Polymerization of lactones in polar protic solvents

Abstract

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

Description

Technical Field

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

[0002] Beta-lactone monomers can be used to form polypropiolactone polymers. Polypropiolactone polymers are biodegradable and, therefore, have many uses for food and / or beverage packaging. Typically, polypropiolactone polymers are formed by contacting beta-lactone monomers and initiators in the presence of an aprotic solvent. For example, see U.S. Patent Application No. 11,492,443. However, these solvents can be expensive and environmentally unfavorable when handled, and the polypropiolactone polymers produced by these technologies may contain byproducts or unreacted chemicals that are unfavorable in food and / or beverage packaging.

[0003] Therefore, there is a need for a technology to prepare polypropiolactone that does not contain chemicals that are considered harmful to humans. What is needed is a technology to produce polypropiolactone polymers with minimal solvent waste. What is needed is a technology to produce polypropiolactone polymers that can be used as films and / or coatings. Summary of the Invention

[0004] Disclosed herein are methods for forming polypropiolactones using polar protic solvents.

[0005] Disclosed is a method comprising contacting one or more β-propiolactone monomers with one or more phosphorus compounds and, optionally, one or more carboxylate compounds in a solution under conditions to form a polypropiolactone polymer. The solution comprises one or more polar protic solvents and one or more phosphorus compounds and, optionally, one or more carboxylate compounds. 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.

[0006] The phosphorus compound may comprise a phosphonium compound or an anionic phosphate compound. The phosphorus compound may comprise a compound having the following structure according to Formula I, II and / or III:

[0007] Formula I:

[0008] Each R 3 is independently at each occurrence a group containing one or more carbon atoms, wherein two or more R 3 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms,

[0009] Solid lines represent covalent bonds, and dashed lines represent ionic bonds.

[0010] where Ra comprising a phosphate group, a carboxylate group, a carbonate group, an alkoxide group, a halide, or any combination thereof; or

[0011] Formula II:

[0012] where R 5 are independently a quaternary ammonium group, a phosphonium group, another onium cation, or any combination thereof; and

[0013] where R 2 as defined herein; or

[0014] Formula III:

[0015] Each R 2 As defined herein; and

[0016] where R b Contains a quaternary ammonium group, a phosphonium group, another onium cation, or any combination thereof.

[0017] The phosphorus compound may include a cationic phosphine compound and a 5-20 Phosphorus compounds may include anionic carboxylates of anionic carboxylates of alkyl groups. Phosphorus compounds may include anionic phosphates and cationic quaternary ammonium compounds. Phosphorus compounds may include one or more C 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.

[0018] The one or more carboxylate compounds may comprise a carboxylate compound and a counterion that is soluble or dispersible in a polar protic solvent. The one or more carboxylate compounds may comprise the formula:

[0019]

[0020] where R 2 and R b As defined herein, and dashed lines are as defined herein.

[0021] When the β-lactone monomer is in contact with the solution, the one or more polar protic solvents may be present in a mass percentage greater than about 90% based on the total mass of the solution. 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. When the β-lactone monomer is in contact with the solution, the β-lactone monomer may be present in the solution at a mass percentage of about 5% to about 35% based on the total mass of the solution. When the β-lactone monomer is in contact with the solution, the β-lactone monomer may be present in the solution at a mass percentage of about 5% to about 25% based on the total mass of the solution. When the β-lactone monomer is in contact with the solution, the β-lactone monomer may be present in the solution at a mass percentage of about 5% to about 20% based on the total mass of the solution.

[0022] The method may further include contacting one or more phosphorus compounds with one or more polar protic solvents to form a solution before contacting the β-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 β-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 β-lactone monomer with the solution. The method may further include contacting the one or more phosphorus compounds, the one or more buffers, the one or more surfactants, and the one or more polar protic solvents to form the solution before contacting the β-lactone monomer with the solution.

[0023] The β-lactone monomer may be contacted with a solution comprising one or more buffers configured to maintain a pH of the solution greater than 7.0. The β-lactone monomer may be contacted with a solution comprising one or more surfactants. The β-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 β-lactone monomer. The β-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 β-lactone monomer and the compound in the solution may be carried out with stirring for about 12 hours to about 24 hours. Substantially all of the β-lactone monomer may be converted into a polypropiolactone polymer or byproduct in about 3 hours or less. The method may further include contacting the compound with water to form the solution prior to the step of contacting the β-lactone monomer with the compound in the solution. The step of contacting the β-lactone monomer and the compound in the solution may be carried out in an oxygen-free environment.

[0024] 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 the byproducts. The separating step may include precipitating the polypropiolactone polymer from the solution; decanting the solution from the polypropiolactone polymer; washing the polypropiolactone polymer with an alcohol to remove a residue of the solution; and drying the polypropiolactone polymer under vacuum to remove a residue of the solution.

