WO2020167621A1

WO2020167621A1 - Particles encapsulated with dicarbonyl-substituted-1- alkenes

Info

Publication number: WO2020167621A1
Application number: PCT/US2020/017413
Authority: WO
Inventors: John Klier; Mengfei HUANG; Mark HOLZER; Jeffrey Sullivan; Aniruddha Palsule; Jeffrey K. UHRIG
Original assignee: Sirrus Inc
Current assignee: Sirrus Inc
Priority date: 2019-02-14
Filing date: 2020-02-10
Publication date: 2020-08-20
Anticipated expiration: 2021-08-14

Abstract

Disclosed are compositions comprising particles encapsulated with 1,1-diester-1-alkene compounds and methods for preparing these compositions. Further disclosed are coatings containing the compositions and methods for using the compositions as coatings.

Description

PARTICLES ENCAPSULATED WITH DICARBONYL-SUBSTITUTED-1- ALKENES

FIELD

[001 ] Disclosed are compositions comprising particles encapsulated with 1 ,1 -dicarbonyl- 1 - alkene compounds and methods for preparing these compositions. Further disclosed are coatings containing the compositions and methods for using the compositions as coatings.

BACKGROUND

[002] Encapsulated particles are used in a wide variety of industries from coatings (encapsulated pigments and fillers), inkjet inks (encapsulated pigments), lighting (encapsulated quantum dots), controlled delivery, plastic additives and many others. Current encapsulation processes are often very difficult, costly or expensive and often difficult to scale.

[003] 1 ,1 -Dicarbonyl-1 -alkenes are compounds which have been known since the 19^th century. Until recently, such compounds have not been commercially viable. Recent advancements in process technology have resulted in technology that facilitates the production of 1 ,1 -dicarbonyl-1 -alkenes on a commercial scale, see Malofsky, et al. US 8,609,885; Malofsky, et al. US 8,884,051 ; Malofsky, et al. US 9,108,914 and Sullivan, et al. US 9,108,914. As a result, a number of applications utilizing these compounds have been developed. One example is disclosed in Stevenson et al. US 9,334,430 which discloses forming a mixture of initiators for 1 ,1 - dicarbonyl-1 -alkenes and 1 ,1 -dicarbonyl-1 -alkenes, polymerizing the 1 ,1 -dicarbonyl-1 -alkenes, quenching the polymers to terminate polymerization and then forming a coating on the formed mixture by polymerizing 1 ,1 -dicarbonyl-1 -alkenes about the particles.

[004] What is needed are encapsulation processes which are facile, cost efficient or and often easy to scale. What is needed are encapsulated particles that provide advantageous properties.

SUMMARY

[005] Disclosed are compositions comprising one or more particles, encapsulated by a polymer comprising one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes; wherein the polymer is bonded to the surface of the particle. The formed structure may have a particle size of about 10 nanometers (nm) to about 10 millimeters (mm). The particles may comprise any particles that can be encapsulated by one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes wherein the particles do not comprise one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes. The particles may be polymers, mixtures of polymers, ceramics, glass, metals, metal oxides, metal salts, naturally occurring or synthetic mixtures of metal based materials (including metals, metal oxides and metal salts which may contain other particulate material in admixture therewith), compounds containing metals, organic compounds, inorganic compounds, mixtures of metal compounds, minerals, carbon based particles, organic pigments, inorganic pigments, biological material, biologically active materials, materials useful for human contact, one or more monomeric compounds, polymer modifiers, corrosion inhibitors, polymerization initiators and catalyst (other than those useful for 1 ,1 -dicarbonylsubstituted~1 -alkenes and one or more polymers and the like. The particles may comprise metals, metal oxides, metal salts, naturally occurring or synthetic mixtures of metal based materials (including metals, metal oxides and metal salts which may contain other particulate material in admixture therewith) organic pigments, inorganic pigments, biological material, biologically active materials, materials useful for human contact, one or more monomeric compounds, polymer modifiers, corrosion inhibitors, polymerization initiators and catalyst (other than those useful for 1 ,1 -dicarbonylsubstituted-1 -a!kenes and one or more polymers). The one or more starting particles may have a particle size of about 10 nm to about 5 mm. The particle may have the polymer comprising one or more 1 ,1 -dicarbonylsubs†ituted-1 -a!kenes bonded to its surface physically or chemically bonded or attached or covalently bonded to a group on the surface of the particle. The particle may comprise a metal oxide, a metal, an inorganic pigment, an organic pigment or a polymer which contains no group at the surface that covalently bonds with the polymer comprising one or more 1 ,1 -dicarbony!substituted-1 -aikenes pendant to the polymer chain. The particles may be unitary in that they contain a single material as described herein. Where the particie is a polymer, the polymer may comprise one or more addition polymers. The particles can be dispersions such as polyurethane, epoxy or polyolefin dispersions. The addition polymer may comprise polymers having polymer chains prepared from monomers having unsaturated groups. The unsaturated groups may be capable of polymerization via free radical or anionic polymerization. The particles may comprise polymers containing polymer chains having unsaturated groups pendant from the polymer chain. The particles may comprise one or more particles of silicon oxide, titanium oxide, aluminum oxide, alkali metal salts, alkaline earth metal salts, transition metal salts, or minerals comprising one or more metals, metal oxides or metal salts. The addition polymers may comprise polymers containing the residue of one or more monomers containing unsaturated groups, including (meth)acry!ates, vinylidene substituted aromatic compounds, olefins, conjugated dienes, unsaturated nitriles, and the like. The particle polymers may have polymer chains having unsaturated groups or nucleophilic groups pendant from the polymer chain. The nucleophilic groups may be any nucleophilic groups which react with the alkene groups of 1 ,1 -dicarbonyl 1 -alkenes. Exemplary nucleophilic groups include hydroxyl, carboxylic acids, amines, benzoic acids, sulfonates, and sulfates and the like. The acids become nucleophilic when at least partially neutralized. Consequently, the acids are nucleophilic when fully neutralized or are deprotonated. The particle polymers may contain about 1 percent by weight or greater of monomers containing nucleophilic functional groups based on the weight of the polymer. The particle polymers may contain from about 1 percent by weight to about 20 percent by weight of the particle polymers of the residue of monomers having nucleophilic functional groups.

[006] The polymer comprising one or more 1 ,1 -dicarbonySsubstituted-1 -a!kenes may comprise the residue of one or more monofunctiona! 1 ,1 -dicarbonylsubstituted-1 -a!kenes and/or multifunctional 1 ,1 -dicarbony!substituted-1 -aikenes. The polymer comprising one or more 1 ,1 - dicarbony!substituted-1 -aikenes may comprise the residue of one or more monofunctional 1 ,1 - dicarbonylsubstituted-1 -alkenes and one or more multifunctional 1 ,1 -dicarbony!substituted-1 - alkenes. The polymer comprising one or more 1 ,1 -dicarbonyi-substituted-1 -alkenes may comprise the residue of multifunctional 1 , 1 -dicarbony! substituted- 1 -alkenes or polyester macromers containing at least one terminal residue of a 1 ,1 -dicarbony!substituted-1 -alkenes. The polymer comprising one or more 1 ,1 -dicarbony!substituted-1 -alkenes containing the residue of multifunctional 1 ,1 -dicarbonyl substituted-1 -a!kenes or polyester macromers containing at least one terminal residue of 1 ,1 -dicarbony!substituted- 1 -alkenes may have groups pendant from the polymer chain which are unsaturated. Such unsaturated groups may be the residue of 1 ,1 dicarbonylsubstituted-1 -alkenes. The polymer comprising one or more 1 ,1 -dicarbonyl-substituted- 1 -alkenes may comprise the residue of one or more 1 ,1 -dicarbony!-substituted-1 -a!kenes having bonded to at ieast one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic polymerization or free radical polymerization, such as hydroxyl alkyl (meth)acry!ates, and the like.

[007] Disclosed are compositions which comprise particles of polymers having polymer chains having unsaturated groups pendant from the polymer chain and the polymer comprising one or more 1 , 1 -dicarbonylsubstituted- 1 -alkenes may contain the residue of one or more monofunctiona! 1 ,1 -dicarbony!substitu†ed-1 -aSkenes and one or more multifunctional 1 ,1 - dicarbonylsubstituted-1 -alkenes wherein the particles are covalently bonded through the pendant unsaturated groups to the polymer comprising one or more 1 ,1 -diearbonylsubstiiuted-l -aikenes. The structure formed may exhibits a core shell structure wherein the core comprises the particle and the shell comprises the polymer comprising one or more 1 ,1 -dicarbonylsubstituted- 1 -alkenes.

[008] The monomers having unsaturated groups may comprise compounds that contain unsaturation in their backbone wherein the unsaturation is capable of polymerization via free radical or anionic polymerization. The monomers having unsaturated groups may comprise one or more acrylates, methacrylates, acrylamides, methacrylamides, vinyl acetates, mono-vinylidene aromatic compounds, olefins, isocyanates, 1 ,1 -dicarbonyl-1 alkenes and conjugated dienes. The monomers having unsaturated groups may comprise one or more acrylates, methacrylates, acrylamides and methacrylamides. The monomers having unsaturated groups may comprise one or more acrylates and/or methacrylates. The monomers having unsaturated groups and functional groups which are nucleophilic may comprise one or more of methacrylic acid, acrylic acid, ethylene acrylic acid, maleic anhydride, 2-Acrylamido-2-methylpropanesulfonic acid, and acetoacetoxyethyl methacrylate. The acids may be partially or completely neutralized or deprotonated.

[009] The multifunctional 1 ,1 -dicarbonyisubstituted- 1 -alkenes may contain two or more 1 ,1 - dicarbonyl alkene groups. The multifunctional 1 ,1 -dicarbonyisubstituted-1 -alkenes comprise one or more compounds prepared from one or more 1 ,1 -dicarbonyl-1 -alkenes and one or more polyols or from two or more 1 ,1 -dicarbonyl-1 -alkenes, one or more polyols and one or more diesters. The compounds containing two or more 1 ,1 -dicarbonyl alkene groups may comprise one or more polyester macromers containing one or more chains of the residue of one or more diols and one or more diesters wherein the residue of the one or more diols and the one or more diesters alternate along the chain and a portion of the diesters are 1 ,1 -diester- 1 -alkenes and at least one terminal end comprises the residue of one of the 1 ,1 -diester-1 alkenes and wherein one or more terminal ends may comprise the residue of one or more diols. The one or more chains of the residue of one or more diols and one or more diesters may contain from 2 to 20 repeating units comprising the residue of at least one diester and one diol. The compounds containing two or more 1 ,1 -dicarbonyl alkene groups may comprise one or more polyester macromers prepared from butane diol and diethyl methylene malonate. The compounds containing two or more 1 ,1 - dicarbonyl alkene groups may comprise one or more compounds prepared from one or more 1 , 1 - dicarbonyl-1 -alkenes and one or more polyols. The compounds containing two or more 1 ,1 - dicarbonyl alkene groups comprise one or more compounds prepared from two 1 , 1 -dicarbonyl- 1 - alkenes and one diol to form a compound wherein the diol is end-capped with the two 1 ,1 - dicarbonyl-1 -alkenes.

[0010] Disclosed is a composition comprising polymers having polymer chains prepared from monomers having unsaturated groups and monomers having unsaturated groups and functional groups which are nucleophilic, wherein the polymer chains are crosslinked by compounds containing two or more 1 ,1 -dicarbonyl alkene groups dispersed in an aqueous dispersion containing one or more surfactants. Any surfactants that form a stable emulsion in water of the recited polymers may be used. The surfactant may be one or more of anionic surfactants or non- ionic surfactants; one or more of non-ionic surfactants. The non-ionic surfactants may increase the rate of polymerization.

[0011] Disclosed is a composition comprising a polymerizable mixture of one or more 1 ,1 - dicarbonylsubstituted-1 -alkenes and one or more 1 , 1 -dicarbonyisubstituied- 1 -aikenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic polymerization or free radical polymerization. The groups capable of anionic polymerization or free radical polymerization include alkenes or dienes, such as conjugated dienes. To enhance polymerization via polymerization the alkene or diene may be adjacent to an electron withdrawing group, such as a carbonyl group. An exemplary class of such compounds includes alkyl (mefh) acrylates having transesterifying groups on the alkyl groups. Exemplary classes of compounds include hydroxyl alkyl (meth)acrylate, g!ycidy! (meth)aerylates, hydroxyl alkyl vinyl ethers and the like. Included in the exemplary compounds are hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyetbyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxylsopropyl acrylate, hydroxyisopropyi methacrylate, hydroxybutyl acrylate, hydroxybutyi methacrylate, hydroxypenty! acrylate, hydroxypentyi methacrylate, 4-hydroxybuty! vinyl ether, and the like. The relative amounts of these monomers are disclosed hereinafter. Also disclosed are copolymers of one or more 1 ,1 - dicarbony!substituted-1 -alkenes and one or more 1 ,1 -dlcarbonylsubstituted-1 -alkenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic polymerization or free radical polymerization. These copolymers have pendant from the polymer chain unsaturated groups. The unsaturated groups may be derived from multifunctional 1 ,1 - dicarbony!substituted-1 -alkenes or from one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic polymerization or free radical polymerization. Disclosed are coatings prepared from the copolymers. The coatings may be deposited on substrates. The substrates may be particles as disclosed herein wherein the coatings may be an encapsulating layer. The substrate may be any other known substrate. The coatings may be cured via free radical polymerization, such as through the use of UV curing and photoinitiators. The coatings may be cured or bonded to substrates or other layers by free radical polymerization, anionic polymerization or Michael Addition of hydroxyl groups or amino groups to the unsaturated groups pendant from the polymer chain. Groups reactive with the copolymers may be located on the surface of the substrates. The coating may be cured by Michael Addition contacting the surface of the coatings with one or more compounds having two or more groups that Michael add to the unsaturated groups pendant from the copolymers under conditions such that Michael additions takes place. Disclosed are substrates having such coatings deposited on their surface wherein the coating may be cured or crosslinked or may be uncured or uncrosslinked. The substrate may contain on its surface nucleophilic groups or groups capable of Michael addition which can initiate polymerization or covalently bond with the copolymers.

[0012] Disclosed is a composition comprising a substrate having nucleophilic groups or unsaturated groups on its one or more surfaces, on one of more surfaces of the substrate is polymer derived from one or more 1 ,1 -dicarbonyisubstituted-1 -alkenes wherein at least one of the 1 ,1 -dicarbony!substituied-1 -a!kenes is one or more multifunctional 1 ,1 -dicarbony!substituted-1 - alkenes wherein at least one of the 1 ,1 -dicarbonylsubstituted-1 -a!kenes is one or more multifunctional 1 ,1 -dicarbonyisubstituted-1 -a!kenes or one or more 1 ,1 -dicarbony!substituted-l - aikenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterificafion and an unsafurated group capable of anionic polymerization or tree radical polymerization; wherein the polymer is covalently bonded to the at least one surface of the substrate. The polymer derived from one or more 1 ,1 - dicarbonylsubstituted-1 -alkenes may be cured or cross-linked or has bonded to its surface one or more monomers or polymers having unsaturated groups or Michael Addition donor groups.

[0013] The substrate may have on one or more of its surfaces nucleophilic groups. At least one of the 1 ,1 -dicarbonyisubstituted-1 -a!kenes may be one or more 1 ,1 -dicarbonylsubstituted-1 - alkenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterificafion and an unsafurated group capable of anionic polymerization or free radical polymerization. At least one of the 1 ,1 - dicarbonylsubstituted-1 -alkenes may be one or more 1 ,1 -dicarbonylsubstituted-1 -aikenes having bonded to at least one of the carbonyl groups the residue of a hydroxyalkyl acrylate. The surface of the polymer layer may be cured. The surface of the polymer layer may be cured by free radical polymerization or anionic polymerization. The composition may have bonded to the surface of the polymer layer is a polymer prepared from monomers or oligomers having unsaturated groups capable of free radical polymerization. The monomers or oligomers having unsaturated groups may be monomers or oligomers having (meth) acrylate groups. The one or more 1 ,1 - dicarbony!substituted-1 -alkenes may contain one or more multifunctional 1 ,1 - dicarbonylsubstituted-1 -alkenes. The composition may have bonded to the surface of the polymer derived from one or more 1 , 1 -dicarbonylsubstituted-1 -aikenes a compound having two or more Michael Addition donor groups. The Michael Addition donor groups comprise functional groups containing active hydrogen atoms. The Michael Addition donor groups may comprise amines, hydroxyl, thiol, or mixtures thereof. The compound having two or more Michael Addition donor groups may be one or more polymers having pendant Michael Addition donor groups. The one or more polymers having pendant Michael Addition donor groups may be one or more of acrylic polyols, amine modified acrylic polyols, polycarbonate polyols, modified acrylic copolymer polyols, polyester polyols, polyether polyols and siloxane polyols. The one or more polymers having pendant Michael Addition donor groups may be one or more acrylic polyols or amine modified acrylic polyols. The one or more polymers having pendant Michael Addition donor groups may be one or more acrylic polyols or amine modified acrylic polyols. The substrate may be a particle or have a defined shape.

[0014] Disclosed is a method comprising contacting one or more of the particles as disclosed herein with one or more 1 ,1 -dicarbonylsubstituted-l -alkenes in an aqueous medium having a pH of from about 4 to about 12 with agitation under conditions such that a polymer of the one or more 1 ,1 -dicarbonyisubstituted-1 -a!kenes is formed about the particle and the polymer is bonded to the surface of the particle. The contacting may take place at a temperature of about 0 ^QC to about 100 ^SC. The particles and the one or more 1 , 1 -dicarbonyisubstituted- 1 -alkenes may be contacted for about 1 hour greater. The particles in water before contacting the particles with the one or more 1 ,1 -dicarbonyisubstituted-1 -a!kenes. The process may be performed in the presence of surfactant in the water at a concentration of about 0.01 percent by weight to about 0.3 percent by weight based on weight of the emulsion.

[0015] Disclosed is method a comprising contacting the formed particles or coated substrates as disclosed herein with a free radical initiator under conditions such that the composition undergoes free radical polymerization. The formed particles or substrates may have unsaturated groups on their surface. The initiator may be a photoinitiator and the composition may be exposed to a source of UV light under conditions such that the composition undergoes free radical polymerization. The structure formed may be a film, coating, sheet or particle and the like.

