FIELD

[001] The invention relates to 1,1-dicarbonyl substituted-l-alkenes cured/polymerized with a property modifying agent. In particular, the compositions are comprised of a 1,1-dicarbonyl substituted-l-alkene, an anionic polymerization initiator ("anionic initiator"), and a property modifying component comprised of an acidic functional group.

BACKGROUND

[002] 1,1-dicarbonyl substituted-l-alkenes have been known for some time and described in U.S. Pat. No. 2,330,033; U.S. Pat. No. 3,221,745 and U.S. Pat. No. 3,523,097; U.S. Pat. No. 3,197,318; U.S. Pat. No. 4,056,543 and U.S. Pat. No. 4,160,864. Despite this the 1,1-dicarbonyl substituted-l-alkenes were not commercialized due to the simultaneous production of detrimental by-products that resulted, for example, stability issues and difficulty in product separation.

[003] 1,1-dicarbonyl substituted-l-alkenes compounds rapidly polymerize at room temperature under mild conditions in the presence of nucleophilic or basic initiating species, which render them both useful, as well as, present problems with their stability and workability. More recently, processes to produce the 1,1-dicarbonyl substituted-l- alkenes that solved some of the stability issues were described in U.S. Pat. No. 8,609,885; U.S. Pat. No. 8,884,405; US2014/0329980; and US 2015/0073110; all incorporated herein by reference in their entirety for all purposes.

[004] The 1,1-dicarbonyl substituted-l-alkenes have been used for certain applications. Recently, some methods were described attempting to further broaden the utility of 1,1-dicarbonylsubstituted-l-alkenes for preparation of polymers with improved properties. For example, copolymerizing two or more 1,1-dicarbonyl substituted-l-alkene monomers having substantially different homopolymer glass transition temperatures (see, for example, U.S. Pat. No. 9,315,597) have been described to produce polymers with a broad range of Tg. The 1,1-dicarbonyl substituted-l-alkenes have been reacted with diols to form polyester macromers, which are then subsequently polymerized to form coatings and the like. (U.S. Pat. No. 9,617,377). The 1,1-dicarbonyl substituted-l-alkenes have been UV polymerized with other radically polymerizable monomers and oligomers in the presence of a UV initiator (e.g., copending US provisional application 62/987,507). [005] None of these, however, address the need to have coatings, adhesives or articles that may require a balance of properties such as toughness, flexibility, strength and hydrophobicity/hydrophilicity while still having sufficient working time/workability to ensure proper application or molding. Accordingly, it would be desirable to provide a composition comprised of a 1,1-dicarbonyl substituted-l-alkene that meets one or more of these desired attributes while still being able to cure at or near ambient conditions with sufficient working time and the like.

SUMMARY

[006] It has been discovered that a reaction of a 1,1-dicarbonyl substituted-l-alkene ("monomer") such as a methylene malonate, anionic initiator (e.g., base or nucleophile), and property modifying component ("PMC") containing an acidic functional group allows for the production of a wide envelope of cured polymer properties and tailoring of desirable working time/workability characteristics during cure/polymerization. The PMC may be a small molecule, an oligomer, polymer or solid particulate or any combination thereof. When the PMC is a solid particulate having acidic functional groups on its surface it may be a core shell rubber having acidic functional groups in or on the shell. Not being bound by any theory or limiting of the invention, the acidic functional group of the PMC may delay the initiation allowing for a useful working time to apply to a substrate or mold the polymer, while also incorporating the PMC into the 1,1-dicarbonyl substituted-l- alkene polymer backbone by chain termination or chain transfer.

[007] A first aspect of the invention is a polymer comprised of the reaction product of a 1,1-dicarbonyl substituted-l-alkene, an anionic polymerization initiator and a property modifying component comprised of an acidic functional group (PMC). The tailorability of 1,1-dicarbonyl substituted-l-alkene (e.g., differing substituents and formation of oligomer/macromer) and readily availability of polymer/oligomers having acidic functional groups, which are examples of the PMC, allows for the formation of desirable polymers for applications such as coatings, adhesives, and molded articles. [008] A second aspect of the invention is a composition comprised of a 1,1- dicarbonyl substituted-l-alkene, an anionic polymerization initiator and a property modifying component comprised of an acidic functional group. The composition may be provided in separate parts wherein the 1,1-dicarbonyl substituted is in a first part and the anionic initiator and PMC is in a second part or each of them are provided in a separate part that are then mixed together when desired to form the polymer of this invention. In another embodiment, the PMC, monomer and anionic polymerization catalyst are in one part, wherein the anionic polymerization initiator is latent (activated, for example, by an external action such as irradiation, heating, mechanical forces or dissolution of an encapsulant).

[009] A third aspect of the invention is an article comprised of the polymer of the first aspect. In an embodiment the article is comprised of the polymer of the first aspect disposed upon a substrate, wherein the polymer is adhered to the substrate. Such articles include, but are not limited, substrates that have been coated or adhered to other substrates. In another embodiment, the article is an article comprised of adhered layers of the polymer such as those formed by additive manufacturing methods.

[0010] A fourth aspect of the invention is a method of forming an article, comprised of mixing the composition of the second aspect, disposing the mixed composition onto a substrate or into a mold and curing the composition to form the article of the third aspect.

[0011] The properties of the polymer may vary widely depending on the monomer/PMC ratio and chemical composition allowing for articles that may vary from elastic to rigid as well as have a wide range of glass transition temperatures (Tg). As such, the polymer, compositions to make polymer and articles made therefrom may be suitable for a myriad of applications such as coatings, adhesives, additive manufactured articles, molding resins, various printing inks including inkjet inks, dental applications (e.g., fillings, inserts and the like) and medical applications among others.

DESCRIPTION OF THE DRAWING

[0012] Figure 1 is a graph of the double conversion of a curable composition of this invention.

DETAILED DESCRIPTION

[0013] The explanations and illustrations presented herein are intended to acquaint others skilled in the art with the invention, its principles, and its practical application. The specific embodiments of the present disclosure as set forth are not intended to be exhaustive or limit the scope of the disclosure.

[0014] One or more as used herein means that at least one, or more than one, of the recited components may be used as disclosed. It is understood that the functionality of any ingredient or component may be an average functionality due to imperfections in raw materials, incomplete conversion of the reactants and formation of by-products.

The 1,1-dicarbonyl-l-alkene

[0015] The 1,1-dicarbonyl substituted-l-alkene compounds are for convenience referred to as "1,1-dicarbonyl alkene(s)" or just "monomer(s)" interchangeably. The 1,1- dicarbonyl alkenes are compounds wherein a central carbon atom is doubly bonded to another carbon atom to form a double bond. The central carbon atom is further bonded to two carbonyl groups. Each carbonyl group is bonded to a hydrocarbyl group through a direct bond or an oxygen atom. Where the hydrocarbyl group is bonded to the carbonyl group through a direct bond, a ketone group is formed. Where the hydrocarbyl group is bonded to the carbonyl group through an oxygen atom, an ester group is formed. The 1,1-dicarbonyl alkene may have a structure as shown below in Formula I, where X ¹ and X ² are an oxygen atom or a direct bond, and where R ¹ and R ² are each hydrocarbyl groups that may be the same or different. Both X ¹ and X ² may be oxygen atoms, such as illustrated in Formula IIA, one of X ¹ and X ² may be an oxygen atom and the other may be a direct bond, such as shown in Formula MB, or both X ¹ and X ² are direct bonds, such as illustrated in Formula IIC. The 1,1-dicarbonyl alkene compounds used herein may have all ester groups (such as illustrated in Formula IIA), all keto groups (such as illustrated in Formula IIC) or a mixture thereof (such as illustrated in Formula MB). Compounds with all ester groups may be preferred in some applications due to the flexibility of synthesizing a variety of such compounds.