[0025] The phosphorus compound may be present in an amount sufficient to cause the ring opening of the β-lactone compound to form a 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. One or more surfactants may be present in an amount sufficient to stabilize the solution. The one or more surfactants may be present in an amount of about 10 ppm to about 200,000 ppm in the solution. One or more buffers may be present in an amount sufficient to maintain the pH of the solution above 7.0. One or more buffers may be present in an amount of about 0.1 g / L to about 10.0 g / L. By-products may be present in the polypropiolactone polymer in an amount of about 10 ppm to about 10,000 ppm. The presence of by-products will not change the pH of the solution below 7.0.

[0026] The phosphorus compound may include a disubstituted phosphate group. 5-20 The cationic quaternary ammonium may be covalently bound to a disubstituted phosphate group. The phosphorus compound may include choline covalently bound to phosphatidic acid. The phosphorus compound may include phosphatidylcholine. The cationic quaternary ammonium may be ionically bound to a disubstituted phosphate group. The phosphorus compound may include one or more C 5-20 The phosphorus compound may include two or more C 5-20 The phosphorus compound may include three or more C 5-20 Alkyl. The phosphorus compound may include four or more C 5-20 The phosphorus compound may include a C 1-20 The phosphorus compound may include an ionically bound phosphorus cation and an anionic carboxylate compound. The phosphorus compound may be in one or more C 5-20 The alkyl group includes at least some unsaturation.

[0027] The one or more surfactants may include a polymer having a repeating group of an alkylene ether and one or more terminal hydroxyl groups. The alkylene ether may include one or more of vinyl ether, propenyl ether, butenyl ether, or any combination thereof. The one or more surfactants may include a nonionic 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 thereof. The one or more buffers may include one or more of phosphate buffered saline, bicarbonate, citric acid, boric acid, diethylbarbituric acid, monoalkaline phosphate, or any combination thereof. Byproducts may include acrylic acid, acrylic acid dimer, 3-hydroxypropionic acid, or any combination thereof.

[0028] The polypropiolactone polymer can have a polydispersity index greater than 1 to about 3.5. The polypropiolactone polymer can have a polydispersity index greater than 1 to about 1.7. The polypropiolactone polymer can have a number average molecular weight of about 1 kg / mol to about 1000 kg / mol. The polypropiolactone polymer can have a weight average molecular weight of about 1 kg / mol to about 2000 kg / mol. The polypropiolactone polymer can be substantially free of beta-lactone monomers and / or acrylic acid. The polypropiolactone polymer can have a melting point of about 70 degrees Celsius to about 130 degrees Celsius. The polypropiolactone polymer can have a crystallization temperature of about 0 degrees Celsius to about 100 degrees Celsius.

[0029] Polypropiolactone polymers can have the following repeating structure:

[0030]

[0031] Each R 1 independently selected from hydrogen, methyl, C 2-10 One or more of alkyl or any combination thereof; and

[0032] x is a real number greater than 1. The variable n can be selected so that the number average molecular weight of the resulting polymer is from about 500 to 2,000,000 g / mol. x can be from 3 to 50,000.

[0033] The β-lactone monomer can have the following structure:

[0034]

[0035] Each R 1 independently selected from hydrogen, methyl, C 2-10 one or more of alkyl or any combination thereof.

[0036] The method may further include contacting carbon monoxide with an epoxide compound to form a beta-lactone monomer. Carbon monoxide and the epoxide compound may be contacted in the presence of a carbonylation catalyst. The epoxide compound may have the following structure:

[0037]

[0038] Each R 1 independently selected from hydrogen, methyl, C 2-10 one or more of alkyl or any combination thereof.

[0039] The present disclosure includes polymer compositions according to the methods disclosed herein, comprising a polypropiolactone polymer having a number average molecular weight of about 1000 g / mol to about 200,000 g / mol; a polydispersity index of greater than 1 to about 3.5; and byproducts present in an amount of 50 ppb or less.

[0040] This technology uses solvents that produce polypropiolactone polymers that are free of undesirable chemicals in food and / or beverage containers. This technology utilizes widely available solvents and can be recycled or easily disposed of after the polypropiolactone polymer is formed because the polymer precipitates from the solvent in which the monomers were reacted. 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 DESCRIPTION OF THE DRAWINGS

[0041] Figure 1 is a gel permeation chromatography ("GPC") trace of the polypropiolactone from Example 1.

[0042] Figure 2 is the GPC trace of polypropiolactone from Example 2.

[0043] Figure 3 is the GPC trace of polypropiolactone from Example 3.

[0044] Figure 4 It is polypropiolactone in CDCl3 1 H NMR spectrum.

