Polymerization of lactones in polar protic solvents.

Abstract

The method includes contacting one or more beta-propiolactone monomers with one or more phosphorus compounds in a solution under conditions such that a polypropiolactone polymer is formed. The solution includes one or more polar protic solvents and one or more phosphorus compounds. The phosphorus compounds contain phosphorus in ionic form, either covalently bound to another compound to form a zwitterion or ionically bound to another compound to form a salt.

Description

[Technical Field]

[0001] The present disclosure relates to methods for making polypropiolactone using polar protic solvents. [Background technology]

[0002] Beta-lactone monomers are useful for forming polypropiolactone polymers. Polypropiolactone polymers are biodegradable and therefore find many applications in food and / or beverage packaging. Typically, polypropiolactone polymers are formed by contacting beta-lactone monomers and an initiator in the presence of an aprotic solvent. See, for example, U.S. Patent Application No. 11,492,443. However, these solvents can be expensive and environmentally undesirable upon disposal, and polypropiolactone polymers produced by these techniques may contain by-products or unreacted chemicals that are undesirable in food and / or beverage packaging.

[0003] Therefore, what is needed is a technique for making polypropiolactone free of chemicals considered harmful to humans. What is needed is a technique for producing polypropiolactone polymers with minimal solvent waste. What is needed is a technique for producing polypropiolactone polymers that can be applied as films and / or coatings. Summary of the Invention

[0004] Disclosed herein is a method for forming polypropiolactone using a polar protic solvent.

[0005] A method is disclosed that includes contacting one or more beta-propiolactone monomers with one or more phosphorus compounds and optionally one or more carboxylate compounds in a solution under conditions such that a polypropiolactone polymer is formed. The solution includes one or more polar protic solvents and one or more phosphorus compounds and optionally one or more carboxylate compounds. The phosphorus compounds contain phosphorus in ionic form, either covalently bound to another compound to form a zwitterion or ionically bound to another compound to form a salt.

[0006] The phosphorus compound may include a phosphonium compound or an anionic phosphate compound. The phosphorus compound may have the following structure according to Formula I, II, and / or III: Formula I: [ka] (In the formula, each R 3 is, separately in each occurrence, a group containing one or more carbon atoms; and R 3 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; Solid lines represent covalent bonds, dotted lines represent ionic bonds, R a contains a phosphate group, a carboxylate group, a carbonate group, an alkoxide group, a halide, or any combination thereof), or Formula II: [ka] (In the formula, R 5 is independently a quaternary ammonium group, a phosphonium group, another omnium cation, or any combination thereof; R 2 is defined herein), or Formula III: [ka] (In the formula, each R 2 is defined herein, R b may include compounds having a quaternary ammonium group, a phosphonium group, another onium cation, or any combination thereof.

[0007] Phosphorus compounds include cationic phosphine compounds and C 5-20 The phosphorus compounds may include anionic carboxylates having anionic carboxylate compounds having alkyl groups. The phosphorus compounds may include anionic phosphates and cationic quaternary ammonium compounds. The phosphorus compounds may include one or more C groups covalently bonded to groups that are anionic or cationic. 5-20 The phosphorus compound may include a cation and an anion covalently bonded to each other. The phosphorus compound may include a cation and an anion ionically bonded to each other.

[0008] The one or more carboxylate compounds may include a carboxylate compound and a counterion that is soluble or dispersible in a polar protic solvent. The one or more carboxylate compounds may have a formula according to the following: [ka] wherein R 2 and R b is defined herein and the dotted line is defined herein.

[0009] The one or more polar protic solvents may be present in a weight percent greater than about 90 percent, based on the total weight of the solution when the beta-lactone monomer and the solution are contacted. The one or more polar protic solvents may include one or more of water, methanol, ethanol, acetic acid, isopropanol, n-butanol, formic acid, or any combination thereof. The one or more polar protic solvents may include water. The beta-lactone monomer may be present in the solution in a weight percent of about 5 percent to about 35 percent, based on the total weight of the solution when the beta-propiolactone monomer and the solution are contacted. The beta-lactone monomer may be present in the solution in a weight percent of about 5 percent to about 25 percent, based on the total weight of the solution when the beta-propiolactone monomer and the solution are contacted. The beta-lactone monomer may be present in the solution in a weight percent of about 5 percent to about 20 percent, based on the total weight of the solution when the beta-propiolactone monomer and the solution are contacted.

[0010] The method may further include contacting one or more phosphorus compounds and one or more polar protic solvents to form a solution before contacting the beta-lactone monomer with the solution. The method may further include contacting one or more phosphorus compounds, one or more buffers, and one or more polar protic solvents to form a solution before contacting the beta-lactone monomer with the solution. The method may further include contacting one or more phosphorus compounds, one or more surfactants, and one or more polar protic solvents to form a solution before contacting the beta-lactone monomer with the solution. The method may further include contacting one or more phosphorus compounds, one or more buffers, one or more surfactants, and one or more polar protic solvents to form a solution before contacting the beta-lactone monomer with the solution.

[0011] The beta-lactone monomer may be contacted with a solution comprising one or more buffers configured to maintain the pH of the solution above 7.0. The beta-lactone monomer may be contacted with a solution comprising one or more surfactants. The beta-lactone monomer may be contacted with a solution comprising one or more buffers and one or more surfactants. The one or more surfactants may be at least partially miscible with the beta-lactone monomer. The beta-lactone monomer and the solution are contacted at a temperature of about 0 degrees Celsius to about 60 degrees Celsius. The step of contacting the beta-lactone monomer and the compound in the solution may be carried out with stirring for a period of about 12 hours to about 24 hours. Essentially all of the beta-lactone monomer may be converted to polypropiolactone polymer or by-products in about 3 hours or less. The method may further include contacting the compound and water to form a solution prior to the step of contacting the beta-lactone monomer and the compound in the solution. The step of contacting the beta-lactone monomer and the compound in the solution may be carried out in an oxygen-free environment.

[0012] The method may further include separating the polypropiolactone polymer from the solution. The separating step may include precipitating the polypropiolactone polymer from the solution and separating the polypropiolactone polymer from by-products. The separating step may include precipitating the polypropiolactone polymer from the solution, decanting the solution from the polypropiolactone polymer, washing the polypropiolactone polymer with alcohol to remove any remaining solution, and drying the polypropiolactone polymer under vacuum to remove any remaining solution.

[0013] The phosphorus compound may be present in an amount sufficient to ring-open the beta-lactone compound to form the polypropiolactone polymer and reduce the formation of by-products. The phosphorus compound may be present in the solution in an amount of 10 ppm to about 200,000 ppm. The one or more surfactants may be present in an amount sufficient to stabilize the solution. The one or more surfactants may be present in the solution in an amount of about 10 ppm to about 200,000 ppm. The one or more buffers may be present in an amount sufficient to maintain the pH of the solution above 7.0. The one or more buffers may be present in an amount of about 0.1 g / L to about 10.0 g / L. The by-products may be present in the polypropiolactone polymer in an amount of about 10 ppm to about 10,000 ppm. The presence of the by-products may not cause the pH of the solution to change below 7.0.

[0014] The phosphorus compound may contain a disubstituted phosphate group. 5-20 The phosphorus compound may include a cationic quaternary ammonium having an alkyl group. The cationic quaternary ammonium may be covalently bonded to a disubstituted phosphate group. The phosphorus compound may include a choline covalently bonded to a phosphatidic acid. The phosphorus compound may include a phosphatidylcholine. The cationic quaternary ammonium may be ionically bonded to a disubstituted phosphate group. The phosphorus compound may include one or more C groups covalently bonded to a phosphorus atom. 5-20 The phosphorus compound may contain two or more C alkyl groups covalently bonded to the phosphorus atom. 5-20 The phosphorus compound may contain three or more C alkyl groups covalently bonded to the phosphorus atom. 5-20 The phosphorus compound may contain four or more C alkyl groups covalently bonded to the phosphorus atom. 5-20 The phosphorus compound may contain an alkyl group connected to the carbonyl of the carboxylate compound. 1-20 The phosphorus compound may include an anionic carboxylate compound having an alkyl group. The phosphorus compound may include an ionically bonded phosphorus cation and an anionic carboxylate compound. The phosphorus compound may include one or more C 5-20 The alkyl group may contain at least some degree of unsaturation.

[0015] The one or more surfactants may include a polymer having repeating alkylene ether groups and one or more terminal hydroxyl groups. The alkylene ether may include one or more of ethylene ether, propylene ether, butylene ether, or any combination thereof. The one or more surfactants may include a non-ionic polymer. The one or more surfactants may include one or more triblock copolymers. The one or more surfactants may include a poloxamer, a fatty salt, or any combination thereof. The one or more buffers may include a monoprotic acid, a polyprotic acid, or a combination of both. The one or more buffers may include one or more of phosphate buffered saline, bicarbonate, citric acid, boric acid, diethylbarbituric acid, mono-alkali phosphate, or any combination thereof. The by-products may include acrylic acid, acrylic acid dimer, 3-hydroxypropionic acid, or any combination thereof.

[0016] The polypropiolactone polymer may have a polydispersity index of greater than 1 to about 3.5. The polypropiolactone polymer may have a polydispersity index of greater than 1 to about 1.7. The polypropiolactone polymer may have a number average molecular weight of about 1 kg / mol to about 1000 kg / mol. The polypropiolactone polymer may have a weight average molecular weight of about 1 kg / mol to about 2000 kg / mol. The polypropiolactone polymer may be substantially free of beta-lactone monomer and / or acrylic acid. The polypropiolactone polymer may have a melting point of about 70 degrees Celsius to about 130 degrees Celsius. The polypropiolactone polymer may have a crystallization temperature of about 0 degrees Celsius to about 100 degrees Celsius.

[0017] Polypropiolactone polymers have the repeating structure according to the following: [ka] wherein each R 1 are independently hydrogen, methyl, C 2-10 alkyl group, or any combination thereof; x is a real number greater than 1. The variable n can be selected so that the resulting polymer has a number average molecular weight of about 500 to 2,000,000 g / mol. x can be 3 to 50,000.

[0018] Beta-lactone monomers have the structure: [ka] wherein each R 1 are independently hydrogen, methyl, C 2-10 alkyl groups, or any combination thereof.

[0019] The method may further include contacting carbon monoxide and an epoxide compound to form a beta-lactone monomer. The carbon monoxide and epoxide compound may be contacted in the presence of a carbonylation catalyst. The epoxide compound may have the structure according to the following: [ka] wherein each R 1 are independently hydrogen, methyl, C 2-10 alkyl groups, or any combination thereof.

[0020] The present disclosure includes a polymer composition according to the methods disclosed herein, comprising a polypropiolactone polymer having a number average molecular weight of from about 1000 g / mol to about 200,000 g / mol, a polydispersity index of from greater than 1 to about 3.5, and by-products present in an amount of 50 parts per billion or less.

[0021] The present technology uses solvents that produce polypropiolactone polymers that do not contain undesirable chemicals in food and / or beverage containers. The technology utilizes solvents that are widely available and can be recycled or easily disposed of after forming the polypropiolactone polymer because the polymer precipitates from the solvent in which the monomers react. By precipitating the polypropiolactone polymer from the solvent, the polymer can be easily applied as a film and / or coating directly from the solvent. [Brief explanation of the drawings]

[0022] [Figure 1] 1 is a gel permeation chromatography ("GPC") trace of polypropiolactone from Example 1. [Figure 2] 1 is a GPC trace of polypropiolactone from Example 2. [Figure 3] 1 is a GPC trace of polypropiolactone from Example 3. [Figure 4] 1H NMR spectroscopy of polypropiolactone in CDCl3. [Figure 5] 1 is a differential scanning calorimetry ("DSC") of polypropiolactone polymer produced from aqueous polymerization in the presence of PEO-PPO-PEO. DETAILED DESCRIPTION OF THE INVENTION

[0023] While the present disclosure has been described in connection with certain specific embodiments, it should be understood that the present disclosure is not limited to the disclosed embodiments, but on the contrary is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims, which scope is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures permitted under law.

