FIELD

[001] Disclosed are processes for the preparation of a carbonyl-substituted alkene, such as methylene malonamides and ketoacrylamide monomers. Also disclosed are the polymeric compositions derived from these carbonyl-substituted alkenes.

BACKGROUND

[002] Carbonyl-substituted alkenes are of interest because they are capable of polymerizing at ambient temperatures upon contact with basic materials. In addition, their functional groups provide great flexibility in forming a variety of compounds and polymerizable compositions. Carbonyl-substituted alkenes include methylene malonates, methylene diketones, methylene keto esters, and the like. Such compounds have been known since 1886 where the formation of diethyl methylene malonate was first demonstrated by W. H. Perkin, Jr. (Perkin, Ber. 19, 1053 (1886)). The early methods for producing methylene malonates suffer significant deficiencies that preclude their use in obtaining commercially viable monomers, including unwanted polymerization of the monomers during synthesis (e.g., formation of polymers or oligomers or alternative complexes), formation of undesirable side products (e.g., ketals or other latent acid-forming species which impede rapid polymerization), degradation of the product, insufficient and/or low yields, and ineffective and/or poorly functioning monomer product (e.g., poor adhesive characteristics, stability, or other functional characteristics), among other problems. The overall poorer yield, quality, and chemical performance of the monomer products formed by prior methods have impinged on their practical use in the production of the above products.

[003] In recent years a number of commonly owned patent applications have been filed which have solved a number of the problems associated with the synthesis of methylene malonates and analogs thereof, for example Malofsky et al., U.S. Patent No. 8,609,885; Malofsky et al., U.S. Patent No. 8,884,051 ; Malofsky et al., U.S. Patent No. 9,108,914; and Sullivan et al., U.S. Patent No. 9,518,001. The synthesis procedures provided therein result in improved yields of heretofore elusive, high quality methylene malonates and other polymerizable compositions. [004] While these methylene malonates achieve the purpose for which they were intended, industry is seeking monomers having improved performance properties for certain applications. Certain applications, such as adhesives and coatings used in electronic applications, have strict performance requirements, many of which methylene malonate systems do not provide. Therefore, there is a need for alternate systems that meet these strict performance standards. There is a need for carbonyl- substituted alkenes, such as methylene malonamide and ketoacrylamide monomers, which provide highly stable amide bonding, thereby giving improved hydrolysis resistance over wider pH and temperature ranges. There is also a need for monomers having improved adhesion and cohesion properties. There is also a need for higher glass transition temperatures and decomposition temperatures.

SUMMARY

[005] Disclosed are novel monomers, polymers made from or including these novel monomers, and a process for making these novel monomers. Disclosed is a composition comprising a carbonyl-substituted alkene including a dicarbonyl compound having an alkylene group between the carbonyl groups; where at least one carbonyl group of the dicarbonyl compound includes an amide group; and where another carbonyl group is a keto group or a carbonyl group including an amide group. The composition may include monomers such as methylene keto malonamides, methylene dimalonamides, and the like. Also disclosed are polymers prepared from a composition containing these compositions or monomers. These polymers may contain any of the compositions or monomers disclosed herein, which may be alone or in combination with other monomers. These polymers may be a copolymer formed with any of the monomers disclosed herein and with any other carbonyl-substituted alkene, such as another 1 , 1 -disubstituted alkene. The copolymers formed may contain multi-functional monomers and/or crosslinkers. The crosslinkers may be a multifunctional 1 , 1 -disubstituted alkene.

[006] Also disclosed is a process comprising: combining, to form a mixture, a dicarbonyl compound having an alkylene group between the carbonyl groups, the dicarbonyl compound being a diamide or ketoamide; formalin or a formaldehyde precursor; and an acid catalyst; and heating the mixture to form a carbonyl-substituted alkene. The process may form methylene keto malonamides, methylene dimalonamides, and the like. The dicarbonyl compound may be a diamide or ketoamide. [007] The starting material, the dicarbonyl compound, may have one or more amide groups. The amide may be a tertiary amide. The acid catalyst may have a pKa of about 2 to about -14. The acid catalyst may be selected from methane sulfonic acid, sulfuric acid, trifluoroacetic acid, or trifluoromethane sulfonic acid. The resulting carbonyl-substituted alkene may have a purity of about 95 mole percent or greater based on the total weight of the carbonyl-substituted alkenes. The carbonyl- substituted alkenes may form an oligomeric complex. The oligomeric complex may include two or more units of methylene malonamide monomers, ketoacrylamide monomers, or a combination thereof. The process described herein may further include a polymerization step to form a polymeric composition.

[008] The carbonyl-substituted alkenes or polymers prepared therefrom may be curable by heat, moisture, UV, or a combination thereof. The carbonyl-substituted alkenes or polymers prepared therefrom may be curable at temperatures of about 0 °C to about 150 °C. The carbonyl-substituted alkenes as described herein, or polymers including these carbonyl-substituted alkenes, may provide a higher glass transition temperature than carbonyl-substituted alkenes without amide groups. The carbonyl- substituted alkenes described herein may provide greater flexibility in the preparation of analogs. The carbonyl-substituted alkenes or polymers prepared therefrom may meet the needs of the industry by exhibiting excellent hydrolytic stability, exceptional adhesion to substrates, shrinkage of about 10% or less, or a combination thereof.

DETAILED DESCRIPTION

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

[0010] Disclosed herein are monomers, polymers made from these monomers, and a process for making these monomers. Disclosed is a composition comprising a carbonyl-substituted alkene including a dicarbonyl compound having an alkylene group between the carbonyl groups; where at least one carbonyl group of the dicarbonyl compound includes an amide group; and where another carbonyl group is a keto group or a carbonyl group including an amide group.

[0011] Also disclosed are polymers including the monomers disclosed herein and/or formed from the processes described herein. These polymers may contain any of the compositions or monomers disclosed herein, which may be alone or in combination with other monomers, such as other 1 , 1-disubstited alkene compounds. These polymers may be a copolymer formed with any of the monomers disclosed herein and with any other carbonyl-substituted alkene. The polymers or copolymers formed may contain multi-functional monomers and/or crosslinkers.

[0012] Also disclosed is a process comprising combining, to form a mixture, a dicarbonyl compound having an alkylene group between the carbonyl groups, the dicarbonyl compound being a diamide or ketoamide; formalin or a formaldehyde precursor; and an acid catalyst; and heating the mixture to form a carbonyl-substituted alkene. The process may form methylene keto malonamides, methylene dimalonamides, and the like. The dicarbonyl compound may be a diamide or ketoamide.