[0016] Disclosed is a method of forming a coating on a substrate comprising applying to the surface of the substrate a composition as disclosed hereinbefore and exposing the composition to conditions under which the unsaturated groups at the surface of the composition undergo free radical or anionic polymerization or Michael addition. Such sub-strates may have unsaturated groups on the surface. The composition may be contacted with a substrate at ambient or elevated temperatures. The composition may be contacted with a substrate at temperatures of about of about 20 °C to about 150 °C or about 20 °C to about 50 °C. [0017] Disclosed is an article having a coating containing the compositions and/or particles as disclosed herein deposited thereon and optionally crosslinked as disclosed herein. The article may have a base coat upon which the coating formulation is deposited. The base coat may contain pigments. The base coat may have a basic pH at the surface. The pigments may be basic. The base coat may have amine groups or hydroxyl groups on the surface that may help with the cure process and adhesion of the coating to the substrate. The coating may be clear. The coating may contain pigments or other known ingredients used in coatings.

[0018] The encapsulated particles disclosed herein may have a polydispersity index of 1.0 or less, 0 50 or less, or 0 40 or less. The particles may be monomodal. The encapsulation process is very simple involving simply contacting of the core particle with the monomer. The encapsulation can be covalent or non-covalent in nature. The encapsulating polymer can provide additional functionality to crosslink or further derivatize the shell. The encapsulation can be initiated directly from the particle surface, therefore reducing or minimizing the side reactions in the aqueous phase. The encapsulation can be done in water or in solvent or potentially in a spray process. The shell can have a variety of properties including molecular weight, glass transition temperature. These properties can be tuned. In principle the core can be liquid or solid, organic or inorganic, and the method is extremely versatile.

DESCRIPTION OF FIGURES

[0019] Figure 1 illustrates the particle size distribution of latex particles encapsulated with polyDEMM .

[0020] Figure 2 illustrates the gel content of UV-curable coating film with the encapsulation HEM A- MM of from 0 to 10 wt%.

[0021] Figure 3 illustrates the results of hardness test of films before and after UV crosslinking.

[0022] Figure 4 illustrates a graph of the contact angle of particles v DEMM content.

[0023] Figure 5 illustrates Fourier-transform infrared (FTIR) spectroscopy diagram.

[0024] Figure 6 illustrates swelling results for methacrylate particles encapsulated by polymers of hydroxylethylmethacrylate modified DEMM.

[0025] Figure 7 illustrates a graph of the glass transition temperature of non-crosslinked and crosslinked films prepared from particles encapsulated with mixtures of DEMM and hydroxyl ethyl methacrylate modified DEMM.

[0026] Figure 8 shows the stress strain, Youngs Modulus and yield strength of cross-linked and non-crosslinked films. [0027] Figure 9 shows dynamic light scattering data which provides the size distribution of the control latex particles (red line) and the latex with the addition of 40 wt% DEMM (green line).

[0028]

DETAILED DESCRIPTION

[0029] The explanations and illustrations presented herein are intended to acquaint others skilled in the art with the disclosure, its principles, and its practical application. The specific embodiments of the present disclosure as set forth are not intended to be exhaustive or limiting of the invention. The scope of the disclosure should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. Other combinations are also possible as will be gleaned from the following claims, which are also hereby incorporated by reference into this written description.

[0030] Unless defined otherwise, all technical and scientific terms used herein have the meaning commonly understood by a person skilled in the art to which this disclosure belongs. The following references provide one of skill with a general definition of many of the terms used in this disclosure: Singleton et at., Dictionary of Microbiology and Molecular Biology (2nd ed. 1994); The Cambridge Dictionary of Science and Technology (Walker ed., 1988); The Glossary of Genetics, 5th Ed., R. Rieger et al. (eds.), Springer Verlag (1991 ); and Hale & Marham, The Harper Collins Dictionary of Biology (1991 ). The following terms have the meanings ascribed to them below, unless specified otherwise.

[0031] Compounds containing 1 ,1 -dicarbonyl 1 -alkenes are compounds that contain two carbonyl groups and a double bond bonded to a single carbon atom referred to as the one carbon atom. The carbonyl groups may be separately in each occurrence bonded to hydrocarbyl groups through a direct bond, oxygen or amino groups. A 1 ,1 -diester- 1 -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.

[0032] The term“monofunctional” refers to the 1 ,1 -dicarbonyl-1 -alkenes, such as 1 , 1 -diester- 1 -alkenes, having only one core unit. The core unit comprises two carbonyl groups and a double bond bonded to a single carbon atom located between the carbonyl groups. The term “difunctional” refers to the 1 ,1 -dicarbonyl 1 -alkenes, such as 1 ,1 -diester-1 -alkenes, having two core units (each including the reactive alkene functionality) bound through a hydrocarbylene linkage between one oxygen atom on each of two core formulas. The term“multifunctional” refers to the 1 ,1 -dicarbonyl 1 -alkenes such as 1 ,1 -diester-1 -alkenes having two or more core units (each core unit including the reactive alkene functionality) bound together through a hydrocarbylene linkage between one oxygen atom on each of two or more core formulas.

[0033] Acid catalyst, as used herein, is an acidic species that catalyzes the transesterification reaction while minimizing or not contributing to side reactions. One or more as used herein means that at least one, or more than one, of the recited components may be used as disclosed. Nominal as used with respect to functionality refers to the theoretical functionality; generally, this can be calculated from the stoichiometry of the ingredients used. Heteroatom refer to atoms that are not carbon or hydrogen such as nitrogen, oxygen, sulfur, and phosphorus; heteroatoms may 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. As used herein percent by weight or parts by weight refer to, or are based on, the weight or the compounds or compositions described unless otherwise specified. Unless otherwise stated parts by weight are based 100 parts of the relevant composition.

[0034] The terms "volatile" refers to compounds which are capable of evaporating readily at normal temperatures and pressures.“Non-volatile” refers to compounds which are not capable of evaporating readily at normal temperatures and pressures. The term“stabilized” ( in the context of “stabilized” 1 ,1 -dicarbonyl 1 -alkenes, such as 1 ,1 -diester-1 - alkenes, or compositions comprising the same,) refers to the tendency of the compounds (or their compositions) to substantially not polymerize with time, to substantially not harden, form a gel, thicken, or otherwise increase in viscosity with time, and/or to substantially show minimal loss in cure speed (cure speed is maintained) with time. Residue with respect to an ingredient used to prepare the compositions disclosed herein means that portion of the ingredient, such as a polyol, a diol, a diester, a 1 ,1 -dicarbonyl-1 -alkene, a dihydrocarbyl dicarboxylate and/or monomers as disclosed herein, that remains in the compound after inclusion as a result of the methods disclosed herein. Substantially all as used herein that greater than 95 percent of the referenced parameter, composition or compound meet the defined criteria, greater than 99 percent of the referenced parameter, composition or compound meet the defined criteria, or greater than 99.5 percent of the referenced parameter, composition or compound meet the defined criteria cured coating as described herein or the number of nucleophilic groups as described herein. Minerals are naturally occurring inorganic materials. Many minerals may contain one or more metals or metal ions.

[0035] Disclosed are particles encapsulated by polymers prepared from one or more 1 ,1 - dicarbonyl 1 -alkenes. Disclosed are processes for preparing the encapsulated particles. Any encapsulation process which facilitates formation of polymers comprising one or more 1 ,1 - dicarbonyl 1 -alkenes about the particles may be utilized to prepare the encapsulated particles. Emulsion polymerization of the 1 ,1 -dicarbonyl 1 -alkenes about the particles may be used.

[0036] The particles encapsulated may be any particles that can tolerate the encapsulation conditions as described herein. The particles can be unitary or a mixture of different materials. The particles may be polymers, mixtures of polymers, ceramics, glass, metals, metal oxides, metal salts, naturally occurring or synthetic mixtures of metal based materials (including metals, metal oxides and metal salts which may contain other particulate material in admixture therewith), compounds containing metals, organic compounds, inorganic compounds, mixtures of metal compounds, minerals, carbon based particles, organic pigments, inorganic pigments, biological material, biologically active materials, materials useful for human contact, one or more monomeric compounds, polymer modifiers, corrosion inhibitors, polymerization initiators and catalysts (other than those useful for 1 ,1 -dicarbonyisubstituted- 1 -alkenes) and one or more polymers and the like. Particles of metal compounds may comprise metal oxides, metal sulphates, metal silicates, metal carbonates, and the like. Particles may comprise elemental metals. Particles may comprise minerals. Exemplary minerals include clays, calcined clays, talc and the like. Clays include kaolin and the like. Carbon based particles include carbon black, graphene, carbon nanotubes and the like. Inorganic pigments may include metal oxides, chromates, molybdates, phosphates, silicates, effect pigments, carbon black, ocher, sienna, umber, hematile, limonite, barium sulfate, zinc phosphate, calcium carbonate, talc, barytes, and the like. Organic pigments may include metallized and non-metallized azo reds, quinacridone reds and violets, perylene reds coppers, phthalocyanine blues and greens, carbazole violet, monoarylide and diarylide yellows, benzimidazolone yellows, tolyl orange, naphthol orange, and the like.

[0037] The particles may be microorganisms, enzymes, antibodies, proteins, agricultural chemicals, genes, exogenous DNA, seeds, essential oils and other agents for agriculture and aquaculture, biocides. The particles may be bioactive molecules (antioxidants, minerals, vitamins, phytosterols, lutein, fatty acids, lycopene, peptides, oils, micronutrients), living cells (probiotics, enzymes, yeast cells), insecticides, herbal extracts, skin moisturizing agents (pyrrolidone carboxylic acid), skin cooling agents, vitamins, aloe vera, essential oils (lavender, rosemary, pine, etc.), therapeutic oils, anti-microbial agents, anti-aging agents, thermo-chromatic dyes, biologically active substances (glycolic acids, alpha hydroxy acids, salicylic acid, alcohols, steroid, risperidone, testosterone, etc.), cosmetic ingredients (antioxidants, sun filter, fragrances, moisturizers, anti-aging, tanning, whitening agents, thermo-sensitive agents, active drugs, anti inflammatory agents, osmotic pressure regulating agents (LHRH derivatives), immunologically active substances (vaccines), enzymes, Hormones (calcitonin), antigens, peptides, plasmid DNA, corrosion inhibitors, pH-sensitive compounds, self-healing materials, film-forming agents and the like.

[0038] Polymer particles may comprise particles of any polymers that can withstand encapsulation conditions. The polymers may comprise polyolefins, polycarbonates, polystyrene polymers and copolymers, polycarbonates, copolymers of carbonates and esters, polyethers, polyamides, poly(meth)acrylates, polyurethanes, polyureas, polyesters, polysiloxanes, polyimides, polyetherketones, polysulfones, polymers of 1 ,1 -dicarbonyl 1 -alkenes, mixtures thereof and the like. The polymers may comprise polyolefins, polycarbonates, polystyrene polymers and copolymers, polycarbonates, copolymers of carbonates and esters, polyethers, polyamides, poly(meth)acrylates, polyurethanes, polyureas, polyesters, polysiloxanes, polyimides, polyetherketones, polysulfones, mixtures thereof and the like. The particle polymers may have polymer chains having unsaturated groups and/or nucleophilic groups pendant from the polymer chain. Any of polymers which can form particles and which have pendant unsaturated groups and/or nucleophilic groups may be utilized in the particles. The nucleophilic groups may be any nucleophilic groups which react with the alkene groups of 1 ,1 -dicarbonyl 1 -alkenes. The nucleophilic groups may be any nucleophilic groups which initiate anionic polymerization of the alkene groups of 1 ,1 -dicarbonyl 1 -alkenes. The unsaturated groups may be capable of polymerization via free radical or anionic polymerization.

[0039] Exemplary nucleophilic groups include carboxylic acid, carboxylate, alcohol, phenol, amine, aniline, imidazole, tetrazole, thiol, boronic acid, glycol, hydrazine and hydroxyl amine groups. Nucleophilic groups may be carboxylic acid groups. The acids become nucleophilic when at least partially neutralized or are deprotonated. Consequently, the acids may be nucleophilic when fully neutralized or are deprotonated. The acceptable level of neutralization is the level of neutralization at which an acceptable level of grafting of the 1 ,1 -dicarbonyl 1 -alkenes to the particles occur. An acceptable level of grafting is that level that provides the desired properties for the encapsulated particles as described herein or the number of nucleophilic groups as described herein. The one or more unsaturated compounds containing nucleophilic groups may be (meth) acrylic acids, (meth)acrylates, hydroxyalkyl methacrylates, and the like. (Meth) acrylate as used herein refers to compounds having a vinyl group bonded to the carbonyl moiety of an alkyl ester wherein the carbon of the vinyl group bonded to the carbonyl group further has a hydrogen or a methyl group bonded thereto. The term (meth) as used in this context refers to compounds having either of a hydrogen or methyl group on the carbon of the vinyl group bonded to the carbonyl group.

[0040] The particles encapsulated may have any particle size that facilitates the use of the particles in any desired use. The particle size of the encapsulated particles may be about 5 nm or greater, 10 nm or greater, or 1 mm or greater. The particle size of the encapsulated particles may be about 10 mm or less, 5 mm or less, 1 mm or less, 500 nm or less or 400 nm or less. The particle size of the particles to be encapsulated may be about 5 nm or greater, 10 nm or greater, or 1 mm or greater. The particle size of the particles to be may be encapsulated about 10 mm or less, 5 mm or less, 1 mm or less, 500 nm or less or 400 nm or less. The amount of the coating on the encapsulated particles may be 1 percent by weight or greater based on the weight of the encapsulated particle, 5 percent by weight or greater, 10 percent by weight or greater. The amount of the coating on the encapsulated particles may be 50 percent by weight or less based on the weight of the encapsulated particle, 40 percent by weight or less or 10 percent by weight or less.

[0041] The polymer comprising one or more 1 ,1 -dicarbonyisubstituted-1 -aikenes may comprise the residue of one or more monofunctionai 1 ,1 -dicarbony!substituted-1 -a!kenes and/or multifunctional 1 ,1 -dicarbonylsubs†ituted-1 -aikenes. The polymer comprising one or more 1 ,1 - dicarbonylsubstituted-1 -alkenes may comprise the residue of one or more monofunctionai 1 ,1 - dicarbonylsubstituted-1 -alkenes and one or more mu!tifunctional 1 ,1 -dicarbonylsubstituted-l - a!kenes. The polymer comprising one or more 1 , 1 -dicarbonyl substituted- 1 -aikenes may comprise the residue of multifunctional 1 ,1 -dicarbonyl substituted- 1 -aikenes or polyester macromers containing at least one terminal residue of a 1 ,1 -dicarbonylsubstituted-l -aikenes. The polymer comprising one or more 1 ,1 -dicarbonyisubstituted-l -aikenes containing the residue of multifunctional 1 ,1 -dicarbonyl substituted- 1 -aikenes or polyester macromers containing at least one terminal residue of 1 ,1 -dicarbonylsubstituted-l -aikenes may have groups which are pendant from the polymer chain which are unsaturated. Such unsaturated groups may be the residue of 1 ,1 -dicarbonylsubstituted-l -aikenes. The polymer comprising one or more 1.1 -dicarbonyl substituted-1 -aikenes may comprise the residue of one or more 1 ,1 -dicarbonyisubstituted-1 - alkenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic polymerization or free radical polymerization, such as a hydroxyl alkyl (meth)acryiate, and the like.

[0042] The 1 ,1 -dicarbonyl-1 -alkenes, such as 1 ,1 -diester-1 -alkenes, comprise a central carbon atom referred to as the 1 carbon atom. Bonded to the 1 carbon atom are carbonyl groups and another carbon atom via a double bond. The double bond, due to being bonded to two carbonyl groups, is highly reactive. The doubly bonded carbons may be part of an alkenyl group that is highly reactive. The alkenyl group may be a C 2-4 alkenyl group, or a methylene group (C=C). The di-carbonyl compounds contain hydrocarbyl groups bonded to directly to the carbonyl groups or to an oxygen or nitrogen bonded to the carbonyl groups wherein the hydrocarbyl groups may contain one or more heteroatoms, including heteroatom containing functional groups. The heteroatom functional groups may contain unsaturated groups that are capable of free radical or anionic polymerization. The hydrocarbyl groups can be any hydrocarbyl groups that can undergo transesterification under the conditions disclosed herein. The hydrocarbyl groups on the ester may be separately in each occurrence alkyl, alkenyl, cycloalkyl, heterocyclyl, alkyl heterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, alkheteroaryl, or polyoxyalkylene, or both of the hydrocarbyl groups may form a 5-7 membered cyclic or heterocyclic ring. The hydrocarbyl groups on the ester may be separately in each occurrence C1 -C15 alkyl, C2-C15 alkenyl, C3-C9 cycloalkyl, C2-20 heterocyclyl, C3-20 alkheterocyclyl, Ce-18 aryl, C7-25 alkaryl, C 7-25 aralkyl, C5-18 heteroaryl or C6-25 alkyl heteroaryl, or polyoxyalkylene, or both hydrocarbyl groups form a 5-7 membered cyclic or heterocyclic ring. The recited groups may be substituted with one or more substituents, which do not interfere with the use of these compounds as described herein. Exemplary substituents include halo, alkylthio, alkoxy, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, ester or unsaturated groups. The hydrocarbyl groups connected to the carbonyl group may be separately in each occurrence C1 -C15 alkyl, C3-C6 cycloalkyl, C4-18 heterocyclyl, C4-18 alkheterocyclyl, C6-18 aryl, C7-25 alkaryl, C7-25 aralkyl, C5-18 heteroaryl or C6-25 alkyl heteroaryl, or polyoxyalkylene. The hydrocarbyl groups connected to the carbonyl group may be separately in each occurrence a C1-6 alkyl. The hydrocarbyl groups connected to the carbonyl group may be separately in each occurrence methyl, ethyl, propyl, butyl, pentyl or hexyl. The hydrocarbyl groups connected to the carbonyl group may be the same for each ester group on the 1 ,1 -dicarbonylsubstituted-1 -alkene compounds. Exemplary compounds are dimethyl, diethyl, ethylmethyl, dipropyl, dibutyl, dihexyl, dicyclohexyl diphenyl, and/or ethyl-ethylgluconate malonates. The compounds may be dimethyl, diethyl dihexyl, and/or dicyclohexyl methylene malonates. The 1 ,1 -dicarbonyl substituted- 1 - alkenes can be prepared as disclosed in Malofsky et al., US 8,609,885 8,884,051 , 9,221 ,739 and 9,527,795; and Malofsky et al. US 9,108,914.