[0016] Where the cured composition is a coating, adhesive or a sealant, it adheres to one or more substrates for the life or most of the life of the structure containing the cured composition. As an indicator of this durability, the curable composition (e.g., adhesive, film, coating, or sealant) may exhibit excellent results during accelerated aging.

[0017] Heteroatom means nitrogen, oxygen, sulfur and phosphorus, more preferred heteroatoms include nitrogen and oxygen. Hydrocarbyl as used herein refers to a group containing one or more carbon atom backbones and hydrogen atoms, which may optionally contain one or more heteroatoms. Where the hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups well known to one skilled in the art. Hydrocarbyl groups may contain cycloaliphatic, aliphatic, aromatic or any combination of such segments. The aliphatic segments can be straight or branched. The aliphatic and cycloaliphatic segments may include one or more double and/or triple bonds. Included in hydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, alkaryl and aralkyl groups. Cycloaliphatic groups may contain both cyclic portions and noncyclic portions. Hydrocarbylene means a hydrocarbyl group or any of the described subsets having more than one valence, such as alkylene, alkenylene, alkynylene, arylene, cycloalkylene, cycloalkenylene, alkarylene and aralkylene. One or both hydrocarbyl groups may consist of one or more carbon atoms and one or more hydrogen atoms. As used herein percent by weight or parts by weight refer to, or are based on, the weight of the solution composition unless otherwise specified.

[0018] A preferred class of 1,1-dicarbonyl alkene compounds is methylene malonates, the core structural unit/formula for which is shown below:

The term "monofunctional" refers to 1,1-dicarbonyl alkene compounds or a methylene malonate having only one core unit or one carbon carbon double bond. The term "difunctional" refers to 1,1-dicarbonyl alkene compounds or a methylene malonate having two core formulas bound through a hydrocarbyl linkage between one oxygen atom on each of two core formulas. The term "multifunctional" refers to 1,1-dicarbonyl alkene compounds or methylene malonates having more than one core formula which forms a chain through a hydrocarbyl linkage between one oxygen atom on each of two adjacent core formulas.

[0019] The 1,1-dicarbonyl alkene may be a 1,1-diester-l-alkene. As used herein, diester refers to any compound having two ester groups. A 1,1-diester-l-alkene is a compound that contains two ester groups and a double bond bonded to a single carbon atom referred to as the one carbon atom. Dihydrocarbyl dicarboxylates are diesters having a hydrocarbylene group between the ester groups wherein a double bond is not bonded to a carbon atom which is bonded to two carbonyl groups of the diester. [0020] The hydrocarbyl groups (e.g., R ¹ and R ² ), each may comprise straight or branched chain alkyl, straight or branched chain alkyl alkenyl, straight or branched chain alkynyl, cycloalkyl, alkyl substituted cycloalkyl, aryl, aralkyl, or alkaryl. The hydrocarbyl group may optionally include one or more heteroatoms in the backbone of the hydrocarbyl group. The hydrocarbyl group may be substituted with a substituent that does not negatively impact the ultimate function of the monomer or the polymer prepared from the monomer. Preferred substituents include alkyl, halo, alkoxy, alkylthio, hydroxyl, nitro, cyano, azido, carboxy, acyloxy, and sulfonyl groups. More preferred substituents include alkyl, halogen, alkoxy, allylthio, and hydroxyl groups. Most preferred substituents include halogen, alkyl, and alkoxy groups.

[0021] As used herein, alkaryl means an alkyl group with an aryl group bonded thereto. As used herein, aralkyl means an aryl group with an alkyl group bonded thereto and include alkylene bridged aryl groups such as diphenyl methyl groups or diphenyl propyl groups. As used herein, an aryl group may include one or more aromatic rings. Cycloalkyl groups include groups containing one or more rings, optionally including bridged rings. As used herein, alkyl substituted cycloalkyl means a cycloalkyl group having one or more alkyl groups bonded to the cycloalkyl ring.

[0022] The hydrocarbyl groups may include 1 to 30 carbon atoms, 1 to 20 carbon atoms, or 1 to 12 carbon atoms. Hydrocarbyl groups with heteroatoms in the backbone may be alkyl ethers having one or more alkyl ether groups or one or more alkylene oxy groups. Alkyl ether groups may be ethoxy, propoxy, and butoxy. Such compounds may contain from about 1 to about 100 alkylene oxy groups, about 1 to about 40 alkylene oxy groups, about 1 to about 12 alkylene oxy groups, or about 1 to about 6 alkylene oxy groups.

[0023] One or more of the hydrocarbyl groups (e.g., R ¹ , R ² , or both) may include a Ci- Ci ₅ straight or branched chain alkyl, a C ₁ -C ₁₅ straight or branched chain alkenyl, a C ₅ -C ₁₈ cycloalkyl, a C ₆ -C ₂₄ alkyl substituted cycloalkyl, a C ₄ -C ₁₈ aryl, a C ₄ -C ₂₀ aralkyl, or a C ₄ -C ₂₀ aralkyl. The hydrocarbyl group may include a Ci-Cs straight or branched chain alkyl, a C ₅ - Ci ₂ cycloalkyl, a C ₆ -C ₁₂ alkyl substituted cycloalkyl, a C ₄ -C ₁₈ aryl, a C ₄ -C ₂₀ aralkyl, or a C ₄ -C ₂₀ aralkyl.

[0024] Alkyl groups may include methyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, ethyl pentyl, and hexyl groups. More preferred alkyl groups include methyl and ethyl. Cycloalkyl groups may include cyclohexyl and fenchyl. Alkyl substituted groups may include menthyl and isobornyl, norbornyl as well as any other bicyclic, tricyclic or polycyclic structure.

[0025] Hydrocarbyl groups attached to the carbonyl group may include methyl, ethyl, propyl, isopropyl, butyl, tertiary, pentyl, hexyl, octyl, fenchyl, menthyl, and isobornyl, cyclic, bicyclic or a tricyclic group such as cyclohexyl, norbornyl, or tricyclodecanyl.

[0026] Monomers may include methyl propyl methylene malonate, dihexyl methylene malonate, di-isopropyl methylene malonate, butyl methyl methylene malonate, ethoxyethyl ethyl methylene malonate, methoxyethyl methyl methylene malonate, hexyl methyl methylene malonate, dipentyl methylene malonate, ethyl pentyl methylene malonate, methyl pentyl methylene malonate, ethyl ethylmethoxy methylene malonate, ethoxyethyl methyl methylene malonate, butyl ethyl methylene malonate, dibutyl methylene malonate, diethyl methylene malonate (DEMM), diethoxy ethyl methylene malonate, dimethyl methylene malonate, di-N-propyl methylene malonate, ethyl hexyl methylene malonate, methyl fenchyl methylene malonate, ethyl fenchyl methylene malonate, 2 phenylpropyl ethyl methylene malonate, 3 phenylpropyl ethyl methylene malonate, ethyl cyclohexyl methylene malonate, and dimethoxy ethyl methylene malonate.

[0027] Some or all of the 1,1-dicarbonyl alkene can also be multifunctional, having more than one core unit and thus more than one alkene group. Exemplary multifunctional 1,1-dicarbonyl alkenes are illustrated by the formula: wherein R ¹ and R ² are as previously defined; X is, separately in each occurrence, an oxygen atom or a direct bond; n is an integer of 1 or greater to any useful amount such as a polymer of 1,000 or 10,000 Daltons or more to typically at most about 1,000,000 or 100,000 and R is hydrogen or a hydrocarbyl group having 1 to 30 carbons, so long as at least one R is hydrogen (i.e., =(¾) and preferably every R is hydrogen. Typically, n is 1 or 2 to 20 or 10.