[0024] Definitions of specific functional groups and chemical terms are described in more detail below. For purposes of the present invention, chemical elements are defined as defined in the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75 th (back cover), and specific functional groups are generally defined as described therein. In addition, general principles of organic chemistry, as well as specific functional moieties and reactivities, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999, Smith and March's Advanced Organic Chemistry, 5 th Edition, John Wiley&Sons, Inc., New York, 2001, Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989, Carruthers, Some Modern Methods of Organic Synthesis, 3 rd Edition, Cambridge University Press, Cambridge, 1987, each of which is incorporated herein by reference in its entirety.

[0025] As used herein, one or more means that at least one, or more than one, of the listed components may be used as disclosed. Residue, with respect to a component or reactant used to prepare a polymer or structure disclosed herein, refers to the portion of the component that remains in the polymer or structure after inclusion as a result of the method disclosed herein. As used herein, substantially or essentially all means that more than 90 percent of the referenced parameter, composition, structure, or compound meets the defined criteria, more than 95 percent, more than 99 percent of the referenced parameter, composition, or compound meets the defined criteria, or more than 99.5 percent of the referenced parameter, composition, or compound meets the defined criteria. As used herein, substantially or essentially free means that the referenced parameter, composition, structure, or compound contains about 10 percent or less, about 5 percent or less, about 1 percent or less, about 0.5 percent or less, about 0.1 percent or less, or about 0.01 percent or less. As used herein, portion means less than the total amount or quantity of a component in a composition, stream, or both. As used herein, precipitate refers to a solid compound in a slurry or blend of liquid and solid compounds. This component or product may exist in different states, such as solid, liquid, or gaseous states, during the disclosed processes. Phase refers to the portion of the reaction mixture that is not soluble in another portion of the reaction mixture. Parts by weight refer to the portion of a component relative to the total weight of the entire composition. As used herein, a composition or mixture includes all components in a stream, reactant stream, product stream, slurry, precipitate, solution, liquid, solid, gas, or any combination thereof that can be contained within a single vessel. In other words, a mixture may contain components that are solid, gaseous (i.e., volatile), and / or liquid at room temperature (i.e., 25 degrees Celsius) or when exposed to elevated temperatures. Certain disclosed polymers may contain one or more asymmetric centers and, therefore, may exist in various stereoisomeric forms, e.g., enantiomers and / or diastereomers.The polymers and compositions thereof may be in the form of individual enantiomers, diastereomers, or geometric isomers, or may be in the form of a mixture of stereoisomers. The disclosed polymers may be enantiopure compounds. Mixtures of enantiomers or diastereomers are disclosed. In certain structures disclosed in this application, portions of the structures are represented by dashed lines indicating that the connected structures are ionically bonded together. [ka] are connected by.

[0026] The disclosed polymers may include one or more crystalline polymorphs and therefore may exist in various crystalline forms.

[0027] As used herein, the term "beta-lactone" refers to a substituted or unsubstituted cyclic ester having a four-membered ring containing an oxygen atom, a carbonyl group, and two optionally substituted methylene groups. When unsubstituted, the beta-lactone is referred to as propiolactone. Substituted beta-lactones include mono-, di-, tri-, and tetra-substituted beta-lactones. Such beta-lactones may be further optionally substituted as defined herein. A beta-lactone contains a single lactone moiety. A beta-lactone may contain two or more four-membered cyclic ester moieties.

[0028] The term "epoxide," as used herein, refers to a substituted or unsubstituted oxirane. Such substituted oxiranes include mono-, di-, tri-, and tetra-substituted oxiranes. Such epoxides may be further optionally substituted as defined herein. An epoxide may contain a single oxirane moiety. An epoxide may contain two or more oxirane moieties.

[0029] As used herein, the term "polymer" refers to a molecule of high relative molecular weight whose structure actually or conceptually comprises multiple repeating units derived from molecules of lower relative molecular weight. Polymers can be composed of or derived from beta-lactone monomers (e.g., polypropiolactone). Such polymers are also referred to as poly(3-hydroxypropionates). The disclosed polymers can be copolymers, terpolymers, heteropolymers, block copolymers, or tapered heteropolymers incorporating two or more different monomers.

[0030] As used herein, the terms "halo" and "halogen" refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), and iodine (iodine, -I).

[0031] The terms "aliphatic" or "aliphatic group," as used herein, refer to a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridged, and spiro-fused polycyclics) and may be fully saturated or contain one or more units of unsaturation, but is not aromatic. Aliphatic groups may contain 1 to 40 carbon atoms, 1 to 20 carbon atoms, 2 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 5 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, or 1 to 2 carbon atoms. Aliphatic groups include, but are not limited to, straight-chain or branched-chain alkyl, alkenyl, and alkynyl groups, and hybrids thereof, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, or (cycloalkyl)alkenyl.

[0032] As used herein, the term "heteroaliphatic" refers to an aliphatic group in which one or more carbon atoms are independently replaced by one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen, or phosphorus. Heteroaliphatic groups can be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and include saturated, unsaturated, or partially unsaturated groups.

[0033] The term "unsaturated," as used herein, means that a moiety has one or more double or triple bonds. The terms "alicyclic," "carbocycle," or "carbocyclic," used alone or as part of a larger moiety, refer to a saturated or partially unsaturated cycloaliphatic monocyclic or polycyclic ring system having 3 to 12 members, as described herein, where the aliphatic ring system is defined below and is optionally substituted as described herein. Alicyclic groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornyl, adamantyl, and cyclooctadienyl. Alicyclic groups can have 3 to 6 carbons. The terms "alicyclic," "carbocycle," or "carbocyclic" also include an aliphatic ring fused to one or more aromatic or non-aromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring. As used herein, the term "alkenyl" refers to a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond by the removal of a single hydrogen atom. As used herein, the term "alkynyl" refers to a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon triple bond by the removal of a single hydrogen atom. As used herein, the term "alkoxy" refers to an alkyl group, as previously defined, attached to the parent molecule through an oxygen atom. Examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, and n-hexoxy. The term "acyl," as used herein, refers to a carbonyl-containing functionality, e.g., -C(=O)R', where R' is hydrogen or an optionally substituted aliphatic, heteroaliphatic, heterocyclic, aryl, heteroaryl group, or substituted (e.g., with hydrogen or an aliphatic, heteroaliphatic, aryl, or heteroaryl moiety) oxygen- or nitrogen-containing functionality (e.g., to form a carboxylic acid, ester, or amide functionality).The term "acyloxy," as used herein, refers to an acyl group attached to a parent molecule through an oxygen atom. The term "aryl," used alone or as part of a larger moiety such as "aralkyl," "aralkoxy," or "aryloxyalkyl," refers to monocyclic and polycyclic ring systems having a total of 5 to 20 ring members, in which at least one ring in the system is aromatic and each ring in the system contains 3 to 12 ring members. The term "aryl" may be used interchangeably with the term "aryl ring," which refers to an aromatic ring system, including, but not limited to, phenyl, biphenyl, naphthyl, anthracyl, and the like, which may bear one or more substituents. As used herein, the term "aryl" also includes within its scope groups in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthymidyl, phenanthridinyl, or tetrahydronaphthyl, where the radical or point of attachment is on the aryl ring.

[0034] The terms "heteroaryl" and "heteroalkoxy," used alone or as part of a larger moiety, e.g., "heteroaralkyl" or "heteroaralkoxy," refer to groups having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms, in which 6, 10, or 14 pi electrons are shared in a cyclic arrangement, and which have 1 to 5 heteroatoms in addition to carbon atoms. The term "heteroaryl" can be used interchangeably with the terms "heteroaryl ring" and "heteroaryl group," either of which includes rings that are optionally substituted. The term "heteroatom" refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur and any quaternized form of a basic nitrogen. Heteroaryl groups can be monocyclic or bicyclic. The term "heteroaralkyl" refers to an alkyl group substituted by a heteroaryl, where the alkyl and heteroaryl portions are independently optionally substituted. The term "partially unsaturated" refers to a ring moiety that contains at least one double or triple bond.

[0035] As described herein, the disclosed compounds may contain "optionally substituted" moieties. The term "substituted," whether preceded by the term "optionally," means that one or more hydrogens of the specified moiety have been replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and if more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituents may be either the same or different at all positions. Combinations of substituents envisioned are those that result in the formation of stable or chemically feasible compounds. The term "stable," as used herein, refers to compounds that are substantially unchanged when subjected to conditions that allow for their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.

[0036] As used herein, the term "alkoxylated" means that one or more functional groups on a molecule (typically, the functional groups are, but are not strictly limited to, alcohol, amine, or carboxylic acid) have had a hydroxy-terminated alkyl chain attached to it. The alkoxylated compound may contain a single alkyl group or may be an oligomeric moiety such as a hydroxyl-terminated polyether. The alkoxylated material may be derived from a parent compound by treating the functional group with an epoxide. Unless otherwise specified, "a," "an," "the," and "at least one" are used interchangeably and mean one or more than one.

[0037] This technology allows for the formation of polypropiolactone polymers in a polar protic solvent containing a phosphorus compound and, optionally, one or more carboxylate compounds, such that, once formed, the polypropiolactone polymer precipitates from the solvent. Optionally, surfactants and / or buffers can be added to control the properties, yield, or rate of formation of the polypropiolactone polymer. Upon precipitation from the solvent, the polypropiolactone is essentially free of unreacted starting components, undesired by-products, and / or solvent. Because this technology reacts essentially all of the beta-lactone monomers, the resulting polypropiolactone is safe for use in products intended for human contact, such as beverage and / or food containers. Additionally, by reacting essentially all of the beta-lactone monomers, the polar protic solvent can be reused.

[0038] The reaction between beta-lactone monomers to form polypropiolactone polymers can proceed as a polymerization reaction, as shown in Scheme 1 below. Scheme 1: [ka]

[0039] The polymer may contain, at one end of a chain segment, a residue of a phosphate or carboxylate anion covalently attached to one end of the polymer chain. The polymer may have a mixture of residues of carboxylate anions and residues of phosphate anions attached to one end of the polymer chain. The other end of the chain segment may be one or more onium cations.

[0040] Polypropiolactone polymers can have any structure of repeating beta-hydroxy units, based on the beta-lactone monomers used. Polypropiolactones can have a structure that is a residue of the beta-lactone monomers used to form the polypropiolactone. Polypropiolactones have the following structure: [ka] wherein each R 1 is independently in each occurrence hydrogen or a carbon-containing group which may have one or more hydrogen or fluorine atoms bonded to a carbon atom, which may optionally contain one or more heteroatoms and / or substituents; x is a real number greater than 1. The variable n can be selected so that the resulting polymer has a number average molecular weight of about 500 to 2,000,000 g / mol. x can be 3 to 50,000.

[0041] The polymer formed may have a residue of an anionic initiator group at the other end of the polymer chain. Such a residue may be based on any known initiator group, which may be added separately to the reaction mixture during the polymerization reaction or may be generated in situ. The initiator residue may be formed from a phosphorus compound and / or a carboxylate compound. The initiator residue may have the formula: D, [ka] wherein D is a residue of one or more anionic initiators; R 2 is, separately in each occurrence, an optionally substituted group containing one or more carbon atoms; R 4 is, independently in each occurrence, a group containing one or more carbon atoms which may contain heteroatoms or may be substituted with functional groups.