[0013] 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 means the theoretical functionality, generally this can be calculated from the stoichiometry of the ingredients used. Generally, the actual functionality is different due to imperfections in raw materials, incomplete conversion of the reactants and formation of by-products. Residual content of a component refers to the amount of the component present in free form or reacted with another material, such as an oligomer or a polymer. Typically, the residual content of a component can be calculated from the ingredients utilized to prepare the component or composition. Alternatively, it can be determined utilizing known analytical techniques. Heteroatom means nitrogen, oxygen, sulfur and phosphorus, more preferred heteroatoms include nitrogen and oxygen. Hydrocarbyl as used herein refers to a group containing one or more carbon atom backbones and hydrogen atoms, which may optionally contain one or more heteroatoms. Where the hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups well known to one skilled in the art. Hydrocarbyl groups may contain cycloaliphatic, aliphatic, aromatic, or any combination of such segments. The aliphatic segments can be straight or branched. The aliphatic and cycloaliphatic segments may include one or more double and/or triple bonds. Included in hydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, alkaryl, and aralkyl groups. Cycloaliphatic groups may contain both cyclic portions and noncyclic portions. Hydrocarbylene means a hydrocarbyl group or any of the described subsets having more than one valence, such as alkylene, alkenylene, alkynylene, arylene, cycloalkylene, cycloalkenylene, alkarylene and aralkylene. As used herein percent by weight or parts by weight refer to, or are based on, the weight or the compositions unless otherwise specified.

[0014] The term“monofunctional” refers to 1 , 1 -disubstituted alkene compounds having only one core unit. The core unit is represented by the combination of the carbonyl groups and the alkylene groups bonded to the 1 carbon atom. The term “difunctional” refers to 1 ,1 -disubstituted alkenes compounds having two core formulas (containing a reactive alkene functionality) bound through a hydrocarbylene linkage between one oxygen atom on each of two core formulas. The term“multifunctional” refers to 1 , 1 -disubstituted alkene compounds having more than one core unit (such as reactive alkene functionality) which may form a chain through a hydrocarbylene linkage between one heteroatom (oxygen atom) or direct bond on each of two adjacent core formulas.

[0015] The term“ketal” refers to a molecule having a ketal functionality; i.e. , a molecule containing a carbon bonded to two -OR groups, where O is oxygen and R represents any alkyl group or hydrogen. The term "volatile" and“non-volatile” refers to a compound which is capable of evaporating readily at normal temperatures and pressures. The term “non-volatile” refers to a compound which is not capable of evaporating readily at normal temperatures and pressures. The term“stabilized” (e.g., in the context of “stabilized” 1 ,1 -disubstituted alkene compounds 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 (i.e., cure speed is maintained) with time.

[0016] 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).

[0017] Disclosed is a composition including a carbonyl-substituted alkene including a dicarbonyl compound having an alkylene group between the carbonyl groups. The carbonyl-substituted alkene may have a carbon with a double bond attached thereto and which is further bonded to two carbon atoms of carbonyl groups. The composition may contain any carbonyl-substituted alkene further containing one or more amide groups bonded to one or more of the carbonyl groups. The composition may include monofunctional and/or polyfunctional monomers. For example, the composition may contain 1 , 1 -dicarbonyl substituted ethylene compounds. 1 , 1- dicarbonyl substituted ethylene compounds refer to compounds having a carbon with a double bond attached thereto and which is further bonded to two carbonyl carbon atoms. Exemplary compounds may include one or more amide groups. The carbonyl- substituted alkene may be a methylene dimalonamide, where each carbonyl group includes an amide group, or a methylene ketomalonamide, where one carbonyl group includes an amide group and the other carbonyl group includes a keto group.

[0018] The carbonyl-substituted alkene may correspond to the formula:

where X is an amide group or a hydrocarbyl group; and where R, separately in each occurrence, is a hydrogen or a hydrocarbyl group with one or more heteroatoms. For example, the carbonyl-substituted alkenes may correspond to the formulas:

where R, separately in each occurrence, is a hydrogen or a hydrocarbyl group with one or more heteroatoms. Exemplary carbonyl-substituted alkenes may be selected from, but are not limited to:

[0019] The carbonyl-substituted alkene compounds disclosed herein may exhibit a sufficiently high purity so that they can be polymerized. The purity of the carbonyl- substituted alkenes may be sufficiently high so that about 70 mole percent or more, about 80 mole percent or more, about 90 mole percent or more, about 95 mole percent or more, or about 99 mole percent or more of the carbonyl-substituted alkene is converted to polymer during a polymerization process. The purity of the carbonyl- substituted alkenes is about 96 mole percent or greater, about 97 mole percent or greater, about 98 mole percent or greater, about 99 mole percent or greater, or about 99.5 mole percent or greater, based on the total weight of the carbonyl-substituted alkenes. The concentration of any impurities containing a dioxane group may be about 2 mole percent or less, about 1 mole percent or less, about 0.2 mole percent or less, or about 0.05 mole percent or less, based on the total weight of the carbonyl- substituted alkenes. The total concentration of any impurity having the alkene group replaced by an analogous hydroxyalkyl group (e.g., by a Michael addition of the alkene with water) may be about 3 mole percent or less, about 1 mole percent or less, about 0.1 mole percent or less, or about 0.01 mole percent or less, based on the total moles in the carbonyl-substituted alkenes.

[0020] Also disclosed is a process for forming the carbonyl-substituted alkenes, starting with a dicarbonyl compound having an alkylene group between the carbonyl groups, where the dicarbonyl compound is a diamide or ketoamide. The process may include combining, to form a mixture, a dicarbonyl compound having an alkylene group between the carbonyl groups, wherein the dicarbonyl compound is a diamide or ketoamide; formalin or a formaldehyde precursor; and an acid catalyst; and heating the mixture; where the process forms a carbonyl-substituted alkene. The resulting carbonyl-substituted alkene may be the compounds disclosed herein, having a carbon with a double bond attached thereto and which is further bonded to two carbon atoms of carbonyl groups. At least one of the carbonyl groups may include an amide group. The resulting carbonyl-substituted alkene may be a methylene dimalonamide, where each carbonyl group includes an amide group, or a methylene ketomalonamide, where one carbonyl group includes an amide group and the other carbonyl group includes a keto group, for example.

