WO2020123579A1

WO2020123579A1 - Polymerization of 1,1-dicarbonyl 1-alkenes

Info

Publication number: WO2020123579A1
Application number: PCT/US2019/065595
Authority: WO
Inventors: John Klier; Aniruddha Palsule; Mengfei HUANG
Original assignee: Sirrus, Inc.
Priority date: 2018-12-11
Filing date: 2019-12-11
Publication date: 2020-06-18

Abstract

Disclosed are emulsion polymers of 1,1-dicarbonyl-1-alkenes having a weight average molecular weight (g/mol) of between about 3,000 and about 1,000,000 and a particle size distribution of between about 10 nm and about 700 nm. Also disclosed are processes for making emulsion polymers of 1,1-dicarbonyl-1-alkenes having a weight average molecular weight (g/mol) of between about 3,000 and about 1,000,000 and a particle size distribution of between about 10 nm and about 700 nm. The processes include the steps of adding 1,1, dicarbonyl 1-alkenes to a mixture of water and surfactant with a shear force or sonication with shear force or sonication.

Description

POLYMERIZATION OF 1,1 -DICARBONYL 1 -ALKENES

FIELD

[001] Disclosed are suspension polymers of 1 ,1 -dicarbonyl-1 -alkenes having a weight average molecular weight (g/mol) of between about 3,000 and about 1 ,000,000 and a particle size distribution of between about 10 nm and about 1 micron. Also disclosed are processes for making suspension polymers of 1 ,1 -dicarbonyl-1 -alkenes having a weight average molecular weight (g/mol) of between about 3,000 and about 1 ,000,000 and a particle size distribution of between about 10 nm and about 1 micron. The processes include the steps of adding 1 ,1 , dicarbonyl 1 -alkenes to nucleophiles with shear force or sonication.

BACKGROUND

[002] 1 ,1 -dicarbonyl-1 -alkenes are increasingly important monomers in forming a variety of compounds and polymerizable compositions because of inherent ability to rapidly polymerize at ambient temperatures upon contact with basic materials. 1 ,1 -dicarbonyl-1 - alkenes include methylene malonates, methylene dimalonamides, methylene keto malonamides, 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)). Early methods for synthesizing methylene malonates suffered from significant deficiencies that precluded preparing commercially viable monomers, (e.g., 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 acidforming 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 poor yield, quality, and chemical performance of the monomers formed by prior methods prevented their practical use in the production of commercial 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, U.S. Patent No. 8,888,051 , Malofsky et al., U.S. Patent No. 9,108,914 and Sullivan et al., U.S. Patent No 9,518,001. The synthesis procedures described therein resulted in improved yields of heretofore elusive, high quality 1 ,1 -dicarbonyl-1 -alkenes.

[004] The availability of high quality 1 ,1 -dicarbonyl-1 -alkenes has led to their use in bulk polymerization processes, which typically operate at or near ambient temperature and can be initiated with a wide number of reagents. However, bulk polymerization is difficult to control resulting in variable performance and poor mechanical properties. These difficulties in bulk polymerization may be particularly pronounced when manufacturing large quantities of polymer, where heat transport issues may occur, especially when there may be shear heat generated by the flow of the high viscosity polymer and/or heat emitted due to the inherent exothermic nature of the polymerization.

[005] Furthermore, the resulting polymer may be characterized by one or more of the following: a generally high level of branching, a high polydispersity index, a high concentration of non-polymer reaction products, a high concentration of monomers and/or oligomers, or a generally high viscosity. For example, when polymerized in bulk, the resulting polymer may have a high viscosity that makes further processing, handling, or polymerization difficult.

[006] Accordingly, solution polymerization processes, which utilize high quality 1 ,1- dicarbonyl-1 -alkenes have been recently developed (Palsule et al., U.S. Patent No. 9,279,022) which solve many of the issues associated with bulk polymerization of 1 ,1 - dicarbonyl-1 -alkenes. However, issues with preparing high molecular weight polymers with good polydispersity and controlling polymer particle size remain.

[007] Thus, what is needed are polymers with minimal polydispersity, of high molecular weight and controlled particle size. What is also needed are methods for preparing such polymers.

SUMMARY

[008] Disclosed are suspension polymers of a 1 ,1 dicarbonyl 1-alkene which have a weight average molecular weight (g/mol) of between about 3,000 and about 1 ,000,000 and a particle size distribution of between about 10 nm and about 1 micron. The 1 ,1 dicarbonyl 1 -alkene may correspond to the formula:

where X¹ and X² separately in each occurrence are an oxygen atom, a direct bond or - NR²; and R¹ and R² separately in each occurrence are hydrocarbyl groups, which are optionally substituted, that are the same or different.

[009] Disclosed is a process for preparing a suspension polymer of a 1 ,1 dicarbonyl 1 - alkene. The process includes the step of adding the 1 ,1 dicarbonyl 1 -alkene to a nucleophile with a shear force or sonication. The 1 ,1 dicarbonyl 1 -alkene may be of the formula above. The nucleophile may be hydroxide ion or a functional monomer containing a nucleophilic group or a group which is convertible to a nucleophilic group.

[0010] Disclosed is a process for making a random copolymer, which includes the step of adding a mixture of 1 ,1 dicarbonyl 1 -alkenes to a nucleophile with a shear force or sonication.

[0011] Disclosed is a process for making a block copolymer which includes the step of adding at least one 1 ,1 dicarbonyl 1 -alkene to a nucleophile with a shear force or sonication to form a mixture and then adding at least another 1 ,1 dicarbonyl 1 -alkene to the mixture with a shear force or sonication.

[0012] The processes for making polymers described herein are sensitive to the pH of the medium. Values of pH of about 4 or greater to about 14 or less may provide superior yields and rapid reaction rates.

BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Fig. 1 illustrates the C¹³ NMR spectra of diethylmethylenemalonate polymer.