[0043] The 1 ,1 - dicarbonylsubstituted -1 -alkene compounds may correspond to formula 1 :

R¹ is separately in each occurrence a group that can undergo replacement or transesterification under the conditions of the methods disclosed herein. R¹ may be separately in each occurrence alkyl, alkenyl, cycloalkyl, heterocyclyl, alkyl heterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, or alkyl heteroaryl, or polyoxyalkylene, or both R¹s form a 5-7 membered cyclic or heterocyclic ring. R¹ may be separately in each occurrence C1 -C15 alkyl, C2-C15 alkenyl, C3-C9 cycloalkyl, C2-20 heterocyclyl, C3-20 alkyl heterocyclyl, O_b-ib aryl, C7-25 alkaryl, C 7-25 aralkyl, C5-18 heteroaryl or C6-25 alkyl heteroaryl, or polyoxyalkylene, or both Ri groups form a 5-7 membered cyclic or heterocyclic ring. The recited groups may be substituted with one or more substituents, which do not interfere with the uses of these compounds as disclosed herein. Exemplary substituents include halo alkylthio, alkoxy, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, ester or unsaturated groups. R¹ may be separately in each occurrence C1 -C15 alkyl, C3-C6 cycloalkyl, C4-18 heterocyclyl, C4-18 alkheterocyclyl, O_b-ib aryl, C7-25 alkaryl, C7-25 aralkyl, C5-18 heteroaryl or C6-25 alkyl heteroaryl, or polyoxyalkylene. R¹ may be separately in each occurrence a C1 -6 alkyl or C_5-6 cycloalkyl. R¹ may be separately in each occurrence methyl, ethyl, hexyl, or cyclohexyl. R¹ may be the same or different for each ester group on the 1 , 1 -disubstituted alkene compounds.

[0044] The 1 ,1 -disubstituted alkene compounds may be methylene malonates which may correspond to formula 2:

wherein R¹ is as described herein before.

[0045] The one or more 1 ,1 -dicarbonyisubsti†u†ed-1 -a!kenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic polymerization or free radical polymerization. These compounds are prepared by transesterifying 1 ,1 -dicarbonyl 1 - alkenes with a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic polymerization or free radical polymerization. The groups capable of transesterifying 1 ,1 -dicarbonyl 1 - alkenes include may hydroxyl groups, glycidyl groups and the like. The groups capable of anionic polymerization or free radical polymerization include alkenes or dienes, such as conjugated dienes. To enhance polymerization via anionic polymerization the alkene or diene may be adjacent to an electron withdrawing group, such as a carbonyl group. An exemplary class of such compounds includes alkyl (meth) acrylates having transesterifying groups on the alkyl groups. Exemplary classes of compounds include hydroxyl alkyl (meth)acrylate, glycidyl (meth)acryiates, hydroxyl alkyl vinyl ethers and the like included in the exemplary compounds are hydroxymethyl acrylate, hydroxymethyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyi acrylate, hydroxypropyl methacrylate, hydroxyisopropyl acrylate, hydroxyisopropyi methacrylate, hydroxybuty! acrylate, hydroxybutyl methacrylate, hydroxypentyl acrylate, hydroxypentyl methacrylate, 4-hydroxybuty! vinyl ether, and the like.

[0046] The 1 ,1 -dicarbonyl-1 -alkene compounds having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic, cationic polymerization or free radical polymerization may correspond to formula 3:

wherein R¹ and R^a are as defined herein and p is separately in each occurrence an integer of 1 or greater, 1 to 6, 2 to 4, or 2.

[0047] The one or more multifunctional 1 ,1 -diearbonylsubstituted-l -alkenes include compounds which contain two or more 1 ,1 -dicarbonyl 1 -alkene groups, and may be difunctional compounds containing 1 ,1 -dicarbonyl 1 - alkene groups or multifunctional compounds containing 1 ,1 -dicarbonyl 1 - alkene groups. Such compounds may comprise two or more 1 ,1 -dicarbonyl 1 - alkene groups connected by the residue of a diol or polyol capable of transesterifying 1 ,1 - dicarbonyl 1 - alkenes.

[0048] Compounds which contain two or more 1 ,1 -dicarbonyl 1 -alkene groups may be polyesters which contain one or more chains containing the residue of one or more diols and one or more diesters wherein a portion of the diesters comprise 1 ,1 -diester-1 -alkenes. The residue of the diols and the diesters can alternate along the chains or can be disposed randomly along the chains. The diesters may further comprise any diester compound that will undergo transesterification with a polyol or diol. Among diester compounds are dihydrocarbyl dicarboxylates. The polyesters may have three or more chains as described. The polyesters having three or more chains contain the residue of a polyol originally having three or greater hydroxyl groups. The three or more chains propagate from each of the three or more hydroxyl groups. The polyols having three or more hydroxyls function as initiators from which each of the chains of the polyester macromers propagate. If the polyol is a diol a single chain is produced because the poyester formed is linear. Where a polyol having three or more hydroxyls is used to prepare the polyester, it may have two or more chains as not all of the hydroxyls may propagate chains. The polyesters may contain one or more chains, may contain two or more chains, or may contain three or more chains. The polyesters may contain eight or less chains, six or less chains, four or less chains or three or less chains. The chains may comprise the residue of one or more polyols, one or more diols and one or more diesters, including one or more 1 ,1 -diester-1 - alkenes and optionally one or more dihydrocarbyl dicarboxylates. The chains may comprise the residue of one or more diols and one or more diesters, including one or more 1 ,1 -diester- 1 -alkenes and optionally one or more dihydrocarbyl dicarboxylates. The polyesters contain the residue of at least one 1 ,1 -diester-1 -alkenes at the terminal end of one of the chains. The polyesters may further comprise one or more diols or dihydrocarbyl dicarboxylates at the terminal end of one or more of the chains. Substantially all or all of the terminal ends of chains may be 1 ,1 -diester-substituted alkenes.

[0049] The polyesters may correspond to Formula 4

wherein Z is separately in each occurrence -R²OH or -Ft¹ ; Ft¹ is separately in each occurrence a hydrocarbyl group which may contain one or more heteroatoms; Ft² is separately in each occurrence a hydrocarbylene group having two or more bonds to oxygen atoms; c is an integer of 1 or more; and n is an integer of about 1 to 3. With respect to Ft² the bonds to oxygen atoms may include bonds to the oxygen of a polyol, a diol, or a diester or the residue thereof depending on the context of use of Ft².

[0050] The polyester may contain one chain of the residue of one or more diols and one or more diesters. These polyester macromers may correspond to Formula 5,

wherein Z, R¹ and R² are as previously defined; and m is an integer of about 1 to 3.

[0051] The polyesters containing the residue of one or more 1 ,1 -diester- 1 -alkenes and the residue of one or more dihydrocarbyl dicarboxylates may correspond to one of Formulas 6 to 9:

wherein D corresponds to the formula

[0052] wherein E corresponds to the formula,

wherein Z, R¹ , R² and m are as previously defined; R³ is separately in each occurrence a hydrocarbylene group having two bonds to the carbonyl groups of one or more of the diesters or to the residue of such diesters depending on the context, wherein the hydrocarbylene group may contain one or more heteroatoms; c is an integer of 1 , or 2 or more; d is an integer of 0 or 1 ; e is an integer of 0 or 1 ; f is the integer 1 ; n is an integer of about 1 to 3; p is an integer of 2 or more; and q is an integer of 1 or more; wherein each pair of d and e must equal 1 . p may be an integer of 3 or greater p may be an integer of 8 or less, 6 or less or 3 less q may be an integer of 4 or less or 3 or less.

[0053] The polyesters may contain in their backbone repeating units comprising the residue of at least one diester and one diol. A significant portion of the diesters are 1 ,1 -diestersubstituted- 1 -alkenes. A portion of the diesters may be 1 ,1 - dihydrocarbyl dicarboxylates. The backbone of polyesters contain a sufficient number of repeating units comprising the residue of at least one diester and one diol to facilitate the use of the polyester macromers as disclosed herein. The number of repeating units comprising the residue of at least one diester and one diol in polyester macromers may be 2 or greater, 4 or greater or 6 or greater. The number of repeating units comprising the residue of at least one diester and one diol in polyester macromers may be 20 or less, 14 or less, 10 or less, 8 or less, 6 or less, or 4 or less. The diesters in some polyester macromers can be all 1 ,1 -diester-1 -alkenes. The diesters in some polyesters can be 1 ,1 -diester- 1 -alkenes and dihydrocarbyl dicarboxylates. The molar ratio of 1 ,1 -diester- 1 -alkenes and dihydrocarbyl dicarboxylates in some polyesters is selected to provide the desired degree of crosslinking in structures prepared from the polyester macromers. The molar ratio of 1 ,1 -diester- 1 -alkenes and dihydrocarbyl dicarboxylates in polyesters may be 1 :1 or greater, 6:1 or greater or 10:1 or greater. The molar ratio of 1 ,1 -diestersubstituted- 1 -alkenes and dihydrocarbyl dicarboxylates in the polyesters may be 15:1 or less, 10:1 or less, 6:1 or less or 4 :1 or less. The polyesters may exhibit a number average molecular weight of about 700 or greater, about 900 or greater, about 1000 or greater or about 1200 or greater. The polyesters may exhibit a number average molecular weight of about 3000 or less, about 2000 or less or about 1600 or less. Number average molecular weight as used herein is determined dividing total weight of all the polymer molecules in a sample, by the total number of polymer molecules in a sample. The polydispersity of the polyesters may be about 1 .05 or greater or about 1 .5 or greater. The polydispersity of the polyesters may be about 4.5 or less or about 2.5 or less, about 2.5 or less or about 1 .5 or less. For calculating the polydispersity the weight average molecular weight is determined using gel permeation chromatography using polymethylmethacrylate standards. Polydispersity is calculated by dividing the measured weight average molecular weight (M_v) by the number average molecular weight (M_n), that is M_v/ M_n.

[0054] The polyesters may be prepared from 1 ,1 -diester-1 -alkenes, diols, polyols and/or dihydrocarbyl dicarboxylates. The choice of specific ingredients, ratios of ingredients and sequence of process steps impact the final structure and content of the polyesters. The polyesters disclosed may be prepared as disclosed in US 9,617,377 incorporated herein by reference in its entirety.

[0055] Polyols useful in preparing difunctional compounds containing 1 ,1 -dicarbonyl 1 - alkene groups, multifunctional compounds containing 1 ,1 -dicarbonyl 1 - alkene groups and polyesters disclosed herein are compounds having a hydrocarbylene backbone with two or more hydroxyl groups bonded to the hydrocarbylene backbone and which may be capable of transesterifying ester compounds under the transesterification conditions disclosed herein. Polyols useful herein fall in two groups. The first group are diols which have two hydroxyl groups bonded to a hydrocarbylene backbone and which function to both initiate and extend the chains of the polyester macromers. Polyols with greater than two hydroxyl groups bonded to the hydrocarbylene backbone may function to initiate more than two chains. Diols may also function to extend the more than two chains. The polyols may have from 2 to 10 hydroxyl groups, from 2 to 4 hydroxyl groups or from 2 to 3 hydroxyl groups. The backbone for the polyols, including diols, may be alkylene, alkenylene, cycloalkylene, heterocyclylene, alkyl heterocyclylene, arylene, aralkylene, alkyl arylene, heteroarylene, alkyl heteroarylene, or poly-oxyalkylene. The backbone may be C1 -C15 alkylene, C2-C15 alkenylene, C3-C9 cycloalkyene, C 2-20 heterocyclylene, C 3-20 alkheterocyclylene, Ce-18 arylene, C7-25 alkarylene, C7-25 aralkylene, C5-18 heteroarylene, C6-25 alkyl heteroarylene or polyoxyalkylene. The alkylene sections may be straight or branched. The recited groups may be substituted with one or more substituents that do not interfere with the transesterification reaction. Exemplary substituents include halo alkylthio, alkoxy, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester. The backbone may be C 2-10 alkylene groups. The backbone may be a C 2-8 alkylene group, which may be straight or branched, such as ethylene, propylene, butylene, pentylene, hexylene, 2-ethyl hexylene, heptylene, 2,2-methyl, 1 ,3-propylene, 2-methyl 1 ,3 propylene or octylene. The diols having a methyl group at the 2 position of an alkylene chain may be used. Exemplary diols include ethane diol, propane diol, butane diol, pentane diol, hexane diol, 2 ethyl hexane diol, heptane diol, octane diol, neopentyl glycol (2,2- methyl, 1 ,3-propane diol), 2-methyl 1 ,3 propane diol, 2-butyl- 1 ,3-propane diol, 2-ethyl-1 ,3- 2_/_oH propane diol and 1 ,4- cyclohexanol. The polyol may correspond to formula 10 '^c ; and the diol may correspond to formula 1 1 : HO— R²— OH

wherein R² is separately in each occurrence a hydrocarbylene group having two or more bonds to the hydroxyl groups of a polyol. R² may be separately in each occurrence alkylene, alkenylene, cycloalkylene, heterocyclylene, alkyl heterocyclylene, arylene, aralkylene, alkarylene, heteroarylene, alkyl heteroarylene, or polyoxyalkylene. R² may be separately in each occurrence C1 -C15 alkylene, C2-C15 alkenylene, C3-C9 cycloalkylene, C 2-20 heterocyclylene, C 3-20 alkheterocyclylene, Ce-18 arylene, C7-25 alkarylene, C7-25 aralkylene, C5-18 heteroarylene, C6-25 alkyl heteroarylene or polyoxyalkylene. The recited groups may be substituted with one or more substituents that do not interfere with the transesterification reaction. Exemplary substituents include halo, alkylthio, alkoxy, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester. R² may be separately in each occurrence a C 2-8 alkylene group, such as ethylene, propylene, butylene, pentylene, hexylene, 2-ethyl hexylene, heptylene, 2-methyl 1 ,3 propylene or octylene. Exemplary C3-C9 cycloalkylenes include cyclohexylene. The alkylene groups may be branched or straight and may have a methyl group on the 2 carbon. Among preferred alkyl arylene polyols are polyols with the structure of -aryl-alkyl-aryl- (such as -phenyl-methyl-phenyl- or -phenyl-propyl- phenyl-) and the like. Among preferred alkyl cycloalkylene poly-yls are those with the structure of -cycloalkyl-alkyl-cycloalkyl- (such as -cyclohexyl-methyl-cyclohexyl- or -cyclohexyl-propyl- cyclohexyl-) and the like. The polyalkylene oxy groups may have alkylene groups of ethylene, propylene or butylene and the butylene groups may be derived from butylene oxides or tetrahydrofuran. c may be an integer of 8 or less, 6 or less, 4 or less or 3 or less c may be an integer of 2 or greater or 3 or greater.

[0056] The one or more dihydrocarbyl dicarboxylates are compounds with two ester groups having a hydrocarbylene group disposed between the ester groups. The one or more dihydrocarbyl dicarboxylates comprise one or more of aromatic dicarboxylates, aliphatic dicarboxylates and cycloaliphatic dicarboxylates or may one or more dihydrocarbyl dicarboxylates wherein one of the hydrocarbyl groups is aliphatic, cycloaliphatic or aromatic and the other may be selected from another class of aliphatic, cycloaliphatic or aromatic groups. The one or more dihydrocarbyl dicarboxylates comprise one or more of aromatic dicarboxylates having 8 to 14 carbon atoms in the backbone, aliphatic dicarboxylates having 1 to 12 carbon atoms in the backbone and cycloaliphatic dicarboxylates having 8 to 12 carbon atoms in the backbone. The one or more dihydro-carbyl dicarboxylates comprise one or more malonates, terephthalates, phthalates, iso-phthalates, naphthalene-2, 6-dicarboxylates, 1 ,3-pheny-lenedioxy diacetates, cyclo-hexanedicarboxylates, cyclohexanediacetates, diphenyl-4, 4'-dicarboxylates, succinates, glutarates, adipates, azelates, sebacates, or mixtures thereof. The one or more dihydro-carbyl dicarboxylates may comprise one or more malonates, isophthalates, terephthalates or sebacates. The one or more dihydrocarbyl dicarboxylates may correspond to formula 12:

wherein R¹ is as previously described; and

R³ is separately in each occurrence a hydrocarbylene group having two bonds to the carbonyl groups of the diester wherein the hydrocarbylene group may contain one or more heteroatoms. R³ may be separately in each occurrence arylene, cycloalkylene, alkylene or alkenylene. R³ may be separately in each occurrence C s-i4 arylene, C 8-12 cycloalkylene, C 1 -12 alkylene or C 2-12 alkenylene.

[0057] The multifunctional monomers may be prepared from 1 , 1 -dicarbonyl-alkenes, such as 1 ,1 -diester-1 -alkenes, and polyols, including diols. Multifunctional monomers comprise a polyol wherein at least two of the hydroxyl groups are replaced by the residue of 1 ,1 -diester- 1 -alkenes. Where there are greater than two hydroxyl groups on the polyol it is possible that not all hydroxyl groups react with 1 ,1 -diester- 1 -alkenes. It is desirable to react substantially all the hydroxyl groups with the 1 ,1 -diester-1 -alkenes. The alternatives discussed hereinbefore for the polyols and 1 ,1 - diester-1 -alkenes as far as structure are also applicable to the multifunctional monomers. Where a polyol with 3 or greater hydroxyl groups are used to prepare the multifunctional monomers they correspond to formula 13

where a diol is used to initiate the multifunctional monomers they correspond to formula 14;

wherein R¹ , R² and c are as defined hereinbefore. The multifunctional monomers can be prepared as disclosed hereinafter and as disclosed in Malofsky US 2014/0329980 and in Sullivan US 9,416,091 , both incorporated herein in their entirety for all purposes.

[0058] The polyesters macromers may contain a volatile solvent. The volatile solvent may be any solvent that does not react with the components or interfere in the curing of the compositions. The solvents may be volatile at about 50 °C or greater. The solvents may be volatile polar solvents or volatile polar aprotic solvents. The polar solvents may exhibit a boiling point of about 100 °C or greater, about 1 10 °C or greater or about 130 °C or greater. The polar solvents may exhibit a boiling point of about 200 °C or less, about 190 °C or less or about 170 °C or less. The polar solvent may be an alkylene glycol ether, an acetate modified alkylene glycol ether, a ketone, or a mixture of any of these solvents, and the like. The volatile solvents are present in sufficient amount to facilitate use of the compositions as desired. The volatile solvents may be present in an amount of about 0 percent by weight or greater of the composition, about 1 percent by weight or greater, about 5 percent by weight or greater, about 10 percent by weight or greater or about 20 percent by weight or greater. The volatile solvents may be present in an amount of about 50 percent by weight or less of the composition, about 40 percent by weight or less of the composition, about 20 percent by weight or less or about 10 percent by weight or less.

[0059] The particle polymers may be polymers having polymer chains prepared from monomers having unsaturated groups and functional groups which are nucleophilic groups and/or monomers having unsaturated groups. The particle polymers crosslinked may be polymers having polymer chains prepared from monomers having unsaturated groups and functional groups which are nucleophilic groups. The particle polymers may be polymers having polymer chains prepared from mixtures of monomers having unsaturated groups and monomers having unsaturated groups and functional groups which are nucleophilic.