[0021] The present teachings relate to a process for producing carbonyl- substituted alkenes, the carbonyl-substituted alkenes produced therefrom, and the polymers formed from the carbonyl-substituted alkenes. The process may relate to the methylenation of starting carbonyl compounds. The process may include contacting a catalyst with a starting carbonyl compound, adding formalin or a formaldehyde precursor, and heating the mixture to form a carbonyl-substituted alkene. The carbonyl-substituted alkenes resulting from the process may include methylene dimalonamides, methylene keto malonamides, and the like.

[0022] The starting carbonyl compound may be a dicarbonyl compound having an alkylene group between the carbonyl groups. The starting carbonyl compound for the process may be a dicarbonyl compound containing one or more keto groups, one or more amide groups, or a combination thereof. One or more amide groups of the starting carbonyl compound may be a secondary amide. One or more amide groups of the starting carbonyl compound may be a tertiary amide. The starting carbonyl compound may be a diamide or ketoamide, for example. The starting carbonyl compound may include one or more hydrocarbyl groups. The hydrocarbyl group may be an alkyl, cycloalkyl, or polyether group. The starting carbonyl compound may correspond to the formula:

wherein X is an amide group or a hydrocarbyl group; and wherein R, separately in each occurrence, is a hydrogen or a hydrocarbyl group with one or more heteroatoms. The starting carbonyl compound may include one or more amide groups and one or more keto groups, corresponding to the formula:

where R’ is a hydrocarbyl group which may contain one or more heteroatoms; and wherein R1 and R2, separately in each occurrence, is a hydrogen or a hydrocarbyl group with one or more heteroatoms. The starting carbonyl compound may include one or more amide groups corresponding to the formula:

wherein R1 and R2, separately in each occurrence, is a hydrogen or a hydrocarbyl group with one or more heteroatoms. R1 , R2, or both, may be, separately in each occurrence, alkyl, alkenyl, C3-C9 cycloalkyl, heterocyclyl, alkyl heterocyclyl, aryl, aralkyl, alkaryl, heteroaryl, or alkheteroaryl, or polyoxyalkylene, or R1 or R2 or both may form a 5-7 membered cyclic or heterocyclic ring. R1 , R2, or both, may be separately in each occurrence C1-C15 alkyl, C2-C15 alkenyl, C3-C9 cycloalkyl, C2-20 heterocyclyl, C3-20 alkheterocyclyl, Ce-ie aryl, C7-25 alkaryl, C 7-25 aralkyl, C5-18 heteroaryl or C6-25 alkyl heteroaryl, or polyoxyalkylene, or R1 , R2, or both, may 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 reactions disclosed herein. Substituents may include halo alkylthio, alkoxy, hydroxyl, nitro, azido, cyano, acyloxy, carboxy, or ester. R1 , R2, or both, may be separately in each occurrence C1-C15 alkyl, C3-C6 cycloalkyl, C4-18 heterocyclyl, C4-18 alkheterocyclyl, Ce-ie aryl, C7-25 alkaryl, C7-25 aralkyl, C5-18 heteroaryl or C6-25 alkyl heteroaryl, or polyoxyalkylene. R1 , R2, or both, may be separately in each occurrence a C1-4 alkyl. R1 , R2, or both, may be separately in each occurrence methyl or ethyl. The starting carbonyl compound may have a molecular weight of about 75 g/mol or greater, about 100 g/mol or greater, or about 140 g/mol or greater. The starting carbonyl compound may have a molecular weight of about 500 g/mol or less, about 400 g/mol or less, or about 300 g/mol or less. For example, the starting carbonyl compound may have a molecular weight of about 100 g/mol to about 400 g/mol (e.g., about 144 g/mol or greater). The starting carbonyl compound may be selected from N,N-dimethyl acetoacetamide, N,N- diethylacetoacetamide amide, N,N-tetramethyl malonamide, N,N-tetraethyl malonamide N,N-tetrapropylyl malonamide, N,N-tetraisopropyl malonamide, N,N- tetrabutyl malonamides and N,N-tetra(2-butyl) malonamide.

[0023] The process includes contacting the starting carbonyl compound with a catalyst. The catalyst may be an acid catalyst. The acid may be any acid that catalyzes the formation of an alkylene group between the carbonyl groups. The acid may have a pKa of about 2 or less, about 1 or less, or about 0 or less. The acid may have a pKa of about -14 or greater, about -10 or greater, or about -6 or greater. For example, the acid may be selected from methane sulfonic acid, sulfuric acid, trifluoroacetic acid, trifluoromethane sulfonic acid, p-toluenesulfonic acid, hydrochloric acid, hydrobromic acid, hydriodic acid, phosphoric acid, acetic acid, etc.

[0024] The catalyst may be added to the starting carbonyl compound, before or after adding the formalin or formaldehyde precursor, and heated for the reaction to occur. The catalyst may be supplied in an amount such that the formation of an alkylene group between the carbonyl compounds is catalyzed. The catalyst may be supplied in an amount of about 0.5 mol % or greater, about 0.75 mol % or greater, or about 1 mol % or greater. The catalyst may be supplied in an amount of about 4 mol % or less, about 4.5 mol % or less, or about 5 mol % or less. The catalyst may be supplied in an amount of about 0.0001 to about 1.0000 equivalents relative to the starting carbonyl materials.

[0025] The process further includes adding formalin or a formaldehyde precursor thereof to the catalyst and starting carbonyl compound to form a mixture. Any formalin or formaldehyde precursor may be used such that, under the disclosed reaction conditions, the formalin or formaldehyde precursor will facilitate the insertion of an alkylene between the carbonyls groups. Exemplary sources of formaldehyde include formaldehyde, trioxane, formalin, or paraformaldehyde. The source of formaldehyde may be substantially free of methanol, water, or both. The formaldehyde may be added in a mole ratio of about 1 :1 or greater, about 1.25:1 or greater, about 1.5:1 or greater, about 2:1 or greater, about 2.15:1 or greater, or about 2.25:1 or greater moles of formalin or formaldehyde precursor to moles of the starting dicarbonyl compound. The formaldehyde may be added in a mole ratio of about 3:1 or less, about 2.85:1 or less, or about 2.75: 1 or less moles of formaldehyde to moles of the starting dicarbonyl compound. The formaldehyde may be added in an amount of about 0.75 equivalents or greater, about 1 equivalent or greater, about 1.1 equivalents or greater, or about 2.0 equivalents or greater relative to the starting material malonamide, ketoamide, or diamide. The formaldehyde may be added in an amount of about 4 equivalents or less, about 3 equivalents or less, or about 2.1 equivalents or less relative to the starting material malonamide, ketoamide, or diamide. The formalin or formaldehyde precursor may be added in a slight excess.

