, and copper; and(v) from 0.01 to 20 % w / w of thiol secondary accelerator, wherein % w / w is calculated as percentage of the weight of unsaturated resin and any reactive diluent, if present.

2. The composition of claim 1 , wherein the chelant is a bispidon ligand of Formula (I) or Formula (l-A):wherein:- 63 -55648278-17513-A-WO - PE963282WO each R in is independently selected from the group consisting of hydrogen, F, Cl, Br, Formula I hydroxyl, Ci-4-alkylO-, -NH-CO-H, -NH-CO-C1-4 alkyl, -NH2,-NH-C1-4 alkyl, and C1-4 alkyl;R1 and R2areindependently selected from the group consisting of C 1—24-al ky I, Ce-io-aryl, and a group containing one or two heteroatoms (e.g. N, O or S) capable of coordinating to a transition metal;R3 and R4 are independently selected from the group consisting of hydrogen, Ci- s-alkyl, Ci-8-alkyl-O-Ci-8-alkyl, Ci-s alkyl-O-Ce-io aryl, Ce-io-aryl, Ci-s-hydroxyalkyl and - (CH2)nC(O)OR5 wherein R5 is independently selected from hydrogen, C1- 12-alkyl, and Ci-4-alkyl-O-Ci-4-alkyl and n is from 0 to 4;X is selected from the group consisting of C=O, -[C(R6)2]y- wherein y is from 0 to3; each R6 is independently selected from the group consisting of hydrogen, hydroxyl, C1-4 alkoxy and C1-4 alkyl; and each D in is independently selected from the group consisting of thiazol-2-yl and Formula (l-A) thiazol-4-yl, or the chelant is a N4py-type ligand of Formula (II):wherein: each R1 and R2 independently represents -R4-R5;R3 represents hydrogen, Ci-s-alkyl, aryl selected from homoaromatic compounds having a molecular weight under 300, or C7-4o arylalkyl, or -R4-R5, each R4 independently represents a single bond or a linear or branched Ci-s-alkyl- substituted-C2-6-alkylene, C2-6-alkenylene, C2-6-oxyalkylene, C2-6-aminoalkylene, C2-6-alkenyl ether, C2-6-carboxylic ester or C2-6-carboxylic amide, and each R5 independently represents an optionally N-alkyl-substituted aminoalkyl group or an optionally alkyl-substituted heteroaryl: selected from the group consisting of pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-55648278-17513-A-WO - PE963282WO triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, or the chelant is a TACN-type ligand of Formula (III):wherein each R20 is independently selected from: Ci-s-alkyl, Cs-s-cycloalkyl, heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1 ,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1 ,4,7-triazacyclononanyl; 1 ,4,8,11-tetraazacyclotetradecanyl; 1 ,4,7,10,13-pentaazacyclopentadecanyl; 1 ,4-diaza-7-thia-cyclononanyl;1 ,4-diaza-7-oxa-cyclononanyl; 1 ,4,7,10-tetraazacyclododecanyl; 1 ,4-dioxanyl;1 ,4,7-trithia-cyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl; heteroaryl selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, aryl selected from homoaromatic compounds having a molecular weight under 300, or C7-4o-arylalkyl group optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulfonate, amine, alkylamine and N+(R21)3,R21 is selected from hydrogen, Ci-s-alkyl , C2-6-alkenyl, C7-4o-arylalkyl, arylalkenyl, Ci-s-oxyalkyl, C2-6-oxyalkenyl, Ci-s-aminoalkyl, C2-6-aminoalkenyl, Ci-s-alkyl ether, C2-6-alkenyl ether, and -CY2-R22,Y is independently selected from H, CHs, C2H5, C3H7 and- 65 -55648278-17513-A-WO - PE963282WOR22 is independently selected from Ci-a-alkyl-substituted heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl;1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl; and wherein at least one of R20 is a -CY2-R22, or the chelant is a cyclam or cross-bridged ligand of Formula (IV):wherein:Q is independently selected fromR- N - [ CR1CR2CR3R4] - andp is 4;R is independently selected from: hydrogen, Ci-6-alkyl,CH2CH2OH, pyridin-2-ylmethyl, and CH2COOH, or one of R is linked to the N of another Q via an ethylene bridge; and R1R2R3R4R5 ANC| R6are independently selected from: H, Ci-4-alkyl, andCi-4-alkylhydroxy, or the chelant is a cross-bridged ligand of the Formula (V):- 66 -55648278-17513-A-WO - PE963282WOwhereinR1is independently selected from H, C1-20 alkyl, C7-4o-alkylaryl, C2-6-alkenyl or C2-6-alkynyl, or the chelant is a trispicen-type ligand of formula (VI):R17R17N-X-NR17R17 (VI), wherein:X is selected from -CH2CH2-, -CH2CH2CH2-, -CH2C(OH)HCH2-; each R17 independently represents a group selected from: R17, Ci-s-alkyl, C3-8-cycloalkyl, heterocycloalkyl selected from the group consisting of: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1 ,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl;1 .4.7-triazacyclononanyl; 1 ,4,8,11-tetraazacyclotetradecanyl;1 ,4,7,10,13-pentaazacyclopentadecanyl; 1 ,4-diaza-7-thia-cyclononanyl;1 ,4-diaza-7-oxa-cyclononanyl; 1 ,4,7,10-tetraazacyclododecanyl; 1 ,4-dioxanyl;1 .4.7-trithia-cyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be connected to the compound via any atom in the ring of the selected heterocycloalkyl; heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl, aryl selected from homoaromatic compounds having a molecular weight under 300, and C7-4o-arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulfonate, amine, alkylamine and N+(R19)3 , whereinR19 is selected from hydrogen, Ci-s-alkyl, C2-6-alkenyl, C7-4o-arylalkyl, C7-4o-arylalkenyl, Ci-s-oxyalkyl, C2-6-oxyalkenyl, Ci-s-aminoalkyl, C2-6-aminoalkenyl, Ci-s-alkyl ether, C2-6-alkenyl ether, and -CY2-RI 8, in which- 67 -55648278-17513-A-WO - PE963282WO each Y is independently selected from H, CH3, C2H5, C3H7; andR18 is independently selected from an optionally substituted heteroaryl: selected from the group consisting of: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1 ,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be connected to the compound via any atom in the ring of the selected heteroaryl; and at least two of R17 are -CY2-R18.