[0042] The prepared polymer has the formula [ka] where D is the residue of one or more anionic initiators. The prepared polymer may be a portion of a polymer chain having a phosphate attached to one end of the chain. Such a polymer may correspond to the formula: [ka] where a is an integer from 1 to 3 and b is an integer from 0 to 2. The variable a can be 1, 2, or 3. The variable b can be 0, 1, or 2. The sum of a and b is 3, In the formula, R 1 and R 2 is described herein, x is as described herein, Z, independently in each occurrence, is hydrogen, the residue of an onium cation, etc. A portion of the polymer chains may have carboxylate groups at some of the ends of the chain. Such polymers have the formula: [ka] where R 2 , R 1 , Z, and x are as previously described; R 4 are described herein. The polymers prepared can include polymers with different initiators as described herein.

[0043] R 1 One or more of the R groups may be carbon-containing groups that may have one or more hydrogen or fluorine atoms bonded to a carbon atom, and the carbon-containing groups may include one or more of unsaturated groups, electrophilic groups, nucleophilic groups, anionic groups, cationic groups, zwitterionic groups, hydrophobic groups, hydrophilic groups, halogen atoms, natural minerals, synthetic minerals, carbon-based particles, UV-active groups, polymers with surfactant properties, and polymerization initiators or reactive heterocyclic rings. The functional groups may be linked to the ring by a linking group (M) that functions to link the functional portion of the group to the cyclic ring. Exemplary linking groups may be carbon-containing groups, ethers, thioethers, polyethers (such as polyalkene ethers), etc. 1one or more of R may be a halogen-substituted alkyl group; a sulfonate-substituted alkyloxy group; an alkylsulfonate alkyloxy group; an alkyl ether-substituted alkyl group; a polyalkylene oxide-substituted alkyl group; an alkyl ester-substituted alkyl group; an alkenyloxy-substituted alkyl group; an aryl ester-substituted alkyl group; an alkenyl group; a cyano-substituted alkyl group; an alkenyl ester-substituted alkyl group; a cycloalkyl-substituted alkyl group; an aryl group; a heteroatom-containing cycloalkenyl, an alkyl ether-substituted alkyl group; a hydroxyl-substituted alkyl group; an alicyclic-substituted alkenyl group; an aryl-substituted alkyl group; a haloaryl-substituted alkyl group; an aryloxy-substituted alkyl group; an alkyl ether-substituted alkaryl group; a heteroatom-containing alicyclic-substituted alkyl group; a heteroatom-containing aryl-substituted alkyl group, an alkylamido-substituted alkyl group, or an alkenyl-substituted alicyclic group; 1 may form a cyclic ring which may optionally contain one or more unsaturated groups; an alkyl group substituted with a beta-lactone group which may optionally contain one or more ether groups and / or one or more hydroxyl groups; a glycidyl ether group, or a benzocyclobutenyl-substituted alkyl group optionally substituted with one or more ether groups. The beta-lactone may be 1 corresponds to the formula where all the R on one carbon atom are hydrogen. 1 can both be H, but one or both R on the other carbon atom 1 is an optionally substituted C 1-40 Aliphatic, optionally substituted C 1-20 R may be heteroaliphatic, optionally substituted aryl, or both. 1 The groups can optionally be joined together to form an optionally substituted ring, optionally containing one or more heteroatoms. 1 One or two of the groups may be alkyl and the others may be hydrogen. 1-20 Alkyl group, C 1-12 Alkyl group, C 1-8 Alkyl group, C 1-4 The R groups on different carbon atoms can be alkyl groups, and the alkyl groups can contain unsaturation, heteroatoms, or heteroatom-containing functional groups.1 One or two of the R groups on the same carbon atom may be methyl or ethyl, and the other may be hydrogen. 1 can be methyl, but other R 1 is hydrogen.

[0044] R 2 R is independently for each carbon-containing group that may contain heteroatoms or one or more unsaturated moieties. 2 may, independently in each occurrence, be one or more alkyl, aryl, alkaryl, or aralkyl groups which may contain heteroatoms or one or more unsaturated moieties; R 2 Two or more of R may form a cycloalkyl group or a cyclic ring containing one or more aryl groups, and such groups may contain heteroatoms and / or unsaturated groups. 2 represents, separately in each occurrence, one or more C 1-20 Alkyl group, C 3-24 Cycloalkyl groups, C 5-24 Aryl group, C 6-24 Alkaryl group, C 6-24 R may be an aralkyl group. 2 represents, separately in each occurrence, one or more C 1-12 Alkyl group, C 3-12 Cycloalkyl groups, C 5-12 Aryl group, C 6-12 Alkaryl group, C 6-12 R may be an aralkyl group. 2 represents, separately in each occurrence, one or more C 1-12 R can be an alkyl group. 2 is, separately in each occurrence, C, which may contain heteroatoms or one or more unsaturated moieties; 1-4 R can be an alkyl group. 2 may, at each occurrence independently, be one or more of a methyl, ethyl, propyl, or butyl group.

[0045] R 3 is, separately in each occurrence, a carbon-containing group; R3 Two or more of R may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms. 3 may, independently in each occurrence, be one or more alkyl, aryl, alkaryl, or aralkyl groups which may contain heteroatoms or one or more unsaturated moieties; R 3 Two or more of R may form a cycloalkyl group or a cyclic ring containing one or more aryl groups, and such groups may contain heteroatoms and / or unsaturated groups. 3 represents, separately in each occurrence, one or more C 1-20 Alkyl group, C 3-24 Cycloalkyl groups, C 5-24 Aryl group, C 6-24 Alkaryl group, C 6-24 R may be an aralkyl group. 3 represents, separately in each occurrence, one or more C 1-12 Alkyl group, C 3-12 Cycloalkyl groups, C 5-12 Aryl group, C 6-12 Alkaryl group, C 6-12 R may be an aralkyl group. 3 represents, separately in each occurrence, one or more C 1-12 R can be an alkyl group. 3 is, separately in each occurrence, C, which may contain heteroatoms or one or more unsaturated moieties; 1-4 R can be an alkyl group. 3 may, at each occurrence independently, be one or more of a methyl, ethyl, propyl, or butyl group.

[0046] R 4 R is, independently in each occurrence, a carbon-containing group that may contain heteroatoms or be substituted with functional groups. 4 may, independently in each occurrence, be one or more alkyl, aryl, alkaryl, or aralkyl groups which may contain heteroatoms or one or more unsaturated moieties; R 4Two or more of R may form a cycloalkyl group or a cyclic ring containing one or more aryl groups, and such groups may contain heteroatoms and / or unsaturated groups. 4 represents, separately in each occurrence, one or more C 1-20 R can be an alkyl group. 4 represents, separately in each occurrence, one or more C 1-12 R can be an alkyl group. 4 represents, separately in each occurrence, one or more C 1-12 R can be an alkyl group. 4 is, separately in each occurrence, C, which may contain heteroatoms or one or more unsaturated moieties; 1-4 R can be an alkyl group. 4 R, in each occurrence, can be independently one or more of a methyl, ethyl, propyl, or butyl group. 4 can form an acrylate group with the carbonyloxy moiety to which it is attached.

[0047] The formed polymer composition may have low polydispersity, for example, a polydispersity index (PDI) of 3.5 or less, 3.0 or less, 2.5 or less, 2.2 or less, 2.0 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, or 1.05 or less. The formed polymer composition may have a PDI of 1.05 or more, 1.1 or more, 1.2 or more, 1.5 or more, or 2.0 or more. The listed PDI values ​​refer to those measured by GPC. The PDI values ​​may be calculated without including GPC peaks resulting from oligomers having an Mn of less than about 5,000 g / mol, less than about 4,500, less than about 4,000, less than about 3,500, less than about 3,000, less than about 2,500, less than about 2,000, less than about 1,500, or less than about 1,000 g / mol.

[0048] The prepared polymers may have a number average molecular weight of greater than about 500 g / mol, 1,000 g / mol, 5,000 g / mol, 10,000 g / mol, 17,000 g / mol, 20,000 g / mol, 25,000 g / mol, 50,000 g / mol, 100,000 g / mol, 200,000 g / mol, 300,000 g / mol, or 500,000 g / mol, when measured as disclosed herein. The prepared polymers may have a number average molecular weight of up to 2,000,000 g / mol or up to 1,000,000 g / mol. The prepared polymers may have a weight average molecular weight of greater than about 500 g / mol, 1,000 g / mol, 5,000 g / mol, 10,000 g / mol, 17,000 g / mol, 20,000 g / mol, 25,000 g / mol, 50,000 g / mol, 100,000 g / mol, 200,000 g / mol, 300,000 g / mol, 500,000 g / mol, 600,000 g / mol, or 700,000 g / mol, when measured as disclosed herein. The prepared polymers may have a number average molecular weight of 2,000,000 g / mol or less, or 1,000,000 g / mol or less. Number and / or weight average molecular weights of polymer compositions refer to those measured by gel permeation chromatography (GPC) using THF as solvent and referenced to monodisperse polymethyl methacrylate standards.

[0049] The polypropiolactone polymers described herein may have a desirable glass transition temperature for use in products such as food and / or beverage containers, or films, coatings, and / or paints. The glass transition temperature may be about -25 degrees Celsius or higher, about -20 degrees Celsius or higher, or about -15 degrees Celsius or higher. The glass transition temperature may be about 0 degrees Celsius or lower, about -5 degrees Celsius or lower, or about -10 degrees Celsius or lower. The glass transition temperature may be measured by any known technique. The glass transition temperature may be measured by differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA).

[0050] The polypropiolactone polymers described herein may have desirable melting temperatures for use in products such as food and / or beverage containers, or films, coatings, and / or paints. The melting temperature may be about 60° C. or higher, about 70° C. or higher, or about 80° C. or higher. The melting temperature may be about 120° C. or lower, about 110° C. or lower, or about 100° C. or lower. The melting temperature may be measured by any known technique. The glass transition temperature may be measured by differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA).

[0051] Polymers containing residues of beta-lactone are disclosed. Functional groups on the beta-lactone can provide functionality to polymers and copolymers prepared from the beta-lactone. The functional groups can act as polymerization initiators, improve adhesion of the polymer to a particular substrate or polymer system, improve hydrophobic or hydrophilic properties, improve hardness or scratch resistance, polymerization catalysts, and the like. Beta-lactone polymers and copolymers can function as intermediate layers in multilayer films, including those films having layers of different polymers. Beta-lactone polymers and copolymers can degrade under certain conditions, allowing the other layers to be easily separated for reuse in recycling. Beta-lactone polymers and copolymers can function as intermediate layers between other polymer coatings and substrates. Beta-lactone polymers and copolymers can degrade under certain conditions, allowing the substrate to be easily separated from other coating layers for reuse in recycling. Beta-lactone polymers and copolymers can be used as outer film or coating layers that can be degraded, or such outer layers can be functionalized to provide a desired set of properties to the structure.

[0052] The polymerizable composition may include: a. one or more beta-lactones; and b. one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions.

[0053] The beta-lactone that may be in the polymerizable composition and that may be used to prepare the polymer may be any beta-lactone that polymerizes under the conditions defined in this application. The beta-lactone may have the general formula: [ka] where R 1 is as mentioned above.