[0026] The process may be accomplished in a continuous process. The reaction may be accomplished without the addition of a solvent. The reaction step may be accomplished at atmospheric pressure. The mixture of starting dicarbonyl compound, catalyst, and formalin or formaldehyde precursor may then be heated. The reaction mixture may be exposed to any temperature at which an alkylene group may be inserted between the carbonyl groups. The reaction mixture may be heated to about 65 °C or greater, about 70 °C or greater, or about 80 °C or greater. The reaction mixture may be heated to about 180 °C or less, about 150 °C or less, about 120 °C or less, about 1 10 °C or less, or about 100 °C or less. For example, the mixture may be heated to about 80 °C or more and about 140 °C or less. The reaction mixture may be exposed to such temperatures for a time period at which an alkylene group may be inserted between the carbonyl groups. The reaction may be exposed to this heating step for about 8 hours or less, about 6 hours or less, or about 5 hours or less. The reaction may be exposed to at this heating step for about 0.5 hours or more, about 1 hour or more, or about 2 hours or more. The reaction mixture may be exposed to heating such that it refluxes. The reaction may be monitored by analytical techniques, such as 1 H NMR and/or GC-MS, to check for conversion to the desired product. The process may achieve a molar yield of about 30% or greater, about 35% or greater, or about 40% or greater. The process may achieve a molar yield of about 80% or less, about 75% or less, or about 70% or less. The conversion of the limiting reagent (e.g., the malonate) may be about 85% or greater, about 90% or greater, about 95% or greater, about 97% or greater, or about 99% or greater.

[0027] At the end of the reaction, any solvent and/or volatiles may be removed. The removal of solvent and/or volatiles may be performed under reduced pressure. Reduced pressure may be, for example, about 200 mmHg or less, about 175 mmHg or less, or about 150 mmHg or less. Reduced pressure may be, for example, about 1 mmHg or greater, about 5 mmHg or greater, or about 10 mmHg or greater. Reduced pressure, such as during distillation, may be performed with a pressure of less than about 1 mmHg. Reduced pressure may be achieved by use of common techniques known in the art for reducing pressure. For example, reduced pressure may be achieved by a rotary evaporator or under vacuum conditions. The removal may be performed at a temperature of about 40 °C or more, about 45 °C or more, or about 50 °C or more. The removal may be performed at a temperature of about 70 °C or less, about 65 °C or less, or about 60 °C or less. For example, the temperature may be about 45 °C to about 65 °C. Distillation may be performed to separate the desired product from the mixture. First pass distillation, for example, may be performed to obtain the monomer. The first pass distillation may be performed at a temperature of about 90 °C or greater or about 100 °C or greater. The first pass distillation may be performed at a temperature of about 120 °C or less, or about 110 °C or less. Multiple fractional distillation may be performed to achieve a desired purity of the monomer. Distillation may be performed under vacuum. For example, the first pass distillation and/or multiple fractional distillations may be performed under vacuum of under 1 mmHg. The isolated product or the crude mixture may be taken up in ether or ethyl acetate and extracted with water, brine, or both. The organic solution obtained may be dried, such as over sodium sulfate.

[0028] The one or more carbonyl-substituted alkene compounds prepared may be isolated using any known processes for recovering such products, see for example Malofsky et al, U.S. Patent Nos. 8,6098985; 8,884,051 and 9,108,914. The desired products are separated from a variety of by-products, side reaction products and impurities. A variety of separation processes or operations may be utilized. Exemplary separation processes include a series of condensation and distillation steps. Exemplary separation units include, hot condensers, condensers, vacuum distillation apparatuses, simple distillation apparatuses and/or fractional distillation apparatuses. Liquid-liquid extraction processes may be employed. Such process may be helpful for removal of salt impurities, for example. In some exemplary embodiments, the separation techniques may be employed at atmospheric pressure, under vacuum, or under elevated pressure, in accordance with sound engineering principles.

[0029] The carbonyl-substituted alkenes may form an oligomeric complex. The oligomeric complex may include two or more units of methylene malonamide monomers, ketoacrylamide monomers, or a combination thereof. For example, the oligomeric complex may correspond to the formula:

where R, separately in each occurrence, may be a hydrogen or a hydrocarbyl group with one or more heteroatoms.

[0030] The compositions disclosed may be utilized to prepare homo and copolymers prepared from or containing a dicarbonyl compound having an alkylene group between the carbonyl groups, where the dicarbonyl compound is a diamide or ketoamide or containing such monomers. For example, the polymeric composition as disclosed herein may correspond to the formula:

where R, separately in each occurrence, is a hydrogen or a hydrocarbyl group with one or more heteroatoms; and where R’ is an amide group or a hydrocarbyl group.

[0031] The polymers prepared from the monomers described herein can also be copolymerized with other 1 , 1 -disubstituted alkene compounds, such as those disclosed in Malofsky et al., U.S. Patent Nos. 8,609,885; 8,884,051 ; 9,108,914; and 9,518,001. The other 1 ,1-disubsituted alkene compounds may be compounds (e.g., monomers) wherein a central carbon atom is doubly bonded to another carbon atom to form an ethylene group. The central carbon atom is further bonded to two carbonyl groups. Each carbonyl group is bonded to a hydrocarbyl group through a direct bond or an oxygen atom. Where the hydrocarbyl group is bonded to the carbonyl group through a direct bond, a keto group is formed. Where the hydrocarbyl group is bonded to the carbonyl group through an oxygen atom, an ester group is formed. The other 1 i-Hici ihctiti ited alkenes may have a structure as shown below in Form la i WIWP

WO 2019/125930 _x , , , , , , PCT/US2018/065608

LΊ ana KZ are an oxygen atom or a direct bond, and where R1 ana KZ are eacn hydrocarbyl groups that may be the same or different. Both X1 and X2 may be oxygen atoms, such as illustrated in Formula IIA, one of X1 and X2 may be an oxygen atom and the other may be a direct bond, such as shown in Formula MB, or both X1 and X2 may be direct bonds, such as illustrated in Formula IIC. The other 1 , 1 -disubstituted alkene compounds used herein may have all ester groups (such as illustrated in

Formula IIA), all keto groups (such as illustrated in Formula IIC) or a mixture thereof