[0014] Fig. 2 illustrates DSC data of a block copolymer.

[0015] Fig. 3 illustrates the C¹³ NMR spectra of polymerized DEMM.

[0016] Fig. 4 illustrated the C¹³ NMR spectra of polymerized EGA.

DETAILED DESCRIPTION

[0017] 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.

[0018] 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.

[0019] The term“monofunctionaT 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. 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 “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.

[0020] 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 etal., 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 ).

[0021] The present disclosure relates to suspension polymers of 1 ,1 -dicarbonyl- 1 -alkenes having a weight average molecular weight (g/mol) of between about 3,000 and about 1 ,000,000 and a particle size distribution of between about 10 nm and about 1 micron, processes for making such suspension polymers, processes for making random copolymers and processes for making block copolymers. The processes for making polymers described herein are sensitive to the pH of the medium. In general, pH values of about 4 or greater or about 14 or less may provide superior yields and rapid reaction rates.

[0022] The 1 ,1 -dicarbonyl-1 -alkene may be a dicarbonyl compound containing one or more ester groups, one or more keto groups, one or more amide groups, or a combination thereof. 1 ,1 -disubstituted alkene compounds are 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.

[0023] The 1 ,1 -dicarbonyl- 1-alkene may correspond to the formula:

wherein X¹ and X², separately in each occurrence, are an oxygen atom or a direct bond; and wherein R¹ and R², separately in each occurrence, are hydrocarbyl groups, which are optionally substituted that are the same or different. The 1 ,1 -dicarbonyl-1 -alkene may include ester groups corresponding to the formula:

wherein R¹ and R², separately in each occurrence, may be hydrocarbyl groups, which are optionally substituted that are the same or different. R¹ and R², separately in each occurrence, may be C1-12 alkyl, optionally substituted or C5-12 cycloalkyl, optionally substituted. R¹ and R², separately in each occurrence, may be C1-8 alkyl, optionally substituted or CM cycloalkyl, optionally substituted. R¹ and R², separately in each occurrence may be methyl, ethyl, hexyl, cyclohexyl, fenchyl, isobomyl or menthyl. R¹ may be methyl, ethyl, hexyl, cyclohexyl. R¹ may be the residue of a diol, polyol, hydroxyl, alkyl, acrylate and the like. The 1 ,1 dicarbonyl 1-alkene may be diethylmethylenemalonate, dicyclohexylmethylenemalonate or dihexylmethylenemalonate. The 1 ,1 dicarbonyl 1- alkene may be dicyclohexylmethylene malonate or dihexylmethylenemalonate. The 1 ,1 dicarbonyl 1 -alkene may correspond to one of the following formulas:

alkyl which

may be optionally substituted. It should be noted that the vinyl residue on the right is not limited to acrylates but may be a vinyl ether, vinyl ester, styri, dienyl, acrylamide, etc. The 1 ,1 dicarbonyl 1-alkene may include keto groups corresponding to the formula:

where R¹ and R², separately in each occurrence, are hydrocarbyl groups, which are optionally substituted that are the same or different. The 1 ,1 dicarbonyl 1-alkene may include one or more ester groups and one or more keto groups corresponding to the formula:

wherein R¹ and R², separately in each occurrence, are hydrocarbyl groups, which are optionally substituted that are the same or different. The 1 ,1 dicarbonyl 1-alkene 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, which is optionally substituted that are the same or different. Other combinations of ester groups, keto groups, and amide groups are also contemplated.

[0024] The hydrocarbyl groups (e.g., R¹ and R²), each comprise straight or branched chain alkyl, straight or branched chain alkyl alkenyl, straight or branched chain alkynyl, cycloalkyl, alkyl substituted cycloalkyl, aryl, aralkyl, or alkaryl. The hydrocarbyl group may optionally include one or more heteroatoms in the backbone of the hydrocarbyl group. The hydrocarbyl group may be substituted with a substituent that does not negatively impact the ultimate function of the monomer or the polymer prepared from the monomer. The substituents may be alkyl, halo, alkoxy, alkylthio, hydroxyl, nitre, cyano, azido, carboxy, acyloxy, and sulfonyl groups. The substituents may include alkyl, halo, alkoxy, alkylthio, and hydroxyl groups. The substituents may include halo, alkyl, and alkoxy groups.

[0025] As used herein, alkaryl means an alkyl group with an aryl group bonded thereto. As used herein, aralkyl means an aryl group with an alkyl group bonded thereto and include alkylene bridged aryl groups such as diphenyl methyl groups or diphenyl propyl groups. As used herein, an aryl group may include one or more aromatic rings. Cycloalkyl groups include groups containing one or more rings, optionally including bridged rings. As used herein, alkyl substituted cycloalkyl means a cycloalkyl group having one or more alkyl groups bonded to the cycloalkyl ring.

[0026] Hydrocarbyl groups include 1 to 30 carbon atoms, 1 to 20 carbon atoms or 1 to 12 carbon atoms. Hydrocarbyl groups with heteroatoms in the backbone may be alkyl ethers having one or more alkyl ether groups or one or more alkylene oxy groups. Alkyl ether groups may be ethoxy, propoxy or butoxy. Such compounds may contain from about 1 to about 100 alkylene oxy groups, about 1 to about 40 alkylene oxy groups, about 1 to about 12 alkylene oxy groups or about 1 to about 6 alkylene oxy groups.

[0027] One or more of the hydrocarbyl groups (e.g., R', R², or both), may be a Ci- 15 straight or branched chain alkyl, a CM₅ straight or branched chain alkenyl, a Cs- is cycloalkyl, a C_6-24 alkyl substituted cycloalkyl, a C_4-18 aryl, a C_4-20 aralkyl, or a C_4-20 aralkyl. The hydrocarbyl group, may be a CM straight or branched chain alkyl, a C5.12 cycloalkyl, a C_6-12 alkyl substituted cycloalkyl, a C-nearyl, a C_4-20 aralkyl, or a C_4-20 aralkyl.