[0054] Homopolymers prepared from the disclosed beta-lactones are disclosed. Copolymers of two or more beta-lactones are disclosed. Compositions are disclosed that include copolymers of one or more of the disclosed beta-lactones with one or more monomers reactive with one or more of the beta-lactones. Compositions are disclosed that include copolymers of one or more of the disclosed beta-lactones with one or more monomers reactive with one or more of the beta-lactones. Such copolymers may include a plurality of one or more diols, difunctional polyalkylene oxides, amine-terminated polyalkylene oxides, one or more difunctional polyesters, lactams, lactides, cyclic lactones, cyclic anhydrides, cyclic ether epoxides, episulfides, aziridines, (meth)acrylates, valerolactones, butyrolactones, glycolides, substituted glycolides, or polyethers. Such comonomers may be one or more of epoxides, oxiranes, lactams, and lactides. The comonomer may be one or more cyclic anhydrides, including succinic anhydride, methylsuccinic anhydride, methyldiglycolic anhydride, methylglutaric anhydride, maleic anhydride, phthalic anhydride, citraconic anhydride, and trans-1,2-cyclohexanedicarboxylic anhydride. These copolymers may contain units derived from beta-propiolactone. The disclosed copolymers may be block copolymers, random copolymers, or one or more chains that may be grafted onto the polymer backbone.

[0055] One or more beta-lactones [ka] It could be.

[0056] One or more beta-lactones [ka] wherein R 10 is R 1 can be the same as

[0057] One or more beta-lactones [ka] It can be, where Ar is any optionally substituted aryl group and R 12 -H, optionally substituted C 1-20 Aliphatic, optionally substituted C 1-20 heteroaliphatic and optionally substituted aryl, R 13 is a fully or partially unsaturated C 2-20 straight chain aliphatic groups. The polymer may be prepared from a mixture of beta-propiolactone and pivalolactone. [ka]

[0058] One or more beta-lactones [ka] It could be.

[0059] The polymer has the formula: [ka] The beta-lactone may be prepared from a mixture of beta-propiolactone and one of the following:

[0060] The polymer can be prepared from a mixture of beta-lactones, where the beta-lactones are provided as a mixture of positional isomers. Any of the above-mentioned beta-lactone comonomers can be provided in combination with their positional isomers. When the beta-lactone comonomers are provided as a mixture of positional isomers, the positional isomer having the largest substituent on the carbon adjacent to the ring oxygen atom is present in molar excess relative to the other positional isomers. The major positional isomer is present in a ratio of 2:1 or greater relative to the minor positional isomer, at least 3:1, at least 5:1, at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, or at least 100:1 relative to the minor positional isomer.

[0061] The polymer may be prepared from a mixture of beta-lactone and one or more cyclic ethers, including tetrahydrofuran, substituted tetrahydrofuran, and epoxides. The epoxides may be substituted epoxides. The epoxides may be one or more of ethylene oxide, propylene oxide, butylene oxide, 4-vinylcyclohexene oxide, 4-ethylcyclohexene oxide, limonene oxide, glycidol ethers, glycidol esters, or cyclohexene oxide. The epoxides may be represented by the formula: [ka] where R 1 is as defined herein. The one or more substituted epoxides may be of the formula: where: [ka] R 10 is R 1 The one or more substituted epoxides may be the same as [ka] It could be.

[0062] The one or more substituted epoxides may have the formula: [ka] wherein Ar can be any optionally substituted aryl group; R 10 is defined above, and R 12 -H, optionally substituted C 1-20 Aliphatic, optionally substituted C 1-20 heteroaliphatic and optionally substituted aryl, R 13 is a fully or partially unsaturated C 2-20 straight chain aliphatic groups;

[0063] The one or more substituted epoxides may have the formula: [ka] It may correspond to one of the following:

[0064] Disclosed are methods for polymerizing beta-lactone using the initiators described herein, optionally in combination with one or more additional co-monomers (collectively, monomers), which may or may not be covalently bound in the final polymer product.

[0065] The polypropiolactone polymer may include one or more inhibitors configured to reduce the formation of polyacrylic acid prior to or during processing to form acrylic acid. The one or more inhibitors may be selected to prevent polyacrylic acid from forming while the beta-lactone is being formed and / or when the polypropiolactone is exposed to heat to form acrylic acid. The inhibitor may include one or more of monomethyl ether hydroquinone, 2-tert-butyl-1,4-benzoquinone, 1,4-benzoquinone, 2,6-di-tert-butylphenol, tert-butylhydroquinone, copper(II) dibutyldithiocarbamate, 2-[1-(2-hydroxy-3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenylacrylate, phenothiazine, 4-methoxyphenol, 4-tert-butylpyrocatechol, 2,6-di-tert-butyl-p-cresol, 6-tert-butyl-2,4-xylenol, 1,1-diphenyl-2-picrylhydrazyl frurazil, 2,6-di-tert-butyl-p-cresol, or any combination thereof.

[0066] The polypropiolactone polymer may further comprise residues of phosphorus compounds and / or surfactants. The polypropiolactone polymer may contain any amount of residues of phosphorus compounds and / or surfactants that does not prohibit the use of the polypropiolactone polymer in downstream products, such as food and / or beverage products. The polypropiolactone polymer may contain a weight percent of residues of phosphorus compounds and / or surfactants of about 5 percent or less, about 3 percent or less, or about 1 percent or less, based on the total weight of the polymer. The polypropiolactone polymer may contain a weight percent of residues of phosphorus compounds and / or surfactants of about 0.01 percent or more, about 0.1 percent or more, or about 0.5 percent or more, based on the total weight of the polymer.

[0067] The phosphorus compound may function to support the polymerization of beta-lactone in a polar protic solvent to form polypropiolactone. The phosphorus compound may be configured as a surfactant, accelerator, catalyst, initiator, or a combination thereof.

[0068] The phosphorus compound can initiate polymerization between beta-lactone monomers to form polypropiolactone polymers. The phosphorus compound can initiate the process of ring-opening the beta-lactone monomers to form intermediates that form repeat units derived from the ring-opened beta-lactone. The phosphorus compound can be any compound known to dissociate or disperse in polar protic solvents to form an initiator. The phosphorus compound can form an anion sufficient to promote the formation of a polymer having repeat units derived from the ring-opened beta-lactone.

[0069] The phosphorus compound may be configured as a surfactant having both hydrophobic and hydrophilic groups so that the phosphorus compound can reduce the surface tension between the polar protic solvent and the beta-lactone monomer. The hydrophobic group may be non-polar. Examples of hydrophobic groups that may be included in the phosphorus compound include C, which may optionally contain unsaturation. 5-20 Examples of hydrophobic groups include alkyl, aryl, or alkyl-aryl groups. The phosphorus compound may contain one or more, two or more, three or more, or four or more hydrophobic groups. The hydrophilic groups may have an electronegativity that allows the molecule to be soluble in polar protic solvents. Examples of hydrophilic groups may include one or more oxygen-, phosphorus-, and / or nitrogen-containing groups.

[0070] The phosphorus compound may be configured as a catalyst or accelerator to increase the rate of polymerization in a polar protic solvent so that polypropiolactone polymer is formed before undesirable amounts of the beta-lactone decompose into other compounds, such as hydroxycarboxylic acids. The phosphorus compound may be selected so that the reaction converts essentially all of the beta-lactone monomer in about 3 hours or less.

[0071] The phosphorus compound may have two or more moieties with different electronegativity values ​​such that the phosphorus compound promotes and / or increases the rate of beta-lactone monomer polymerization into polypropiolactone polymers. The phosphorus compound may include at least one moiety that is cationic and another moiety that is anionic. The anionic and cationic moieties may be linked by a covalent or ionic bond. If covalently linked, the phosphorus compound may be configured or function as a zwitterion. In other words, the phosphorus compound may be a single molecule containing cationic and anionic moieties. If the cationic and anionic moieties are ionically bonded, the phosphorus compound may be configured as a salt that dissociates in polar protic solvents.

[0072] The phosphorus compound may be present in the solution of the method for forming the polymer in a weight percent sufficient to ring-open the beta-lactone compound to form the polypropiolactone polymer and reduce the formation of by-products. The phosphorus compound may be present in the polypropiolactone polymer in a weight percent of about 0.01 percent or more, about 0.1 percent or more, or about 0.5 percent or more, based on the total weight of the solution equal to 100%. The phosphorus compound may be present in a concentration of about 5 percent or less, about 3 percent or less, or about 1 percent or less, based on the total weight of the solution equal to 100%.

[0073] The polymerizable composition includes one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions. The phosphate anions can initiate the polymerization of one or more beta-lactones and comonomers polymerizable therewith. The presence of one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions can promote the in situ formation of carboxylate anions that can initiate the polymerization of such monomers. The presence of one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions can result in the preparation of a polymer, with both the phosphate anions and the carboxylate anions initiating the polymer chain. The one or more salts or zwitterions of one or more onium cations and one or more phosphate anions can function to catalyze or accelerate the polymerization of the monomers.

[0074] The method can include any number of different phosphorus compounds sufficient to ring-open the beta-lactone compound to form the polypropiolactone polymer and reduce the formation of by-products. The solution can include one or more, two or more, three or more, four or more, or multiple phosphorus compounds. The method can include phosphorus compounds configured as zwitterions, as well as different phosphorus compounds that include a carboxylate or phosphate anion and an omnium cation ionically combined to form a salt.

[0075] The carboxylate or phosphate anion and omnium cation of the phosphorus compound may include any compound sufficient to promote ring-opening of the beta-lactone monomer while reducing the formation of by-products in the polypropiolactone and / or polar protic solvent. As described herein, the carboxylate or phosphate anion and omnium cation may be ionically or covalently bonded together.

[0076] The anion of the phosphorus compound can include one or more of phosphate, carboxylate, carbonate, alkoxide, halogen, or a combination thereof. The anion can include any number of substitutions, such as one or more, two or more, three or more, or four or more substitutions at the oxygen atom of the phosphate or the carbonyl of the carboxylate or carbonate. The anionic moiety can be phosphatidic acid.

[0077] The omnium cation can include one or more of a phosphonium compound, a quaternary ammonium compound, or any combination thereof. The omnium cation can have one or more, two or more, three or more, or four or more substitutions at the nitrogen and / or phosphorus atoms of the quaternary ammonium and / or phosphonium compound.

[0078] The phosphorus compound comprises a phosphate anion covalently bonded to an omnium cation. The omnium cation covalently bonded to the phosphate anion may optionally comprise one or more C 1-20 Quaternary ammonium containing alkyl or aryl groups, one or more C 1-20 The omnium cation may comprise hydrogen, a phosphonium containing alkyl or aryl group, or any combination thereof. 1-20 It may additionally include one or more, two or more, or three or more substitutions of alkyl, aryl, or alkyl-aryl, or any combination thereof, on the nitrogen or phosphorus atom. The omnium cation may include choline.

[0079] The phosphorus compound has the formula I: Formula I: [ka] and the phosphonium compounds corresponding to the formula: 3 is, separately in each occurrence, a carbon-containing group; R 3 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; R acontains a phosphate group, a carboxylate group, a carbonate group, a phosphate group, a halide, or any combination thereof;

[0080] The phosphorus compound has the formula II: Formula II: [ka] or wherein R 5 are independently a quaternary ammonium group, a phosphonium group, another omnium cation, or any combination thereof; R 2 is defined herein.

[0081] The phosphorus compound may be configured as a salt and may have the formula III: Formula III: [ka] wherein each R 2 is defined herein, R b comprises a quaternary ammonium group, a phosphonium group, another onium cation, or any combination thereof.