[0028] In exemplary embodiments R ² may be, separately in each occurrence, straight or branched chain alkyl, straight or branched chain alkenyl, straight or branched chain alkynyl, cycloalkyl, alkyl substituted cycloalkyl, aryl, aralkyl, or alkaryl, wherein the hydrocarbyl groups may contain one or more heteroatoms in the backbone of the hydrocarbyl group and may be substituted with a substituent that does not negatively impact the ultimate function of the compounds or polymers prepared from the compounds. Exemplary substituents may be those disclosed as useful with respect to Rl. In certain embodiments R ² may be, separately in each occurrence, Ci-15 straight or branched chain alkyl, C 2-15 straight or branched chain alkenyl, C5-18 cycloalkyl, C6-24 alkyl substituted cycloalkyl, C4-18 aryl, C4- 20 aralkyl or C4-20 aralkyl groups. In certain embodiments R ² may be separately in each occurrence Ci-s straight or branched chain alkyl, C5-12 cycloalkyl, C6-12 alkyl substituted cycloalkyl, C4-18 aryl, C4- 20 aralkyl or C4-20 alkaryl groups.

[0029] In an embodiment, X is O and R ² is the residue of a diol, wherein a polyester is formed. The polyesters may be formed from any suitable 1,1-dicarbonyl alkene such as the malonates described above and as described in U.S. Pat. No. 9,969,822 from col. 19, line 49 to col. 20, line 3 and a polyol incorporated herein by reference. Examples of suitable polyol include, for example, those described in U.S. Pat. No. 9,969,822 from col. 20, line 18 to col. 21, line 26, incorporated herein by reference. Examples of diols may include ethylene diol 1,3-propylene diol, 1,2 propylene diol, 1-4-butanediol, 1 ,2-butane diol, 1 ,3-butane diol, 2,3-butane diol, 1,5-pentane diol, 1,3- and 1,4- cyclohexanedimethanols or combinations thereof. Examples of triols may include 1,2,3- propane triol, 1,2,3-butane triol, trimethylolpropane, 1,2,4-butane triol or combination thereof. Likewise, the polyol may be even higher functional, for example, di(trimethylolpropane), pentaerythritol, dipentaerythritol or combination thereof. Any combination of polyols such as multiple diols, triols, tetraols, pentaols, hexaols or mixtures thereof may be used.

[0030] The amount of 1,1-dicarbonyl alkene present in the composition and resultant polymeric reaction product may be any amount depending on the desired properties of the resultant polymer. For example, the amount of the 1,1-dicarbonyl alkene may be at least about 20% by weight, but more typically is at least about 40%, 50% or 60% to about 90%, 95% or 99% by weight of the composition.

[0031] The 1,1-dicarbonyl alkene may be produced and purified by the methods described in U.S. Pat. Nos. 8,609,8985; 8,884,051; 9,108,914 and 9,518,001 and Int. Pub. WO 2017/197212. Examples of such monomers are available under the tradenames CHEMILIAN and FORZA and include, for example, methylene malonate, dihexyl methylene malonate, dicyclohexyl methylene malonate and multifunctional polyester methylene malonates available from Sirrus, Inc., Loveland, OH.

Property Modifying Component (PMC)

[0032] The property modifying component is comprised of an acidic functional group such as carboxylic acid functional group or a carboxylic acid anhydride functional group or a combination thereof.

[0033] The PMC may be small molecule, an oligomer, polymer, solid particle having acidic functional groups. The acidic functional groups may be pendant from the polymer backbone, at the terminus of the backbone whether linear or branched or any combination thereof including dendritic. The amount of acidic functional groups may range from 1 to any useful amount, but typically is at most about 10, when the PMC is an oligomer or polymer. Desirably, there are 2 or more acidic functional groups when the PMC is an oligomer or polymer. The polymer or oligomer PMC is desirably soluble, for example, to realize homogeneous distribution, in the 1,1-dicarbonyl substituted alkenes at the concentration wanted to realize the intended modification of the 1,1-dicarbonyl substituted alkene polymerization product. The polymer or oligomer PMC may have an alkenyl group (e.g., from about 1 to 3 alkenyl groups per molecule/chain).

[0034] In some embodiments, a solvent may be used to dissolve the 1,1-dicarbonyl substituted alkene and PMC. Useful solvents may include any solvent that dissolves the 1,1-dicarbonyl substituted alkenes and PMC polymer or oligomer. Solvents may be any polar solvent, a protic solvent, water or combination thereof. Solvents may, for example, include alcohols, ethers, ketones and the like.

[0035] In another embodiment, the PMC may be an insoluble particulate in the 1,1- dicarbonyl substituted alkenes. When the PMC is insoluble, the pot-life of the composition, for example, when the PMC is combined with 1,1 dicarbonyl substitured-1- alkene in one part may be extended. This may be due, without being limiting in anyway, the suppression of a carboxylic acid to Michael addition of the carboxylic acid to the 1,1- dicarbonyl substituted-l-alkenes.

[0036] When the PMC is insoluble, it may have any useful particle or droplet size that realizes the desired modification of the properties of the cured composition. The size range (e.g., equivalent spherical diameter) is typically less than 30 micrometers to about 50 nanometers. Desirably, the particles are at most about 20 micrometers, 10 micrometers, 5 micrometer, 2 micrometers, 1.5 micrometers to 100 nanometers or 200 nanometers. In an embodiment, the PMC may be soluble with the 1,1-dicarbonyl substituted alkenes with or without a solvent and upon curing, phase separate out to form domains (particulates) within the cured composition having a domain size as mentioned above. The size of the PMC may be determined by known particle size techniques such as laser scattering or microscopy techniques such as those known in the art.

[0037] In another embodiment, the PMC is an oligomer or polymer, the article formed may have differing microstructures from continuous interpenetrating polymeric networks or discontinuous phase interpenetrated within a continuous phase, wherein either phase may be predominately comprised of the PMC or polymerized 1,1-dicarbonyl alkene. [0038] The PMC when it is a polymer may have any useful molecular weight or molecular weight average (Mw). Illustratively the molecular weight may be from about 300, 500 or 1000 to about 20,000 or 10,000 g/moles. Likewise, the Mw may range from 300, 500, 1000 to 30,000; 20,000 or 10,000 g/moles.

[0039] The PMC may be a carboxyl or anhydride containing polyolefin, polyether, polyester, polyether-ester, polyamide, polyurethane, silicone, polystyrene, rubber including a core shell rubber, a carboxylic acid (e.g., naturally occurring carboxylic acid), fatty acid toll oil fatty acids or any combination thereof. The acids may be saturated or may contain various unsaturated and/or aromatic moiities. The natural occurring carboxylic acid maybe any natural occurring carboxylic acid, for example, abietic acid, gallic acid, alginic acid, azelaic acid, caffeic acid, malic acid, pyruvic acid, niacin, citric acid, biotin, abietic acid, cholic resin, pectin, alginic acid, gum rosin (a mixture of naturally occurring natural acids) or combination thereof. The fatty acid may be any fatty acid derived from any animal fat or vegetable oil and maybe saturated or unsaturated. Exemplary oils include linseed, palm, coconut, palm, olive, tung, soybean, peanut, sunflower, cotton seed, rapeseed, or combination thereof. Any fatty acid derived from the aforementioned oils and fats may be used. In an embodiment, the fatty acid is dimerized to form a dimer, trimer acid or higher polymeric acids. Typically, readily available dimer acids contain some small fraction of monomeric acid, trimer acid and higher polymeric acid. Such Dimer acids are readily available, for example, from Oleon NV. Ertevelde, Belgium under the tradename RADIACID. In another embodiment, an unsaturated oil may be grafted with maleic anhydride at the unsaturated bond to form a pendant anhydride, which may then be further reacted to form a carboxylic acid group. The PMC may have a first acid disassociation constant in which the logarithm of said acid disassociation constant in water is about 3 to 14 (see pKa discussion below).