(such as illustrated in Formula MB). Such compositions may further include one or more compounds containing the core unit of two or more 1 ,1 -disubstituted alkene compounds wherein one of the carbonyl groups of each compound is bonded (e.g., through oxygen atoms) to a polyvalent hydrocarbyl group, wherein the composition is crosslinked when polymerized. The other 1 ,1 -disubstituted alkenes may include one or R1

- N

\ more amine groups. For example, an -XR group of Formula I may be: ^R2

Formula MB

Formula 11C

[0032] The higher purity of the compositions provides greater control of the homo and copolymers so that desired molecular weights and polydispersities can be prepared. The carbonyl-substituted alkenes, such as 1 , 1 -disubstituted alkenes, in the polymers function to plasticize the polymers, which may be undesirable for many applications. Thus, lower amounts of 1 , 1 -disubstituted alkenes may result in better control of the properties of the polymers. The polymers contain about 3 weight percent or less of 1 ,1 -disubstituted alkenes, about 2 weight percent or less of 1 , 1 -disubstituted alkenes, or about 1 weight percent or less of 1 , 1 -disubstituted alkenes. The polymers prepared may have molecular weights of about 5,000 daltons or greater, molecular weights of about 10,000 daltons or greater or molecular weights of about 500,000 daltons or greater. The polymers may have molecular weights of about 1 ,000,000 daltons or less or about 100,000 or less. The polymers prepared may have polydispersities of about 1 or greater. The polymers may have polydispersities of about 3 or less, about 2 or less or about 1.1 or less.

[0033] The presence of multifunctional 1 ,1 -disubstituted alkenes in polymerizable compositions may function to crosslink polymers prepared therefrom. Therefore, the multifunctional 1 , 1 -disubstituted alkenes may be present as crosslinkers. Crosslinking may further increase the glass transition temperature of the resulting polymers. The multifunctional 1 , 1 -disubstituted alkenes may be present in a sufficient amount to increase the glass transition temperature of the resulting polymers. The multifunctional 1 ,1 -disubstituted alkenes may be present in an amount of about 1 weight percent or greater, about 5 weight percent or greater, or about 15 weight percent or greater. The multifunctional 1 , 1 -disubstituted alkenes may be present in an amount of 100 weight percent or less. The multifunctional 1 , 1 -disubstituted alkenes may be present in an amount of about 30 weight percent or less or about 15 weight percent or less. It is therefore possible to tailor a polymerizable composition or polymer to exhibit a desired glass transition temperature.

[0034] The polymerizable compositions disclosed herein can be polymerized by exposing the composition to free radical polymerization conditions, to anionic polymerization conditions, or both. Free radical polymerization conditions are well known to those skilled in the art such as disclosed in Sutoris et al. , U.S. Patent No. 6,458,956. In certain embodiments the polymerizable compositions are exposed to anionic polymerization conditions. The polymerizable compositions are contacted with any anionic polymerization initiator or with any nucleophilic material. As 1 , 1- disubstituted alkenes, which may be highly electrophilic, contacts any nucleophilic material, this 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 are contacted with. Thus, the polymerizable composition will continue until all available unreacted 1 , 1 -disubstituted 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. The polymerization can proceed at any reasonable temperature including at ambient temperatures, from about 20 to 35 °C, depending on ambient conditions. The polymerization can be performed in bulk, without a solvent or dispersant, or in a solvent or dispersant.

[0035] According to certain embodiments, a suitable polymerization initiator can generally be selected from any agent that can initiate polymerization substantially upon contact with a selected polymerizable composition. In certain embodiments, it can be advantageous to select polymerization initiators that can induce polymerization under ambient conditions and without requiring external energy from heat or radiation. In embodiments wherein the polymerizable composition comprises one or more 1 , 1 - disubstituted alkene compounds, a wide variety of polymerization initiators can be utilized including most nucleophilic initiators capable of initiating anionic polymerization. Exemplary initiators include metal carboxylate salts, alkaline earth carboxylate 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. Other polymerization initiators can also be suitable including certain plastics (e.g., ABS, acrylic, and polycarbonate plastics) and glass-fiber impregnated plastics. Additional suitable polymerization initiators for such polymerizable compositions are also disclosed in Malofsky et al., U.S. Patent App. Publication No. 2015/0073110. In some embodiments the polymerization initiator may be encapsulated using any encapsulation method compatible with the polymerization of the 1 , 1 -disubstituted alkenes. In some embodiments the encapsulated initiator (activation agent) may be as disclosed in Stevenson et al. U.S. Patent No. 9,334,430.

[0036] Polymerization can be terminated by contacting the polymeric mixture with an anionic polymerization terminator. In some embodiments the anionic polymerization terminator is an acid. It may desirable to utilize a sufficient amount of the acid to render the polymerization mixture slightly acidic, i.e. , having a pH of about 7 or less, about 6 or less. 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.

[0037] The polymerizable compositions may be polymerized in bulk, which is in the absence of a solvent or dispersant, in a solution or in an emulsion. Polymerization in bulk can be performed by contacting the polymerizable composition which may include any of the other ingredients disclosed herein with a suitable substrate and an activator and allowing the composition to polymerize.