3. The composition of claim 2, wherein the chelant is selected from the group consisting of iron(1 +), chloro[dimethyl 9,9-dihydroxy-3-methyl-2,4-di(2-pyridinyl-kN)-7-[(2-pyridinyl-kN)methyl]-3,7- diazabicyclo[3.3.1 ]nonane-1 ,4-dicarboxylate-kN3,kN7]-, chloride(1 :1) and 1 ,4,7-trimethyl-1 ,4,7- triazononane.

4. The composition of claim 2, wherein the chelant is capable of chelating at least one transition metal ion through four donor nitrogen atoms.

5. The composition of any of claims 1 to 4, wherein the peroxide is an organic peroxide, for example a hydroperoxide or a ketone peroxide.

6. The composition of any of claims 1 to 5, wherein the thiol secondary accelerator is is of formula (VII):whereinZ is a covalently bonding bridging moiety;R30is independently selected from the group consisting of a C1-30 branched or straight chain alkyl; C1-30 branched or straight chain alkenyl, C5-45 cycloalkyl, C5-45-cycloalkenyl, Ce-45-aryl, Ce-45-arylalkyl, Ce-45-alkylaryl, Ci-s-oxyalkyl, C2-6-oxyalkenyl, Ci-8-aminoalkyl, C2-6-aminoalkenyl, Ci-s-alkyl ether, C2-6-alkenyl ether, and -CY2-RI 8, in which each Y is independently selected from H, CH3, C2H5, C3H7 andR30or Z may comprise a heteroatom link based on O, N, S, P or terminal groups based on those heteroatoms and further wherein the heteroatom link may contain an epoxy- 68 -55648278-17513-A-WO - PE963282WO group or a siloxane or a polysiloxane group including branched or linear equivalents, that can also contain additional functionality which includes an acrylate, unsaturated carbon-carbon bonds, alcohol or acid groups, and still further wherein the crosslinker can be a silicone-thiol resin and wherein R30or Z groups can be an alcohol functionality and further wherein the thiol or polythiol may further comprise an acrylic or polyacrylic groups that may have comonomers or monomers with functionality comprising free allyl groups, free thiol groups, unsaturated carbon-carbon-bonds including the use of ethylene glycol dimethacrylate, or alcohol groups incorporated by the use of hydroxyethylmethacrylate, or acids from acrylic acid, or epoxy groups further comprising polymeric crosslinkers derived from polyurethanes and polyesters,R32and R33are selected from the group identified for R30; m, n, and o are independently 0 or 1 ; and p is an integral value from 1 to 10, preferably is an integral value from 3 to 6; and wherein the siloxane or polysiloxane is linear or branched polymer or derivatized polymer with acetoxy, oxime, amine, or alkoxy substituents having a weight average (Mw) molecular weight of between 200 and 50,000 inclusive, and may further comprise a copolymers thereof including copolymers of polypropylene oxide and polyethylene oxide:and wherein- 69 -55648278-17513-A-WO - PE963282WOR34to R40are independently selected from the group for R30above; and a, b, and c are independently selected from 0 to 3,000 inclusive.

7. The composition of any of claims 1 to 5, wherein the thiol secondary accelerator is selected from the group consisting of:(A) ethylene bis(thioglycolate)(B) trimethylolpropane tris(3-mercaptopropionate)- 70 -55648278-17513-A-WO - PE963282WO(D) dipentaerythritol hexakis(3-mercaptopropionate)wherein the molecular weight of segments for I + m + n being adjusted so that the weight average (Mw) MW totals to ~500-2000 and wherein I + m + n independently total to a range between ~ 10-40.

8. The composition of any claims 1 to 5, wherein the thiol secondary accelerator has a thiol equivalent weight (calculated by dividing the molecular weight of the thiol secondary accelerator by the number of thiol functional groups per molecule) of at least 80 Daltons and a thiol equivalent weight of not more than 450 Daltons.

9. The composition of any of claims 1 to 8, wherein the thiol secondary accelerator is present at a concentration of between about 0.1 to about 5 % w / w.- 71 -55648278-17513-A-WO - PE963282WO10. The composition of any of claims 1 to 9, wherein the unsaturated resin is an unsaturated polyester resin or a vinyl ester resin.11 . The composition of any of claims 1 to 10, which comprises a complex comprising the chelant and the transition metal ion selected from the group consisting of ions of iron, manganese, vanadium and copper.

12. A method of preparing a composition as defined in any of claims 1 to 11 , the method comprising contacting a first formulation comprising an unsaturated resin as defined in any of claims 1 to 11 and a second formulation comprising a peroxide as defined in any of claims 1 to 11.

13. The method of claim 12 wherein the first formulation further comprises a complex as defined in claim 11 and a thiol secondary accelerator as defined in any of claims 1 to 11 .

14. A method of preparing a composition as defined in any of claims 1 to 10, the method comprising contacting a first formulation comprising an unsaturated resin as defined in any of claims 1 to 10 and a second formulation comprising a peroxide as defined in any of claims 1 to 10, wherein the first formulation is substantially absent the transition metal ion.

15. A kit comprising a first formulation as defined in either of claims 13 or 14 and a second formulation as defined in either of claims 13 or 14, wherein the kit is provided for use in application of a two-component coating.- 72 -55648278-1

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