[0040] The PMC may be any carboxylic acid such as monocarboxylic acids or dicarboxylic acids having linear or branched alkane chains of 3 or 5 to 30, 20 or 15 carbons or mixtures thereof. Examples may include hexanoic acid, hexanedioic acid, heptanoic acid, heptanedioic acid, octanoic acid, octanedioic acid, nonanoic acid, nonanedioic acid, decanoic acid, decanedioic acid, 2,3-dimethylbutanedioic, 2,2-dimethylbutanedioic acid, 3-methylheptanedioic acid or mixtures thereof. The PMC may be a sterically hindered carboxylic acid with a short and highly branched alkyl chemical structure such as 2, 2,3,5- Tetramethylhexanoic acid, 2,4-Dimethyl-2-isopropylpentanoic acid, 2,5-Dimethyl-2- ethylhexanoic acid, 2,2-Dimethyloctanoic acid, 2,2-Diethylhexanoic acid or those available under the tradename VERSATIC acids from Hexion Inc. Columbus, OH. As an illustration, the PMC when it is a small monocarboxylic acid it typically will have a pKa of about 3 to 6 with it being understood that pKa is the logarithm of the acid disassociation constant in water. It is also understood that in some cases where multiple carboxylic acid groups are contained in a polymer, the pKa may be difficult to ascertain, but these are contemplated as described herein.

[0041] The PMC may be a carboxyl terminated polybutadiene, carboxyl terminated polyisoprene, carboxyl terminated copolymer of butadiene and acrylonitrile (CTBN), or combination thereof. The PMC may be a homopolymer of a conjugated diene or copolymer of a conjugated diene, especially a diene/nitrile copolymer. The conjugated diene is preferably butadiene or isoprene, with butadiene being especially preferred. When a copolymer with the conjugated diene is employed with a nitrile monomer, the nitrile monomer is desirably acrylonitrile. Preferred copolymers are butadiene- acrylonitrile copolymers. The PMC conjugated diene copolymers contain, in the aggregate, no more than about 30 wt % of polymerized unsaturated nitrile monomer, and preferably no more than about 26 wt % of polymerized nitrile monomer. These conjugated dienes and copolymers thereof generally contain from about 1.5, more preferably from about 1.8, to about 2.5, more preferably to about 2.2 carboxyl groups per molecule, on average. [0042] Suitable carboxyl-functional butadiene and butadiene/acrylonitrile copolymers are commercially available from CVC Thermoset Specialties as Hypro ^® 2000x162 carboxyl-terminated butadiene homopolymer and Hypro ^® 1300x31, Hypro ^® 1300x8, Hypro ^® 1300x13, Hypro ^® 1300x9 and Hypro ^® 1300x18 carboxyl-terminated butadiene/acrylonitrile copolymers. The molecular weight (Mw) of these copolymers are typically from about 2000 to about 6000, more preferably from about 3000 to about 5000. [0043] In a particular embodiment, the PMC may be a core shell rubber. Any core shell rubber having, for example, carboxyl groups in or on the shell (polymer of the shell contains carboxyl or anhydride groups) of the core shell rubber particle may be used such as described in U.S. Pat. No. 4,315,085. The core-shell rubber component is a particulate material having a rubbery core. Illustrative core-shell rubber compositions are disclosed in U.S. Pat. No and 7,625,977. The rubbery core of such core shell rubber may have a Tg of less than -25°C, more preferably less than -50° C, and even more preferably less than -70° C. The Tg of the rubbery core may be well below -100° C. The core-shell rubber also has at least one shell portion that preferably has a Tg of at least 50°C. By "core," it is meant an internal portion of the core-shell rubber. The core may form the center of the core-shell particle, or an internal shell or domain of the core-shell rubber. A shell is a portion of the core-shell rubber that is exterior to the rubbery core. The shell portion (or portions) typically forms the outermost portion of the core-shell rubber particle. The shell material is preferably grafted onto the core or is cross-linked. The rubbery core may constitute from 50 to 95%, especially from 60 to 90%, of the weight of the core-shell rubber particle. The molecular weight average Mw of the shell polymer may be from 10,000 to 500,000 g/moles.

[0044] The PMC may be a carboxyl terminated ester that is solid or liquid. Exemplary polyesters include polyesters obtained by the reaction of acids with epoxies such as described by WO1998023661A1. The polyester may be one that is linearterminated with a diol that is reacted with trimellitic anhydride to acid functionalize the polyester. The acid functional polyester may be a solid acid terminated polyester such as described by US Pat. App. No. 2007/0260003. An acid functional polyester polyol may also be used as a PMC, such as those commercially available under the tradename DICAP from Geo Specialty Chemicals, Ambler, PA. An alkyd (e.g., reaction product of a polybasic, a polyhydric alcohol, fatty acids, multifunctional fatty acids and anhydrides) having unreacted carboxylic acid groups may also be used. The alkyd may be a long oil, medium oil, or short oil alkyd resin such as those commercially available from Deltech Corp. Baton Rouge, LA.

[0045] The PMC may also be a carboxyl functional polyurethane such as those used to make polyurethane dispersions prior to being neutralized, for example, with a base. Examples of such carboxyl terminate polyurethanes that may be useful include, for example, those described in U.S. Pat. Nos. 5,473,011 and 7,589,148.

[0046] The PMC may be a polyolefin containing an anhydride or carboxyl groups such those known in the art. Examples of these may include ethylene (meth)acrylic acid copolymers such as those available from DuPont under the tradename NUCREL, The Dow Chemical Company under the tradename PRIMACOR and ExxonMobil under the tradename ESCOR. Other examples may include acid or anhydride grafted polyolefins (e.g., polyethylene, polypropylene that are linear, branched, or copolymers with alkenes having more than 3 carbons to 20 carbons). Examples of such grafted polyolefins may include maleic anhydride grafted polyethylenes available from The Dow Chemical Company under the tradename AMPLIFY GR.

[0047] The PMC may be any suitable polystyrene containing a carboxyl or anhydride such as those known in the art including, for example, copolymers of styrene and maleic anhydride. Examples of polystyrene containing a carboxyl or anhydride may include copolymers of styrene and maleic anhydride, which may include other copolymers. Suitable such copolymer may include those commercially available from Polyscope Polymer BV under the tradename XIRAN.

[0048] The PMC may a silicone containing a carboxyl or anhydride such as those known in the art including, for example, carboxyl terminated silicone fluids available from Momentive under the tradename MAGNASOFT and carboxyl terminated polydimethylsiloxane available from Gelest Inc. under product code DMS-B25, DMS-B31, DMS B12 and the like.

[0049] In an embodiment, the carboxyl group may be neutralized with a base to form a salt that is then rehydrolyzed in situ when curing or prehydrolyzed prior to curing to form the carboxyl group that participates in the curing. For example, the PMC may be a copolymer of a methylene malonate and a vinyl acetate as described by Matsumara and Tanaka, Journal of Environmental Polymer Degradation, Vol. 2, No. 2. 1994 illustrated by: where R is H or a hydrocarbyl group and m and an n may be any useful integers so long as m + n is greater than 2 to typically 1000 or 100, wherein the salt may be hydrolyzed as and act as a PMC. Any residual neutralized acid (e.g., not hydrolyzed) may act as an anionic initiator.

[0050] The PMC may be an acid that is the Michael addition product of a mercapto- carboxylic acid compound and an acrylate or 1,1-dicarbonyl alkene. The mercapto- carboxylic acid may be any carboxylic acid such as those described herein having a thiol group. The mercapto-acid may have one or more mercapto groups or acid groups. The acrylate may any suitable acrylate such as those known in the art and may be a monofunctional or multifunctional acrylate. The 1,1-dicarbonyl alkene may be any suitable such as those described herein. Such PMC may be formed by the method described in copending U.S. application 63/115,159, incorporated herein by reference. As an illustration, the acrylate may be an isobornyl acrylate and 3-mercaptopropionic acid or dicyclohexyl methylidene malonate (DCHMM) and 3-mercaptopropionic acid as shown below:

[0051] The anhydride may be any anhydride compound analogous to the carboxyl containing compounds described above. The anhydrides as described for the carboxyl compounds may be soluble and insoluble in the same fashion, with it being desirable for them to be liquids and soluble in the 1,1-dicarbonyl alkene. Examples of anhydrides include maleic anhydride, nadic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecenylsuccinic anhydride, and octenylsuccinic anhydride and the like. The PMC may be any copolymer of maleic anhydride and other radically polymerizable comonomer, which may be further hydrolyzed to form a carboxyl group. An example, of such a copolymer is copolymer of maleic anhydride and a vinyl ether such as those available from Ashland Global Holdings Inc., under the tradename GANTREZ.