[0045] Figure 5 is a differential scanning calorimetry ("DSC") curve of a polypropiolactone polymer prepared by aqueous phase polymerization in the presence of PEO-PPO-PEO. DETAILED DESCRIPTION

[0046] While the present disclosure has been described in conjunction with certain embodiments, it should be understood that the disclosure is not limited to the disclosed embodiments, but on the contrary, the disclosure 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 as is permitted by law.

[0047] Definitions of specific functional groups and chemical terms are described in more detail below. For purposes of this invention, chemical elements are identified according to the Periodic Table of the Elements (CAS version, Handbook of Chemistry and Physics, 75th ed., inside 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 March's Advanced Organic Chemistry, 5 th Edition, John Wiley & Sons, Inc., New York, 2001; Larock, Comprehensive Organic Transformations, VCHPublishers, Inc., New York, 1989; Carruthers, Some Modern Methods of Organic Synthesis, 3 rd Edition, Cambridge University Press, Cambridge, 1987; the entire contents of each of which are incorporated herein by reference.

[0048] As used herein, "one or more" means that at least one or more than one of the components can 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 methods disclosed herein. As used herein, "substantially or substantially all" means that greater than 90% of the referenced parameter, composition, structure, or compound meets the defined criteria, greater than 95%, greater than 99% of the referenced parameter, composition, or compound meets the defined criteria, or greater than 99.5% of the referenced parameter, composition, or compound meets the defined criteria. As used herein, "substantially or substantially free of" means that the referenced parameter, composition, structure, or compound contains about 10% or less, about 5% or less, about 1% or less, about 0.5% or less, about 0.1% or less, or about 0.01% or less. As used herein, "portion" means less than the full or total amount of a component in a composition, stream, or both. As used herein, "precipitate" refers to a solid compound or a mixture of liquid and solid compounds in a slurry. In the disclosed processes, components or products can exist in different states, such as solid, liquid or gaseous. Phase refers to a portion of the reaction mixture that is insoluble in another portion of the reaction mixture. Parts by weight refers to the number of components relative to the total weight of the entire composition. The compositions or mixtures used herein include all components of a stream, reactant stream, product stream, slurry, precipitate, solution, liquid, solid, gas or any combination thereof that can be contained in a single container. In other words, the mixture can include components that are solid, gaseous (i.e., volatile), and / or liquid at room temperature (i.e., 25 degrees Celsius) or when exposed to high temperatures. Certain polymers disclosed may contain one or more asymmetric centers and therefore may exist in various stereoisomeric forms, such as enantiomers and / or diastereomers. Polymers and compositions thereof may be in the form of individual enantiomers, diastereomers or geometric isomers, or may be in the form of mixtures of stereoisomers. The disclosed polymers may be enantiomerically pure compounds. Mixtures of enantiomers or diastereomers are disclosed. In certain structures disclosed in this application, portions of the structures are connected by dashed lines - this indicates that the connected structures are ionically bonded together.

[0049] The disclosed polymers may include one or more crystalline polymorphs and, therefore, may exist in various crystalline forms.

[0050] The term "β-lactone" as used herein refers to a substituted or unsubstituted cyclic ester having a four-membered ring comprising an oxygen atom, a carbonyl group, and two optionally substituted methylene groups. When unsubstituted, the β-lactone is referred to as propiolactone. Substituted β-lactones include monosubstituted, disubstituted, trisubstituted, and tetrasubstituted β-lactones. These β-lactones may further be optionally substituted as defined herein. The β-lactone comprises a single lactone moiety. The β-lactone may comprise two or more four-membered ring ester moieties.

[0051] As used herein, the term "epoxide" refers to a substituted or unsubstituted oxirane. Such substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted 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.

[0052] As used herein, the term "polymer" refers to a molecule of high relative molecular mass whose structure includes multiple repeating units derived, actually or conceptually, from molecules of lower relative molecular mass. A polymer can be composed of or derived from a β-lactone monomer (e.g., polypropiolactone). Such polymers are also known as poly(3-hydroxypropionate). The disclosed polymers can be copolymers, terpolymers, heteropolymers, block copolymers, or tapered heteropolymers comprising two or more different monomers.

[0053] As used herein, the terms "halo" and "halogen" refer to an atom selected from the group consisting of fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br) and iodine (iodo, -I).

[0054] As used herein, the term "aliphatic" or "aliphatic group" refers to a hydrocarbon moiety that can be straight chain (i.e., unbranched), branched, or cyclic (including fused, bridged, and spirocyclic polycyclics), and can be fully saturated or can contain one or more unsaturated units, but is not aromatic. Aliphatic groups can contain 1-40 carbon atoms, 1-20 carbon atoms, 2-20 carbon atoms, 1-12 carbon atoms, 1-8 carbon atoms, 1-6 carbon atoms, 1-5 carbon atoms, 1-4 carbon atoms, 1-3 carbon atoms, or 1 or 2 carbon atoms. Aliphatic groups include, but are not limited to, straight or branched chain alkyl, alkenyl, and alkynyl groups, and hybrids thereof, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, or (cycloalkyl)alkenyl.