[0082] The onium cation can be derived from any onium compound that enhances the formation of the polymer disclosed herein. The onium cation can include one or more of nitrogen, phosphorus, sulfur, antimony, or arsenic. The onium cation can include one or more of nitrogen, phosphorus, or sulfur. The onium cation can include one or more of nitrogen or phosphorus. The onium cation can include one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations. The onium cation can include one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations. The one or more quaternary nitrogen-containing cations or quaternary phosphonium cations can include one or more tetraalkylammonium anions or tetraalkylphosphonium anions.

[0083] The one or more quaternary nitrogen-containing cations may contain four carbon-containing groups bonded to the amine nitrogen, and two or more of the carbon groups may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms. The one or more quaternary nitrogen-containing cations may contain one or more nitrogen-containing heterocycles. The one or more nitrogen-containing heterocycles may contain optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium moieties. The one or more quaternary nitrogen-containing cations may contain one or more optionally substituted imidazolium. The one or more quaternary nitrogen-containing cations may include one or more ammonium, amidinium, and guanidinium cations. The three or more quaternary ammonium cations may be represented by the formula: [ka] where R 1 is as defined herein. The one or more guanidinium cations are of the formula: [ka] where R 3 is as defined herein.

[0084] The one or more quaternary ammonium cations may be one or more tetraalkylammonium anions or onium cations based on nitrogen-containing heterocycles, such as optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium. The one or more quaternary ammonium cations may be one or more tetraalkylammonium or N-alkyl-substituted imidazolium cations. The one or more tetraalkylammonium cations may contain one or more of methyl, ethyl, propyl, or butyl groups. The butyl group may be n-butyl or tert-butyl. The one or more tetraalkylammonium cations may be tetramethylammonium, tetraethylammonium, or tetratert-butylammonium cations.

[0085] The one or more quaternary phosphonium cations may be one or more phosphonium cations containing four carbon-containing groups. The one or more quaternary phosphonium cations may be one or more tetraalkylphosphonium cations. The one or more quaternary phosphonium cations may be one or more tetraalkylphosphonium cations having the formula: [ka] where R 3 is as defined herein.

[0086] The phosphate anion can be any phosphate anion that allows one or more onium cations and one or more salts or zwitterions of the phosphate anion to perform the functions disclosed herein. The phosphate anion can have 1 to 3 onium cations bonded to oxygen groups. The phosphate anion can have 0 to 2 optionally substituted groups containing a nitrogen atom bonded to an oxygen. The phosphate anion has the formula: [ka] where R 2 is as defined herein, a is an integer from 1 to 3, and b is an integer from 0 to 2. The variable a can be 1, 2, or 3. The variable b can be 0, 1, or 2. The sum of a and b is 3. The anion can be a mixture of compounds where a and b are different for each anion in the mixture. The phosphate anion has the formula: [ka] where R 2 is as defined herein.

[0087] The one or more salts of one or more onium cations and one or more phosphate anions can be any such salt that provides the properties disclosed herein. Such salts are formed from the phosphate anions and onium cations disclosed herein, as well as the various anions and cations described herein. The one or more salts of one or more onium cations and one or more phosphate anions can be represented by the formula: [ka] can correspond to In the formula, R 2 is, separately in each occurrence, an optionally substituted group containing one or more carbon atoms; Z' is, separately in each occurrence, an onium cation as described herein, including the mutations described herein; a is, separately in each occurrence, 1, 2, or 3; b is, separately in each occurrence, 0, 1, or 2; and the sum of a and b is 3. The one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions have the formula: [ka] corresponds to one of the In the formula, R 3 , R 2 , a, and b are as defined herein. The one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions have the formula: [ka] may correspond to one of In the formula, R 3 and R 2 is as defined herein. The one or more salts of the one or more quaternary nitrogen-containing cations and the one or more phosphate anions have the formula: [ka] where R corresponds to 3 and R 2is as defined herein. The one or more salts of the one or more quaternary nitrogen-containing cations and the one or more phosphate anions have the formula: [ka] where R 1 and R 2 is as defined herein.

[0088] The polymerizable composition may include one or more onium cations, one or more phosphate anions, and one or more zwitterions comprising an optionally substituted carbon group between the anion and the cation having bonds to the anion and the cation. The one or more zwitterions may be any of the defined zwitterions that provide the properties disclosed herein. Such zwitterions are formed from the phosphate anions and onium cations disclosed herein, as well as the various anions and cations described herein. The one or more zwitterions containing one or more onium cations, one or more phosphate anions, and an optionally substituted hydrocarbylene moiety between the anion and the cation may be represented by the formula [ka] where R 2 , R 3 , Z′, a, and b are as defined herein; R 7 are independently optionally substituted carbon-containing moieties. Zwitterions have the formula: Zwitterions may correspond to one of the formulas: [ka] wherein R 3 , R 2 , R 7 , a, and b are as defined herein. The one or more zwitterions of the one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and the one or more phosphate anions are represented by the formula: [ka] wherein R 3 , R 2 , R 7 is as defined herein. The one or more zwitterions comprising one or more quaternary nitrogen-containing cations and one or more phosphate anions are represented by the formula: [ka] where R 3 , R 2 , R 7 is as defined herein. The one or more zwitterions of the one or more quaternary nitrogen-containing cations and the one or more phosphate anions have the formula: [ka] where R 3 , R 2 , R 7 is as defined herein. The one or more zwitterions of the one or more quaternary nitrogen-containing cations and the one or more phosphate anions have the formula: [ka] where R 3 , R 2 , R 7 is as defined herein. The carboxylate compound can be any compound sufficient to disperse or dissociate in a polar protic solvent and promote the formation of a propiolactone polymer. The carboxylate compound can contain any carboxylate group sufficient to promote the polymerization of one or more beta-lactones so that polypropiolactones are formed from repeating units derived from the ring-opened beta-lactone and the residue of the carboxylate compound. The carboxylate compound can contain carboxylate groups ionically bonded with sufficient counterions so that the carboxylate is dissociable or dispersible in the polar protic solvent. The counterions can be alkaline earth metals, alkali metals, phosphonium groups, quaternary ammonium groups, other onium groups, or any combination thereof. The carboxylate compound can have a structure according to the following: [ka] wherein R 2 and R b is defined herein and the dotted line is defined herein.

[0089] The formation of the polypropiolactone polymer can be carried out in a polar protic solvent. The polar protic solvent can have a polarity at least equal to or less than that of water. The polar protic solvent can be any solvent capable of dissolving beta-lactone and insoluble in polypropiolactone having a number average molecular weight greater than about 2000 g / mol. The polar protic solvent can have any saturation point with the beta-lactone monomer, such that at least about 5 percent of the total mass of the solution can be beta-lactone monomer.

[0090] The solution may contain any amount of polar protic solvent sufficient to promote the formation of polypropiolactone when the beta-lactone monomer and the phosphorus compound are contacted. The polar protic solvent may be present in a weight percent of about 70 percent or more, about 80 percent or more, or about 90 percent or more, based on the total weight of the solution summing to 100 percent. The polar protic solvent may be present in a weight percent of about 98 percent or less, about 95 percent or less, or about 92 percent or less.

[0091] The polar protic solvent may have a boiling point such that the polar protic solvent is separable from the polypropiolactone polymer without decomposing the polypropiolactone from the application of heat. The polar protic solvent may have a boiling point selected such that the precipitated polypropiolactone polymer separates from the polar protic solvent and can be applied as a film, coating, and / or paint.

[0092] The polar protic solvent may be a solvent containing acidic protons. The polar protic solvent may contain one or more amine and / or hydroxyl groups. Because it is desirable for the polypropiolactone polymer to precipitate from solution after the polymerization reaction has begun, the polar protic solvent may be selected based on whether the solvent can dissolve polypropiolactone. Examples of polar protic solvents may include one or more of water, methanol, ethanol, acetic acid, isopropanol, n-butanol, formic acid, or any combination thereof.

[0093] The surfactant may function to reduce the surface tension between the beta-lactone monomer, the phosphorus compound, the polar protic solvent, or any combination thereof. The surfactant may be at least partially miscible with the beta-lactone monomer and the polar protic solvent simultaneously. The surfactant may act in combination with the phosphorus compound to reduce the surface tension between the beta-lactone monomer and the polar protic solvent. The surfactant may be absent if the phosphorus compound has multiple functions as a surfactant and an accelerator, catalyst, and / or initiator.

[0094] The surfactant contains hydrophobic and hydrophilic groups to improve the promotion of beta-lactone monomer polymerization in polar protic solvents. The surfactant may contain the same or different hydrophobic and / or hydrophilic groups compared to the phosphorus compound. The hydrophobic groups may be non-polar. Examples of hydrophobic groups that may be included in the phosphorus compound include C, which may optionally contain unsaturation. 5-20 Examples of hydrophilic groups include alkyl, aryl, or alkyl-aryl groups. Hydrophilic groups can have an electronegativity that allows the molecule to be soluble in polar protic solvents. Examples of hydrophilic groups can include one or more oxygen-, phosphorus-, and / or nitrogen-containing groups.

[0095] Any surfactant that reduces the surface tension between the beta-lactone monomer and the polar protic solvent when the beta-lactone monomer polymerizes to form the polypropiolactone polymer can be used. The surfactant can include one or more polymers having repeating alkylene ether groups and one or more terminal hydroxyl groups. The surfactant can include one or more alkylene ethers, including one or more ethylene ethers, propylene ethers, butylene ethers, or any combination thereof. The surfactant can include a non-ionic polymer. The surfactant can include one or more triblock copolymers. The surfactant can include a poloxamer containing poly(tetrahydrofuran), poly(propylene glycol), and poly(ethylene oxide), or any combination thereof. The solution can include any number of different surfactants sufficient to stabilize the solution. The solution can include one or more, two or more, three or more, four or more, or a combination of different surfactants.

[0096] The surfactant may be present in a weight percent sufficient to stabilize the solution. The surfactant may be present in a weight percent sufficient to reduce the surface tension between the beta-lactone monomer or derivative thereof and the polar protic solvent.

[0097] The solution may include a buffer mixed with the polar protic solvent before, after, or during contact with the beta-lactone, phosphate buffer, and / or surfactant. The buffer may function to maintain the pH of the solution containing the polar protic solvent above 7.0 so that undesired by-products are reduced. Any single or combination of buffers sufficient to maintain the pH above 7.0 may be used in the solution. The solution may include one or more, two or more, three or more, four or more, or multiple buffers. Any buffer sufficient to maintain the pH of the solution above 7.0 may be used. The buffer may include one or more of phosphate buffered saline, bicarbonate, citric acid, boric acid, diethylbarbituric acid, mono-alkaline phosphate, or any combination thereof.

[0098] In polar solvents, the beta-lactone may reach a saturation point at about 50 weight percent or less, based on the total weight of the solution. The beta-lactone monomer may be present in the polar protic solvent at any weight percent sufficient to form a polypropiolactone polymer when contacted with the phosphorus compound. The beta-lactone monomer may be present at a weight percent of about 2 percent or more, about 5 percent or more, or about 7 percent or more, based on the total weight of the solution. The beta-lactone monomer may be present at a concentration of about 35 percent or less, about 30 percent or less, about 20 percent or less, or about 10 percent or less, based on the total weight of the solution.