[0052] The amount of PMC may be any useful amount but as described below is generally present in an amount that may slow the polymerization initially but does not hinder it substantially. Typically, the amount by weight is from about 0.1%, 1%, 5% or 10% to about 70%, 40%, 30% or 25%. The particular amount by weight may vary depending on the molecular weight average of the PMC when it is a polymer and the amount of acidic functional groups. Anionic Initiator

[0053] The anionic initiator may by any suitable anionic initiator that initiates anionic polymerization upon contact with the 1,1-dicarbonyl substituted alkenes. In certain embodiments, the anionic initiator may induce polymerization under ambient conditions without requiring external energy from heat or radiation or high mechanical forces such as high shear mixing causing for example the cracking or rupture of an encapsulant. [0054] A wide variety of anionic initiators may be used including most nucleophilic initiators capable of initiating anionic polymerization. Exemplary initiators include alkali metal salts, alkaline earth metal salts, ammonium salts, amines, halides (halogen containing salts), metal oxides, and mixtures containing such salts or oxides. Exemplary anions for such salts include anions based on halogens, acetates, benzoates, sulfur, carbonates, silicates and the like. Examples of anionic initiators may include glass beads having a basic constituent such as soda-lime silica glass, ceramic beads (comprised of various metals, nonmetals and metalloid materials), clay minerals (including hectorite clay and bentonite clay), and ionic compounds such as sodium silicate, sodium benzoate, and calcium carbonate. Additional suitable anionic initiators are also disclosed in U.S. Pat. No. Publication No. 9,181,365 (col. 9, lines 45-57) and U.S. Pat. No. 9,334,430 incorporated herein by reference.

[0055] The amine anionic initiator may be any primary, secondary or tertiary amine and may be an alkyl or substituted alkyl amine. The alkyl or substituted alky may be any hydrocarbyl group typically having from 1 to 30 carbons and 1 to 6 heteroatoms such as sulfur and oxygen. In an embodiment the amines include, for example, substituted (e.g., 1 or 2 heteroatoms) or unsubstituted Ci - C ₅ mono- and diamines, aromatic amines, and mixtures thereof. The amine compounds may have molecular weights from about 50 to about 10,000. In general, the lower molecular weight amines may be desired, for example, to enhance ease of mixing. Lower molecular weight amines generally have a molecular weight of less than about 1500 g/moles or less than about 1000 g/mol. Examples of amines include ethylamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, butylamine, dibutylamine, tributylamine, butanolamine, dibutanolamine, tributanolamine, propanolamine, dipropanolamine, tripropanolamine, propylamine, dipropylamine, tripropylamine, ethylenediamine, triethylenediamine, N,N-dimethylbenzylamine, isophoronediamine, ethyl l-methyl-3- piperidinecarboxylate, ethyl-l-methyl-4-piperidinecarboxylate, bis(2,2- morpholylethyl)ether (DMDEE), and mixtures thereof.

[0056] The anionic initiator may be employed in any amount sufficient to anionically polymerize the composition to the desired full or partial cure. The anionic initiator typically is used in an amount of about 0.01 to 20%, or about 0.1 or 0.25 to 8%, of about 0.5 to 5% or about 0.75 to 2% by weight of the composition or just the weight of the monomer and PMC of the composition (i.e., excluding other ingredients such as inert fillers). Illustratively, the ratio of the anionic initiating groups/PMC acidic functional groups may be from about 0.003, 0.004, 0.01, 0.1, 1, 2, or 3 to about 300, 100, 50, 20 or 10 and the ratio of use may vary depending on the particular PMC, initiator and 1,1- dicarbonyl alkene employed.

[0057] In some embodiments the anionic initiator may be latent to enable a one part composition, wherein each of the components is contained in one package together that is activated, for example, upon discharge from the package and application of some force. For example, the composition may be discharge and mixed by a static or dynamic mixer activating the latent initiator. In other embodiments the anionic initiator may be activated by irradiating, heating or exposing to a solvent, for example that dissolves a coating or encapsulant enveloping the initiator.

[0058] The composition may be contained separately and brought together and mixed to polymerize the composition. Suitable separate packaging or delivery systems may include those known in the art. Illustrative examples include those involving separate rigid tubes in which each material is dispensed by a separate plunger and mixed upon exiting using a static or dynamic mixing nozzles such as described by Craig Blum, Two Component Adhesive Cartridge Systems, FAST, July 2008. In another illustration, two or more compartmented sausage containers may be used such as described in U.S. Pat. Nos. 4,009,778; 4,126,005; 4,227,612; 6,129,244; 8.313,006 and 9,821,512. [0059] The latent anionic initiator may be any employing an encapusulant. An illustrative example those described in U.S. Pat. No. 9,334,430 incorporated herein by reference in its entirety for all purposes.

[0060] In another embodiment, the anionic initiator may be a latent base such as those that absorb radiation such as radiation in the UV or visible region and forms a base or nucleophilic anionic initiator

[0061] Examples of photolatent bases include photocleavable carbamates (e.g., 9- xanthenylmethyl, fluorenylmethyl, 4-methoxyphenacyl, 2,5-dimethylphenacyl, benzyl, and others), which have been shown to generate primary or secondary amines after photochemical cleavage. Other photolatent bases which generate primary or secondary amines include certain O-acyloximes, sulfonamides, and formamides. Acetophenones, benzophenones, and acetonaphthones bearing quaternary ammonium undergo photocleavage to generate tertiary amines in the presence of a variety of counter cations (borates, dithiocarbamates, and thiocyanates). Examples of these photolatent ammonium salts are N-(benzophenonemethyl)tri-N-alkyl ammonium tetraarylborates or alkyltriarylborates or dialkyldiaryl borates. Sterically hindered a-aminoketones generate tertiary amines. Exemplary photolatent bases useful for practicing the present disclosure include 5-benzyl-l,5-diazabicyclo[4.3.0]nonane, 5-(anthracen-9-yl-methyl)- l,5-diaza[4.3.0]nonane, 5-(2'-nitrobenzyl)-l,5-diazabicyclo[4.3.0]nonane, 5-(4'- cyanobenzyl)-l,5-diazabicyclo[4.3.0] nonane, 5-(3'-cyanobenzyl)-l,5- diazabicyclo[4.3.0]nonane, 5-(anthraquinon-2-yl-methyl)-l,5-diaza[4.3.0]nonane, 5-(2'- chlorobenzyl)-l,5-diazabicyclo[4.3.0]nonane, 5-(4'-methylbenzyl)-l,5- diazabicyclo[4.3.0]nonane, 5-(2', 4', 6'-trimethylbenzyl)-l,5-diazabicyclo[4.3.0] nonane, 5- (4'-ethenylbenzyl)-l,5-diazabicyclo[4.3.0]nonane, 5-(3'-trimethylbenzyl)-l,5- diazabicyclo[4.3.0]nonane, 5-(2',3'-dichlorobenzyl)-l,5-diazabicyclo[4.3.0]nonane, 5- (naphth-2-yl-methyl-l,5-diazabicyclo[4.3.0]nonane, l,4-bis(l,5- diazabicyclo[4.3.0]nonanylmethyl)benzene, 8-benzyl-l,8-diazabicyclo[5.4.0] undecane, 8-benzyl-6-methyl-l,8-diazabicyclo[5.4.0] undecane, 9-benzyl-l,9- diazabicyclo[6.4.0]dodecane, 10-benzyl-8-methyl-l,10-diazabicyclo[7.4.0]tridecane, 11- benzyl-1, ll-diazabicyclo[8.4.0]tetradecane, 8-(2'-chlorobenzyl)-l,8- diazabicyclo[5.4.0]undecane, 8-(2',6'-dichlorobenzyl)-l,8-diazabicyclo[5.4.0] undecane,

4-(diazabicyclo[4.B.0]nonanylmethyl)-l,l'-biphenyl, 4,4'- bis(diazabicyclo[4.B.0]nonanylmethyl)-ll'-biphenyl, 5-benzyl-2-methyl-l,5- diazabicyclo[4.3.0]nonane, 5-benzyl-7-methyl-l,5,7-triazabicyclo[4.4.0]decane, and combinations thereof.