[0038] The polymerizable compositions may be prepared by emulsion polymerization. For example, the polymerizable compositions may be prepared by the process disclosed in Stevenson et al., U.S. Patent No. 9,249,265 incorporated herein by reference in its entirely for all purposes. Disclosed in Stevenson et al., U.S. Patent No. 9,249,265 is a process comprising the steps of: agitating a mixture including: about 25 weight percent or more of a carrier liquid, a surfactant (e.g., an emulsifier) and one or more monomers to form micelles of the one or more monomers in the carrier liquid, wherein the one or more monomers includes one or more 1 , 1 -disubstituted alkenes; reacting an activator with at least one of the monomers in the micelle for initiating the anionic polymerization of the one or more monomers; and anionically polymerizing the one or more monomers. The polymerization process may include one or more surfactants for forming an emulsion having micelles or a discrete phase including a monomer (e.g., a 1 , 1 -disubstituted alkene compound) distributed throughout a continuous phase (e.g., a continuous phase including a carrier liquid). The surfactant may be an emulsifier, a defoamer, or a wetting agent. 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 monomer and carrier liquid. The surfactants according to the teachings herein include one or more surfactants for improving the stability of emulsion (i.e., for improving the stability of the dispersed phase in the carrier liquid phase). The surfactant and/or the amount of surfactant may be selected so that all of the monomer micelles are covered by a layer of the surfactant. The surfactant may include an amphoteric surfactant, a nonionic surfactant, or any combination thereof. The surfactant may be free of anionic surfactants during the polymerization process. One example of a preferred surfactant (e.g., an emulsifier) is an ethoxylate, such as an ethoxylated diol. For example, the surfactant may include 2,4,7,9-tetramethyl-5- decyne-4,7-diol ethoxylate. The surfactant may include a poly(alkene glycol). Another example of a preferred surfactant is a poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) copolymer. Another example of a preferred surfactant is a surfactant including an alcohol, an ethoxylated alcohol, or both. For example, the surfactant may include CARBOWET® 138 nonionic surfactant (including alkyl alcohol, polyethylene glycol, ethoxylated Cg-Cn alcohols). Another example of a preferred surfactant is a surfactant including a sorbitan, a sorbitol, or a polyoxyalkene. For example, the surfactant may include sorbitan monopalmitate (nonionic surfactant). Other examples of preferred surfactants include branched polyoxyethylene (12) nonylphynyl ether (IGEPAL® CO-720) and poly(ethylene glycol) sorbitol hexaoleate (PEGSH). The amount of the surfactant (e.g., the amount of the emulsifier) may be sufficient to form a layer that substantially encapsulates the monomer and subsequent polymer particles. The amount of surfactant may be sufficient so that the discrete phase has a diameter of about 10 mm or less, about 1 mm or less, about 300 pm or less, or about 100 pm or less. The amount of the surfactant is may be sufficient so that the discrete phase has a diameter of about 0.01 pm or more, about 0.1 pm or more, about 1 pm or more, about 10 pm or more, or about 50 pm or more. 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, and about 6 weight percent or less or about 3 weight percent or less, based on the total weight of the emulsion. The weight ratio of the surfactant to the total weight of the monomer and polymer in the emulsion (e.g., at the end of the polymerization process) is about 0.0001 or more, about 0.002 or more, about 0.005 or more or about 0.01 or more. The weight ratio of the surfactant to the total weight of the monomer and polymer in the emulsion (e.g., at the end of the polymerization process) is about 5 or less (i.e. , about 5: 1 or less), about 1 or less, about 0.5 or less, and or about 0.1 or less. The carrier liquid may be water. The polymerization process may include a step of applying shear forces or sonication to a mixture including at least the surfactant and the carrier fluid for forming an emulsion. For example, the process may include stirring or otherwise agitating the mixture for creating the emulsion.

[0039] The polymerizable compositions disclosed herein may be polymerized in solution via anionic polymerization processes. The polymerizable compositions may be polymerized utilizing the method disclosed in Palsule et al. , U.S. Patent No. 9,279,022. According to the process disclosed in Palsule et al. , U.S. Patent No. 9,279,022 the process comprises the steps of mixing one or more 1 , 1 -disubstituted alkenes and a solvent; adding an activator; reacting the activator with the one or more 1 ,1 -disubstituted alkenes to initiate the anionic polymerization of the one or more 1 , 1- disubstituted alkenes; and anionically polymerizing the one or more 1 , 1 -disubstituted alkenes to form a polymer. The concentration of the monomer in the solution polymerization process may be sufficiently low so that after polymerization, the solution can flow. If the concentration of the monomer is too high, the solution becomes too viscous at the end of the polymerization process and the solution may be difficult to handle. The concentration of the monomer in the solution polymerization process may be sufficiently high so that the polymerization process is economical. The one or more monomers is present at a concentration of about 0.5 weight percent or more, about 2 weight percent or more, about 5 weight percent or more or about 8 weight percent or more, based on the total weight of the solvent and monomer. The one or more monomers may be present at a concentration of about 90 weight percent or less, about 75 weight percent or less, about 50 weight percent or less, about 30 weight percent or less, or about 20 weight percent or less. If the monomer is added at multiple times (such as continuous and/or sequential monomer addition), it will be appreciated that the amount of the one or more monomers refers to the total amount of monomer and polymer and by-products of the monomer that are present when the addition of monomer has been completed. The polymerization process includes one or more solvents selected so that the monomer and solvent form a single phase. The solvent may not chemically react with the other components of the solution polymerization system during the polymerization process. For example, the solvent may not react with the monomer. As another example, the solvent may not react with the activator. Solvents include organic solvents, or mixtures of organic solvents. Such solvents, or solvent mixtures typically are in a liquid state at the reaction temperature(s) (e.g., during activation and/or during polymerization. The pressure of the solvent (e.g., organic solvent) and of the monomer at the polymerization temperature should be sufficiently low so that the risk of the reactor failing from over-pressure is reduced or eliminated. For example, the partial pressure of the solvent, of the monomer, or both, at the polymerization temperature may be about 500 Torr or less, about 200 Torr or less, about 50 T orr or less, or about 5 T orr or less. It may be desirable for the solvent to be substantially or entirely free of any solvent that may react with the monomer via Michael addition. However, by selecting reaction conditions so that the polymerization reaction is sufficiently fast, it may be possible to employ such monomers in the solvent polymerization process. For example, by selecting parameters such as monomer feed rates, reaction temperature, monomer type, and pH, it may be possible to employ a solvent including or consisting of a protic solvent, such as an alcohol. The solution polymerization may be initiated using an activator capable of initiating anionic polymerization of the 1 , 1 -disubstituted alkene containing compound. The solvent and/or one or more of the monomers (e.g., the 1 ,1 -disubstituted alkene compounds) may further contain other components to stabilize the monomer prior to exposure to polymerization conditions or to adjust the properties of the final polymer for the desired use. Prior to the polymerization reaction, one or more inhibitors may be added to reduce or prevent reaction of the monomer. Such inhibitors may be effective in preventing anionic polymerization of the monomer, free radical polymerization of the monomer, reaction between the monomer and other molecules (such as water), or any combination thereof.

[0040] The polymerization processes disclosed may include a step of applying shear forces to a mixture including at least the monomer and the solvent or carrier. For example, the process may include stirring or otherwise agitating the mixture for creating the solution or emulsion, for dispersing or removing a precipitated polymer, for controlling thermal gradients, or any combination thereof. The polymerization processes may include a reaction temperature at which the partial pressure of the solvent is generally low. For example, the partial pressure of the solvent and/or the monomer may be about 400 Torr or less, about 200 Torr or less, about 100 Torr or less, about 55 Torr or less, or about 10 Torr or less. The reaction temperature may be about 80 °C or less, about 70 °C, about 60 °C or less, about 55 °C or less, about 45 °C or less, about 40 °C or less or about 30 °C or less. The reaction temperature typically is sufficiently high that the solvent or carrier liquid and the monomer are in a liquid state. For example, the reaction temperature may be about -100 °C or more, about -80 °C or more, about -30 °C or more, or about 10 °C or more. When polymerizing a 1 , 1 -disubstituted alkene compound, it may be desirable to add one or more acid compounds to the solution, to the monomer, or both, so that the initial pH of the solution is about 7 or less, about 6.8 or less, about 6.6 or less, or about 6.4 or less. The polymerization process may be stopped prior to the completion of the polymerization reaction or may be continued until the completion of the polymerization reaction. The reaction rate may be sufficiently high, and/or the reaction time is sufficiently long so that the polymerization reaction is substantially complete.