[0099] After separating the polypropiolactone polymer from solution, the polypropiolactone polymer may be essentially free of by-products because the by-products and unreacted reactants (i.e., beta-lactone monomer and / or hydroxycarboxylic acid) are retained in solution. Because some of the by-products and reactants can be harmful to humans, separating the polypropiolactone polymer from solution via, for example, precipitation, reduces or avoids the presence of undesirable by-products or unreacted reactants in the polypropiolactone polymer, increasing the use of the polymer for beverage and / or food containers or packaging, etc. While the reaction proceeds, phosphorus compounds, buffers, and / or surfactants may reduce the amount of by-products formed so that the pH of the solution does not change below 7.0, increasing the yield of polypropiolactone polymer and / or enhancing the properties of the polypropiolactone polymer, such as melting temperature, glass transition temperature, number average molecular weight, weight average molecular weight, or any combination thereof. The by-products may include one or more of acrylic acid compounds, crotonaldehyde, 3-hydroxybutanone, tetrahydrofuran, or any combination thereof. The by-products and / or reactants (i.e., beta-lactone monomers) may be present in the polypropiolactone polymer in amounts that are safe for human contact. The by-products and / or reactants may be essentially free of the polypropiolactone polymer. The by-products and / or reactants may be present in an amount of about 100 parts per million or less, about 500 parts per billion or less, or about 50 parts per billion or less, based on the total polypropiolactone polymer. The by-products and / or reactants may be present in an amount of about 1 part per billion or more, about 10 parts per billion or more, or about 25 parts per billion or more.

[0100] The present technology provides for forming a polypropiolactone polymer by contacting a beta-lactone monomer, a phosphorus compound, and a polar protic solvent. First, the polar protic solvent may be contacted with the phosphorus compound under conditions to form a solution. Then, second, a solution of the beta-lactone, the polar protic solvent, and the phosphorus compound is contacted. First, the beta-lactone monomer is contacted with the polar protic solvent to form a solution, and second, a solution of the phosphorus compound, the beta-lactone monomer, and the polar protic solvent is contacted. The beta-lactone monomer, the phosphorus compound, and the polar protic solvent are contacted simultaneously. Optionally, a surfactant and / or buffer may be added to the solution containing the polar protic solvent before, after, or simultaneously with the phosphorus compound and / or beta-lactone monomer.

[0101] After contacting the phosphorus compound, beta-lactone monomer, and polar protic solvent, an initial amount of polypropiolactone polymer may precipitate shortly thereafter with a number average molecular weight of about 2,000 g / mol or greater. The period for reacting the reactants is the time necessary for the polymer to precipitate. The initial amount of polypropiolactone polymer may precipitate in about 30 seconds or greater, about 5 minutes or greater, or about 30 minutes or greater. The initial amount of polypropiolactone polymer may precipitate in about 24 hours or less, about 12 hours or less, or about 3 hours or less.

[0102] The beta-lactone may have a half-life in a polar protic solvent that allows for the formation of polypropiolactone in the presence of a phosphorus compound before substantial by-products are produced from the beta-lactone. The beta-lactone may have a half-life in a polar protic solvent of about 160 minutes or more, about 190 minutes or more, or about 220 minutes or more. The beta-lactone may have a half-life in a polar protic solvent of about 300 minutes or less, about 270 minutes or less, or about 240 minutes or less.

[0103] The solution of the phosphorus compound, beta-lactone monomer, and polar protic solvent can be stirred for a period of time to convert essentially all of the beta-lactone monomer to polypropiolactone polymer before the beta-lactone monomer decomposes. Stirring can be carried out during mixing of the polar protic solvent and the phosphorus compound, during combination of the beta-lactone monomer and the solution containing the polar protic solvent and the phosphorus compound, and / or throughout the reaction to form polypropiolactone. The period can be about 24 hours or less, about 12 hours or less, or about 3 hours or less. The period can be about 30 minutes or more, about 1 hour or more, or about 2 hours or more. The solution can be stirred by any known technique to promote reaction of the beta-lactone monomer to form polypropiolactone polymer, such as a stirring blade, impeller, rocker, roller, magnetic stir bar, vortex mixer, stirring rod, stirring spatula, or any combination thereof.

[0104] The method can be carried out in any vessel sufficient to promote the reaction under conditions such that undesired by-products are reduced. The vessel can be equipped with a heating mechanism to control the temperature of the reaction, a stirring device, or an apparatus to reduce or prevent oxygen exposure within the reaction vessel, as described herein.

[0105] The method of contacting the beta-lactone monomer, the polar protic solvent, and the phosphorus compound can be carried out in an oxygen-free environment to avoid decomposition of the beta-lactone monomer. The method can be carried out under a nitrogen or argon flow in a glove box or using a Schlenk line. A solution of the polar protic solvent and the phosphorus compound can be formed outside the oxygen-free environment and then contacted with the beta-lactone monomer in the oxygen-free environment.

[0106] The solution containing the beta-lactone monomer and the polar protic solvent and phosphorus compound may be contacted at above, below, or equal to ambient temperature (i.e., 25 degrees Celsius). The reaction may proceed at any temperature sufficient for the reaction to proceed at a reasonable rate so that the polypropiolactone polymer precipitates before the end of the half-life of the beta-lactone monomer. The solution containing the beta-lactone monomer and the polar protic solvent and phosphorus compound may be contacted at about 0 degrees Celsius or above, about 15 degrees Celsius or above, or about 25 degrees Celsius or above. The solution containing the beta-lactone monomer and the polar protic solvent and phosphorus compound may be contacted at about 60 degrees Celsius or below, about 45 degrees Celsius or below, or about 30 degrees Celsius or below.

[0107] After essentially all of the beta-lactone has reacted in the polar protic solvent, the polar protic solvent can be separated from the polypropiolactone polymer that precipitates from the solution. The polar protic solvent can be separated by any known technique for separating two compounds in different phases. The separation technique can be carried out via decanting, evaporation, drying, filtration, settling, or any combination thereof.

[0108] Two or more techniques for separating the polar protic solvent from the polypropiolactone polymer may be used in sequence to reduce the presence of undesirable compounds that may come into contact with the polypropiolactone polymer. The polar protic solvent may be decanted from the polypropiolactone polymer, the polypropiolactone polymer may then be washed with the same or a different polar protic solvent, and the polypropiolactone polymer may be subjected to drying to remove the same or a different polar protic solvent used for washing.

[0109] The techniques disclosed herein involve contacting a beta-lactone monomer, a phosphorus compound, and a polar protic solvent to form and precipitate a polypropiolactone polymer. The solvent can then be separated from the polypropiolactone polymer so that the polypropiolactone polymer is in the form of, or configured to be applied as, a coating, film, and / or paint. One example of an application technique is applying heat to the solution to evaporate the solvent from the polypropiolactone polymer. Heat can be applied at any temperature sufficient to evaporate the solvent. Heat can be applied at a temperature of about 80° C. or higher, about 85° C. or higher, or about 90° C. or higher. Heat can be applied at a temperature of about 100° C. or lower, about 95° C. or lower, or about 90° C. or lower. Heat can be applied for any time sufficient to remove all or substantially all of the solvent from contact with the polypropiolactone polymer. Heat may be applied for about 1 minute or more, about 5 minutes or more, or about 20 minutes or more. Heat may be applied for about 60 minutes or less, about 45 minutes or less, or about 30 minutes or less.

[0110] The beta-lactones used to form the described polypropiolactone polymers can be formed by contacting an epoxide and carbon monoxide under conditions sufficient to form the beta-lactone compound. Examples of process conditions and solvents for the formation of beta-lactones can be found in, at least, U.S. Patent No. 8,445,703, incorporated herein by reference. The epoxide and carbon monoxide can be contacted in the presence of a carbonylation catalyst and / or a suitable solvent. The carbonylation catalyst can have any structure, including a sufficient Lewis acid with a metal center and a metal carbonyl cation ionically bonded to the Lewis acid. Examples of carbonylation catalysts can include porphyrin-metal carbonyl catalysts, salen-metal carbonyl catalysts, or a combination of both. Additional examples of carbonylation catalysts can be found in U.S. Patent Nos. 6,852,865, 8,481,756, 10,221,278, and 8,445,703, which are incorporated herein by reference in their entireties.