[0062] An example of a photolatent base is available from BASF under the trade designation "CGI-90", which is reported to be 5-benzyl-l,5-diazabicyclo[4.3.0]nonane (see, e.g., WO 2014/176490 (Knapp et al.)), which generates l,5-diazabicyclo[4.3.0]non-

5-ene (DBN) upon exposure to radiation (see, e.g., US2013/0345389 (Cai et al), 2-benzyl- l-(3,5-dimethoxyphenyl)-2-(dimethylamino)butan-l-one available from BASF under the trade designation CGI 277, p-(Ethylthio)phenyl methylcarbamate and 6-Nitroveratryl chloroformate diethyl amine.

[0063] When using a photolatent base, the composition may also include a photosentizer. Photosensitizers are compounds when used in conjunction with a photolatent base improve or allow the accelerates the activation of the latent anionic initiator or allows for the activation at longer wavelengths than the absorbance of the photolatent base. A photosensitizer may be a compound having an absorption spectrum that overlaps or closely matches the emission spectrum of the radiation source to be used and that can, for example, improve the energy transfer to the photolatent base. Exemplary classes of photosensitizers include aromatic carbonyl compounds, for example benzophenone, thioxanthone, anthraquinone and 3-acylcoumarin derivatives or dyes such as eosine, rhodamine and erythrosine dyes. Additional exemplary photoinitiators include: thioxanthones, such as thioxanthone, 2-isopropylthioxanthone, 2- chlorothioxanthone, l-chloro-4-propoxythioxanthone, 2-dodecylthioxanthone, 2,4- diethylthioxanthone, 2,4-dimethylthioxanthone, 1-methoxycarbonylthioxanthone, 2- ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)-thioxanthone, 4- butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methylthioxanthone, l-cyano-3- chlorothioxanthone, l-ethoxycarbonyl-3-chlorothioxanthone, l-ethoxycarbonyl-3- ethoxythioxanthone, l-ethoxycarbonyl-3-aminothioxanthone, l-ethoxycarbonyl-3- phenylsulfurylthioxanthone, 3,4-di-[2-(2-methoxyethoxy)ethoxycarbonyl]-thioxanthone, l,3-dimethyl-2-hydroxy-9H-thioxanthen-9-one 2-ethylhexylether, l-ethoxycarbonyl-3- (l-methyl-l-morpholinoethyl)-thioxanthone, 2-methyl-6-dimethoxymethyl- thioxanthone, 2-methyl-6-(l,l-dimethoxybenzyl)-thioxanthone, 2- morpholinomethylthioxanthone, 2-methyl-6-morpholinomethylthioxanthone, N- allylthioxanthone-3,4-dicarboximide, N-octylthioxanthone-3,4-dicarboximide, N-(l,l,3,3- tetramethylbutyl)-thioxanthone-3,4-dicarboximide, 1-phenoxythioxanthone, 6- ethoxycarbonyl-2-methoxythioxanthone, 6-ethoxycarbonyl-2-methylthioxanthone, thioxanthone-2-carboxylic acid polyethyleneglycol ester, 2-hydroxy-3-(3,4-dimethyl-9- oxo-9H-thioxanthon-2-yloxy)-N,N,N-trimethyl-l-propana minium chloride; 2.

Benzophenones, such as benzophenone, 4-phenyl benzophenone, 4-methoxy benzophenone, 4,4'-dimethoxy benzophenone, 4,4'-dimethyl benzophenone, 4,4'- dichlorobenzophenone 4,4'-bis(dimethylamino)-benzophenone, 4,4'- bis(diethylamino)benzophenone, 4,4'-bis(methylethylamino)benzophen-one, 4,4'-bis(p- isopropylphenoxy)benzophenone, 4-methyl benzophenone, 2,4,6-trimethyl- benzophenone, 4-(4-methylthiophenyl)-benzophenone, 3,3'-dimethyl-4-methoxy benzophenone, methyl-2-benzoylbenzoate, 4-(2-hydroxyethylthio)-benzophenone, 4-(4- tolylthio)-benzophenone, l-[4-(4-benzoyl-phenylsulfanyl)-phenyl]-2-methyl-2-(toluene- 4-sulfonyl)-propan-l-one, 4-benzoyl-N,N,N-trimethylbenzenemethanaminium chloride, 2-hydroxy-3-(4-benzoylphenoxy)-N,N,N-trimethyl-l-propanamini um chloride monohydrate, 4-(13-acryloyl-l,4,7,10,13-pentaoxamidecyl)-benzophenone, 4-benzoyl-N, N-dimethyl-N-[2-(l-oxo-2-propenyl)oxy]ethyl-benzenemethanami nium chloride;