[0041] The carbonyl-substituted alkenes or polymers prepared therefrom may be curable by heat, moisture, UV, or a combination thereof. The carbonyl-substituted alkenes or polymers prepared therefrom may be curable at temperatures of about -10 °C or greater, about -5 °C or greater, or about 0 °C or greater. The carbonyl-substituted alkenes or polymers prepared therefrom may be curable at temperatures of about 200 °C or les, about 175 °C or less, or about 150 °C or less.

[0042] The conversion of the monomer to polymer may be about 30 weight percent or more, about 60 weight percent or more, about 90 weight percent or more, about 95 weight percent or more, or about 99 weight percent or more. The conversion of monomer to polymer may be about 100 weight percent or less.

[0043] The polymerizable compositions 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, in certain embodiments, 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.

[0044] 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. Such thickening agents and other compounds may be used to increase the viscosity of a polymerizable system from about 1 to 3 cPs to about 30,000 cPs, or more.

[0045] Stabilizers may be included in the polymerizable compositions to increase and improve the shelf life and to prevent spontaneous polymerization. Generally, 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 (e.g., methanesulfonic acid (“MSA”)), and vapor phase stabilizers (e.g., trifluoroacetic acid (“TFA”)). Free-radical stabilizers may include phenolic compounds (e.g., 4-methoxyphenol or mono methyl ether of hydroquinone (“MeHQ”) and butylated hydroxy toluene (BHT)). Stabilizer packages for 1 , 1 -disubstituted alkenes are disclosed in Malofsky et al., U.S. Patent Nos. 8,609,885 and 8,884,051. Additional free radical polymerization inhibitors are disclosed in Sutoris et al., U.S. Patent No. 6,458,956. Generally, only 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 (MeHQ). 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 composition, 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 composition, 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 are 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 composition, about 5 parts per million by weight or greater or about 10 parts per million by weight or greater. The free radical polymerization stabilizers are present in an amount of about 5000 parts per million by weight or less based on the weight of the composition about 1000 parts per million by weight or less or about 500 parts per million by weight or less.

[0046] The present teachings relate to polymeric compositions, such as solid polymeric compositions, their preparation and cross-linking, and their uses. The polymerizable compositions and polymers disclosed herein may be utilized and a number of applications. Exemplary applications include adhesives, sealants, coatings, components for optical fibers, potting and encapsulating materials for electronics, resins and pre-polymers as raw materials in other systems, and the like. The polymeric compositions as disclosed herein may be useful in, but not limited to, any of the following areas: hydrogels; molecular electronics; antimicrobial applications; water soluble polymers; oligoaniline side chains; flocculation; super water-absorbing polymers (SAPs); thickening agents; binders; soil conditioners; super absorbent materials; filtering aids; flocculating agents; crosslinkers; suspending agents; lubricants; oil recovery agents; waste water treatment; highly stretchable self-healing poly (N,N-dimethylacrylamide) hydrogels; crosslinked gels in the form of membranes, coatings, and formed objects; ophthalmic lenses; contact lenses; intraocular lenses; thermally expandable thermoplastic microspheres; the like; or a combination thereof.

[0047] The polymerizable compositions exhibit a number of advantageous properties including rapid reactivity, room or low temperature reactivity, tailorable rheological characteristics, and the like. Polymers prepared from the polymerizable compositions exhibit a number of advantageous properties including for example, high glass transition temperature, high degradation temperature, high heat resistance, high stiffness and modulus, good rigidity and the like. The polymerizable compositions may allow for a variety of curing options, such as heat, moisture, UV, or a combination thereof. The carbonyl-substituted alkenes or polymers thereof may exhibit dimensional stability, high peel strength, excellent hydrolytic stability, low odor with no out-gassing; fast, 100% complete cure; low temperature cure; outstanding chemical resistance; exceptional adhesion to similar and dissimilar substrates; no or low shrinkage; or a combination thereof. The carbonyl-substituted alkenes may exhibit a higher glass transition temperature due to the presence of one or more amide groups within the monomer as compared to monomers without an amide group. The presence of amide groups may provide for greater flexibility in the preparation of analogs. The present teachings may allow for solvent-free formulations, halogen-free formulations, or both.

[0048] Other components commonly used in curable compositions may be used in the compositions of this invention. Such materials are well known to those skilled in the art and may include ultraviolet stabilizers and antioxidants and the like. The compositions of the invention may also contain durability stabilizers known in the art. Among preferred durability stabilizers are alkyl substituted phenols, phosphites, sebacates and cinnamates. [0049] The process disclosed allows the preparation of 1 , 1 -disubstituted alkenes at higher yields than previously possible. The product yield may be about 90 percent or greater, about 93 percent or greater, or about 95 percent of greater.

[0050] Molecular weights as described herein are number average molecular weights which may be determined by Gel Permeation Chromatography (also referred to as GPC) using a polymethylmethacrylate standard.