[0060] Monomers having unsaturated groups comprise compounds that contain unsaturation in their backbone wherein the unsaturation is capable of polymerization via free radical or anionic polymerization. The monomers having unsaturated groups may comprise one or more of 1 ,1 - dicarbonyl-1 -alkenes (as disclosed herein), acrylates, methacrylates, acrylamides, methacrylamides, unsaturated nitriles, vinyl esters, vinylidene substituted aromatic compounds, olefins, isocyanates, conjugated dienes, vinyl monomers, N-vinyl pyro!iidone; ailyl methacrylate, vinyl toluene, vinyl benzophenone, dlallyl phthaiate, 1 ,3-buiy!ene glycol dimethacrylate, 1 ,6- hexanedioldiacrylate, and divinyl benzene. The monomers having unsaturated groups may comprise one or more of acrylates, methacrylates, acrylamides, methacrylamides, unsaturated nitriles, vinyl esters, vinylidene substituted aromatic compounds, olefins, isocyanates, conjugated dienes, vinyl monomers, N-vinyi pyrollidone; ally! methacrylate, vinyl toluene, vinyl benzophenone, dia!lyl phthaiate, 1 ,3-butylene glycol dimethacrylate, 1 ,6-hexanedio!diacry!ate, and divinyl benzene. Exemplary vinyl esters include vinyl acetate and vinyl propionate. Exemplary vinyl monomers include vinyl chloride, vinylidene chloride and N-vinyi pyrollidone. Exemplary conjugated dienes include butadiene and isoprene. Unsaturated nitriles include, but are not limited to, acrylonitrile, methacrylonitrile, ethacrylonitrile, fumaronitrile and mixtures thereof. The unsaturated nitrile may be acrylonitrile. The use of the term“(meth)" followed by another term such as acrylate, acrylonitrile, or acrylamide, as used throughout the disclosure, refers to both acrylate, acrylonitrile, or acrylamide and methacrylate, methacrylonitrile, or methacrylamide,

[0061] Vinylidene substituted aromatic monomers comprise vinylidene, alkenyl groups, bonded directly to aromatic structures. The vinylidene substituted aromatic monomers may contain one or more aromatic rings, may contain one or two aromatic rings, or may contain one aromatic ring. The aromatic rings can be unsubstituted or substituted with a substituent that does not interfere with polymerization of the vinylidene substituted aromatic monomers, or the fabrication of the polymers formed into desired structures. The substituents may be halogens or alkyl groups, such as bromine, chlorine or Ci to C₄ alkyl groups; or a methyl group. Alkenyl groups comprise straight or branched carbon chains having one or more double bonds, or one double bond. The alkenyl groups useful for the vinylidene substituted aromatic monomers may include those that when bonded to an aromatic ring are capable of polymerization to form copolymers. The alkenyl groups may have 2 to 10 carbon atoms, 2 to 4 carbon atoms or 2 carbon atoms. Exemplary vinylidene substituted aromatic monomers include styrene, alpha methyl styrene, N- phenyl-maleimide and chlorinated styrenes; or alpha-methyl styrene and styrene. The vinylidene substituted aromatic monomers may be mono-vinylidene aromatic monomers, which contain one unsaturated group. Vinylidene aromatic monomers include but are not limited to those described in U.S. Pat. Nos. 4,666,987; 4,572,819 and 4,585,825, which are herein incorporated by reference.

[0062] (Meth) acrylate as used herein refers to compounds having a vinyl group bonded to the carbonyl moiety of an alkyl ester wherein the carbon of the vinyl group bonded to the carbonyl group further has a hydrogen or a methyl group bonded thereto. The term (meth) as used in this context refers to compounds having either of a hydrogen or methyl group on the carbon of the vinyl group bonded to the carbonyl group. (Meth)acrylates useful include those that correspond to the formula 17:

[0063] wherein R^a is separately in each occurrence H or— CH₃; and R^b may be a C i to C 30 alkyl group or C

alkyl group wherein the alkyl group may contain a nucleophilic group as described herein. The nucleophilic group may be capable of initiating anionic polymerization. Examples of the one or more (meth)acrylates include lower alkyl (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)(acrylate) and hexyl (meth) acrylate; hydroxyethyl methacrylate, hydroxypropyl methacrylate, aminoalkyl (meth)acrylate, N-alkyl aminoalkyl (meth)acrylate, N,N-dialkyl aminoalkyl (meth)acrylate; urieido (meth)acrylate; (meth)acrylonitrile and (meth)acrylamide.

[0064] The polymers crosslinked may contain nucleophilic groups. The nucleophilic groups may be pendant from the polymer chain. The polymers formed may contain the residue of one or more monomers having unsaturated groups and functional groups which are nucleophilic groups. The polymers may be polymers prepared from one or more monomers having unsaturated groups. The polymers maybe copolymers of one or more unsaturated monomer and one or more unsaturated compounds containing one or more nucleophilic groups which comprise the addition reaction product of one or more unsaturated monomers and one or more unsaturated monomers containing one or more nucleophilic groups. The unsaturated monomers containing one or more nucleophilic groups useful are those which can polymerize under free radical or anioinic polymerization conditions. The one or more unsaturated monomers containing one or more nucleophilic groups may contain one nucleophilic group. The copolymers may contain more than one different nucleophilic group or may contain only one species of nucleophilic group. The copolymers may be prepared from more than one unsaturated compound each containing different type of nucleophilic group. The copolymers may be prepared from one species of unsaturated compounds each containing the same nucleophilic group. The one or more copolymers of one or more unsaturated monomers and one or more unsaturated monomers containing one or more nucleophilic groups may contain a mixture of copolymers that contain polymer chains of differing amounts of nucleophilic groups.

[0065] The one or more unsaturated compounds containing nucleophilic groups may contain any nucleophilic group that reacts with compounds containing two or more 1 ,1 -dicarbonyl 1 - alkene groups. Nucleophilic group as used herein is a group which donates an electron pair to make a covalent bond. Exemplary nucleophilic groups include carboxylic acid, alcohol, phenol, hydroxyl, amine, aniline, imidazole, tetrazole, thiol, boronic acid, glycol, hydrazine, hydroxyl amine benzoic acids, sulfonates, and sulfates and the like. Exemplary nucleophilic groups include hydroxyl, carboxylic acids, amines, benzoic acids, sulfonates, and sulfates and the like. Nucleophilic groups may be carboxylic acid groups. The one or more unsaturated compounds containing nucleophilic groups may be (meth) acrylic acids, (meth)acrylates, hydroxyalkyl methacrylates, and the like. The one or more unsaturated compounds containing nucleophilic groups may be methacrylic acid and or acrylic acid. The monomers having unsaturated groups and functional groups which are nucleophilic may comprise one or more (meth)acrylates, one or more acrylamides, (meth)acrylic acids, unsaturated anhydrides and the like. The monomers having unsaturated groups and functional groups which are nucleophilic may comprise one or more of methacrylic acid, acrylic acid, ethylene acrylic acid, maleic anhydride, 2-Acrylamido-2- methylpropanesulfonic acid, and acetoacetoxyethyl methacrylate.

[0066] The amount of one or more unsaturated monomers containing one or more nucleophilic groups is selected to provide the desired level of crosslinking, grafting or encapsulation. The amount of the monomers containing the nucleophilic groups on the one or more copolymers of one or more unsaturated monomers and one or more unsaturated compounds containing a nucleophilic group may be about 0.1 percent by weight of the copolymer or greater based on the weight of the copolymer, about 0.5 percent by weight about 1 .0 percent by weight or greater or about 5 percent by weight or greater. The concentration of the one or more unsaturated monomers containing one or more nucleophilic groups on the one or more copolymers of one or more unsaturated monomers and one or more unsaturated compounds containing nucleophilic groups may be about 100 percent by weight of the copolymer or less greater based on the weight of the copolymer, about 50 percent by weight or less, about 30 percent by weight or less, about 20 percent by weight or less or about 15 percent by weight or less. The copolymers of one or more unsaturated monomers and one or more unsaturated monomers containing a nucleophilic group may contain unsaturated monomers in an amount of about 0 percent by weight or greater of the copolymers, about 1 percent by weight or greater, about 50 percent by weight or greater about 80 percent by weight or greater or about 90 percent by weight or greater. The copolymers of one or more unsaturated monomers and one or more unsaturated compounds containing a nucleophilic group may contain unsaturated monomers in an amount of about 99.5 percent by weight of the copolymers or less, about 99 percent by weight or less, 85 percent by weight or less, 80 percent by weight or less, about 70 percent by weight or less or about 50 percent by weight or less. The copolymers may contain one or more of the unsaturated monomers disclosed herein. The polymer chains alternatively can be any polymers dispersed in water that contain functional groups which are nucleophilic, such as polyolefin dispersions, alkyd dispersions, polyurethane dispersions and epoxy-based dispersions.

[0067] The polymerizable compositions containing monomers may further contain other components to stabilize the compositions prior to exposure to polymerization conditions or to adjust the properties of the final polymer for the desired use. For example, a suitable plasticizer can be included with a reactive composition. Exemplary plasticizers are those used to modify the rheological properties of adhesive systems including, for example, straight and branched chain alkyl-phthalates such as diisononyl phthalate, dioctyl phthalate, and dibutyl phthalate, trioctyl phosphate, epoxy plasticizers, toluene-sulfamide, chloroparaffins, adipic acid esters, sebacates such as dimethyl sebacate, castor oil, xylene, 1 -methyl-2-pyrrolidone and toluene. Commercial plasticizers such as HB-40 partially hydrogenated terpene manufactured by Solutia Inc. (St. Louis, MO) can also be suitable. For example, one or more dyes, pigments, toughening agents, impact modifiers, rheology modifiers, natural or synthetic rubbers, filler agents, reinforcing agents, thickening agents, opacifiers, inhibitors, fluorescence markers, thermal degradation reducers, thermal resistance conferring agents, surfactants, wetting agents, or stabilizers can be included in a polymerizable system. 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. The 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.

[0068] Stabilizers can be included in the monomers to increase and improve the shelf life and to prevent spontaneous polymerization. One or more anionic polymerization stabilizers and or free-radical stabilizers may be added to the compositions. Anionic polymerization stabilizers are generally electrophilic compounds that scavenge bases and nucleophiles from the composition or growing polymer chain. The use of anionic polymerization stabilizers can terminate additional polymer chain propagation. Exemplary anionic polymerization stabilizers are acids, exemplary acids are carboxylic acids, sulfonic acids, phosphoric acids and the like. Exemplary stabilizers include liquid phase stabilizers, such as methanesulfonic acid (“MSA”), and vapor phase stabilizers, such as trifluoroacetic acid (“TFA”). Free-radical stabilizers may include phenolic compounds, such as 4-methoxyphenol or mono methyl ether of hydroquinone (“MeFIQ”) and butylated hydroxy toluene (BFIT)). Stabilizer packages for 1 , 1 -disubstituted alkenes are disclosed in Malofsky et al., U.S. Patent No. 8,609,885 and Malofsky et al., U.S. Patent No. 8,884,051 . Additional free radical polymerization inhibitors are disclosed in Sutoris et al., U.S. Patent No. 6,458,956. Minimal quantities of a stabilizer are needed and, only about 150 parts-per-million or less may be included. A blend of multiple stabilizers may be included such as, for example a blend of anionic stabilizers (MSA) and free radical stabilizers (MeFIQ). The one or more anionic polymerization stabilizers are present in sufficient amount to prevent premature polymerization. The anionic polymerization stabilizers may be present in an amount of about 0.1 part per million or greater based on the weight of the monomers, about 1 part per million by weight or greater or about 5 parts per million by weight or greater. 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 monomers, about 500 parts per million by weight or less or about 100 parts per million by weight or less. 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 1 parts per million or greater based on the weight of the monomers, about 5 parts per million by weight or greater or about 10 parts per million by weight or greater. The free radical polymerization stabilizers may be present in an amount of about 5000 parts per million by weight or less based on the weight of the monomers, about 1000 parts per million by weight or less or about 500 parts per million by weight or less.

[0069] The polymers having polymer chains prepared from monomers having unsaturated groups and functional groups which are nucleophilic groups or mixtures of monomers having unsaturated groups and monomers having unsaturated groups and functional groups which are nucleophilic may be prepared by any conventional process for preparing addition polymers via free radical polymerization or anionic polymerization. Examples of these known polymerization processes include bulk, mass-solution, or mass-suspension polymerization, generally known as mass polymerization processes. For a good discussion of how to make monovinylidene aromatic copolymer containing compositions see“Modern Styrenic Polymers” of Series In Polymer Science (Wiley), Ed. John Scheirs and Duane Priddy, ISBN 0 471 497525. Also, for example, U.S. Pat. Nos. 3,660,535; 3,243,481 ; and 4,239,863, which are incorporated herein by reference. The copolymers may be prepared using polymerization techniques known in the art. The copolymers may be prepared by emulsion polymerization. The copolymers may be formed in an emulsion containing one or more surfactant.

[0070] Surfactants useful include natural or synthetic substances which, in water, lower the surface tension of the water or of other liquids. Surfactants which can be used include anionic, cationic, nonionic, and ampholytic surfactants or mixtures thereof. The polymerization process includes one or more surfactants for forming an emulsion having micelles or a discrete phase including monomers distributed throughout a continuous phase of water. The surfactant may be an emulsifier, a defoamer, or a wetting agent. The surfactant may include an ionic surfactant, an amphoteric surfactant, a nonionic surfactant, or any combination thereof. The surfactant may be present in a sufficient quantity so that a stable emulsion is formed by mixing or otherwise agitating a system including the monomers and water. The amount of surfactant needed may as little as necessary to provide some charge to the polymer surface. The surfactants according to the teachings herein include one or more surfactants for improving the stability of the suspension, such as for improving the stability of the dispersed phase in the water. The amount of surfactant provides colloidal stability to the polymerizing and polymerized particles.

[0071] Exemplary surfactants include alkyl polysaccharides, aikyiamine ethoxylates, amine oxides, castor oil ethoxylates, ceto-oleyl and salts thereof, ceto-stearyl and salts thereof, decyl alcohol ethoxylates, dinonyl phenol ethoxylates, dodecy! phenol ethoxylates, end-capped ethoxylates, ethoxylated a!kanolamides, ethylene glycol esters, fatty acid alkanoiamides, fatty alcohol alkoxylates, lauryl and salts thereof, mono-branched, nonyl phenol ethoxylates, octyl phenol ethoxylates, random copolymer alkoxylates, sorbitan ester ethoxylates, stearic acid ethoxylates, synthetic, tali oil fatty acid ethoxylates, tallow amine ethoxylates, alkyl ether phosphates and salts thereot, alkyl phenol ether phosphates, alkyl phenol ether sulfates and salts thereof, alkyl naphthalene sulfonates and salts thereof, condensed naphthalene sulfonates and salts thereof, aromatic hydrocarbon sulphonic acids and salts thereof, fatty alcohol sulfates and salts thereof, alkyl ether carboxylic acids and salts thereof, alkyl ether sulfates and salts thereof, mono-alkyl sulphosucclnamafes, di-aikyi suiphosucdnates, alkyl phosphates and salts thereof, alkyl benzene sulphonic acids and salts thereof, alpha olefin sulfonates and salts thereof, condensed naphthalene sulfonates and salts thereof, poiycarboxylates and salts thereof, alkyl dimethyiamines, stearic acid and salts thereof alkyl amidopropylamines, sulfonic acid and salts thereof, stearic adds and salts thereof, quaternized amine ethoxylates, quaternary ammonium compounds, and mixtures or combinations thereof. [0072] Non-limiting examples of amphoteric surfactants include amine oxide surfactants, sultaine surfactants, betaine surfactants, or any combination thereof Sultaine and betaine surfactants may include hydroxysultaines and hydroxybutaines. Exemplary amphoteric surfactants include cocamine oxide, cocoamidopropylamine oxide, cetamine oxide, decyiamine oxide, lauramine oxide, myristylamine oxide, cetyl amine oxide, steramine oxide, cocam idopropyl hydroxysultaine, capryl/capramidopropyl betaine, cocamidopropyi betaine, cetyl betaine, cocamidopropyi betaine, laurylamidopropyi betaine, or any combination thereof. Non-limiting examples of cationic surfactants include quaternary ammonium chloride surfactants, quaternary ammonium methyl sulfate surfactants, ester quaternarie surfactants, or any combination thereof. Without limitation, exemplary cationic surfactants that may be employed include cetrimonium chloride, stearaikonium chloride, o!eaikonium chloride, stearamidopropalkonium chloride, alkyl dimethyl benzyl ammonium chlorides, alkyl dimethyl ethylbenzyl ammonium chlorides, didecyl dimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, benzalkonium chloride, methyl bis(hydrogenated tallow amldoethyl)-2-hydroxyethyl ammonium methyl sulfate, methyl bisftaiiowamido ethy!)-2-hydroxyethyl ammonium methyl sulfate, methyl bisitaliowamido ethyi)-2- tal!ovv imidazo!inium methyl sulfate, diaikyi ammonium methosulfate, dialkylester ammonium methosu!fate, dipaimitoy!ethyi hydroxyethy!mmonium methosulfate, dialkyl ammonium methosulfate, dialkylester ammonium methosulfate, methyl bis[etbyl(tallowate)]--2-hydroxyethyi ammonium methyl sulfate methyl bis[ethy!(ta!lowate)]-2-hydroxyetbyl ammonium methyl sulfate, or any combination thereof. Non-limiting examples of nonionic surfactants include a!koxy!ate surfactants, amide surfactants, ester surfactants, ethoxylate surfactants, lactate surfactants, triglyceride surfactants, or any combination thereof exemplary nonionic surfactants that may be employed include polya!koxy!ated alphafic bases, poiyalkoxyiated amides, alkylphenol a!koxy!ates, alkylphenol block copolymers, alkyl phenol efhoxylates, polyaikyiene oxide block copolymers, glyceryl cocoate, alcohol alkoxylates, butyl based block copolymers, polyaikyiene oxide block copolymer, N,N-dimethy!decanamide (N,N-dimethy!capramide), N,N- dimethyioctanamide (N,N-dimethylcapry!amide), tatty aikanolamides, oleyi diethanolamide, iauryl dlethanolamlde, coco diethanolamide, fatty diethanolamides. polyethylene glycol cocamides, polyethylene glycol lauramides, iauryl monoethanolamide, myristy! monoethanolamide, coco monoisopropanolamide, alkyl ether phosphates, phosphate esters, glyceryl monostearate, glycerol monooleate, polyglyceryl decaoieates, polyglyceroi esters, polyglycerol polyricinoleates, neutralized alcohol phosphates, capric triglyceride, caprylic triglyceride, tridecyl alcohol phosphate ester, nony!phenol ethoxylate phosphate ester, trimethylopropane tricaprylate tricaprate polyol ester, methyl capry!ate/caprate, methyl laurate, methyl myristate, methyl palmitate, methyl oleate, alcohol phosphates, trimethyioipropane trieaprylate/caprate polyol ester, pentaerythritol trieaprylate/caprate polyol ester, pentaerythrityl tetracapry!ate/tetracaprate, nonylphenol phosphate ester, phosphate esters of an alkyl polyethoxyethanol, canola oil methyl ester, soybean oil methyl ester, pentaerythritol tetracapry!ate/caprate, trimethyioipropane trlcaprylate/ caprate, amine neutralized phosphate ester, fatty alkyl ethoxylates, alcohol ethoxylates, fatty acid ethoxylates, tallow amine ethoxylates, octyl phenol ethoxylates, nonyl phenol ethoxylate, castor oil ethoxyiate, poiyalkoxylated a!phatic bases, polyalkoxyiated amides, octyl phenol ethoxylate, tristyrylphenol ethoxylate, ammonium salt of ethoxylated polyary!phenol sulfates, tristyrylphenol ethoxyiate phosphate ester, potassium salt of tristyrylphenol ethoxylate phosphate ester, ethoxylated coco amine, sorbital trioleate ethoxyiate, sorbital monooleate ethoxylate, iauryi lactyi lactate, capric triglyceride, caprylic triglyceride, hydrogenated vegetable oil, or any combination thereof.