Coumarins, such as Coumarin 1, Coumarin 2, Coumarin 6, Coumarin 7, Coumarin 30, Coumarin 102, Coumarin 106, Coumarin 138, Coumarin 152, Coumarin 153, Coumarin 307, Coumarin 314, Coumarin 314T, Coumarin 334, Coumarin 337, Coumarin 500, 3- benzoyl coumarin, 3-benzoyl-7-methoxycoumarin, 3-benzoyl-5,7-dimethoxycoumarin, 3- benzoyl-5,7-dipropoxycoumarin, 3-benzoyl-6,8-dichlorocoumarin, 3-benzoyl-6-chloro- coumarin, 3,3'-carbonyl-bis[5,7-di(propoxy)coumarin], 3,3'-carbonyl-bis(7- methoxycoumarin), 3,3'-carbonyl-bis(7-diethylamino-coumarin), 3-isobutyroylcoumarin, 3-benzoyl-5,7-dimethoxy-coumarin, 3-benzoyl-5,7-diethoxy-coumarin, 3-benzoyl-5,7- dibutoxycoumarin, 3-benzoyl-5,7-di(methoxyethoxy)-coumarin, 3-benzoyl-5,7- di(allyloxy)coumarin, 3-benzoyl-7-dimethylaminocoumarin, 3-benzoyl-7- diethylaminocoumarin, 3-isobutyroyl-7-dimethylaminocoumarin, 5,7-dimethoxy-3-(l- naphthoyl)-coumarin, 5,7-diethoxy-3-(l-naphthoyl)-coumarin, 3- benzoylbenzo[f]coumarin, 7-diethylamino-3-thienoylcoumarin, 3-(4-cyanobenzoyl)-5,7- dimethoxycoumarin, 3-(4-cyanobenzoyl)-5,7-dipropoxycoumarin, 7-dimethylamino-3- phenylcoumarin, 7-diethylamino-3-phenylcoumarin, the coumarin derivatives disclosed in JP 09-179299-A and JP 09-325209-A, for example 7-[{4-chloro-6-(diethylamino)-S- triazine-2-yl}amino]-3-phenylcoumarin; 4. 3-(aroylmethylene)-thiazolines, such as 3- methyl-2-benzoylmethylene- -naphthothiazoline, 3-methyl-2-benzoylmethylene- benzothiazoline, 3-ethyl-2-propionylmethylene- -naphthothiazoline; Rhodanines, such as 4-dimethylaminobenzalrhodanine, 4-diethylaminobenzalrhodanine, 3-ethyl-5-(3- octyl-2-benzothiazolinylidene)-rhodanine; other Compounds, such as acetophenone, 3- methoxyacetophenone, 4-phenylacetophenone, benzil, 4,4'-bis(dimethylamino)benzil, 2- acetylnaphthalene, 2-naphthaldehyde, dansyl acid derivatives, 9,10-anthraquinone, anthracene, pyrene, aminopyrene, perylene, phenanthrene, phenanthrenequinone, 9- fluorenone, dibenzosuberone, curcumin, xanthone, thiomichler's ketone, a-(4- dimethylaminobenzylidene) ketones, e.g. 2,5-bis(4- diethylaminobenzylidene)cyclopentanone, 2-(4-dimethylamino-benzylidene)-indan-l- one, 3-(4-dimethylamino-phenyl)-l-indan-5-yl-propenone, 3-phenylthiophthalimide, N- methyl-3,5-di(ethylthio)-phthalimide, N-methyl-3,5-di(ethylthio)phthalimide, phenothiazine, methylphenothiazine, amines, e.g. N-phenylglycine, ethyl 4- dimethylaminobenzoate, butoxyethyl 4-dimethylaminobenzoate, 4- dimethylaminoacetophenone, triethanolamine, methyldiethanolamine, dimethylaminoethanol, 2-(dimethylamino)ethyl benzoate, poly(propylenegylcol)-4- (dimethylamino) benzoate. The weight ratio of photolatent anioinic initiators (e.g., base) to the weight of photosensitizers may be range from 0.5/1 to 10/1 or 1/1 to 5/1. [0064] The composition may be comprised of further components that may vary depending on the application. The further components may be one or more dyes, pigments, toughening agents, rheology modifiers, fillers, reinforcing agents, thickening agents, opacifiers, inhibitors, fluorescence markers, thermal degradation reducers, thermal resistance conferring agents, surfactants, wetting agents, or stabilizers can be included the composition. For example, thickening agents and plasticizers such as vinyl chloride terpolymer (comprising vinyl chloride, vinyl acetate, and dicarboxylic acid at various weight percentages) and dimethyl sebacate respectively, can be used to modify the viscosity, elasticity, and robustness of a system. In certain embodiments, such thickening agents and other compounds can be used to increase the viscosity of a polymerizable system from about 1 to 3 cPs to about 30,000 cPs, or more.

[0065] In some embodiments, the filler may also act as a rheological modifier and a PMC wherein the surface of the filler has carboxyl groups such as acid oxidized carbon blacks. Desirably such carbon blacks have an oil absorption (OAN) of about 80 to 200 ccs per 100 grams. Preferably, the oil absorption of the carbon is at least about 90, more preferably at least about 100, and most preferably at least about 110 to preferably at most about 180, more preferably at most about 165 and most preferably at most about 150 ccs/100 grams.

[0066] Anionic or free radical polymerization stabilizers may be present in sufficient amount to prevent premature polymerization of the composition. Preferably, the anionic polymerization stabilizers such as methane sulfonic acid are present in an amount of about 0.1 part per million or greater based on the weight of the curable composition, more preferably about 1 part per million by weight or greater and most preferably about 5 parts per million by weight or greater. However, the PMC when contained in the same part as the 1,1-dicarbonyl alkene may not need a anionic stabilizer, because the PMC itself may act as a stabilizer. The anionic polymerization stabilizers may be present in an amount of about 1000 parts per million by weight or less based on the weight of the composition, more preferably about 500 parts per million by weight or less and most preferably about 100 parts per million by weight or less. [0067] The composition may comprise one or more free radical stabilizers. The one or more free radical stabilizers may be present in sufficient amount to prevent premature polymerization. The free radical polymerization stabilizers may be present in an amount of about 10 ppm or less based on the weight of the total composition, about 100 ppm by weight or greater, or about 1000 ppm by weight or greater. The free radical polymerization stabilizers may be present in an amount of about 10,000 ppm by weight or less based on the weight of the total composition, about 8000 ppm by weight or less, or about 5000 ppm by weight or less. The free radical inhibitors that may be used include: tocopherol (e.g., including vitamin E), 4-tert-Butylpyrocatechol; tert-Butylhydroquinone; 1,4-Benzoquinone; 6-tert-Butyl-2,4-xylenol; 2-tert-Butyl-l,4-benzoquinone; 2,6-Di-tert- butyl-p-cresol; 2,6-Di-tert-butylphenol; Hydroquinone; 4-Methoxyphenol; Phenothiazine; 2,2'-methylenebis(6-tert-butyl-4-methylphenol) or a combination thereof. Free radical stabilizers preferably include phenolic compounds (e.g., 4-methoxyphenol, mono methyl ether of hydroquinone ("MeHQ") butylated hydroxytoluene ("BHT")). Stabilizer packages for 1,1-disubstituted alkenes are disclosed in U.S. Patent No. 8,609,885 and U.S. Patent No. 8,884,051, each incorporated by reference. Additional free radical polymerization inhibitors are disclosed in U.S. Patent No. 6,458,956 and are hereby incorporated by reference.

[0068] The composition may contain a filler in certain embodiments such as printing dyes or additive manufacturing techniques such as polyjetting and inkjetting, which are described below. Examples of filler include talc, wollastonite, mica, clay, montmorillonite, smectite, kaolin, calcium carbonate, glass fibers, glass beads, glass balloons, glass milled fibers, glass flakes, carbon fibers, carbon flakes, carbon beads, carbon milled fibers, metal flakes, metal fibers, metal coated glass fibers, metal coated carbon fibers, metal coated glass flakes, silica, other ceramic particles, ceramic fibers, ceramic balloons, aramid particles, aramid fibers, polyacrylate fibers, graphite, and various whiskers such as potassium titanate whiskers, aluminum borate whiskers and basic magnesium sulfate whiskers. The fillers may be incorporated alone or in combination. [0069] The compositions and polymers made therefrom may be used in any number of applications. Exemplary applications include adhesives, sealants, coatings, components for optical fibers, potting and encapsulating materials for electronics, resins molded articles, and the like.

[0070] To form the polymer or article from the composition, the composition is provided and each ingredient mixed together and then the mixed composition is allowed to react to form the polymer or article. In an embodiment, the composition is provided in at least two separate components prior to mixing as previously described. Desirably, 1,1-dicarbonyl substituted carbonyl and PMC are provided in a first component and the anionic initiator is provided in another component. The composition may be provided in a singular container having a plurality of chambers that separates each of the components from reacting prior to mixing of the component. The components may be dispensed through a common orifice causing each of the ingredients of the composition to mix. To aid the mixing through the orifice, a static or dynamic mixer may be employed.

[0071] In another embodiment, the composition is provided in one component or container together, wherein the anionic initiator is latent as described previously. The ingredients in the composition may be dispensed under sufficient mixing (mechanical force) such that the latent anionic initiator is activated causing the reaction to form the polymer reaction product. Alternatively, the composition may be dispensed and then subjected to heating, irradiating or mixing with a solvent to activate the latent anionic initiator to cause the polymerization reaction.

[0072] When a photolatent anionic initiator (e.g., photolatent base) is used, the radiation source may be any suitable one such as those known in the art. Illustratively, the radiation is UV and the UV sources may be any suitable device such as those known in the art and include, for example, commercially available UV light emitting diodes (LEDs) and mercury lamps with or without filters.

[0073] The temperature, time and pressure may be any useful such as ambient conditions. The temperature may be increased to accelerate the reaction or decreased to slow the reaction compared to ambient temperature (~20 to 25°C). Elevated or decreased pressure from near ambient pressures are not needed, but may be employed if desired, for example, when adhering two substrates such as a veneer to a substrate. [0074] In some embodiments, the composition allows for a method where the cure or reaction rate is initially slowed allowing for a useful working time to apply or mold the composition after mixing. The working time may be from about 30 seconds to 5 or 10 minutes where the reaction rate is reduced and then accelerates as shown in the examples.