[0028] Alkyl groups may be methyl, propyl, isopropyl, butyl, tertiary butyl, hexyl, ethyl pentyl or hexyl groups. Alkyl groups may be methyl or ethyl. The cycloalkyl groups include cyclohexyl and fenchyl. Alkyl substituted groups may be menthyl or isobomyl. Hydrocarbyl groups attached to the carbonyl group include methyl, ethyl, propyl, isopropyl, butyl, tertiary, pentyl, hexyl, octyl, fenchyl, menthyl, and isobornyl.

[0029] Monomers may be methylpropylmethylenemalonate, dihexylmethylenemalonate, di-isopropylmethylenemalonate, butylmethylmethylenemalonate,

ethoxyethylethylmethylenemalonate, methoxyethylmethylmethylenemalonate, hexylmethylmethylenemalonate, dipentylmethylene malonate,

ethylpentylmethylenemalonate, methylpentylmethylenemalonate,

ethylethylmethoxymethylenemalonate, ethoxyethylmethylmethylenemalonate, butylethylmethylenemalonate, dibutylmethylenemalonate, diethylmethylenemalonate, diethoxyethylmethylenemalonate, dimethylmethylenemalonate, di-N- propylmethylenemalonate, ethylhexylmethylenemalonate,

methylfenchylmethylenemalonate, ethylfenchylmethylene malonate, 2- phenylpropylethylmethylenemalonate, 3-phenylpropylethylmethylenemalonate or dimethoxyethylmethylenemalonate.

[0030] Some or all of the 1 ,1-disubstituted alkenes may also be multifunctional having more than one core unit and thus more than one alkene group. Exemplary multifunctional 1 ,1 -disubstituted alkenes are illustrated by the formula:

where R¹ separately in each occurrence is a hydrocarbyl group, which is optionally substituted, that are the same or different; R³ is CM alkyl optionally substituted or (- CHR⁴)_nO); R⁴ is hydrogen or CM alkyl optionally substituted; and n is an integer from 2 to 8. R³ may be CM alkyl optionally substituted; R⁴ may be hydrogen or CM alkyl optionally substituted and n may be integer from 2 to 4. The 1 ,1 -dicarbonyl-1 alkenes may contain about 0.1 percent by weight or greater of multifunctional 1 ,1 -dicarbonyl-1 alkenes, or about 2 percent by weight or greater of multifunctional 1 ,1 -dicarbonyl- 1 alkenes. The 1 ,1 - dicarbonyl-1 alkenes may contain about 5 percent by weight or less of multifunctional 1 ,1 - dicarbonyl-1 alkenes, or about 1 percent by weight or less of multifunctional 1 ,1 - dicarbonyl-1 alkenes.

[0031] The multifunctional monomers may be prepared from 1 ,1 -diester- 1 -alkenes and polyols, including diols. Where the polyol has greater than two hydroxyl groups, preparation of a multifunctional monomer is desired before chain extension. 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 of the hydroxyl groups react with

1 .1 -diester-1 -alkenes. It is desirable to react substantially all of 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 the formula:

Where diols are used to initiate the multifunctional monomers they correspond to formula:

where R¹ and R³ are as defined above and c is greater than 1. The multifunctional monomers can be prepared as disclosed in Malofsky et al., U.S. Patent Application No. 2014/0329980, Sullivan et al., U.S. Patent No. 9,416,091 and Palsule et al., U.S. Patent No. 9,617377. Polyols are compounds having a hydrocarbylene backbone with two or more hydroxyl groups bonded to the hydrocarbylene backbone and which may capable of transesterifying ester compounds under the transesterification conditions disclosed in the references above. 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 both to initiate and extend the chains of the polyester macromers. Polyols with greater than two hydroxyl groups bonded to the hydrocarbylene backbone 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, alkarylene, heteroarylene, alkheteroarylene, or polyoxyalkylene. The backbone may be C1-15 alkylene, C2-15 alkenylene, C3-9 cycloalkylene, C2-20 heterocyclylene, C3-20 alkheterocyclylene, Ce-ie arylene, C7-25 alkarylene, C7-25 aralkylene, C5-18 heteroarylene, Ce-25 alkyl heteroarylene or polyoxyalkylene. The alkylene sections may be straight or branched. The recited groups may be substituted with one or more substituents which 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 C2-10 alkylene groups. The backbone may be a C2-8 alkylene group, which may be straight or branched, such as ethylene, propylene, butylene, pentylene, hexylene, 2- ethyl hexylene, heptylene, 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, 2-methyl 1 ,3 propylene glycol, neopentyl glycol and 1 ,4- cyclohexanol. The polyol may correspond to the formula:

; the diol may correspond to the formula:

where 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, alkheteroarylene, or polyoxyalkylene. R² may be separately in each occurrence C1-15 alkylene, C2-15 alkenylene, C3-9 cycloalkylene, heterocyclylene,

alkheterocyclylene,

arylene, C7-25 alkarylene, C7-25 aralkylene, C5-18 heteroarylene, Ce-25 alkyl heteroarylene or polyoxyalkylene. The recited groups may be substituted with one or more substituents which 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 C2-8 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. Alkarylene polyols include polyols with the structure of -aryl-alkyl-aryl- (such as -phenyl-methyl-phenyl- or -phenyl- propyl-phenyl-) and the like. Alkyl cycloalkylene poly-yls include those with the structure of -cycloalkyl-alkyl-cycloalkyl- (such as -cyclohexyl-methyl-cyclohexyl- or - cyclohexyl-propyl-cyclohexyl-) and the like. The variable c may be an integer of 8 or less, 6 or less, 4 or less, or 3 or less and c may be an integer of 1 or greater, 2 greater or 3 or greater.