[0073] Exemplary surfactants include ethoxylates, such as an ethoxylated diol. The surfactant may include 2,4,7,9-tetramethyl-5-decyne-4,7-dioi ethoxylate. The surfactant may include a poly(alkene glycol). The surfactant may be a polyethylene g!ycol)-biock-poiy(propyiene glycol)- b!oek-poiy{ethyiene glycol) copolymer. The surfactant may include including an alcohol, an ethoxylated alcohol, or both. The surfactant may include CARBOWET® 138 nonionic surfactant (including alkyl alcohol, polyethylene glycol, ethoxylated C9-C1 1 alcohols). Another exemplary surfactant is a surfactant including a sorbitan, a sorbitol, or a poiyoxyalkene, such as sorbitan monopalmitate (nonionic surfactant). Exemplary surfactants include branched polyoxyethylene ( 12) nonylphynyi ether (IGEPAL® CG-720) and poly(e†hylene glycol) sorbitol hexaoleate (PEGSH).

[0074] Exemplary surfactants include compounds of formula 18:

wherein x is an integer between 7 and 40 or x is 7-8, 9-10, or 40. The surfactant may be Triton X- 405 surfactant.

[0075] The compositions polymerized may contain branching agents commonly used in preparing addition polymers. The branching agents may be unsaturated compounds containing two or more unsaturated groups such as vinylidene substituted aromatic monomers having 2 or more vinylidene groups. Other branching agents may include other difunctional and in general multifunctional (functionality >2) monomers, multifunctional initiators and multifunctional chain transfer agents and the like. The branching agents may be present in polymerizable compositions in an amount of about 0.001 percent by weight of the composition or greater, about 0.002 percent by weight or greater or about 0.003 percent by weight or greater. The branching agents may be present in polymerizable compositions in an amount of about 0.5 percent by weight of the composition or less, about 0.2 percent by weight or less or about 0.1 percent by weight or less.

[0076] Compositions containing the polymers, particles and encapsulating polymers, may contain impact modifiers. The terms impact modifiers and rubbers are used interchangeably herein. Various impact modifiers may be used in the compositions disclosed; such as diene rubbers, ethylene propylene rubbers, ethylene propylene diene (EPDM) rubbers, ethylene copolymer rubbers, acrylate rubbers, polyisoprene rubbers, silicon rubbers, silicon-acrylate rubbers, polyurethanes, thermoplastic elastomers, halogen containing rubbers, and mixtures thereof. Also suitable are inter-polymers of rubber-forming monomers with other copolymerizable monomers. The rubbers may be present in the formulated composition in sufficient amount to provide the desired impact properties to the composition. Desired impact properties include increased izod, charpy, gardner, tensile, falling dart, and the like. The rubbers may be diene rubbers such as polybutadiene, polyisoprene, polypiperylene, polychloroprene, and the like or mixtures of diene rubbers, that is, any rubbery polymers of one or more conjugated 1 ,3-dienes, such as 1 ,3-butadiene. The impact modifiers may be included at during polymerization or blended with the copolymers thereafter.

[0077] In preparing the polymers having polymer chains prepared from monomers having unsaturated groups and functional groups which are nucleophilic groups or mixtures of monomers having unsaturated groups and monomers having unsaturated groups and functional groups which are nucleophilic the monomers and other additives may be contacted and subjected to known polymerization processes.

[0078] The encapsulated particles comprise one or more particles as disclosed encapsulated by 1 ,1 -dicarbonyl-substituted-1 -alkenes. The particles and the polymers of 1 ,1 -dicarbonyi- substituted-1 -a!kenes are described herein. The polymers of 1 ,1 -dicarbonyi-substituted-l -aikenes may be physically bonded to the particles. The polymers are physically bonded to the particles where there are no groups on the surface of the particles that form covalent bonds with the polymers of 1 ,1 -dicarbony!-substituted-1 -alkenes.

[0079] The encapsulated particles may have the polymers of 1 ,1 -dicarbonyl-substituted- 1 - a!kenes covalently bonded to the surface of the particles. Where the particles have on their surface nucleophilic groups which initiate anionic polymerization or unsaturated groups which participate in anionic or tree radical polymerization the polymers of 1 .1 -dicarbonyl-substituted-1 - alkenes may be covalently bonded to the surface of the particles. Covalent bonding is achieved by forming the polymers of 1 J -dicarbonyl-substituted-l -alkenes by anionic polymerization or free radical polymerization under conditions that the polymers of 1 ,1 -dicarbonyl-substituted-1 -alkenes polymerize and the nucleophilic groups which initiate anionic polymerization or unsaturated groups on the particles participate in or initiate polymerization of the 1 ,1 -dicarbony!-substituted- 1 -alkenes. Anionic polymerization processes for 1 ,1 -dicarbonyl-substituted-1 -alkenes are disclosed in US 8,809,885; US 9,279,022; and US 9,315,597. The free radical polymerization conditions are disclosed in US 6,458,956 and US 9,249,265, incorporated herein by reference. The 1 ,t -dicarbonyi-substituted-1 -a!kenes polymerize via anionic polymerization at relatively mild conditions in the presence of anionic polymerization initiators. Anionic polymerization initiators generally include nucleophilic compounds and basic compounds initiators for anionic polymerization are disclosed US 9,181 ,365, incorporated herein by reference. Nucleophilic groups disposed on the surface of the particies may be carboxylic acids, hydroxyl groups, amino groups, and the like. The nucleophilic groups on the surface of the particles may be carboxylic acids, hydroxyl groups, amino groups. The nucleophilic groups on the surface of the particles may be carboxylic acids. The nucleophilic groups may be neutralized or deprotonated. The polymers of 1 J -dicarbonyi-substituted-l -alkenes may be grafted to the surface of the particles by covalent bonding. Alternatively, if the particles contain groups that undergo Michael Addition with unsaturated groups the particies may be covalently bonded to the 1 ,1 -dicarbonyl-1 -alkenes by Michael addition. Groups that undergo Michael Addition include amino and hydroxyl groups.

[0080] The encapsulated particles may have a particle size adapted for the desired use of the particles. The particle size of the encapsulated particles may be influenced by the size and/or type of the particles encapsulated. The encapsulated particles may have a layer of the polymers of 1 ,1 -dicarbonyl-substituted-1 -alkenes having a thickness sufficient for the desired use of the encapsulated particies and for the nature of the particies. The particle size of the encapsulated particles and the ratio of the thickness of the encapsulate layer to the thickness of the particle may be influenced by the use of composition of the particles and the intended use of the particles.

[0081] Generally, any of the particles disclosed may be encapsulated with polymers of 1 ,1 - dicarbonyl-substituted-1 -alkenes having groups pendant from the polymer chains which contain unsaturated groups which polymerize via free radical polymerization, such as the residue of hydroxyl alkyl (meth)aeryiates. The amount of groups pendant from the polymer chains which contain unsaturated groups which polymerize via free radical polymerization is that amount which allow crosslinking of a plurality of particles via free radical polymerization.

[0082] The encapsulated particles may comprise a core shell structure. The particle is the core and the layer of comprising one or more 1 ,1 -dicarbonyl-substituted-1 -aSkenes is the shell. The core may be any particle as disclosed herein. The core may be a particle of a polymer as disclosed herein. The core may be physically bonded to the shell layer. The shell layer may be covalently bonded to the core or grafted to the core. The core may be a polymer having nucleophilic groups, such as groups which initiate anionic polymerization, and/or unsaturated groups capable of anionic polymerization or free radical polymerization and the encapsulation layer may be covalently bonded or grafted to the shell. The polymer core may contain an impact modifier. The encapsulation layer may contain free radically polymerizable groups, such as the residue of hydroxyl alkyl (meth)acryiates.

[0083] The particles comprising a polymer of an addition polymer, which may optionally have polymer chains having unsaturated groups and/or nucleophilic groups pendant from the polymer chain, may be prepared by emulsion polymerization. In such process, the monomers may be dispersed in water with a surfactant. The method may comprise contacting water and a surfactant to form a micellar dispersion and adding to the micellar dispersion one or more polymerization initiators and monomers having unsaturated groups or mixtures of monomers having unsaturated groups and monomers having unsaturated groups and functional groups which are nucleophilic to form polymers with polymer chains. The amount of surfactant chosen is that amount that forms a stable emulsion and facilitates formation of the copolymer. The concentration of the surfactant may be about 0.001 weight percent or more, about 0.01 weight percent or more, about 0.1 weight percent or more or about 0.5 weight percent or more, based on the total weight of the emulsion. The concentration of the surfactant may be about 15 weight percent or less, about 10 weight percent or less, about 6 weight percent or less, or about 3 weight percent or less, based on the total weight of the emulsion. The dispersion of the monomers in water may be achieved with an appropriate form of agitation. Polymerization of the monomers may be improved by adjusting the pH of the dispersion. Any pH of the dispersion which enhances the polymerization may be used. The pH of the emulsion may be about 4 or greater or about 7 or greater; about 4 to about 10; or about 7 to about 10.

[0084] A redox initiation process may be used to prepare the copolymers. The reaction temperature may be maintained at a temperature lower than 100° C throughout the course of the reaction. The reaction temperature may be from about 30° C to about OS'" C or from about 50° C to about 90° C. The monomer mixture may be added neat or as an emulsion in water. The monomer mixture may be added in one or more additions or continuousiy, linearly or not, over the reaction period, or combinations thereof. The redox system includes an oxidant and a reductant. One or more oxidants such as, for example, hydrogen peroxide, sodium peroxide, potassium peroxide, t-butyi hydroperoxide, t-amy! hydroperoxide, cumene hydroperoxide, ammonium and/or aikaii metal persulfates, sodium perborate, perphosphoric acid and salts thereof, potassium permanganate, and ammonium or aikaii metal salts of peroxydisulfuric acid, typically at a level of 0.01 percent to 3.0 percent by weight, based on dry polymer weight, may be used. Exemplary reductants include sodium sulfoxylate formaldehyde, alkali metal and ammonium salts of sulfur-containing acids, such as sodium sulfite, bisulfite, thiosulfate, hydrosulfite, sulfide, hydrosulfide or dithionite, formadinesuifinic acid, hydroxymethanesu!fonic acid, acetone bisulfite, amines such as ethanolamine, glycolic acid, giyoxyiic acid hydrate, ascorbic acid, isoascorbic acid, lactic acid, glyceric acid, malic acid, 2-hydroxy-2- sulfinatoacetic acid, tartaric acid and salts of the preceding acids typically at a level of 0.01 percent to 3.0 percent by weight, based on dry polymer weight, may be used. Redox reaction catalyzing metal salts of iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium, or cobalt may optionally be used. The oxidant and reductant may be added to the reaction mixture in separate streams, which may be concurrently with the monomer mixture.

[0085] A chain transfer agent such as, for example, isopropanol, halogenated compounds, n- butyl mercaptan, n-amyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, alkyl thioglycolate, mercaptopropionic acid, and alkyl mercaptoalkanoate in an amount of 0.001 to 0.05, or about 0.0025 to 0.05 moles per kg dry polymer weight, may be used. Linear or branched C4- C22 alkyl mercaptans such as n-dodecyl mercaptan and t-dodecyl mercaptan may be used. Chain transfer agent(s) may be added in one or more additions or continuously, linearly or not, over most or all of the entire reaction period or during limited portion(s) of the reaction period such as, for example, in the kettle charge and in the reduction of residual monomer stage.

[0086] However, at least 40 percent by weight, at least 75 percent by weight, or at least 95 percent by weight, based on dry polymer weight, of the polymer is formed by redox polymerization in the presence of 0.001 to 0.05 moles chain transfer agent per kg dry polymer weight. By“at least 40 percent by weight, based on dry polymer weight, of the emulsion polymer is formed by redox polymerization in the presence of 0.001 to 0.05 moles chain transfer agent per kg dry polymer weight” is meant herein that at least 40 percent by weight, based on dry polymer weight, of the emulsion polymer is formed by redox emulsion polymerization and that this polymerization is effected contem-poraneously with the prior presence and/or addition of a total of 0.001 to 0.05 moles chain transfer agent per kg dry polymer weight. The emulsion polymerization is contemplated to include embodiments where some of the polymer is introduced by a polymer seed, formed in situ or not, or formed during hold periods or formed during periods wherein the monomer feed has ended, and residual monomer is being converted to polymer. [0087] The emulsion polymer may be prepared by a multistage emulsion polymerization process, in which at least two stages differing in composition are polymerized in sequential fashion. Such a process usually results in the formation of at least two mutually incompatible polymer compositions, thereby resulting in the formation of at least two phases within the polymer particles. Such particles are composed of two or more phases of various geometries such as, for example, core/shell or core/sheath particles, core/shell particles with shell phases incompletely encapsulating the core, core/shell particles with a multiplicity of cores, and interpenetrating network particles. In all of these cases the majority of the surface area of the particle will be occupied by at least one outer phase and the interior of the particle will be occupied by at least one inner phase. Each of the stages of the multi-staged emulsion polymer may contain the same monomers, surfactants, redox initiation system, chain transfer agents, etc. as disclosed herein above for the emulsion polymer. The polymerization techniques used to prepare such multistage emulsion polymers are well known in the art such as, for example, U.S. Pat. Nos. 4,325,856; 4,654,397; and 4,814,373. The emulsion polymerization may be performed for a time period wherein the desired polymer is prepared.

[0088] The process disclosed may include the use of seeds to initiate formation of polymer particles. Any seed that enhances formation of particles may be utilized. Exemplary classes of seeds include those used in forming acrylate-based lattices and styrene based lattices. Exemplary seeds include silica nanoparticles and carboxy!ated latex cores. Carboxylated latex cores may be made by conventional emulsion polymerization.

[0089] During the polymerization process, a solution may be stirred, sonicated or otherwise agitated to create the solution. For example, a solution including the monomer, the solvent, surfactant and any polymer may be mixed at a rate of about 10 rpm or more, about 50 rpm or more, about 200 rpm or more, or about 1 ,000 rpm or more using other means of agitation, such as sonicatlon. When using sonication, the frequency may be about 0.2 kHz or more, about 1 kHz or more, about 5 kHz or more, about 20 kHz or more or about 50 kHz or more. The frequency may be about 1000 kHz or less, about 500 kHz or less, about 200 kHz or less, or about 100 kHz or less.

[0090] The polymers may have a number average molecular weight or a weight average molecular weight that is about 3,000 g/mole or greater, about 50,000 g/rnole or greater, about 200,000 g/mole or greater, about 300,000 g/mole or greater, about 500,000 g/ ole or greater, about 750,000 g/mole or greater or about 900,000 g/mole or greater. The particle polymers may have a number average molecular weight or a weight average molecular weight that is about 1 ,000.000 g/moie or less, about 800,000 g/mo!e or less, about 600,000 g/mo!e or less and about 400,000 g/moie or less, about 100,000 g/moie, or less or about 25,000 g/moie.

[0091] The polymer particle size and/or particle si2e distribution (e.g., after the completion of polymerization) may be controlled based on process considerations, based on product control considerations, based on application requirements, or any combination thereof. For example, there may be a need tor emulsion particles having a unimodal particle size distribution, a multi modal particle size distribution (e.g., a bimodai distribution) or a narrow particle size distribution, or any combination thereof. The particle size distribution of the polymers prepared herein may about 10 nm or greater, about 100 nm or greater, about 300 nm or greater, about 600 nm or greater about 800 nm or greater. The particle size distribution ot the polymers prepared herein may about 1 micron or less, about 700 nm or less, about 500 nm or less, about 300 nm or less about 100 nm or less or about 50 nm or less. Particle size is controlled by choice of polymerization conditions with emulsion or microemulsion conditions providing small particles and suspension and mini-emulsion polymers yielding large particles.

[0092] The resulting polymer may be characterized by a polydispersity index ot greater than about 1 .00 or about 1 .05 or more. The resulting polymer may be characterized by a polydispersity index ot about 20 or less, about 7 or less, about 4 or less or about 2 3 or less. The resulting polymer may have a narrow molecular weight distribution such that the polydispersity index is about 1 .9 or less, about 1 .7 or less, about 1 .5 or less, or about 1 .3 or less.

[0093] The particle polymers having polymer chains prepared from monomers having unsaturated groups or mixtures of monomers having unsaturated groups and monomers having unsaturated groups and functional groups which are nucleophilic may be crosslinked by compounds containing two or more 1 ,1 -dicarbonyl 1 -alkene groups. The two or more 1 ,1 - dicarbonyl 1 -alkene groups are contacted with the polymers under conditions such that crosslinking occurs. The contacting may be in an emulsion after the polymers are formed. The contacting may take place after the polymer is removed from the emulsion. The copolymer may be in any form such that the two or more 1 ,1 -dicarbonyl 1 -alkene groups can be contacted with the polymer or a portion thereof. Particles of the copolymer may be contacted with the two or more 1 ,1 -dicarbonyl 1 -alkene groups. Alternatively, the polymer may be applied to a substrate or formed into a structure, such as a sheet and contacted with two or more 1 ,1 -dicarbonyl 1 -alkene groups.