[0111] Enumerated Embodiments The following examples are offered to illustrate the invention but are not intended to limit its scope. Unless otherwise indicated, all parts and percentages are by weight. Embodiment 1. a) contacting one or more beta-propiolactone monomers with one or more phosphorus compounds and optionally one or more carboxylate compounds in solution under conditions such that a polypropiolactone polymer is formed; the solution comprises one or more polar protic solvents, and one or more phosphorus compounds, and optionally one or more carboxylate compounds; A method wherein the phosphorus compound comprises phosphorus in ionic form, either covalently bound to another compound to form a zwitterion or ionically bound to another compound to form a salt. Embodiment 2. The method of embodiment 1, wherein the phosphorus compound comprises a phosphonium compound or an anionic phosphate compound. Embodiment 3. The phosphorus compound is of Formula I, II, and / or III: Formula I: [ka] (In the formula, each R 3 is, separately in each occurrence, a hydrocarbyl group; R 3 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; R a contains a phosphate group, a carboxylate group, a carbonate group, an alkoxide group, a halide, or any combination thereof), or Formula II: [ka] (In the formula, R 5 is independently a quaternary ammonium group, a phosphonium group, another omnium cation, or any combination thereof; R 2 is defined herein), or Formula III: [ka] (In the formula, each R 2 is defined herein, Solid lines represent covalent bonds, dotted lines represent ionic bonds, R b comprises one or more of a quaternary ammonium group, a phosphonium group, another onium cation, or any combination thereof). Embodiment 4. The phosphorus compound is a cationic phosphine compound, and C 5-20 4. The method of embodiments 1-3, comprising an anionic carboxylate having an anionic carboxylate group with an alkyl group. Embodiment 5. The method of embodiments 1-3, wherein the phosphorus compound comprises an anionic phosphoric acid and a cationic quaternary ammonium compound. Embodiment 6. The phosphorus compound comprises one or more C covalently bonded to a group that is anionic or cationic. 5-20 6. The method of any one of embodiments 1 to 5, comprising an alkyl group. Embodiment 7. The method of any one of embodiments 1-6, wherein the phosphorus compound comprises a cation and an anion covalently bonded to one another. Embodiment 8. The method of any one of embodiments 1-7, wherein the phosphorus compound comprises a cation and an anion ionically bonded to each other. Embodiment 9. The method of any one of the preceding embodiments, wherein the one or more carboxylate compounds comprise a carboxylate group and a counterion that is soluble or dispersible in a polar protic solvent. Embodiment 10. The one or more carboxylate compounds are according to the formula: [ka] wherein R 2 and R b 10. The method of any one of the preceding embodiments, wherein x is as defined herein and the dotted line is as defined herein. Embodiment 11. The method of any one of the preceding embodiments, wherein the one or more polar protic solvents are present in a weight percent greater than about 90 percent, based on the total weight of the solution when the beta-lactone monomer and the solution are contacted. Embodiment 12. The method of any one of the preceding embodiments, wherein the one or more polar protic solvents comprise one or more of water, methanol, ethanol, acetic acid, isopropanol, n-butanol, formic acid, or any combination thereof. Embodiment 13. The method of any one of the preceding embodiments, wherein the one or more polar protic solvents comprise water. Embodiment 14. The method of any one of the preceding embodiments, wherein the beta-lactone monomer is present in the solution in a weight percent of about 5 percent to about 35 percent, based on the total weight of the solution at the time the beta-propiolactone monomer and the solution are contacted. Embodiment 15. The method of any one of the preceding embodiments, wherein the beta-lactone monomer is present in the solution in a weight percent of about 5 percent to about 25 percent, based on the total weight of the solution at the time the beta-propiolactone monomer and the solution are contacted. Embodiment 16. The method of any one of the preceding embodiments, wherein the beta-propiolactone monomer is present in the solution in a weight percent of about 5 percent to about 20 percent, based on the total weight of the solution at the time the beta-propiolactone monomer and the solution are contacted. Embodiment 17. The method of any one of the preceding embodiments, further comprising: a) contacting one or more phosphorus compounds and one or more polar protic solvents to form a solution before contacting the beta-lactone monomer with the solution. Embodiment 18. The method of any one of the preceding embodiments, further comprising: a) contacting one or more phosphorus compounds, one or more buffers, and one or more polar protic solvents to form a solution before contacting the beta-lactone monomer with the solution. Embodiment 19. The method of any one of the preceding embodiments, further comprising: a) contacting one or more phosphorus compounds, one or more surfactants, and one or more polar protic solvents to form a solution before contacting the beta-lactone monomer with the solution. Embodiment 20. The method of any one of the preceding embodiments, further comprising: a) contacting one or more phosphorus compounds, one or more buffers, one or more surfactants, and one or more polar protic solvents to form a solution before contacting the beta-lactone monomer with the solution. Embodiment 21 The method of any one of the preceding embodiments, wherein the beta-lactone compound is contacted with a solution comprising one or more buffers configured to maintain the pH of the solution above 7.0. Embodiment 22. The method of any one of the preceding embodiments, wherein the beta-lactone monomer is contacted with a solution comprising one or more surfactants. Embodiment 23 The method of any one of the preceding embodiments, wherein the beta-lactone monomer is contacted with a solution comprising one or more buffers and one or more surfactants. Embodiment 24. The method of any one of the preceding embodiments, wherein the one or more surfactants are at least partially miscible with the beta-lactone monomer. Embodiment 25. The method of any one of the preceding embodiments, wherein the beta-lactone and the solution are contacted at a temperature of from about 0 degrees Celsius to about 60 degrees Celsius. Embodiment 26 The method of any one of the preceding embodiments, wherein the step of contacting the beta-lactone monomer and the compound in solution is carried out with stirring for a period of about 12 hours to about 24 hours. Embodiment 27. The method of any one of the preceding embodiments, wherein essentially all of the beta-lactone monomer is converted to polypropiolactone polymer or by-products in about 3 hours or less. Embodiment 28. 10. The method of any one of the preceding embodiments, further comprising: a) contacting the compound and water to form a solution prior to the step of contacting the beta-lactone monomer and the compound in solution. Embodiment 29 The method of any one of the preceding embodiments, wherein the step of contacting the beta-lactone monomer and the compound in solution is carried out in an environment that is oxygen-free. Embodiment 30. 12. The method of any one of the preceding embodiments, further comprising: a) separating the polypropiolactone polymer from the solution. Embodiment 31. a) precipitating a polypropiolactone polymer from solution; 10. The method of any one of the preceding embodiments, further comprising: b) separating the polypropiolactone polymer from the by-products. Embodiment 32. The step of separating the polypropiolactone polymer from the solution comprises: a) precipitating a polypropiolactone polymer from solution; b) decanting the solution from the polypropiolactone polymer; c) washing the polypropiolactone polymer with alcohol to remove any residue of the solution; d) drying the polypropiolactone polymer under vacuum to remove any residue of the solution. Embodiment 33. The method of any one of the preceding embodiments, wherein the phosphorus compound is present in an amount sufficient to ring-open the beta-lactone compound to form a polypropiolactone polymer and reduce the formation of by-products. Embodiment 34. The method of any one of the preceding embodiments, wherein the phosphorus compound is present in the solution in an amount of from 10 ppm to about 200,000 ppm. Embodiment 35. The method of any one of the preceding embodiments, wherein the one or more surfactants are present in an amount sufficient to stabilize the solution. Embodiment 36. The method of any one of the preceding embodiments, wherein the one or more surfactants are present in the solution in an amount from about 10 ppm to about 200,000 ppm. Embodiment 37. The method of any one of the preceding embodiments, wherein the one or more buffers are present in an amount sufficient to maintain the pH of the solution above 7.0. Embodiment 38. The method of any one of the preceding embodiments, wherein the one or more buffers are present in an amount of from about 0.1 g / L to about 10.0 g / L. Embodiment 39. The method of any one of the preceding embodiments, wherein the by-products are present in the polypropiolactone polymer in an amount from about 10 ppm to about 10,000 ppm. Embodiment 40. The method of any one of the preceding embodiments, wherein the presence of the by-products does not change the pH of the solution below 7.0. Embodiment 41 The method of any one of the preceding embodiments, wherein the phosphorus compound comprises a disubstituted phosphate group. Embodiment 42. The phosphorus compound is C 5-20 10. The method of any one of the preceding embodiments, comprising a cationic quaternary ammonium having an alkyl group. Embodiment 43 The method of any one of the preceding embodiments, wherein the cationic quaternary ammonium is covalently attached to the disubstituted phosphate group. Embodiment 44 The method of any one of the preceding embodiments, wherein the phosphorus compound comprises choline covalently bound to phosphatidic acid. Embodiment 45 The method of any one of the preceding embodiments, wherein the phosphorus compound comprises a phosphatidylcholine. Embodiment 46 The method of any one of the preceding embodiments, wherein the cationic quaternary ammonium is ionically bonded to the disubstituted phosphate group. Embodiment 47. The phosphorus compound comprises one or more C covalently bonded to a group that is anionic or cationic. 5-20 13. The method of any one of the preceding embodiments, comprising an alkyl group. Embodiment 48. The phosphorus compound comprises two or more C covalently bonded to the phosphorus atom. 5-20 13. The method of any one of the preceding embodiments, comprising an alkyl group. Embodiment 49. The phosphorus compound comprises three or more C groups covalently bonded to groups that are anionic or cationic. 5-20 13. The method of any one of the preceding embodiments, comprising an alkyl group. Embodiment 50. The phosphorus compound has four or more C covalently bonded to the phosphorus atom. 5-2013. The method of any one of the preceding embodiments, comprising an alkyl group. Embodiment 51. A C carboxylate compound in which a phosphorus compound is connected to the carbonyl of a carboxylate compound. 1-20 10. The method of any one of the preceding embodiments, comprising an anionic carboxylate compound having an alkyl group. Embodiment 52 The method of any one of the preceding embodiments, wherein the phosphorus compound comprises an ionically bonded phosphorus cation and an anionic carboxylate compound. Embodiment 53. The phosphorus compound comprises one or more C 5-20 13. The method of any one of the preceding embodiments, wherein the alkyl group includes at least some degree of unsaturation. Embodiment 54. The method of any one of the preceding embodiments, wherein the one or more surfactants comprise a polymer having alkylene ether repeating groups and one or more terminal hydroxyl groups. Embodiment 55. The method of any one of the preceding embodiments, wherein the alkylene ether comprises one or more of ethylene ether, propylene ether, butylene ether, or any combination thereof. Embodiment 56. The method of any one of the preceding embodiments, wherein the one or more surfactants comprise a non-ionic polymer. Embodiment 57. The method of any one of the preceding embodiments, wherein the one or more surfactants comprise one or more triblock copolymers. Embodiment 58. The method of any one of the preceding embodiments, wherein the one or more surfactants comprise a poloxamer, a fatty acid salt, or any combination thereof. Embodiment 59. The method of any one of the preceding embodiments, wherein the one or more buffers comprise a monoprotic acid, a polyprotic acid, or a combination of both. Embodiment 60. The method of any one of the preceding embodiments, wherein the one or more buffers comprise one or more of phosphate buffered saline, bicarbonate, citric acid, boric acid, diethylbarbituric acid, mono-alkaline phosphate, or any combination thereof. Embodiment 61. The method of any one of the preceding embodiments, wherein the by-products include acrylic acid, acrylic acid dimer, 3-hydroxypropionic acid, or any combination thereof. Embodiment 62. The method of any one of the preceding embodiments, wherein the polypropiolactone polymer has a polydispersity index of greater than 1 to about 3.5. Embodiment 63. The method of any one of the preceding embodiments, wherein the polypropiolactone polymer has a polydispersity index of greater than 1 to about 1.7. Embodiment 64. The method of any one of the preceding embodiments, wherein the polypropiolactone polymer has a number average molecular weight of from about 1 kg / mol to about 1000 kg / mol. Embodiment 65. The method of any one of the preceding embodiments, wherein the polypropiolactone polymer has a weight average molecular weight of from about 1 kg / mol to about 2000 kg / mol. Embodiment 66. The method of any one of the preceding embodiments, wherein the polypropiolactone polymer is substantially free of beta-lactone monomers and / or acrylic acid. Embodiment 67. The method of any one of the preceding embodiments, wherein the polypropiolactone polymer has a melting point of about 70 degrees Celsius to about 130 degrees Celsius. Embodiment 68. The method of any one of the preceding embodiments, wherein the polypropiolactone polymer has a crystallization temperature of from about 0 degrees Celsius to about 100 degrees Celsius. Embodiment 69. The polypropiolactone polymer comprises a repeating structure according to the following: [ka] wherein each R 1 are independently hydrogen, methyl, C 2-10 alkyl group, or any combination thereof; 10. The method of any one of the preceding embodiments, wherein x is a real number greater than 1 and up to 50,000. Embodiment 70. The beta-lactone monomer has the structure: [ka] wherein each R 1 are independently hydrogen, methyl, C 2-10 10. The method of any one of the preceding embodiments, wherein the alkyl group is selected from one or more of: a substituted or unsubstituted alkyl group; ... Embodiment 71. The method of any one of the preceding embodiments, further comprising: a) contacting carbon monoxide and an epoxide compound to form a beta-lactone monomer. Embodiment 72 The method of embodiment 71, wherein the carbon monoxide and the epoxide compound are contacted in the presence of a carbonylation catalyst. Embodiment 73. The epoxide compound has the structure: [ka] wherein each R 1 are independently hydrogen, methyl, C 2-10 73. The method of embodiment 71 or 72, wherein the alkyl group is selected from one or more of: a substituted or unsubstituted alkyl group; ... Embodiment 74. a) a number average molecular weight of about 1,000 g / mol to about 200,000 g / mol; b) a PDI of greater than 1 to about 3.5, and c) a by-product present in an amount of 50 parts per billion or less. [Example]

[0112] The following examples are provided to illustrate the present disclosure but are not intended to limit its scope.

[0113] GPC was performed on an Agilent 1260 Infinity II HPLC system equipped with two PLgel 300 x 7.5 mm (PL111-6500) size-exclusion columns and a multi-detector (refractive index and viscometer). GPC was performed in chloroform solvent at a rate of 1.0 mL / min and maintained at 40 °C. Polymer molar mass was determined using a conventional calibration curve of the RI signal generated with monodisperse polymethyl methacrylate ("PMMA") polymer standards. PMMA standards range from 500 g / mol to 2,000,000 g / mol (Agilent EasiVial, part number: PL2020-0201). Polypropiolactone polymer was dissolved in HPLC-grade chloroform [approximately 5 mg / mL] and then filtered through a 0.2 mm PVDF filter.

[0114] 1 H NMR spectroscopy is performed on a 400 MHz Varian INOVA spectrometer. Spectra are referenced to prothio-chloroform (7.26 ppm). Polypropiolactone polymer samples are dissolved in CDCl3 (99.8% deuterated; Cambridge Isotope) at a concentration of 10 mg / mL.

[0115] Differential scanning calorimetry ("DSC") was performed using N 2(g) On a TA Instruments Q20 Series Differential Scanning Calorimeter, the temperature was measured at 10°C x min. -1 The thermal history of the polymer is as follows: the polymer is melted at 130°C to erase the thermal and solvent memory, and then heated at 10°C x min. -1 The sample was cooled to -30°C at a rate of 10°C x min. -1 The polymer is then heated again to 130°C at a ramp rate of 10°C x 10 min and then rapidly cooled to -30°C [melt-quench]. -1 Reheat to a ramp rate of [1 / 2].