[0032] The 1 ,1 -disubstituted alkene compound is prepared using a method which results in a sufficiently high purity so that it can be polymerized. The purity of the 1 ,1 -disubstituted alkene compound may be sufficiently high so that 70 mole percent or more, 80 mole percent or more, 90 mole percent or more, 95 mole percent or more, or 99 mole percent or more of the 1 ,1 -disubstituted alkene compound is converted to polymer during a polymerization process. The purity of the 1 ,1 -disubstituted alkene compound is about 85 mole percent or more, about 90 mole percent or more, about 93 mole percent or more, about 95 mole percent or more, about 97 mole percent or more or about 99 mole percent or more, based on the total weight of the 1 ,1 -disubstituted alkene compound. If the 1 ,1 - disubstituted alkene compound includes impurities, about 40 mole percent or about 50 mole percent or more of the impurity molecules are the analogous 1 ,1 -disubstituted alkane compound. The concentration of any impurities having a dioxane group is 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 1 ,1-disubstituted alkene compound. 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), is about 3 mole percent or less, about 1 mole percent or less, about 0.1 mole percent or less, and about 0.01 mole percent or less, based on the total moles in the 1 ,1-disubstituted alkene compound. The 1 ,1 -disubstituted alkene compounds are prepared by a process including one or more (e.g., two or more) steps of distilling a reaction product or an intermediate reaction product (e.g., a reaction product or intermediate reaction product of a source of formaldehyde and a malonic acid ester).

[0033] The 1 ,1-disubstituted alkene compound may include a monomer produced according to the teachings of Malofsky et al., U.S. Patent No. 8,609,885. Other examples of monomers which may be employed include the monomers taught in International Patent Application Publication Nos. WO2013/066629 and WO 2013/059473.

[0034] The suspension polymers disclosed herein may be prepared by processes which includes the step of adding a 1 ,1-disubstituted alkene to a nucleophile with a shear force or sonication. Nucleophile as used herein is an atom or molecule which donates an electron pair to make a covalent bond. A compound, such as a functional monomer, having a group which is convertible to a nucleophile is a monomer having group that can be modified to exhibit nucleophilic properties. An example is a carboxylate, carboxylic acid, hydroxyl, amino, acetate, amido groups or salts thereof and the like.

[0035] The nucleophile may be selected from a strong base (pH over 9), a moderately strong base (pH from 8-9), or a weak base (pH from over 7 to 8), or a combination thereof. The nucleophile may comprise a basic material selected from an organic material, an inorganic material or an organo-metallic material, or a combination thereof. The nucleophile may be at least one member selected from: sodium acetate; potassium acetate; acid salts of sodium, potassium, lithium, copper, and cobalt; tetrabutyl ammonium fluoride, chloride, and hydroxide; an amine whether primary, secondary or tertiary; an amide; salts of polymer bound acids; benzoate salts; 2,4-pentanedionate salts; sorbate salts; propionate salts; secondary aliphatic amines; piperidene, piperazine, N- methylpiperazine, dibutylamine, morpholine, diethylamine, pyridine, triethylamine, tripropylamine, triethylenediamine, N,N-dimethylpiperazine, butylamine, pentylamine, hexylamine, heptylamine, nonylamine, decylamine; salts of amines with organic monocarboxylic acids; piperidine acetate; metal salt of a lower monocarboxylic acid; copper(ll) acetate, cupric acetate monohydrate, potassium acetate, zinc acetate, zinc chloracetate, magnesium chloracetate, magnesium acetate; salts of acid containing polymers; salts of polyacrylic acid co-polymers.

[0036] The nucleophile may be hydroxide ion in water. The pH of water is about 2 or greater, about 4 or greater, about 6 or greater, about 8 or greater, about 10 or greater or about 12 or greater. The pH of water is about 14 or less, about 11 or less, about 9 or less, about 7 or less, about 5 or less or about 3 or less.

[0037] The 1 ,1-disubstituted alkene may be dicyclohexylmethylene malonate, the temperature of water may be at ambient temperature and the pH may be about 12. The 1 ,1 -disubstituted alkene may be dihexylmethylenemalonate, the temperature of the water may be at ambient temperature and the pH may be about 7. [0038] The nucleophile may be a functional monomer. The functional monomer may include an unsaturated group. The functional monomer may be acrylates, methacrylates, acrylamides, vinyl acetate, mono-vinyledene aromatics, acrylic acids or methacrylamides. The functional monomer may be dimethylaminoethyl acrylate, acetoacetoxylethyl methacrylate, hydroxyethylacrylate, 4-vinyl benzoic acid, methacrylic acid, acrylamidopropane sulfonic acid or the HCI salt of aminoethylmethacrylate. The functional monomer may be dimethylaminoethyl acrylate, acetoacetoxylethyl methyacrylate, hydroxyethylacrylate, 4-vinyl benzoic acid, methacrylic acid, acrylamidopropane sulfonic add or the HCI salt of aminoethylmethacrylate are converted to the anion prior to the addition of the1 ,1 -disubstituted alkene.

[0039] The processes disclosed herein may include another monomer that is a 1 ,1- disubstituted alkene compound having a hydrocarbyl group bonded to each of the carbonyl groups through a direct bond (e.g., a carbon-carbon bond) or an oxygen atom, such as a monomer having one or more features described above.

[0040] Accordingly, also disclosed herein are methods of forming a random copolymer of at least two 1 ,1 -disubstituted alkene compounds. The methods include the step of adding the at least two 1 ,1 -disubstituted alkenes to a nucleophile with a shear force or sonication. The at least two 1 ,1 -disubstituted alkenes may be dihexylmethylenemalonate and diethylmethylenemalonate, for example.

[0041] Also disclosed herein are methods of forming a block copolymer of at least two 1 ,1 -disubstituted alkene compounds. The methods include the steps of adding at least one 1 ,1 -disubstituted alkene to a nucleophile with a shear force or sonication to form a mixture and then adding a second 1 ,1 -disubstituted alkene to the mixture. The at least two 1 ,1 -disubstituted alkenes may be dihexylmethylenemalonate and diethylmethylenemalonate, for example.