[0094] The polymer and the compound containing two or more 1 ,1 -dicarbonyl 1 -alkene groups may be contacted at any ratio such that the polymer or a portion of the copolymer contacted with the compound with two or more 1 ,1 -dicarbonyl 1 -alkene groups crosslinks. The compound with two or more 1 ,1 -dicarbonyl 1 -alkene groups may be contacted with the polymer in an amount based on the weight of the polymer and the compound with two or more 1 ,1 - dicarbonyl 1 -alkene groups of from about 0.5 percent by weight or greater, about 1 .0 percent by weight or greater or about 2.0 percent by weight or greater. The compound with two or more 1 ,1 - dicarbonyl 1 -alkene groups may be contacted with the polymer in an amount based on the weight of the polymer and the compound with two or more 1 ,1 -dicarbonyl 1 -alkene groups of about 15 percent by weight or less, or about 10 percent by weight or less. Below 1 percent, the improvement in properties of coatings prepared from the composition is not significant. Up to 15 percent by weight, the properties of coatings prepared from the composition show significant improvement. The compounds with two or more 1 ,1 -dicarbonyl 1 -alkene groups may be contacted with the polymers at about -40 °C or greater, about 0 °C or greater or about 20 °C or greater. The compounds with two or more 1 ,1 -dicarbonyl 1 -alkene groups may be contacted with the polymers at about 150 °C or less, or about 100 °C or less or about 50 °C or less. Slight overpressure may be used as well. The compounds with two or more 1 ,1 -dicarbonyl 1 -alkene groups may be contacted with the polymers for a time sufficient to result in crosslinking of the polymers or the desired portion of the polymers. The contacting time may be about 1 hour or greater, about 10 hours or greater or about 20 hours or greater. The contacting time may be about 70 hours or less.

[0095] The encapsulated particles may be prepared by dispersing the particles in a carrier liquid. A surfactant may be added to the carrier liquid to stabilize and enhance the dispersion of the particles in the carrier liquid. The pH of the dispersion may be modified. A polymerization initiator is added the dispersion if the particles do not have groups on their surface that initiate polymerization. One or more 1 ,1 -dicarbonyl 1 -alkenes are added to the mixture under conditions that the one or more 1 ,1 -dicarbonyl 1 -alkenes undergo polymerization. As the one or more 1 ,1 - dicarbonyl 1 -alkenes undergo polymerization they encapsulate the particles. If the particles are known initiators or have groups on their surface which initiate polymerization, for instance anionic polymerization, at least a portion of the polymers formed from the one or more 1 ,1 -dicarbonyl 1 - alkenes covalently bond to the surface of the particles. The carrier liquid and the formed dispersion may be subjected to sheer forces during the preparation of the dispersion and the polymerization of the one or more 1 ,1 -dicarbonyl 1 -alkenes. The encapsulated particles may be removed from the dispersion before use or delivered for use in the carrier liquid.

[0096] The carrier liquid may be any liquid that remains liquid during the disclosed process and which is inert to the reactants and any materials added during the process. Exemplary carrier liquids include water, glycols and the like. Water may be the carrier liquid. The surfactants useful and the amounts of surfactant used may be the same as disclosed with respect to emulsion polymerization of the addition polymers. The concentration of particles in the dispersion is selected to form particles of the desired structure in a reasonably efficient manner. The pH of the dispersion is adjusted to enhance the polymerization of the one or more 1 ,1 -dicarbonyl 1 -alkenes as disclosed herein before. The pH can be adjusted by adding a base such as sodium hydroxide or an acid such as a mineral acid.

[0097] The polymerization intiator may be any anionic polymerization initiator or with any nucleophilic material. As the 1 ,1 -dicarbonyl alkenes are highly electrophilic contact with any nucleophilic material can initiate anionic polymerization. Anionic polymerization is commonly referred to as living polymerization because the terminal portion of the polymeric chains are nucleophilic and will react with any unreacted 1 ,1 -disubstituted alkenes they come into contact with. Thus the polymerizable composition will continue until all available unreacted 1 ,1 -dicarbonyl- 1 - alkenes polymerize or the polymerizing mixture is subjected to a quenching step. In a quenching step the mixture is contacted with an acid which terminates the polymeric chain ends and stops further polymerization. It is advantageous to select polymerization initiators that can induce polymerization under ambient conditions and without requiring external energy from heat or radiation. 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. The mixtures containing such compounds can be naturally occurring or synthetic. Specific examples of exemplary polymerization initiators for 1 ,1 -disubstituted alkene compounds can include glass beads (being an amalgam of various oxides including silicon dioxide, sodium oxide, and calcium oxide), 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 exemplary polymerization initiators for such polymerizable compositions are also disclosed in U.S. Patent Publication No. 2015/00731 10, which is hereby incorporated by reference.

[0098] The polymerization can proceed at any reasonable temperature including at ambient temperatures, from about 20 to 35 °C, depending on ambient conditions. Polymerization can be terminated by contacting the polymeric mixture with an anionic polymerization terminator. In some embodiments the anionic polymerization terminator is an acid. Exemplary anionic polymerization terminators include, for example, mineral acids such as methane sulfonic acid, sulfuric acid, and phosphoric acid and carboxylic acids such as acetic acid and trifluoroacetic acid. [0099] During formation of the dispersion and polymerization the dispersion and reaction mixture may be subjected to shear. Any method of subjecting the dispersion and reaction mixture to shear which stabilizes the dispersion and facilitates polymerization of the 1 ,1 -dicarbonyl alkenes may be used. The dispersion may be stirred, sonicated or otherwise agitated. For example, dispersion may be mixed at a rate of about 10 rpm or more, about 50 rpm or more, about 200 rpm or more, or about 1 ,000 rpm or more using other means of agitation, such as sonication. When using sonication, the frequency may be about 0.2 kHz or more, about 1 kHz or more, about 5 kHz or more, about 20 kHz or more or about 50 kHz or more. The frequency may be about 1000 kHz or less, about 500 kHz or less, about 200 kHz or less, or about 100 kHz or less

[00100] The polymerization step may proceed until all of the 1 , 1 -dicarbonyl alkenes polymerize or when the desired amount of 1 ,1 -dicarbonyl alkenes polymerize, such as when the desired encapsulation layer thickness is reached. The encapsulated particles may be recovered from the dispersion by techniques known to those skilled in the art.

[00101] The encapsulated particles may be recovered from the dispersion and used as solids in a variety of applications. The recovered encapsulated particles may be added to or mixed with other materials for use in desired applications. The encapsulated particles may be used in the form of a dispersion. The solids content of the dispersion may be adjusted to fit the final application. Additives may be added to the dispersion to improve the performance of the encapsulated particles in the final application.

[00102] The compositions disclosed may contain one or more wetting agents which facilitate the application of such compositions to substrates. Any wetting and or levelling agent which enhances the application of the compositions to a substrate may be used. Exemplary classes of wetting agents include polyether modified polydi-methyl siloxanes, fluorinated hydrocarbons and the like. The wetting agents may be poly-ether modified polydimethyl siloxanes. The wetting and/or levelling agents are present in sufficient amount to facilitate application of the compositions to a substrates surface. The wetting agents may be present in an amount of about 0.01 percent by weight or greater of the composition, about 0.5 percent by weight or greater or about 1 percent by weight or greater. The wetting agents may be present in an amount of about 5 percent by weight or less of the composition, about 2 percent by weight or less or about 1 percent by weight or less. The formed compositions may further contain one or more UV stabilizers which inhibit the degradation of structures containing the polyester macromers. Any UV stabil-izer which inhibits degradation due to exposure to UV radiation may be used. Exemplary classes of ultraviolet light stabilizers include benzophenones, benzotriazoles and hindered amines (commonly known as hindered amine light stabilizers (HALS). Exemplary UV light stabilizers include Cyasorb UV-531 2-hydroxy-4-n-octoxybenzophenone, Tinuvin 571 2-(2H-benzotriazol-2-yl)-6-dodecyl-4- methylphenol, branched and linear Tinuvin 1 ,2,3 bis-(1 -octyloxy-2,2,6,6, tetramethyl-4-piperidinyl) sebacate and Tinuvin 765, bis(1 ,2,2,6,6,-pentamethyl-4-piperidinyl) sebacate. The UV light stabilizers are present in sufficient amount to enhance long-term durability of the compositions containing polyester macromers. The UV light stabilizers should be selected so as to not affect the stability or pot life of the composition by premature polymerization, either by initiating or catalyzing free radical polymerization, anionic polymerization or Michael addition across the alkene double bond. The UV light stabilizers may be present in an amount of about 0.01 percent by weight or greater of the composition, about 0.1 percent by weight or greater or about 0.2 percent by weight or greater. The UV light stabilizers may be present in an amount of about 5 percent by weight or less of the composition, about 3 percent by weight or less, about 2 percent by weight or less or about 1 percent by weight or less. The composition may further comprise defoamers and/or deaerators. The compositions may foam during processing which can cause problems with respect to surface and appearance of a coating. Any defoamer and/or deaerator which prevents foaming or the formation of bubbles and which does not negatively impact the properties of the composition may be used. Exemplary defoamers are silicone defoamers, silicone free defoamers, polyacrylate defoamers, mixtures thereof and the like. Exemplary de-foamers include FOAM BLAST™ 20F, FOAM BLAST™ 30 silicone defoaming compounds and FOAM BLAST™550 polyacrylate defoamers available from Emerald; TEGO AIREX™ 920 polyacrylate defoamer and TEGO AIREX™ 980 from Degussa, SILMER ACR™ Di-10 and ACR™ Mo-8 polydimethylsiloxane acrylate copolymer from Siltech Corporation, FOAMEX N™ or TEGO AIREX™ 900 silicone based defoamers available from Degussa or BYK™ 1790 silicone-free defoamer from BYK Chemie. The defoamer/deaerator is pre-sent in the compositions in a sufficient amount to prevent formation of bubbles and/or foam. If too much is used, adhesion to the desired surfaces and adhe-sives may be negatively impacted. The defoamer and/or deaerator may be present in an amount of about 0.01 percent by weight or greater based on the weight of the composition , about 0.05 percent by weight or greater or about 0.1 percent by weight or greater. The defoamer/deaerator may be present in an amount of about 2.0 percent by weight or less or about 1 .0 percent by weight or less based on the weight of the composition.

[00103] These compositions disclosed may contain an additive to improve scratch resistance. Any additive which improves scratch resistance may be utilized. Exemplary scratch resistance additives may include silicates, aluminas, zirconias, carbides, oxides, nitrides or any other fillers with high hardness. Exemplary scratch resistance additives may include alumina (e.g., alpha alumina), silica, zirconia, boron carbide, silicon carbide, cerium oxide, glass, diamond, aluminum nitride, silicon nitride, yttrium oxide, titanium diboride, aluminosilicates (i.e.“Zeeospheres” from 3M), titanium carbide, combinations thereof, and the like. Exemplary scratch resistance additives may be silicates and aluminas. Exemplary scratch resistance additives may include nanometer sized silica fillers. The scratch resistance additives may have a particle size of about 10 micrometers or less or about 5 micrometers or less. The scratch resistance additives may be present in a sufficient amount to enhance the surface hardness and abrasion resistance of a coating and in an amount such that a homogeneous dispersion can be prepared. The scratch resistance additives may be present in an amount of about 0.1 percent by weight or greater of the composition or about 0.5 percent by weight or greater. The scratch resistance additives may be present in an amount of about 5 percent by weight or less of the composition, about 2 percent by weight or less or about 1 percent by weight or less.

[00104] These compositions may comprise an additive to improve surface slip properties. Any known composition that improves surface slip properties may be used. Exemplary surface slip additives may be a polyester modified polydimethyl siloxanes, waxes and the like. Exemplary waxes include those based on polyethylene, polytetrafluoroethylene or polypropylene wax dispersions in acrylate monomers, such as the EVERGLIDE™ or S-395 or SST series of products from Shamrock Technologies, or polyamide particles such as ORGASOL™ from Arkema, or montan wax with reactive acrylate groups, such as CERIDUST™ TP 5091 from Clariant, or CERAFLOUR™ wax powders from Byk-Chemie. The wax may be in powder form having a particle size which is smaller than the desired thickness of the coating prepared from the composition. The maximum particle size may be about 30 microns or less, about 25 microns or less, about 20 microns or less or about 15 microns or less. The wax may be highly crystalline. Exemplary waxes comprise a polyethylene, polypropylene, polyamide, polytetrafluoro-ethylene, or blends and / copolymers thereof. The wax may be crystalline polyethylene or polytetrafluoroethylene or blends of polyethylene with polytetrafluoroethylene. The surface slip additives may be present in an amount of about 0.1 percent by weight or greater of the composition or about 0.5 percent by weight or greater. The surface slip additives may be present in an amount of about 5 percent by weight or less of the composition, about 2 percent by weight or less or about 5 percent by weight or less.

[00105] The compositions disclosed herein can be used to prepare coatings. Such structures may be cured and/or cross-linked. The cross-linked compositions may be cross-linked through unsaturated groups pendant from the 1 ,1 -dicarbonyl-1 -alkene based polymers of the encapsulation layer when exposed to free radical polymerization conditions. The compositions containing the encapsulated particles may be cured via free radical polymerization as discussed. The compositions may be contacted with photoinitiators and exposed to ultraviolet light for curing.

[00106] Any known photoinitiator which initiates free radical polymerization may be utilized. Representative, non-limiting examples of the photoinitiators include benzophenone derivatives, acylphosphine oxide, bis-acylphosphine oxide, and a-hydroxy ketone. Representative non limiting examples of a-hydroxy ketones include 2-hydroxy-2-methyl-1 -phenyl-propan-1 -one, 1 -[4- 2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-propane-1 -one, 1 - hydroxycyclohexylphenylketone, camphorquinone, and combinations thereof. Bis-acylphosphine oxides and acylphosphine oxides are well known materials that are disclosed, for example, in U.S. Pat. Nos. 4,737,593; 4,792,632; 5,399,770; 5,472,992; and 6,486,228. A representative non limiting example of an acylphosphine oxide is diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide. A representative non-limiting example of a bisacylphosphine oxide is phenylbis(2,4,6- trimethylbenzoyl)-phenylphosphineoxide. Combinations of bisacylphosphine oxide and acylphosphine oxides can be employed, such as a combination of diphenyl(2,4,6- trimethylbenzoyl)phosphine oxide and phenylbis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide. The amount of photoinitiator used is chosen to facilitate cure of the encapsulated particles. The amount of photoinitator based on the weight of the encapsulated particles present may be about 0.1 percent by weight or greater or about 0.5 percent by weight or greater. The amount of photoinitator based on the weight of the encapsulated particles present may be about 1 .0 percent by weight or less or about 0.5 percent by weight or less. Exemplary conditions for curing using UV light sources and photoinitiators include the following. Two types of medium pressure mercury lamps may be used to induce the polymerization: (i) a high intensity lamp (Minicure 1ST) where the exposure time (0.1 -1 s) is controlled by the web speed; the fluence rate is measured by radiometry (International Light IL-390) to be of the order of 6000 Wm_2 at the sample position; (ii) a low intensity lamp (Novacure from EFOS) for the monitoring in real time of the curing reaction upon continuous UV exposure, the light intensity could be varied here in a range 100-1000 Wm_2.

[00107] Disclosed are articles comprising substrates containing pigmented base coats on the substrates with coatings disclosed herein. The base coats may have a basic character. The coatings may be clear and function as clear coats. The coatings disclosed may contain any additional components utilized in coating such as pigments, adhesion promotors, fire retardants, and ingredients as disclosed herein and the like. Coatings disclosed herein may contain pigments and function as stand-alone coatings of base coats with a clear coat disposed above such base coats. [00108] The coatings may cure and/or crosslink when exposed to certain conditions. The coatings may cure as disclosed herein before. When the coatings are exposed to relatively strong bases and or elevated temperatures they cure and crosslink at the same time. If they are exposed to mildly basic materials at relatively low temperatures, less than about 50 °C or less than about 40 °C they may not completely cure or crosslink. Such coatings or films may be cured by exposure to elevated temperatures to cure as disclosed herein. The coatings may have a thickness of about 0. 01 micrometers or greater, about 0.04 micrometers or greater or about 0.1 micrometers or greater. The coating may be cured and/or crosslinked. The coating may have a thickness of about 160 micrometers or less, about 140 micrometers or less, about 100 micrometers or less, about 60 micrometers or less, about 40 micrometers or less, about 10 micrometers or less, about 2 micrometers or less or about 1 micrometers or less.

[00109] The compositions disclosed may be cured by contact with polymers having pendant Michael donors. The pendant Michael Addition donor groups may comprise functional groups containing active hydrogen atoms. The one or more polymers having pendant Michael Addition donor groups may comprise one or more of acrylic polyols, amine modified acrylic polyols, polycarbonate polyols, modified acrylic copolymer polyols, polyether amines, polyester polyols, polyether polyols and siloxane polyols. Such curing may be performed in the presence of Michael Addition catalysts. Compounds that catalyze Michael Addition include acids and bases. Compounds that catalyze Michael Addition may be present in an amount of about 0.01 percent by weight or greater based on the weight of the formulation, about 0.05 percent by weight or greater, about 0.1 percent by weight or greater or about 0.3 percent by weight or greater. Compounds that catalyze Michael Addition may be present in an amount of about 1 percent by weight or less based on weight of the formulation, about 0.5 percent by weight or less or about 0.2 percent by weight or less.

EMBODIMENTS

[00110] 1 . A composition comprising:

one or more particles selected from that can tolerate the encapsulation conditions;

encapsulated by a polymer comprising one or more 1 ,1 -dicarbonylsubstituted-1 -aikenes; wherein the polymer is bonded to the surface of the particle and the composition of the particle is different from the composition of the polymer

[00111 ] 2. The composition according to Embodiment 1 wherein the particles comprise polymers, mixtures of polymers, ceramics, glass, metals, metal oxides, metal salts, naturally occurring or synthetic mixtures of metal based materials (including metals, metal oxides and metal salts which may contain other particulate material in admixture therewith), compounds containing metals, organic compounds, inorganic compounds, mixtures of metal compounds, minerals, carbon based particles, organic pigments, inorganic pigments, biological material, biologically active materials, materials useful for human contact, one or more monomeric compounds, polymer modifiers, corrosion inhibitors, polymerization initiators and catalyst (other than those useful for 1 ,1 -diearbonylsubstituted-1 -aikenes and one or more polymers and the like.

[00112] 3. The composition according to Embodiment 1 or 2 wherein the formed structure has a particle size of about 10 nm to about 10 mm.

[00113] 4. The composition according to Embodiment 1 to 3 wherein the one or more particles have a particle size of about 10 nm to about 5 mm.

[00114] 5. The composition according to any one of the preceding embodiments wherein the particle has the polymer comprising one or more 1 ,1 ~dicarbonylsubstituted-1 -aikenes bonded to its surface or covalently bonded to a group on the surface of the particle.