[0075] In an embodiment the substrate is coated by the composition forming an article with the polymer reaction product of the composition adhered to the substrate. In another embodiment, the composition is interposed on two or more substrates, reacted to adhere the two or more substrates together. In another embodiment, after the ingredients of the composition are mixed and, as necessary, the anionic initiator activated, the composition may be dispensed, cast or injected into a mold and allowed to cure or react to form a shaped article. The dispensing to form a coated article or article comprised of two substrates adhered together by the composition's polymer reaction product may be any suitable dispensing method such as those known in the art (e.g., spraying, painting, caulk gunning, extruding and the like). The substrates may be any suitable substrate such as a ceramic, metal, metalloid, glass, plastic, wood, a composite of any of the aforementioned, or combination thereof.

[0076] In an embodiment, the composition may be used to form an article employing known forming techniques such as additive manufacturing techniques. Illustratively, when the composition is comprised of a latent anionic initiator, exemplary additive manufacturing methods may include, but are not limited to the following photopolymerization 3D printing techniques. Stereolithography (SLA), where a UV laser beam is rastered upon a vat of the curable composition initiating polymerization and is built up layer by layer, which is illustrated by U.S. Pat. Nos 4,575,330 and 5,256,340. Digital light processing (DLP) where an image is flashed at once upon a vat using projections of graphics using conventional light sources employing mirrors typcially, with subsequent layers being built up by changing the image layer by layer (see, for example, U.S. Pat. Nos. 5,236,637 and 10,001,641. Continuous liquid interface production (CLIP) as described in U.S. Pat. No. 9,211, 678 and Daylight polymer printing (DPP) as described in U.S. Pat. Appl. 2018/0141268. Other exemplary 3D printing methods include those employing the polymer as a binder that is sprayed upon a powder bed that is then irradiated and layer built up to form the article (Binder Jetting "BJ" see for example U.S. Pat. No. 5,340,656) or within a printing ink that is irradiated for example layer by layer by using (polyjet or inkjet, see for example, U.S. Pat. Pub. 2018/0029291), or a thin sheet is irradiated with a subsequent sheet layer to the previous sheet and it being irradiated to laminate it to its previous sheet (Sheet lamination, "SL" see for example U.S. Pat. No. 5,876,550).

ILLUSTRATIVE EMBODIMENTS

[0077] The following examples are provided to illustrate the curable compositions and the polymers formed from them but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise noted. Table 1 shows the ingredients used in the examples and comparative examples.

Method of Mixing

[0078] For each example and comparative example in Table 2, maleic anhydride was first dissolved in acetone and mixed with PES or dissolved straight into DEMM to make a first solution. A second solution was prepared by mixing the anionic initiator, TEA or EMPC, with BEHA solvent (where applicable). Lastly, the two solutions were combined and well mixed. For each example and comparative example in Table 3, the PMC, DMBA, and solvent were well mixed and allowed to rest for an hour. After this hour, each solution had returned to room temperature. Then, this mixture was added to PES and well mixed. All solutions for each example and comparative example in Table 1 and Table 2 were mixed with a FlackTek SpeedMixer at 1500 rpm for 1 minute. Pot Life Measurement

[0079] The pot life of each example and comparative example was measured as the time elapsed between initially mixing the methylene malonate containing component with the anionic initiator containing component and the point when the mixture ceased flowing under its own weight when its vial was inverted. For this test, 2 grams of sample were cured in 5 mL vials.

Final Double Bond Conversion Measurement

[0080] Final double bond conversion for the cured films was determined by FTIR spectroscopy. FTIR spectra were collected by attenuated total reflectance of the liquid mixtures immediately after mixing, and then again of the cured polymer after 1 week. The conversion was determined by the ratio of the area of the peak between 829-775 cm ¹ of the cured film to the same area immediately after mixing (before cure). These peaks were normalized by the areas of their carbonyl peaks at 1850-1650 cm ¹ .

Tensile Testing

[0081] For all tensile tests, tensile specimens were prepared by casting 100-micron films from the liquid mixtures immediately after mixing between two glass plates separated by 100-micron spacers. Within one hour of the films curing solid, they were cut into strips with a paper cutter to widths of 19 mm. These strips continued curing at room temperature for one week before evaluating their tensile properties. An Instron Testing Machine in tension mode with a 1 kN load cell was used for tensile testing. The cured polymer strips were loaded into the Instron clamps with a gap of approximately 40 mm between clamps. Strain-to-break tests were then initiated with a pull rate of 0.2 in/min. All recorded data for the Young's Modulus, elongation at break, and the max tensile strength represents an average of five test results. Real-Time Double Bond Conversion Measurement

[0082] The double bond conversion plot vs. time shown in Figure 1 was measured using real-time FTIR spectroscopy. Samples were loaded into an FTIR in transmission mode using a cell consisting of two glass slides separated by a 0.85 mm-thick rubber spacer. The spacer had a hole cut out in the center which was filled with a PES formulation that had been mixed with PMC and anionic initiator immediately prior to FTIR testing. Double bond conversion was monitored by the ratio of the current area of the FTIR peak from 6284-6119 cm ¹ to the same peak's initial area.

[0083] From the results of the Examples and Comparative Examples shown in Table 2, it is readily apparent that the use of the PMC enables for improved workability (e.g., longer pot-life) while realizing desired properties such as flexibility and the like (C. Ex. 1 compared to Examples 1 and 2). This is also shown by the Figure 1 corresponding to Example 12, which shows the C=C conversion, where the conversion rate is hindered initially allowing for desired workability during application and then fast curing.

[0084] From the results shown in Table 3, it is also apparent that the PMC may be used to increase the elongation and strength of the cured film. The particular properties may vary depending on the amount of PMC and type of PMC allowing for tuning of the cured polymer properties.

[0085] Examples 14-16 employing PMCs that are the Michael addition products of a mercapto carboxylic acid and a 1,1-dicarbonyl alkene are made in the same manner as described above. 3 mercaptopropionic acid (Sigma) and DCHMM are reacted at a 1:1 molar ratio at room temperature for 1 day to form a Michael addition reaction product (DCHMM-3MPA). Consumption of DCHMM was confirmed to be complete by 1H NMR. The test specimens are made in a like manner as described above with the amounts of each component shown in Table 4 as well as the results obtained for the specimens for each Example.

[0086] Examples 17 to 21 are made using sodium benzoate initiator that is dissolved in neodecanoic acid 5-10 g of solution at given molar ratios shown in Table 5 in 20mL glass vials. The solutions are heated using a heat gun for approximately 1 minute to give homogeneous solutions. Molar ratio of 83:1 and 100:1 yielded cloudy solutions. Molar ratio of 150:1 and above gave clear solutions. Polymer are prepared by adding 4.5 g PES to a 10 g capacity plastic jar, adding 0.5 g acid:salt solution, and mixing the contents for 1 minute at 2500 rpm with a SpeedMixer DAC 150.1 FVZ-K. Approximately 3 g of material is poured out onto an aluminum weighing dish. The remaining material is observed until the material no longer flows under its own weight when the jar was rocked back and forth. The time between addition of the NAB/acid initiator solution and end of flow was recorded as the non-flow time (NFT). Cure quality and Shore D hardness were evaluated for the jar material after overnight cure at ambient conditions. The C=C double bond conversion is measured by FTIR in a manner as described above at differing times shown in Table 5.

Table 1 Table 2

Table 3 ^a 200 ppm of MSA was added to Comp. Ex. 1 to extend pot life long enough to cast tensile specimens. With no added MSA, the pot life would be <1 minute.

Table 4

Table 5

NM = Not measured.