[0042] Also disclosed herein are homopolymers which are formed by adding a 1 ,1- disubstituted alkene to a nucleophile with a shear force or sonication. The nucleophile may be hydroxide ion in water and the resultant homopolymer is homo- diethylmethylenemalonate, homo-dicyclohexylmethylene malonate, homo- dihexylmethylenemalonate, or a homopolymer of a 1 ,1 -dicarbonyl alkene having at least one of the hydrocarbyl groups as the residue of a hydroxyl alkyl acrylate such as a homopolymer containing the monomer of the structure:

[0043] The polymerization processes disclosed may include a step of applying shear forces to a mixture including at least the monomer and water. 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. 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, 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 sonication. When using sonication, the frequency is about 0.2 kHz or more, about 1 kHz or more, about 5 kHz or more, or about 20 kHz or more. Typically, the frequency is about 1000 kHz or less, about 500 kHz or less, about 200 kHz or less, or about 100 kHz or less.

[0044] 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 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 (i.e., for improving the stability of the dispersed phase in the water). The necessary amount of surfactant provides colloidal stability to the polymerizing and polymerized particles.

[0045] Surfactants that may be employed include alkyl polysaccharides, alkylamine ethoxylates, amine oxides, castor oil ethoxylates, ceto-oleyl and salts thereof, ceto- stearyl and salts thereof, decyl alcohol ethoxylates, dinonyl phenol ethoxylates, dodecyl phenol ethoxylates, end-capped ethoxylates, ethoxylated alkanolamides, ethylene glycol esters, fatty acid alkanolamides, 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, tall oil fatty acid ethoxylates, tallow amine ethoxylates, alkyl ether phosphates and salts thereof, 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 sulphosuccinamates, di-alkyl sulphosuccinates, alkyl phosphates and salts thereof, alkyl benzene sulphonic acids and salts thereof, alpha olefin sulfonates and salts thereof, condensed naphthalene sulfonates and salts thereof, polycarboxylates and salts thereof, alkyl dimethylamines, stearic acid and salts thereof alkyl amidopropylamines, sulfonic acid and salts thereof, stearic acids and salts thereof, quatemised amine ethoxylates, quaternary ammonium compounds, and mixtures or combinations thereof.

[0046] The polymerizable compositions disclosed herein may be polymerized in water via anionic polymerization processes. The polymerizable compositions may be polymerized utilizing the method disclosed in Palsule et al., U.S. Serial Number 14810741 , filed July 28, 2015. According to the disclosure of Palsule et al. the process comprises the steps of mixing one or more 1 ,1 -disubstituted alkenes and water; adding a nucleophile; reacting the nucleophile 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 water polymerization process may be sufficiently high so that the polymerization process is economical. The one or more monomers may be 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 water 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 water 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.

[0047] The polymerization processes disclosed may include a step of applying shear forces to a mixture including at least the monomer and water. 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 water 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 100 °C or less, 80 °C or less, about 70 °C or less, about 60 °C or less, about 55 °C or less, or about 45 °C or less, about 40 °C or less, or about 30 °C or less. The reaction temperature may be sufficiently high that the water 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. The reaction temperature may about ambient temperature, such as from about 15 °C or to about 30 C.

[0048] 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 is as disclosed herein. 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.

[0049] 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.

[0050] 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/mole or greater, about 200,000 g/mole or greater, about 300,000 g/mole or greater, about 500,000 g/mole or greater, about 750,000 g/mole or greater or about 900,000 g/mole or greater. The polymers may have a number average molecular weight or a weight average molecular weight that is about 1 ,000,000 g/mole or less, about 800,000 g/mole or less, about 600,000 g/mole, or less and about 400,000 g/mole or less, about 100,000 g/mole, or less or about 25,000 g/mole.

[0051] The polymer particle size and/or particle size 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 for emulsion particles having a unimodal particle size distribution, a multi-modal particle size distribution (e.g., a bimodal 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 of 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 miniemulsion polymers yielding large particles.

[0052] 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 carboxylated latex cores. Carboxylated latex cores may be made by conventional emulsion polymerization. Addition of 1 ,1 -dicarbonyl 1-alkenes results in the polymerization form the surface of the core latex, which is an example of using an organic emulsion polymer as a seed.

[0053] Disclosed are polymers whose polymerization is initiated by hydroxyl ions. Such polymers have a hydroxyl group on one end. The formed polymers are addition polymers formed through the 1 -alkene groups, which is in essence a polyolefin chain with the carbonyl groups as described herein pendant from the polyolefin chain. The other end of the polymer may have the residue of an anionic polymerization inhibitor.

[0054] Polymerization can be terminated by contacting the polymeric mixture with an anionic polymerization terminator. The anionic polymerization terminator may be an acid. It may be desirable to utilize a sufficient amount of the acid to render the polymerization mixture slightly acidic, having a pH of less than 7, less than about 6. Exemplary anionic polymerization terminators include, for example, mineral acids such as methane sulfonic add, sulfuric acid, and phosphoric acid and carboxylic acids such as acetic acid and trifluoroacetic acid.

[0055] .The resulting polymer may be characterized by a polydispersity index of greater than about 1 .00 or about 1.05 or more. The resulting polymer may be characterized by a polydispersity index of 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.

[0056] The 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.

[0057] 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 adds, phosphoric acids and the like. Exemplary stabilizers include liquid phase stabilizers (e.g., methanesulfonic add (“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 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. 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 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 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 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. [0058] The polymerizable compositions and polymers disclosed herein may be utilized and a number of applications. Exemplary applications include coatings, films, etc.

[0059] 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.