[0116] Example 1 In a glovebox, 100 μL of beta-propiolactone monomer was added to a 2 mL crimp-top gas chromatography vial. The vial was sealed under a nitrogen atmosphere. Outside the glovebox, an aqueous solution containing alpha-lecithin [125 mg, 0.12 wt%] and Pluronic [300 mg, 0.3 wt%] was prepared in 100 mL of phosphate-buffered saline [PBS]. Under a nitrogen atmosphere, approximately 900 μL of the solution was added to the beta-propiolactone monomer and the solution was gently stirred. A white solid precipitated within a few minutes. The solution was allowed to stir overnight to completely consume the beta-propiolactone monomer. The water was decanted off, and the polymer was washed three times with isopropanol [1 mL x 3]. The resulting solid was dried under vacuum overnight to obtain 95 mg of polypropiolactone polymer [95%, Mn(GPC) = 98,000 g / mol, PDI = 1.5].

[0117] Example 2 In a glovebox, 200 μL of betapropiolactone monomer was added to a 2 mL crimp-top vial. The vial was sealed under a nitrogen atmosphere. Outside the glovebox, an aqueous solution containing octadecyl-trimethylammonium dimethylphosphate [ODTMA DMP] [150 mg, 0.15 wt.%] and Pluronic [300 mg, 0.3 wt.%] was prepared in 100 mL of deionized water. Under a nitrogen atmosphere, approximately 800 μL of the solution was added to the betapropiolactone monomer and the solution was gently stirred. A white solid precipitated within a few minutes. The solution was allowed to stir overnight to completely consume the betapropiolactone monomer. The water was decanted off, and the polymer was washed three times with isopropanol [1 mL x 3]. The resulting solid is dried under vacuum overnight to give 53 mg of polypropiolactone polymer [27%, Mn(GPC)=218,000 g / mol, PDI=1.2].

[0118] Example 3 In a glovebox, 200 μL of betapropiolactone monomer was added to a 2 mL crimp-top vial. The vial was sealed under a nitrogen atmosphere. Outside the glovebox, an aqueous solution containing trihexyl(tetradecyl)phosphonium decanoate [THTDPD] [150 mg, 0.15 wt%] was prepared in 100 mL of deionized water. Under a nitrogen atmosphere, approximately 800 μL of the solution was added to the betapropiolactone monomer and the solution was gently stirred. A white solid precipitated within a few minutes. The solution was allowed to stir overnight to completely consume the betapropiolactone monomer. The water was decanted off, and the polymer was washed three times with isopropanol [1 mL x 3]. The resulting solid was dried under vacuum overnight to yield 13 mg [7%, Mn (GPC) = 59,300 g / mol, PDI = 1.5].

[0119] result FIG. 1 is a gel permeation chromatography (“GPC”) trace of polypropiolactone from Example 1.

[0120] FIG. 2 is a GPC trace of polypropiolactone from Example 2.

[0121] FIG. 3 is a GPC trace of polypropiolactone from Example 3.

[0122] Figure 4 is a H NMR spectroscopy of polypropiolactone in CDCl3.

[0123] Figure 5 shows differential scanning calorimetry of polypropiolactone polymer produced from aqueous polymerization in the presence of PEO-PPO-PEO. First heating cycle [line A, 10°C / min under N2(g)]. Cooling cycle [line B, 10°C / min under N2(g)]. Second heating cycle [line C, 10°C / min under N2(g)].

[0124] Examples 1-3 (see above for experimental setup and preliminary results) describe a process for the aqueous polymerization of beta-propiolactone monomer. The structure of each of the compounds used in the polymerization of beta-propiolactone monomer is shown in Scheme 1 below. The results for each example are shown in Table 1. Generally, yields are low to high [7-95%]. Surprisingly, the isolated polymers are of high molar mass [M] with low dispersity. n >50 kDa, PDI <1.5, Figure 1]. 1 H NMR spectroscopy confirms the structure of poly(3-hydroxypropionic acid) [Figure 34]. Thermal properties suggest that the surfactant used plasticizes the polymer, as a depression of the melting point is observed for the final polymer [Figure 5]. Scheme 1. Phosphorus compounds and surfactants used in the polymerization of beta-propiolactone in water. [ka] [Table 1]

Claims

1. a) contacting one or more beta-propiolactone monomers with one or more phosphorus compounds and optionally one or more carboxylate compounds in solution under conditions such that a polypropiolactone polymer is formed; the solution comprises one or more polar protic solvents, and the one or more phosphorus compounds, and optionally the one or more carboxylate compounds; A method wherein the phosphorus compound comprises phosphorus in ionic form, either covalently bound to another compound to form a zwitterion or ionically bound to another compound to form a salt.

2. The method of claim 1 , wherein the phosphorus compound comprises a phosphonium compound or an anionic phosphate compound.

3. The phosphorus compound is represented by Formula I, II, and / or III: Formula I: 【Chemistry 1】 (In the formula, each R ３ is, separately in each occurrence, a hydrocarbyl group; R ３ two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; R ａ contains a phosphate group, a carboxylate group, a carbonate group, an alkoxide group, a halide, or any combination thereof), or Formula II: 【Chemistry 2】 (In the formula, R ５ is independently a quaternary ammonium group, a phosphonium group, another omnium cation, or any combination thereof; R ２ is defined herein), or Formula III: 【Transformation 3】 (In the formula, each R ２ is defined herein, Solid lines represent covalent bonds, dotted lines represent ionic bonds, R ｂ 10. The method of claim 1, wherein R 1 comprises one or more of the following: a quaternary ammonium group, a phosphonium group, another onium cation, or any combination thereof.

4. The phosphorus compound is a cationic phosphine compound, and C ５－２０ The method of any one of claims 1 to 3, comprising an anionic carboxylate having an alkyl group-containing anionic carboxylate compound.

5. The method of any one of claims 1 to 3, wherein the phosphorus compound comprises an anionic phosphoric acid and a cationic quaternary ammonium compound.

6. The phosphorus compound may comprise one or more C groups covalently bonded to a group that is anionic or cationic. ５－２０ The method of any one of claims 1 to 5, comprising an alkyl group.

7. The method of any one of claims 1 to 6, wherein the phosphorus compound comprises a cation and an anion covalently bonded to each other.

8. The method of any one of claims 1 to 7, wherein the phosphorus compound comprises a cation and an anion ionically bonded to each other.

9. 10. The method of any one of the preceding claims, wherein the one or more carboxylate compounds comprise a carboxylate compound and a counterion that are soluble in the polar protic solvent.

10. The one or more carboxylate compounds are according to the formula: 【Chemistry 4】 wherein R ２ and R ｂ 10. A method according to any one of the preceding claims, wherein: is defined herein and the dotted line is defined herein.

11. 10. The method of any one of the preceding claims, wherein the one or more polar protic solvents are present in a weight percent greater than about 90 percent, based on the total weight of the beta-lactone monomer and the solution when contacted.

12. 10. The method of any one of the preceding claims, wherein the one or more polar protic solvents comprise one or more of water, methanol, ethanol, acetic acid, isopropanol, n-butanol, formic acid, or any combination thereof.

13. 10. The method of any one of the preceding claims, wherein the one or more polar protic solvents comprise water.

14. 10. The method of any one of the preceding claims, wherein the beta-lactone monomer is present in the solution in a weight percent of about 5 percent to about 35 percent, based on the total weight of the solution when the beta-propiolactone monomer and the solution are contacted.

15. 10. The method of any one of the preceding claims, further comprising: a) contacting the one or more phosphorus compounds, one or more buffers, one or more surfactants, and the one or more polar protic solvents to form the solution before contacting the beta-lactone monomer with the solution.

16. 10. The method of any one of the preceding claims, wherein the beta-lactone compound is contacted with a solution comprising one or more buffers configured to maintain the pH of the solution above 7.

0.

17. 10. The method of any one of the preceding claims, wherein the one or more surfactants are at least partially miscible with the beta-lactone monomer.

18. 10. The method of any one of the preceding claims, wherein the beta-lactone and solution are contacted at a temperature of from about 0 degrees Celsius to about 60 degrees Celsius.

19. 10. The method of any one of the preceding claims, wherein essentially all of the beta-lactone monomer is converted to the polypropiolactone polymer or by-products in about 3 hours or less.

20. 10. The method of any one of the preceding claims, further comprising: a) contacting the compound and water to form the solution prior to the step of contacting the beta-lactone monomer and the compound in the solution.

21. 10. The method of any one of the preceding claims, wherein the step of contacting the beta-lactone monomer and the compound in the solution is carried out in an environment that is oxygen-free.

22. 10. The method of any one of the preceding claims, further comprising: a) separating the polypropiolactone polymer from the solution.

23. a) precipitating the polypropiolactone polymer from the solution; 10. The method of any one of the preceding claims, further comprising: b) separating the polypropiolactone polymer from the by-products.

24. separating the polypropiolactone polymer from the solution; a) precipitating the polypropiolactone polymer from the solution; b) decanting the solution from the polypropiolactone polymer; c) washing the polypropiolactone polymer with alcohol to remove residues of the solution; d) drying the polypropiolactone polymer under vacuum to remove residues of the solution.

25. 10. The method of any one of the preceding claims, wherein the phosphorus compound is present in an amount sufficient to ring-open the beta-lactone compound so as to form the polypropiolactone polymer and reduce the formation of by-products.

26. 10. The method of any one of the preceding claims, wherein the phosphorus compound is present in the solution in an amount of from 10 ppm to about 200,000 ppm.

27. 10. The method of any one of the preceding claims, wherein the one or more surfactants are present in an amount that is sufficient to stabilize the solution.

28. 10. The method of any one of the preceding claims, wherein the one or more surfactants are present in the solution in an amount from about 10 ppm to about 200,000 ppm.

29. 10. The method of any one of the preceding claims, wherein the by-products are present in the polypropiolactone polymer in an amount from about 10 ppm to about 10,000 ppm.

30. 10. The method of any one of the preceding claims, wherein the presence of the by-products does not change the pH of the solution below 7.

0.

31. 10. The method of any one of the preceding claims, wherein the one or more buffers comprise a monoprotic acid, a polyprotic acid, or a combination of both.

32. 10. The method of any one of the preceding claims, wherein the by-products comprise acrylic acid, acrylic acid dimer, 3-hydroxypropionic acid, or any combination thereof.

33. 10. The method of any one of the preceding claims, wherein the polypropiolactone polymer has a polydispersity index of from greater than 1 to about 1.

7.

34. 10. The method of any one of the preceding claims, wherein the polypropiolactone polymer has a weight average molecular weight of from about 1 kg / mol to about 2000 kg / mol.

35. 10. The method of any one of the preceding claims, wherein the polypropiolactone polymer is substantially free of beta-lactone monomers and / or acrylic acid.

36. 10. The method of any one of the preceding claims, wherein the polypropiolactone polymer has a melting point of from about 70 degrees Celsius to about 130 degrees Celsius.

37. The polypropiolactone polymer has a repeating structure according to: 【Transformation 5】 wherein each R １ are independently hydrogen, methyl, C ２－１０ alkyl group, or any combination thereof; 10. The method of any one of the preceding claims, wherein x is a real number greater than 1 and up to 50,000.

38. 10. The method of any one of the preceding claims, further comprising: a) contacting carbon monoxide and an epoxide compound to form said beta-lactone monomer.

39. a) a number average molecular weight of about 1000 g / mol to about 200,000 g / mol; b) a PDI of greater than 1 to about 3.5, and 10. A polymer composition according to any one of the preceding claims comprising the polypropiolactone polymer having: c) by-products present in an amount of 50 parts per billion or less.

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