[00115] 8. The composition according to any one of the preceding embodiments wherein the particle does not contain a group at the surface that covalently bonds with the polymer comprising one or more 1 ,1 -dicarbonylsubstituted-1 -aikenes.

[00116] 7. The composition of embodiment 6 wherein the particle contains no group at the surface that covalently bonds with the polymer comprising one or more 1 , 1 -dicarbony!substituted- 1 -aikenes pendant to the polymer chain.

[00117] 8. The composition according to any one of the preceding embodiments wherein the particle is a polymer comprising an addition polymer.

[00118] 9. The composition according to any one of the preceding embodiments wherein the particle is one or more polymers comprising polymer chains prepared from monomers having unsaturated groups.

[00119] 10. The composition according to any one of the preceding embodiments wherein the particle polymers have polymer chains having unsaturated groups or nucleophilic groups pendant from the polymer chain.

[00120] 1 1 . A composition according to the previous embodiments wherein the addition polymers are prepared from monomers having unsaturated groups in their backbone wherein the unsaturation is capable of polymerization via free radical or anionic polymerization.

[00121 ] 12. A composition according to the previous embodiments wherein the addition polymers comprise polymers containing the residue of one or more of a (meth)acryiate, a vinyiidene substituted aromatic compound, an olefin, a conjugated diene, an unsaturated nitrile, or mixtures thereof. [00122] 13. A composition according to the previous embodiments wherein the monomers having unsaturated groups comprise one or more of 1 ,1 -dicarbonyl-1 -alkenes acrylates, methacrylates, acrylamides, methacrylamides, mono-vinylidene aromatic compounds, olefins, isocyanates, vinyl ethers, vinyl esters, and conjugated dienes.

[00123] 14. A composition according to the previous embodiments wherein the monomers having unsaturated groups comprise one or more of acrylates, methacrylates, acrylamides, and methacrylamides.

[00124] 15. A composition according to the previous embodiments wherein the monomers having unsaturated groups comprise one or more of acrylates and methacrylates.

[00125] 16. A composition according to the previous embodiments wherein the monomers having unsaturated groups and functional groups which are nucleophilic comprise on or more of methacrylic acid, acrylic acid, ethylene acrylic acid, maleic anhydride, 2-Acrylamido-2- methylpropanesulfonic acid, and acetoacetoxyethyl methacrylate.

[00126] 17. A composition according to any of the preceding embodiments wherein the nucleophilic groups pendant from the particle polymers comprise one or more of hydroxyl, carboxylic acids, amines, benzoic acids, sulfonates, and sulfates.

[00127] 18. A composition according to any one of the preceding embodiments wherein the particle polymers contain about 1 percent by weight or greater of monomers containing nucleophilic functional groups based on the weight of the polymer.

[00128] 19. A composition according to any of the preceding embodiments wherein the particle polymers contain from about 1 percent by weight to about 20 percent by weight of the particle polymers of the residue of monomers having nucleophilic functional groups.

[00129] 20. A composition according to the previous embodiments wherein the polymer comprising one or more 1 ,1 -dicarbonylsubstiiuted-1 -alkenes comprises the residue of one or more monofunctional 1 ,1 -dicarbonylsubstituted-l -alkenes and/or multifunctional 1 ,1 - dicarbony!substituted-1 -alkenes.

[00130] 21 . A composition according to the previous embodiments wherein the polymer comprising one or more 1 ,t -dicarbony!substituted-1 -alkenes comprises the residue of one or more monofunctional 1 ,1 -dicarbonyisubstituted-1 -alkenes and one or more multifunctional 1 ,1 - dicarbonylsubstituted-l -alkenes.

[00131] 22. A composition according to the previous embodiments wherein the polymer comprising one or more 1 ,1 -dicarbonylsubstituted-l -alkenes comprises the residue of one or more 1 ,1 -dicarbonylsubstituted-l -alkenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable ot undergoing transesterification and an unsaturated group capable of anionic polymerization or free radical polymerization

[00132] 23. A composition according to the previous embodiments wherein the polymer comprising one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes comprises the residue of one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes having bonded to at least one of the carbonyl groups the residue of a hydroxyl alkyl (meth)acrylate.

[00133]

[00134] 24. A composition according to the previous embodiments wherein the polymer comprising one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes comprises the residue of multifunctional 1 ,1 -dicarbonyl substituted- 1 -alkenes or polyester macromers containing at least one terminal residue of a 1 ,1 -dicarbonylsubstituted-1 -aikenes

[00135] 25. A composition according to the previous embodiments wherein the particles comprise polymers have polymer chains having unsaturated groups pendant from the polymer chain and the polymer comprising one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes comprises the residue of one or more monofunctional 1 ,1 -dicarbonylsubstituted-1 -alkenes and one or more multifunctional 1 ,1 -dicarbonylsubstituted-1 -alkenes wherein the particles are covalently bonded through the pendant unsaturated groups to the polymer comprising one or more 1 ,1 - dicarbonylsubstltuted-1 -alkenes.

[00136] 26. The composition according to Embodiment 25 wherein the structure formed exhibits a core shell structure wherein the core comprises the particle and the shell comprises the polymer comprising one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes

[00137] 27. The composition of any one of the preceding embodiments wherein the particles comprise one or more particles of silicon oxide, titanium oxide, aluminium oxide, alkali metal salts, alkaline earth metal salts, transition metal salts, or minerals comprising one or more metals, metal oxides or metal salts.

[00138] 28. The composition of any one of the preceding embodiments wherein the polydispersity index of the encapsulated particles Is 1 .0 or less.

[00139] 29. The composition of any one of the preceding embodiments wherein the polydispersity index of the encapsulated particles is 0.50 or less.

[00140] 30. The composition of any one of the preceding embodiments wherein the polydispersity index of the encapsulated particles is 0.40 or less.

[00141 ] 31 . A method comprising:

contacting one or more of the particles according to any one of Embodiments 1 to 26 with one or more 1 , 1 -dicarbonylsubstituted-1 -alkenes in an aqueous medium having a pH of from about 4 to about 12 with agitation under conditions such that a polymer of the one or more 1 ,1 - dicarbony!substituted-1 -aikenes is formed about the particle, the polymer is bonded to the surface of the particle.

[00142] 32. The method according to Embodiment 33 wherein the particle is about 10 nm to about 5 mm.

[00143] 33. The method according to Embodiment 31 or 32 wherein the contacting occurs at a temperature of about 0 G to about 100 ^eC.

[00144] 34. The method according to Embodiment 31 to 33 wherein the particles and the one or more 1 ,1 -dicarbonyisubstitu†ed-1 -aikenes are contacted for about 1 hour greater.

[00145] 35. The method according to any one of Embodiments 31 to 33 comprising dispersing the particles in water before contacting the particles with the one or more 1 ,1 - dicarbony!substituted-1 -aikenes.

[00146] 36. The method according to any one of Embodiments 31 to 35 wherein a surfactant is dispersed in water before the one or more 1 ,1 -dicarbonyisubstituted-1 -aikenes are contacted with the dispersion containing the particles.

[00147] 37. The method according to any one of Embodiments 31 to 36 wherein the process is performed in the presence of surfactant in the water at a concentration of about 0.01 percent by weight to about 0.3 percent by weight based on weight of the emulsion.

[00148] 38. A method comprising contacting a composition according to any one of

Embodiments 1 to 30 with a free radical initiator under conditions such that the composition undergoes free radical polymerization.

[00149] 39. A method according to Embodiment 38 wherein the initiator is a photo-initiator and the composition is exposed to a source of UV light under conditions such that the composition undergoes free radical polymerization.

[00150] 40. The method of Embodiment 38 or 39 wherein the structure formed is a film.

[00151 ] 41 . A composition comprising a cross-linked composition according to any one of

Embodiments 1 to 30.

[00152] 42. A composition according to Embodiment 41 wherein the composition is a coating.

[00153] 43. A composition comprising a substrate having a coating according to Embodiment 41 or 42 deposited on the surface of the substrate.

[00154] 44. A composition comprising a polymerizable mixture of one or more 1 ,1 - dicarbony!substituted-1 -aikenes and one or more 1 ,1 -dicarbonylsubstituted-1 -aikenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic polymerization or free radical polymerization

[00155] 45. A composition comprising copolymers of one or more 1 ,1 -dicarbonylsubstiiuted-l - a!kenes and one or more 1 , 1 -dicarbonylsubstituted-l -aikenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic polymerization or free radical polymerization, wherein the copolymers have pendant from the polymer chain unsaturated groups.

[00156] 46. A composition according to Embodiment 45 wherein the composition is a coating.

[00157] 47. A composition comprising a substrate having a coating according to Embodiment

45 or 46 deposited on the surface of the substrate.

[00158] 48. A composition according to any one of Embodiments 44 to 47 wherein the copolymer is cross-linked by free radical polymerization, anionic polymerization or Michael addition.

[00159] 49. A composition comprising a substrate having nucleophilic groups or unsaturated groups on its one or more surfaces, on one of more surfaces of the substrate is polymer derived from one or more 1 ,1 -dicarbony!substituted-1 -a!kenes wherein at least one of the 1 ,1 - dicarbonylsubstituted-1 -aikenes is one or more multifunctional 1 ,1 -dicarbony!substituted-l - alkenes wherein at least one of the 1 ,1 -dicarbony!substituted-l -alkenes is one or more multifunctional 1 ,1 -dicarbonylsubstituted-1 -alkenes or one or more 1 ,1 -dicarbonylsubstituted-1 - aikenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic poiymerization or free radical poiymerization; wherein the polymer is covalently bonded to the at least one surface of the substrate

[00160] 50. The composition according to Embodiment 49 wherein the polymer derived from one or more 1 ,1 -dicarbony!substituted-l -alkenes is cured or cross-linked or has bonded to its surface one or more monomers or polymers having unsaturated groups or Michael Addition donor groups.

[00161] 51 . The composition according to Embodiment 49 or 50 wherein the substrate has on one or more of its surfaces nucleophilic groups.

[00162] 52. The composition according to any one of Embodiments 49 to 51 wherein at least one of the 1 ,1 -dicarbonylsubstituted-1 -a!kenes is one or more 1 ,1 -dicarbonyisubstituted-1 - a!kenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic polymerization or free radical polymerization.

[00163] 53. The composition according to any one of Embodiments 49 to 51 wherein at least one of the 1 ,1 -dicarbony!substituted-1 -aikenes is one or more 1 ,1 -dicarbony!substituted-l - a!kenes having bonded to at least one of the carbonyl groups the residue of a hydroxya!ky! acrylate.

[00164] 54. The composition according to Embodiment 52 or 53 wherein the surface of the polymer layer is cured.

[00165] 55. The composition according to Embodiment 52 or 53 wherein the surface of the polymer layer is cured by free radical polymerization.

[00166] 56. The composition according to Embodiment 49 to 53 wherein bonded to the surface of the polymer layer is a polymer prepared from monomers or oligomers having unsaturated groups.

[00167] 57. The composition according to Embodiment 56 wherein the monomers or oligomers having unsaturated groups comprise monomers or oligomers having (meth) acrylate groups.

[00168] 58. The composition according to Embodiment 49 to 53 wherein the polymer of the one or more 1 ,1 -dicarbonylsubstituted-l -alkenes contains the residue of one or more multifunctional 1.T-dicarbonylsubstituted-T-alkenes.

[00169] 58. The composition according to Embodiment 58 wherein bonded to the surface of the polymer derived from one or more 1 ,1 -dicarbonylsubstituted-l -alkenes is a compound having two or more Michael Addition donor groups.

[00170] 59. A composition according to Embodiment 58 wherein the Michael Addition donor groups comprise functional groups containing active hydrogen atoms.

[00171] 60. A composition according to Embodiment 58 or 59 wherein the pendant Michael

Addition donor groups comprise amines, hydroxyl, thiol, or mixtures thereof.

[00172] 61 A composition according to any one of embodiments 58 to 60 wherein the compound having two or more Michael Addition donor groups comprises one or more polymers having pendant Michael Addition donor groups.

[00173] 62. A composition according to any one of embodiments 58 to 61 wherein the one or more polymers having pendant Michael Addition donor groups comprise one or more of acrylic polyols, amine modified acrylic polyols, polycarbonate polyols, modified acrylic copolymer polyols, polyester polyols, polyether polyols and siloxane polyols. [00174] 62 A composition according to any one of embodiments 58 to 60 wherein the one or more polymers having pendant Michael Addition donor groups comprise one or more acrylic polyols or amine modified acrylic polyols.

[00175] 63. A composition according to embodiments 49 to 63 wherein the substrate is a particle or has a defined shape.

ILLUSTRATIVE EMBODIMENTS OF THE INVENTION

[00176] The following examples are provided to illustrate the invention but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise indicated.

[00177] Example 1 Encapsulation of titanium oxide (T1O2)

Titanium oxide, rutile, high purity 99.9 percent having a particle size of 300 nm is mixed with Dl water at a pH of 8 to a concentration of 5 percent by weight and a dispersion is formed by exposure to ultrasonic mixing for 30 minutes. Diethyl methylene malonate (DEMM) is added at a constant rate of 0.5ml/minute to weight ratios of DEMM to T1O2 of 0, 7, 14, 21 , 28 and 35 weight percent. The mixture is mixed using a magnetic stirrer while the DEMM polymerizes. The same experiments are performed with 0.6 weight percent Triton X-405 surfactant in the starting dispersion. Particles sizes analysis is conducted by Dynamic Light Scattering (DLS). The grafting of polymerized DEMM to the Ti02 surface is evaluated by isolation of the resulting encapsulated particles with condensed polymer, drying in air overnight and measuring with Thermo Gravimetric Analyzer (TGA). The data for the samples prepared without surfactant is shown in Tables 1 and 2. The data from experiments with surfactant present is shown in Tables 3 and 4.

Table 1 DLS Data No Surfactant

Table 2 TGA Data No Surfactant

Table 3 DLS Data Surfactant

Table 4 TGA Data Surfactant

[00178] The DLS analysis shows that the resulting encapsulated T1O2 is mono-modal (single peak), and the particle size increases with the addition of more DEMM monomer. This result indicates homogeneous encapsulation of poly DEMM on T1O2 particle. The increasing amount of polymer in dispersion is shown by TGA result, which indicates the successful encapsulation of polyDEMM. The grafting of polyDEMM to the T1O2 surface is evaluated by isolation of the resulting encapsulated particles and washing extensively with chloroform. Very low levels of polyDEMM remained on the surface (less than 10% of the original poly DEMM) indicating polymerization around the T1O2 but not grafting to the T1O2 surface.

[00179] Example 2 Encapsulation of T1O2 with Diethyl methylene malonate and a polyester macromer of Butane Diol and Dimethyl methylene malonate

Titanium oxide, rutile, high purity 99.9 percent having a particle size of 30 nm and coated with silicon and aluminum 6.0-7.5 percent is mixed with Dl water at a pH of 6 to a concentration of 20 percent by weight and a dispersion is formed by exposure to ultrasonic mixing for 30 minutes. Diethyl methylene malonate (DEMM) or a polyester of Butane Diol and Diethyl methylene malonate (BDPE) is added at a constant rate of 0.5ml/minute to weight ratio of DEMM/BDPE to T1O2 of 0.4:1. The mixture is mixed using a magnetic stirrer while the DEMM/BDPE polymerizes. The grafting of poly DEMM/BDPE to the T1O2 surface is evaluated by isolation of the resulting encapsulated particles with condensed polymer, washing the dried mixture with chloroform for three times, drying in air overnight and measuring with Thermo Gravimetric Analyzer (TGA). Verification experiments are conducted by adding two drops of DEMM into a glass vial with and without T1O2 nanoparticles, reacting overnight and dissolving it in chloroform for NMR measurement. The same experiments are performed with 0.6 weight percent Triton X-405 surfactant in the starting dispersion. The data for the samples prepared with DEMM is shown in Table 5. The data from experiments with BDPE is shown in Table 6.

Table 5

Table 6

[00180] This example shows that encapsulant polyDEMM can be washed off by CHCI3 which suggests the physical attachment on T1O2 nanoparticle instead of chemical grafting. T1O2 nanoparticle with Si and Al coated could initiate DEMM polymerization indicated by NMR result, but the conversion is low, and the reaction rate is very slow.

[00181] Example 3 Methylene Malonate Encapsulation of Silicon Oxide (S1O2)

A dispersion of S1O2 is formed at a concentration of 10 percent by weight of S1O2 in water. The pH is adjusted to 7 with a pH strip. Various amounts of DEMM are added at a constant rate of 0.5 ml into 4 g of the dispersion. The mixture is stirred with a magnetic bar for 1 hour at ambient temperature. The particle size of the DEMM-encapsulated S1O2 nanoparticles are measured with dynamic light scattering. The results are in Table 7.

Table 7

The results show the dispersion after encapsulation is homogeneous with no aggregation. The color of the dispersion transforms from semi-transparent (0 wt% DEMM) to white dispersion (10- 50 wt% DEMM). The DLS analysis shows that the encapsulated nanoparticle exhibits a mono peak and the intensity-average particle size increases gradually with the addition of DEMM monomer.

[00182] Example 4 DEMM Encapsulation of Silicon Oxide (S1O2)

A dispersion of S1O2 is formed at a concentration of 10 percent by weight of S1O2 in water. The pH is adjusted to 7 with a pH strip. 40 weight percent of DEMM based on the weight of the dispersion is added to 4 g of the dispersion. The mixture is stirred with a magnetic bar for 1 hour at ambient temperature. The particle size of the DEMM-encapsulated S1O2 nanoparticles are measured with dynamic light scattering. The particle size increases from 267.0 nm of bare S1O2 to 1330 nm of polyDEMM-encapsulated-SiC>2. The particle size distribution is mono-peak.

[00183] Example 5 Methylene Malonate Encapsulation of Acrylate Latex particles containing 5 percent Methacrylic acid

A latex emulsion is prepared by emulsion polymerization from butyl acrylate, methyl methacrylate and methacrylic acid (weight ratio 0.475:0.475:0.5) the solid content of the final latex is 40 weight percent, with a particle size of the 238.5. The pH of the emulsion is modified using a pH strip to 7. 0.4 g of DEMM is added at a constant rate of 0.5ml/minute with stirring using a magnetic bar. The mixture is allowed to react for 30 minutes. The particle size is measured of a portion of the latex before encapsulation and of a portion of the latex after encapsulation. The results are compiled in Table 8.

Table 8

The DLS analysis shows the resulting encapsulated latex is mono-modal (single peak). The particle size increases by 4.2 nm with the addition of 20% DEMM. A homogeneous latex is formed during encapsulation process without visualized aggregations.