ILLUSTRATIVE EMBODIMENTS

[0060] 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 : Polymerization of Diethylmethylenemalonate In Water

[0061] Three drops of diethylmethylenemalonate (0.0187 g, 0.00011 moles) was added to 1.76 g of distilled water (pH not controlled) with stirring which led to immediate formation a stringy white residue. After five minutes, the sample was placed in an oven at 80 °C and left to dry overnight. C¹³ NMR spectra (Cr(AcA)₃ 0.4%, 0.7 CDCI₃ and 50-75 mg of polymer) (Fig. 1 ) revealed that diethylmethylenemalonate polymerized to the linear polymer illustrated below:

Example 2: Polymerization of Diethylmethylenemalonate In Water at Different pH Values

[0062] Diethylmethylenemalonate (15 mg) was dispersed into 100 mg DaO at ambient temperature. The pH was adjusted with aqueous sodium hydroxide (1 M) or HCI (1 M) to the desired value and the reaction mixture was initially stirred for 1 minute to 90 hours before being quenched by being diluted into a mixture of (CD₃)₂S=0 and CDCIa which dissolved the polymer product. ¹H NMR spectra was used to measure the conversion of monomer to polymer, as the -CH2 ester peaks are found at distinct chemical shifts in the polymer versus the monomer. The conversion of monomer to polymer versus pH and time are shown below in Table 1. Notably, as can be seen below, polymerization takes place at all pH values measured in Table 1.

Example 3: Suspension Polymerization of Diethylmethylenemalonate In Distilled Water at Different pH Values

[0063] 10 wt% of diethylmethylenemalonate was added to 5g distilled water maintained at a measured pH at a constant rate of 0.5ml/min and stirred at 10OOrpm under ambient environment for two hours. The results are tabulated in Table 2.

[0064] The molecular weight measure by GPC at certain pH values at 25 °C as shown in Table 3.

Example 4: Suspension Polymerization of 2-Hydroxymethyl Methacrylate- Diethylmethylenemalonate In Distilled Water at Different pH Values

[0065] 10 wt% of 2-hydroxymethyl methacrylate-diethylmethylenemalonate was added to 5g distilled water maintained at a measured pH at a constant rate of 0.5ml/min and stirred at lOOOrpm under ambient environment for two hours. The results are tabulated in Table

4.

Example 5: Suspension Polymerization of High Tg-2-Hydroxymethyl Methacrylate- Diethylmethylenemalonate In Distilled Water at Different pH Values

[0066] 10 wt% of high Tg 2-hydroxymethyl methacrylate-diethylmethylenemalonate was added to 5g distilled water maintained at a measured pH at a constant rate of 0.5ml/min and stirred at ambient temperature for two hours. The results are tabulated in Table 5.

Example 6: Suspension Polymerization of Low Tg-2-Hydroxymethyl Methacrylate- Diethylmethylenemalonate In Distilled Water at Different pH Values

[0067] 10 wt% of low Tg 2-hydroxymethyl methacrylate-diethylmethylenemalonate was added to 5g distilled water maintained at a pH 7 at a constant rate of 0.5ml/min and stirred at ambient temperature for two hours. The monomer could be initiated and fully polymerized into polymer in 8 min.

Example 7: Synthesis of Random Copolymer of Diethylmethylenemalonate and Low Tg Diethylmethylenemalonate

[0068] Diethylmethylenemalonate and low Tg diethylmethylenemalonate were mixed in various weight ratios and a 10 wt% mixture was at a constant rate of 0.5 ml/minute into 5 g of distilled water at pH 7 and stirred at ambient temperature for two hours. The polymer product was dried, and the DSC was measured. The results are shown in Table 6 and indicate that Tg of the copolymer could be modified by use of excess low Tg diethylmethylenemalonate.

Example 8: Synthesis of Block Copolymer of Diethylmethylenemalonate and Low Tg Diethylmethylenemalonate

[0069] Low Tg diethylmethylenemalonate (10 wt% mixture) was added into 5 g of distilled water at pH 7 and stirred at ambient temperature for two hours. The polymer product was dried, and the DSC measured. The DSC data illustrated in Figure 2 revealed the presence of two Tg at -44.83C and 30.9C which is very close to the Tg of pure poly low Tg diethylmethylenemalonate and pure poly diethylmethylenemalonate, respectively.

Example 9: Polymerization of Diethylmethylenemalonate Initiated by Neat Undiluted Functional Monomers

[0070] A 1 :1 by weight ratio of diethylmethylenemalonate to functional monomer was prepared by stirring diethylmethylenemalonate into functional monomer at ambient temperature without adjusting the pH. After 1 minute and 65 hours, the reaction mixture was diluted to about 3% with CDCI₃. ¹ H NMR spectra was used to measure the conversion of monomer to polymer, as the -CH₂ ester peaks are found at distinct chemical shifts in the polymer versus the monomer. The conversion of monomer to polymer versus time are shown below in Table 7.

Example 9: Polymerization of Diethylmethylenemalonate Initiated by Neutralized Functional Monomers

[0071] Functional monomer was neutralized with 1 M NaOH and solvent removed by nitrogen blow drying. A 1 :1 by weight ratio of diethylmethylenemalonate to functional monomer was prepared by stirring diethylmethylenemalonate into neutralized functional monomer at ambient temperature. After 1 minute and 65 hours, the reaction mixture was diluted to about 3% with CDCI₃. ¹H NMR spectra was used to measure the conversion of monomer to polymer, as the -CH₂ ester peaks are found at distinct chemical shifts in the polymer versus the monomer. The conversion of monomer to polymer versus time are shown below in Table 8.

Example 10: Polymerization of Diethylmethylenemalonate In the Presence by Sodium Methacrylate [0072] Sodium methacrylate was dissolved in Dl water at 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt% and 0.4 wt%. Diethylmethylenemalonate (10 wt%) was added dropwise into the sodium methacrylate solution at ambient conditions. The mixture was stirred using a stir bar at 1000 rpm overnight. The polymer product was dried in oven at 50 °C, dissolved in tetrahydrofuran and measure GPC for molecular weight distribution. The molecular weight, polydisperse index and area percent are shown in Table 9.