[0051] The composition, processes, and polymers disclosed may further comprise any one or more of the features described in this specification in any combination, including the preferences and examples listed in this specification, and includes the following features: one or more amide groups of the dicarbonyl compound may be a tertiary amide; the molecular weight of the dicarbonyl compound may be about 100 g/mol to about 400 g/mol; the formalin or formaldehyde precursor may be supplied in a ratio of about 1.5 to about 1.0 moles of formaldehyde to moles of the dicarbonyl compound; the mixture may be heated to about 80 °C or greater; the mixture may be heated to about 80 °C to about 140 °C; the acid catalyst may have a pKa of about 2 to about -14; the acid catalyst may be selected from methane sulfonic acid, sulfuric acid, trifluoroacetic acid, and trifluoromethane sulfonic acid; the carbonyl-substituted alkene may have a purity that is about 95 mole percent or greater, based on the total weight of the carbonyl-substituted alkenes; the carbonyl-substituted alkene may correspond to the formula:

where X may be an amide group or a hydrocarbyl group; where R, separately in each occurrence, may be a hydrogen or a hydrocarbyl group with one or more

heteroatoms; the carbonyl-substituted alkene may correspond to:

or where R, separately in each occurrence, may be a hydrogen or a hydrocarbyl group with one or more heteroatoms; the carbonyl-substituted alkene may be selected from:

the carbonyl-substituted alkenes may form an oligomeric complex comprising two or more units of methylene malonamide or ketoacrylamide monomers; the oligomeric complex may correspond to the formula:

or where R, separately in each occurrence, may be a hydrogen or a hydrocarbyl group with one or more heteroatoms; the process may further comprise a polymerization step for forming a polymeric composition; the polymeric composition may correspond to the formula:

where R, separately in each occurrence, may be a hydrogen or a hydrocarbyl group with one or more heteroatoms; where R’ may be an amide group or a hydrocarbyl group; the carbonyl-substituted alkenes or polymers prepared therefrom may be curable by heat, moisture, UV, or a combination thereof; the composition is copolymerized with other 1 , 1 -disubstituted alkene compounds to form a polymeric composition; the other 1 , 1 -disubstituted alkene compounds correspond to the formula:

where X ¹ and X ² , separately in each occurrence, are an oxygen atom or a direct bond; where R ¹ and R ² , separately in each occurrence, are hydrocarbyl groups that are the same or different; the polymeric composition includes multifunctional 1 , 1 -disubstituted alkenes that act as crosslinkers and/or function to crosslink polymers prepared therefrom; the carbonyl-substituted alkenes or the polymers prepared therefrom may exhibit excellent hydrolytic stability; the carbonyl-substituted alkenes or the polymers prepare therefrom may be curable at temperatures of about 0 °C to about 150 °C, or about 20 °C to about 25 °C (e.g., about room temperature); the carbonyl-substituted alkenes or the polymers prepared therefrom may exhibit exceptional adhesion to substrates; the carbonyl-substituted alkenes or the polymers prepared therefrom may exhibit shrinkage of about 10% or less; a carbonyl-substituted alkene formed by the process as described herein; a polymer prepared from the carbonyl-substituted alkenes as described herein. All references cited herein are incorporated herein by reference in their entirety for all purposes. ILLUSTRATIVE EMBODIMENTS

[0052] The following examples are provided to illustrate the disclosed compositions but are not intended to limit the scope thereof. All parts and percentages are by weight unless otherwise stated.

Example 1

[0053] N,N-dimethyl acetoacetamide, in an amount of 1.0 equivalent, is charged to a three-necked round bottom flask fitted with a thermocouple, an addition funnel and a vacuum take-off adapter with a receiver for short-path distillation. Methanesulfonic acid is added to the reaction pot in an amount of 0.01 equivalents. The mixture is heated to 80 °C. Formalin is added to the reaction pot dropwise in an amount of 1.1 equivalents. Upon complete addition, the reaction is stirred at 80 °C for 2-3 hours. The reaction is monitored by ¹ H NMR and GC-MS to check for conversion to desired product. Volatiles are removed under reduced pressure at about 45 °C to about 55 °C. A first-pass distillation is then performed at about 100 °C to obtain the monomer in about 98% purity.

[0054] This process allows for the synthesis of N,N-dimethyl-2-methylene-3- oxobutanamide, or:

A/,A/-dimethyl-2-methylene-3-oxobutanamide

Example 2

[0055] N,N-diethylacetoacetamide amide, in an amount of 1.0 equivalent, is charged to a three-necked round bottom flask fitted with a thermocouple and first pass distillation set up. Methanesulfonic acid is added to the reaction pot in an amount of 0.01 equivalents. Formalin is added in an amount of 1.1 equivalents. The flask is heated to 80 °C. The reaction is allowed to proceed for two hours and is monitored by GC-MS. Volatiles are removed under reduced pressure at about 45 °C to about 65 ° C. First-pass distillation is performed at about 105 °C to obtain crude monomer. Multiple fractional distillations are performed to obtain pure monomer having about 96% to about 97% purity. [0056] The reaction follows the following reaction scheme:

Example 3

[0057] An amide (32.44 g, 120 mmol), and methanesulfonic acid (100 mI_), are charged to a three-necked round bottom flask equipped with a short length of fractioning column connected to a condenser from the top. The flask is heated to 80 °C with gentle air sparge. Commercial formalin (10.73 g, 132 mmol, 1.1 equivalents) is added dropwise into the reactor flask. After addition, the pot temperature is gradually increased to 136 °C over a period of 1.5 hours. The reaction is allowed to proceed for two hours when all water is removed. The mixture is then taken in ethyl acetate (60 ml_), followed by washing with 15% aqueous sodium chloride solution (2x60 ml_), deionized water (60 ml_) and brine (120 ml_), sequentially. The mixture is dried with sodium sulfate, concentrated to afford the crude product. Distillation under reduced pressure is performed to obtain 12 g (35% yield) of colorless, clear, viscous oil having a purity of about 99% or greater, as measured by NMR.

[0058] The reaction follows the following reaction scheme:

Mol. Wt.: 270.41 37% aq. solution

Mol. Wt.: 282.42 d = 1 .09

32.45g (120 mmol) 10.73g (132 mmol)

[0059] Parts by weight as used herein refers to 100 parts by weight of the composition specifically referred to. Any numerical values recited in the above application include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, from 20 to 80, or from 30 to 70, it is intended that values such as 15 to 85, 22 to 68, 43 to 51 , 30 to 32 etc. are expressly enumerated in this specification. For values which are less than one, one unit is considered to be 0.0001 , 0.001 , 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value, and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner. Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. The use of“about” or “approximately” in connection with a range applies to both ends of the range. Thus, “about 20 to 30” is intended to cover“about 20 to about 30”, inclusive of at least the specified endpoints. The term“consisting essentially of” to describe a combination shall include the elements, ingredients, components or steps identified, and such other elements ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms “comprising” or “including” to describe combinations of elements, ingredients, components or steps herein also contemplates embodiments that consist essentially of the elements, ingredients, components or steps. Plural elements, ingredients, components or steps can be provided by a single integrated element, ingredient, component or step. Alternatively, a single integrated element, ingredient, component or step might be divided into separate plural elements, ingredients, components or steps. The disclosure of“a” or“one” to describe an element, ingredient, component or step is not intended to foreclose additional elements, ingredients, components or steps.