[00184] Example 6 Methylene Malonate Encapsulation of Acrylate Latex particles containing 40 percent Methacrylic acid A latex emulsion is prepared by emulsion polymerization from methyl methacrylate and methacrylic acid (weight ratio 0.6:0.4) the solid content of the final latex is 25 weight percent, with a particle size of the 238.37. The pH of the emulsion is modified to 7 using a pH strip. Various amounts of DEMM are added at a constant rate of 0.5ml/ to 5 g of the latex with stirring using a magnetic bar. The mixture is reacted for 2 hours. The particle size is measured of a portion of the latex before encapsulation and of a portion of the latex after encapsulation. The results are compiled in Table 9.

Table 9

The DLS analysis shows that the encapsulated latex nanoparticle is mono-peak, the intensity- average particle size increases gradually with the addition of DEMM monomer.

[00185] Example 7 Methylene Malonate Encapsulation of Acrylate Latex particles containing 20 percent Methacrylic acid

A latex emulsion is prepared by emulsion polymerization from methyl methacrylate and methacrylic acid (weight ratio 0.8:0.2). 5 percent of ethylene glycol dimethacrylate is incorporated in the polymer. The solid content of the final latex is 25 weight percent, with a particle size of the 123.23 nm. The pH of the emulsion is modified using NaOH to 5. Some agglomerations are formed and the emulsion is centrifuged to separate the latex formed out. 20 weight percent of DEMM is added at a constant rate of 0.5ml/minute to 5 g of the latex with stirring using a magnetic bar. The mixture is reacted for 2 hours. The particle size is measured of a portion of the latex before encapsulation and of a portion of the latex after encapsulation. The results are compiled in Table 10.

Table 10

[00186] Example 8 DEMM and Methylene Malonate containing hydroxyethyl methacrylate groups Encapsulation of Acrylate Latex particles containing 10 percent Methacrylic acid

A latex emulsion is prepared by emulsion polymerization from meth acrylic acid, methyl methacrylate and butyl acrylate. 1 percent of ethylene glycol dimethacrylate is incorporated in the polymer. The solid content of the final latex is 25 weight percent, with a particle size of the 123.23 nm. The pH of the emulsion is modified using a NaOH to 6. Some agglomerations are formed and the emulsion is centrifuged to separate the latex formed out. 30 weight percent of a 1 :1 mixture of DEMM and ethyl methacrylate methylene malonate is added at a constant rate of 0.5ml/minute to 5 g of the latex with stirring using a magnetic bar. The mixture is reacted for overnight. 2 percent by weight of PDMA is mixed into 0.2 grams of methylmethacrylate and added to the latex. The formed mixture is stirred and swelled for 2 hours in the absence of light. The latex is dried in an oven. The latex is deposited onto a substrate and exposed to UV light in nitrogen overnight. A film is formed. The film is dissolved into DMF dimethyl formamide and swelling ratio is measured. A latex film without UV curing fully dissolves in DMF. A latex film with UV curing overnight exhibits a swelling ratio of 84% and forms a well-shaped gel.

[00187] Example 9

A functional latex is synthesized through emulsion polymerization with the incorporation of 10 wt% methacrylic acid. The anionic carboxyl group on the latex particle surface initiates DEMM polymerization in ambient environment and enables the formation of a grafted structure with latex particles as the core and polyDEMM as the shell. Various amounts of DEMM (0 wt%, 10 wt%, 20 wt%, 30 wt% and 40 wt%) are added into the latex at room temperature and allowed to react for 1 h. Fig. 1 shows the increasing average particle size along with the increasing of DEMM amount. The particle size distribution is mono-dispersed, which suggests the encapsulation process is homogeneous, Figure 9. The contact angle was measured by dropping 4 pL and imaging on dried latex film. Data represents the average of 20 measurements. The asterisk (^*) denotes p < 0.00001 sample significance. The water contact angle on coatings formed from encapsulated latex particles (10 wt%, 20 wt%, 30 wt% and 40 wt% DEMM) had an average increase of 17.44° compared with the control latex (0 wt% DEMM) and did not change with the increasing amount of grafted DEMM in Fig 4, suggests the carboxy group had been fully consumed with 10 wt% of polyDEMM encapsulation. These results strongly support MM-grafted-latex particle structure. They also demonstrate a very simple, controllable, room temperature post-addition process to obtain these functional polymers. [00188] A crosslinked coating film can be fabricated by crosslinking the unreacted HEMA groups. Gel content is determined by soaking the UV-cured film in DMF for 3 days to extract the non-crosslinked fraction in order to verify the formation of the crosslinked network, Fig. 2. The coating film without FIEMA-MM completely dissolves in DMF, however, a sharp-edged gel formed with FIEMA-MM encapsulated coating film, Fig. 2. The gel content increases with increasing FIEMA-MM content in the latex. This result suggests that the crosslinking reaction between the introduced vinyl groups enabled the formation of a crosslinked network. Thus, the gel content can be controlled by varying FIEMA-MM content.

[00189] A hardness test (QBY film pendulum hardness tester, AliExpress) is conducted to measure the stiffness of the coating film before and after UV irradiation, Fig. 3. Without FIEMA- MM encapsulation, UV irradiation does not change the hardness. Flowever, two- and three-folds increase are observed on samples prepared from 50 wt% FIEMA-MM and 100 wt% FIEMA-MM latex materials respectively. The dense crosslinking network enables an elevated hardness which significantly improved the mechanical property of the coating film.

[00190] Example 10 Coating films (crosslinked and non-crosslinked) Prepared with different FIEMA-MM content.

Synthesize 10 wt% MAA latex by emulsion polymerization. (BA: MMA: MAA=5.4: 3.6: 1 ). Modify the pH of latex to 6 with sodium hydroxide solution, then centrifuge to get rid of large agglomerations. Add FIEMA-MM (0 wt%, 2.5 wt%, 5 wt%, 7.5 wt% and 10 wt% to the solid weight of latex into 10 g latex, stir constantly at room temperature overnight. Dissolve 3 wt% photoinitiator 2,2-Dimethoxy-2-phenylacetophenone (DMPA) into 0.2 g ethanol and add into the latex, mix for 1 h. Drawdown the latex and dry in air. Expose the film on UV lamp with 365 nm wavelength for 1 h. Measure film properties.

[00191 ] Dynamic light scattering study of DEMM encapsulation

Method:

(1 ) Prepare 5g MAA latex (pH 6), add 0 wt%, 10 wt%, 20 wt%, 30 wt% and 40 wt% DEMM into the latex, keep stirring at room temperature for 2h.

(2) Measure particle size distribution with dynamic light scattering (DLS).

[00192] Results of testing the particle size increases linearly with the addition of DEMM. See Figure 1 showing a graph of particle size against DEMM content.

[00193] Contact angle study of DEMM encapsulation

Method:

(1 ) Prepare 5g MAA latex (pH 6), add 0 wt%, 10 wt%, 20 wt%, 30 wt% and 40 wt% DEMM into the latex, keep stirring at room temperature for 2h. (2) Dry the film and measure surface contact angle with tensiometer.

Result:

A graph of the contact angle of particles versus DEMM content is shown in Figure 5.

[00194] Fourier-transform infrared (FTIR) spectroscopy testing.

Method:

(1 ) Prepare MAA latex, MAA latex encapsulated with 10 wt% DEMM, pure polyDEMM initiated in water at pH 7, pure poly methacrylate acid, and sodium dodecyl sulfate surfactant.

(2) Measure FTIR spectrum and make comparison.

A Fourier-transform infrared (FTIR) spectroscopy diagram is shown in Figure 5.

[00195] Grafting efficiency of HEMA-MM onto MAA latex.

Method:

Highly crosslinked MAA latex was synthesized using a semi-batch emulsion polymerization method (refer to the latex synthesis method provided in the main text). Ethylene glycol dimethacrylate (EGDMA, Sigma-Aldrich) was used as the crosslinking agent. The ratio between MMA : BA : MAA : EGDMA was 25.5 : 59.5 : 10:5. The synthesized latex had a gel content of 96.1 wt% in chloroform. Next, various amounts of HEMA-MM (y = 2.5 wt%, 5 wt%, 7.5 wt%, 10 wt%) were added dropwise into the latex (pH=6), mixed, and reacted under ambient conditions overnight. The grafted latex was dried on a PTFE bowl at room temperature for 2 days to allow for water evaporation. The dried film (with weight, mi) was placed inside a glass vial and immersed in chloroform for 2 days. The self-polymerized HEMA-MM was next extracted using chloroform and dissolved. Next, the solvent was removed from the vial, and the swollen film was allowed to dry in the hood overnight. The weight the dried film was taken as m_å. The grafting efficiency was calculated based on the following equation:

[00196] Study of gel content and swelling ratio of UV crosslinked film

Method:

(1 ) Weighing coatings films as mi .

(2) Immersing the coatings into DMF for 48 h

(3) Weighing the swelled gel as m₂.

(4) The swollen coating are heated at 200 °C to evaporate any remnant solvent.

(5) Weighing the dried sample as m₃.

(6) The swelling ratio is calculated based on the equation: Swelling ratio (%)= m₂/ mi x100%. The gel content was calculated based on the equation: Gel content (%) = m₃/mi x100%. All results are measured in triplicate.

Figure 6 shows the swelling results for methacrylate particles encapsulated with polymers prepared from mixtures of DEMM and hydroxyl ethyl methacrylate modified DEMM. Figure 2 shows the gel content of particles of methacrylate polymers encapsulated with polymers prepared from mixtures of DEMM and hydroxyl ethyl methacrylate modified DEMM.

[00197] Glass transition temperature study before and after UV curing

Method: Measure the coating film before and after UV crosslinking with dynamic mechanical test. The mode was set as ‘Multi-frequency-strain’ and used Temp Ramp/ Freq Ramp’ as test procedure. The temperature range was -40 °C-80 °C. Figure 9 shows a graph of Tg for non- crosslinked and crosslinked films

Figure 7 shows a graph of the glass transition temperature of non-crosslinked and crosslinked films prepared from particles encapsulated with mixtures of DEMM and hydroxyl ethyl methacrylate modified DEMM

[00198] Flardness test result of non-crosslinked film and crosslinked film

Equipment model: QBY-II, the test is based on GB 1730-79.

Method:

(1 ) Place the coating film under the pendulum on top of the equipment where the pendulum pointed to 0°.

(2) Put the pendulum on 5°and loose immediately, the counter will count the oscillation automatically. (3) Compare the number of oscillations between each coating films. Film with higher hardness will result in more cycles measured by the tester.

Figure 3 shows the results of the hardness test of crosslinked and non-crosslinked films.

[00199] Tensile test result of non-crosslinked film and crosslinked film

Method:

(1 ) Cut the coating film into 5cm^*0.5cm size, 4 pieces for each sample.

(2) Use tensile tester to stretch the film at a rate of 5 cm/min until it breaks.

(3) Compare the stress-strain curve between samples.

Figure 11 shows the stress strain, Youngs Modulus and yield strength of cross-linked and noncrosslinked films.

Claims

1 . A composition comprising:

encapsulated by a polymer comprising one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes;

wherein the polymer is bonded to the surface of the particle and the composition of the particle is different from the composition of the polymer.

2. The composition according to Claim 1 wherein the particles comprise polymers, mixtures of polymers, ceramics, glass, metals, metal oxides, metal salts, naturally occurring or synthetic mixtures of metal based materials (including metals, metal oxides and metal salts which may contain other particulate material in admixture therewith), compounds containing metals, organic compounds, inorganic compounds, mixtures of metal compounds, minerals, carbon based particles, organic pigments, inorganic pigments, biological material, biologically active materials, materials useful for human contact, one or more monomeric compounds, polymer modifiers, corrosion inhibitors, polymerization initiators and catalyst (other than those useful for 1 ,1 - dicarbonylsubstituted-1 -alkenes and one or more polymers and the like.

3. The composition according to Claim 1 or 2 wherein the formed structure has a particle size of about 10 nm to about 10 mm.

4. The composition according to Claim 1 to 3 wherein the one or more particles have a particle size of about 10 nm to about 5 mm.

5. The composition according to any one of the preceding claims wherein the particle has the polymer comprising one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes bonded to its surface or covalently bonded to a group on the surface of the particle.

6. The composition according to any one of the preceding claims wherein the particle does not contain a group at the surface that covalently bonds with the polymer comprising one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes.

7. The composition according to any one of the preceding claims wherein the particle is a polymer comprising an addition polymer.

8. The composition according to any one of the preceding claims wherein the particle polymers have polymer chains having unsaturated groups or nucleophilic groups pendant from the polymer chain.

9. A composition according to the previous claims wherein the addition polymers are prepared from monomers having unsaturated groups in their backbone wherein the unsaturation is capable of polymerization via free radical or anionic polymerization.

10. A composition according to the previous claims wherein the addition polymers comprise polymers containing the residue of one or more of a (meth)acryiate. a vinylidene substituted aromatic compound, an olefin, a conjugated diene, an unsaturated nitrile, or mixtures thereof.

1 1 . A composition according to the previous claims wherein the monomers having unsaturated groups comprise one or more of 1 ,1 -dicarbonyl-1 -alkenes acrylates, methacrylates, acrylamides, methacrylamides, mono-vinylidene aromatic compounds, olefins, isocyanates, vinyl ethers, vinyl esters, and conjugated dienes.

12. A composition according to any of the preceding claims wherein the nucleophilic groups pendant from the particle polymers comprise one or more of hydroxyl, carboxylic acids, amines, benzoic acids, sulfonates, and sulfates.

13. A composition according to any of the preceding claims wherein the particle polymers contain from about 1 percent by weight to about 20 percent by weight of the particle polymers of the residue of monomers having nucleophilic functional groups.

14. A composition according to the previous claims wherein the polymer comprising one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes comprises the residue of one or more monofunctional 1 ,1 -dicarbonylsubstituted-1 -a!kenes and/or multifunctional 1 ,1 -dicarbonylsubstituted-1 -alkenes.

15. A composition according to the previous claims wherein the polymer comprising one or more 1 ,1 -dicarbony!subsiituied-1 -aikenes comprises the residue of one or more 1 ,1 - dicarbonylsubstituted-1 -alkenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic polymerization or free radical polymerization.

16. A composition according to the previous claims wherein the polymer comprising one or more 1 ,1 -dicarbonylsubstituted-l -alkenes comprises the residue of one or more 1 ,1 - dicarbonylsubstituted-1 -alkenes having bonded to at least one of the carbonyl groups the residue of a hydroxyl alkyl (meth)acrylate.

17. A composition according to the previous claims wherein the polymer comprising one or more 1 ,1 -dicarbonyisubstituted-1 -a!kenes comprises the residue of multifunctional 1 ,1 -dicarbonyl substituted-1 -alkenes or polyesters containing at least one terminal residue of a 1 ,1 - dicarbonylsubstituted-1 -alkenes.

18. A composition according to the previous claims wherein the particles comprise polymers have polymer chains having unsaturated groups pendant from the polymer chain and the polymer comprising one or more 1 ,1 -dicarbony!substituted-1 -alkenes comprises the residue of one or more monofunctional 1 ,1 -dicarbonyisubstituted-1 -alkenes and one or more multifunctional 1 ,1 - dicarbonylsubstituted-1 -alkenes wherein the particles are covalently bonded through the pendant unsaturated groups to the polymer comprising one or more 1 ,1 -dicarbonylsubstituted-1 -aikenes.

19. The composition according to Claim 25 wherein the structure formed exhibits a core shell structure wherein the core comprises the particle and the shell comprises the polymer comprising one or more 1 ,1 -dicarbony!substituted-1 -a!kenes

20. The composition of any one of the preceding claims wherein the particles comprise one or more particles of silicon oxide, titanium oxide, aluminium oxide, alkali metal salts, alkaline earth metal salts, transition metal salts, or minerals comprising one or more metals, metal oxides or metal salts.

21 . The composition of any one of the preceding claims wherein the polydispersity index of the encapsulated particles is 1 .0 or less.

22. A method comprising:

contacting one or more of the particles according to any one of Claims 1 to 26 with one or more 1 ,1 -dlcarbony!subs†itu†ed-1 -alkenes in an aqueous medium having a pH of from about 4 to about 12 with agitation under conditions such that a polymer of the one or more 1 ,1 - dicarbonylsubstituted-1 -alkenes is formed about the particle, the polymer is bonded to the surface of the particle.

23. The method according to Claim 22 wherein the particle is about 10 nm to about 5 mm.

24. The method according to Claim 22 or 23 wherein the contacting occurs at a temperature of about 0 ^eC to about 100 ⁹C.

25. The method according to any one of Claims 22 to 24 comprising dispersing the particles in water before contacting the particles with the one or more 1.1 -dicarbonyisubstituted-l -alkenes.

26. The method according to any one of Claims 22 to 25 wherein a surfactant is dispersed in water before the one or more 1 ,1 -dicarbonylsubstituted-1 -alkenes are contacted with the dispersion containing the particles

27. The method according to any one of Claims 22 to 26 wherein the process is performed in the presence of surfactant in the water at a concentration of about 0.01 percent by weight to about 0.3 percent by weight based on weight of the emulsion.

28. A method comprising contacting a composition according to any one of Claims 1 to 21 with a free radical initiator under conditions such that the composition undergoes free radical polymerization.

29. A method according to Claim 28 wherein the Initiator Is a photo-initiator and the composition is exposed to a source of UV light under conditions such that the composition undergoes free radical polymerization.

30. The method of Claim 28 or 29 wherein the structure formed Is a film.

31 . A composition comprising a cross -linked composition according to any one of Claims 1 to

21 .

32. A composition according to Claim 31 wherein the composition is a coating.

33. A composition comprising a substrate having nucleophilic groups or unsaturated groups on its one or more surfaces, on one of more surfaces of the substrate is polymer derived from one or more 1 ,1 -dicarbony!substituted-1 -alkenes wherein at least one of the 1 ,1 - dicarbonylsubstituted-1 -alkenes is one or more multifunctional 1 ,1 -dicarbonyisubstituted-1 - alkenes wherein at least one of the 1 ,1 -dicarbonylsubstituted-l -alkenes is one or more multifunctional 1 ,1 -dicarbony!substituted-1 -a!kenes or one or more 1 ,1 -dicarbony!substituted-1 - alkenes having bonded to at least one of the carbonyl groups the residue of a compound containing a functional group capable of undergoing transesterification and an unsaturated group capable of anionic polymerization or free radical polymerization: wherein the polymer is covalently bonded to the at least one surface of the substrate.

34. The composition according to Claim 33 wherein the polymer derived from one or more 1 ,1 -dicarbony!substituted-1 -alkenes is cured or cross-linked or has bonded to its surface one or more monomers or polymers having unsaturated groups or Michael Addition donor groups.

35. The composition according to Claim 33 or 34 wherein the substrate has on one or more of its surfaces nucleophilic groups.