Example 11 : Polymerization of HEMA- Diethylmethylenemalonate In the Presence by Sodium Methacrylate

[0073] Sodium methacrylate was dissolved in Dl water at 0 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt% and 0.4 wt%. HEMA- Diethylmethylenemalonate (10 wt%) was added dropwise into the sodium methacrylate solution at ambient conditions. The mixture was stirred using a stir bar at 1000 rpm overnight. The polymer product was dried in oven at 50 °C, dissolved in tetrahydrofuran and measure GPC for molecular weight distribution. The molecular weight, polydisperse index and area percent are shown in Table 10.

Example 12: Comparison of Polymerization of Diethyl Methylene Malonate and Cyanoacrylate In Water

[0074] The pH of 5 g of distilled water in glass vials was adjusted to 2 and 7. DEMM (10 wt%) and ethyl cyanoacrylate (EGA, Sigma-Aldrich, 10 wt%) were separately added dropwise into discrete glass vials which included the above distilled water and stirred at 1000 rpm overnight. The results are shown in Table 1 1.

[0075] At pH 7, the both DEMM and EGA polymerize. However, DEMM polymerizes slower and in a more controlled fashion than EGA. At pH 2, DEMM remained as monomer droplet due to low reactivity while EGA fully polymerized into a sticky polymer. Accordingly, DEMM has a unique curing window for functional group initiation when compared with EGA.

Example 13: Selective Grafting and Functionalization of DEMM In comparison to Cyanoacrylate onto Carboxylate Monomer

[0076] The pH of a 1 wt% methacrylate acid water solution was adjusted to pH 5. Then 10 wt% DEMM and EGA were added dropwise to separate portions of the above 1 wt% methacrylate acid solution and stirred overnight. EGA addition resulted in polymerization to form a large aggregate in two minutes. In contrast, DEMM addition resulted in formation of a milky white dispersion, which demonstrates the more controlled polymerization of DEMM when compared to the uncontrolled polymerization of EGA.

[0077] The C¹³ NMR spectra of the reaction products are illustrated in Figs 3 and 4. As can be seen in Fig. 3, a MAA-polyDEMM connection bond was found at around 63 pp which is similar to the predicted result of 62.9 ppm. A MAA-polyECA connection bond was not found in the measured C¹³ NMR illustrated in Fig. 4. Such a bond would be expected to display a resonance at 65.3 ppm.

[0078] An experiment using 5 wt% MAA solution at pH 5 and 5 wt% EGA addition provided the same result as above, which suggests little or no initiation of EGA polymerization by the carboxyl group. Example 14: Grafting of DEMM onto Water-Soluble Polymers (Bulk polymerization of DEMM)

[0079] Water-soluble polymers (i.e., alginate (Sigma-Aldrich), polymethyl methacrylate add (PMAA, Sigma-Aldrich) and poly acrylic acid (PAA, Sigma-Aldrich)) are mixed with diethyl methylene malonate (DEMM) in a glass vial (ratio 1 : 10) and are reacted overnight at ambient conditions. All of the above water-soluble polymers (alginate, PMAA, PAA) polymerize DEMM, since these polymers contain anionic carboxyl groups as an initiator. The bulk polymerization of DEMM is demonstrated by the above examples...

[0080] 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, 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.

Claims

CLAIMS What is claimed is:

1. A suspension polymer of a 1 ,1 -disubstituted alkene having a weight average molecular weight (g/mol) of between about 3,000 and about 1 ,000,000 and a particle size distribution of between about 10 nm and about 1 micron.

2. The suspension polymer of claim 1 , wherein the 1 ,1 -disubstituted alkene is of formula:

wherein:

X¹ and X² separately in each occurrence are an oxygen atom, a direct bond or - NR²; and

R¹ and R² separately in each occurrence are hydrocarbyl groups, which are optionally substituted, that are the same or different.

3. The suspension polymer of claim 2, wherein R¹ and R² are independently C1-12 alkyl, optionally substituted or C5-12 cycloalkyl, optionally substituted.

4. The suspension polymer of claim 3, wherein R¹ and R² are independently is C2-8 alkyl, optionally substituted or CM cycloalkyl, optionally substituted.

5. The suspension polymer of claim 2, wherein R¹ is fenchyl, isobomyl or menthyl

6. The suspension polymer of claim 2, wherein the 1 ,1 -disubstituted alkene is diethylmethylenemalonate, dicyclohexylmethylenemalonate or dihexylmethylenemalonate.

7. The suspension polymer of claim 1 , wherein the 1 ,1 -disubstituted alkene is dicyclohexylmethylene malonate or dihexylmethylenemalonate, or corresponds to one of the following formulas:

wherein R is CM alkyl which may be optionally substituted.

8. The suspension polymer of claim 1 , wherein the 1 ,1-disubstituted alkene comprises a multifunctional 1 ,1 -disubstituted alkene.

9. The suspension polymer of claim 8, wherein the multifunctional 1 ,1 -disubstituted alkene is of formula:

wherein:

R¹ separately in each occurrence is a hydrocarbyl group, which is optionally substituted, that are the same or different; and

R³ is C2-8 alkyl optionally substituted or (-CHR⁴)_nO);

R⁴ is hydrogen or C1-8 alkyl optionally substituted; and

n is an integer from 2 to 8.

10. The suspension polymer of claim 9, wherein:

R³ is C2-6 alkyl optionally substituted;

R⁴ is hydrogen or CM alkyl optionally substituted; and

n is an integer from 2 to 4.

11. The suspension polymer of claims any one of claims 8 to 10 wherein the multifunctional 1 ,1 -disubstituted alkene is present in an amount of about 0.1% to about 5% percent by weight of the 1 ,1 -disubstituted alkene present.

12. The suspension polymer of any one of claims 1 to 1 1 wherein the polymer particle size is uni-modal.

13. The suspension polymer of any one of claims 1 to 1 1 wherein the polymer particle size is poly-modal.

14. A suspension polymer of a 1 ,1 -disubstituted alkene made by a process comprising adding the 1 ,1 -disubstituted alkene to a nucleophile with a shear force or sonication.

15. The suspension polymer of claim 14, wherein the 1 ,1 -disubstituted alkene is of formula:

wherein:

16. The suspension polymer of claim 15, wherein R¹ and R² are independently C1-12 alkyl, optionally substituted or C5-12 cycloalkyl, optionally substituted.

17. The suspension polymer of claim 15, wherein R¹ and R² are independently C2-8 alkyl, optionally substituted or CM cycloalkyl, optionally substituted.

18. The suspension polymer of claim 15, wherein R¹ is fenchyl, isobomyl or menthyl

19. The suspension polymer of claim 15, wherein the 1 ,1 -disubstituted alkene is diethylmethylenemalonate, dicyclohexylmethylene malonate or dihexylmethylenemalonate.

20. The suspension polymer of claim 14, wherein the 1 ,1 -disubstituted alkene is dicyclohexylmethylene malonate or dihexylmethylenemalonate, or corresponds to one of the following formulas:

wherein R is CM alkyl which may be optionally substituted.

21. The suspension polymer of claim 14, wherein the 1 ,1-disubstituted alkene comprises a multifunctional 1 ,1-disubstituted alkene.

22. The suspension polymer of claim 21 , wherein the multifunctional 1 ,1-disubstituted alkene is of formula:

wherein:

R³ is C2-8 alkyl optionally substituted or (-CHR⁴)_nO);

R⁴ is hydrogen or C1-8 alkyl optionally substituted; and

n is an integer from 2 to 8.

23. The suspension polymer of claim 22, wherein:

R³ is C2-6 alkyl optionally substituted;

R⁴ is hydrogen or CM alkyl optionally substituted; and

n is an integer from 2 to 4.

24. The suspension polymer of any one of claims 21 to 23 wherein the multifunctional 1 ,1 -disubstituted alkene is present in an amount of about 0.1% to about 5% by weight of the 1 ,1-disubstituted alkene present.

25. The suspension polymer of any of claims 14-24, wherein the nucleophile is hydroxide ion in water.

26. The suspension polymer of claim 25, wherein the water is at a temperature between about 0 °C and about 100 °C.

27. The suspension polymer of claim 25, wherein the water is at ambient temperature.

28. The suspension polymer of any one of claims 25-27, wherein the pH of the water is adjusted to between about pH 2 to about pH 14, prior to addition of the1 ,1- disubstituted alkene.

29. The suspension polymer of claim 25, wherein the 1 ,1-disubstituted alkene is dicyclohexylmethylene malonate, the temperature of the water is at ambient temperature and the pH is about 12.

30. The suspension polymer of claim 25, wherein the 1 ,1-disubstituted alkene is dihexylmethylenemalonate, the temperature of the water is at ambient temperature and the pH is about 7.

31. The suspension polymer any one of claims 14-24, wherein the nucleophile is a functional monomer.

32. The suspension polymer of claim 31 , wherein the functional monomer includes an unsaturated group.

33. The suspension polymer of claim 32, wherein the functional monomer comprises acrylates, methacrylates, acrylamides, vinyl acetate, mono-vinyledene aromatics, acrylic acids and methacrylamides.

34. The suspension polymer of claim 33, wherein the functional monomer is dimethylaminoethyl acrylate, acetoacetoxylethyl methacrylate, hydroxyethylacrylate, 4-vinyl benzoic acid, methacrylic acid, acrylamidopropane sulfonic acid or the HCI salt of aminoethylmethacrylate.

35. The suspension polymer of claim 34, wherein dimethylaminoethyl acrylate, acetoacetoxylethyl methyacrylate, hydroxyethylacrylate, 4-vinyl benzoic acid, methacrylic acid, acrylamidopropane sulfonic acid or the HCI salt of aminoethylmethacrylate are converted to an anion prior to the addition of the1 ,1- disubstituted alkene.

36. A random co-polymer comprising at least two 1 ,1-disubstituted alkenes made by a process comprising adding a mixture of 1 ,1-disubstituted alkenes to a nucleophile with a shear force or sonication.

37. The random co-polymer of claim 36, wherein the mixture of 1 ,1 -disubstituted alkenes includes dihexylmethylenemalonate and diethylmethylenemalonate.

38. A block polymer comprising at least two 1 ,1 -disubstituted alkenes made by a process comprising adding at least one 1 ,1 -disubstituted alkene to a nucleophile with a shear force or sonication to form a mixture and then adding at least another 1 ,1 -disubstituted alkene to the mixture with a shear force or sonication.

39. The block polymer of claim 38, wherein the first 1 ,1 -disubstituted alkene is dihexylmethylenemalonate and the second 1 ,1 -disubstituted alkene is diethylmethylenemalonate

40. A suspension polymer of diethylmethylenemalonate, wherein the polymer has a weight average molecular weight (g/mol) of between about 3000 and about 1 ,000,000.

41. A method for synthesizing a homopolymer comprising adding a 1 ,1 -disubstituted alkene to a nucleophile with application of a shear force or sonication.

42. The method of claim 41 , wherein the nucleophile is hydroxide ion in water and the homopolymer is homo-diethylmethylenemalonate, homo-dicyclohexylmethylene malonate, homo-dihexylmethylenemalonate or the homopolymer of the structure:

43. A method for synthesizing a random co-polymer comprising adding a mixture of 1 ,1 -disubstituted alkenes to a nucleophile with a shear force or sonication.

44. A method for synthesizing a block polymer comprising at adding at least one 1 ,1 - disubstituted alkene to a nucleophile with a shear force or sonication to form a mixture and then adding at least one other 1 ,1 -disubstituted alkene to the mixture with a shear force or sonication.