[0055] 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.

[0056] The term "unsaturated" as used herein refers to a portion having one or more double or triple bonds. The terms "alicyclic", "carbocycle" or "carbocyclic" used alone or as part of a larger portion refer to a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic ring system with 3 to 12 members as described herein, wherein the alicyclic ring system is optionally substituted as defined below and 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 3-6 carbons. The terms "alicyclic", "carbocycle" or "carbocyclic" also include alicyclic rings fused to one or more aromatic or non-aromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, wherein the free radical or point of attachment is on the alicyclic ring. As used herein, the term "alkenyl" refers to a monovalent group derived from a straight or branched aliphatic moiety having at least one carbon-carbon double bond by removing a single hydrogen atom. As used herein, the term "alkynyl" refers to a monovalent group derived from a straight or branched aliphatic moiety having at least one carbon-carbon triple bond by removing a single hydrogen atom. As used herein, the term "alkoxy" refers to an alkyl group as previously described attached to the parent molecule through an oxygen atom. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, and n-hexoxy. As used herein, the term "acyl" refers to a carbonyl-containing functional group, such as -C(=O)R', where R' is hydrogen or an optionally substituted aliphatic, heteroaliphatic, heterocyclic, aryl, heteroaryl, or a substituted (e.g., with hydrogen or an aliphatic, heteroaliphatic, aryl, or heteroaryl moiety) oxygen- or nitrogen-containing functional group (e.g., forming a carboxylic acid, ester, or amide functional group). As used herein, the term "acyloxy" refers to an acyl group attached to the parent molecule via an oxygen atom. The term "aryl," used alone or as part of a larger moiety such as "aralkyl," "aralkyloxy," or "aryloxyalkyl," refers to monocyclic and polycyclic ring systems having a total of 5 to 20 ring members, wherein at least one ring in the system is aromatic, and wherein each ring in the system contains 3 to 12 ring members. The term "aryl" can be used interchangeably with the term "aromatic ring," wherein "aryl" refers to an aromatic ring system, including but not limited to phenyl, biphenyl, naphthyl, anthracenyl, and the like, which may bear one or more substituents. Similarly, the term "aryl" as used herein also includes groups in which an aromatic ring is fused to one or more other rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, wherein the radical or point of attachment is on the aryl ring.

[0057] The terms "heteroaryl" and "heteroaryl-", used alone or as part of a larger moiety, such as "heteroaralkyl" or "heteroaralkoxy", refer to groups having 5-14 ring atoms, preferably 5, 6 or 9 ring atoms; having 6, 10 or 14 pi electrons shared in a cyclic arrangement; and having from 1 to 5 heteroatoms in addition to carbon atoms. The term "heteroaryl" may be used interchangeably with the terms "heteroaryl ring" and "heteroaryl group", any of which terms include rings that are optionally substituted. The term "heteroatom" refers to nitrogen, oxygen or sulfur, and includes any oxidized form of nitrogen or sulfur, as well as any quaternized form of a basic nitrogen. A heteroaryl group may be monocyclic or bicyclic. "Heteroaralkyl" refers to an alkyl group substituted with a heteroaryl group, wherein the alkyl and heteroaryl portions are independently optionally substituted. The term "partially unsaturated" refers to a ring portion that includes at least one double or triple bond.

[0058] As described herein, disclosed compounds may contain "optionally substituted" moieties. Regardless of whether or not the term "optionally" is present in front, the term "substituted" refers to that one or more hydrogens of a designated moiety are replaced by suitable substituents. Unless otherwise indicated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure can be substituted by one or more substituents selected from a specific group, the substituents at each position may be the same or different. The combination of substituents envisioned is that which results in the formation of stable or chemically feasible compounds. The term "stable" as used herein refers to compounds that are substantially unchanged when under conditions that allow their production, detection, and in certain embodiments, their recovery, purification, and use for one or more purposes disclosed herein.

[0059] As used herein, the term "alkoxylated" refers to a molecule to which one or more functional groups (typically, but not strictly limited to, alcohols, amines, or carboxylic acids) have attached a hydroxyl-terminated alkyl chain. Alkoxylated compounds may contain a single alkyl group, or they may be oligomeric moieties, such as hydroxyl-terminated polyethers. Alkoxylated materials may be derived from the parent compound by treating the functional groups with epoxides. Unless otherwise indicated, "a," "an," "the," and "at least one" are used interchangeably and mean one or more than one.

[0060] This technology allows the formation of polypropiolactone polymers in polar protic solvents containing a phosphorus compound and optionally one or more carboxylate compounds, so that once the polypropiolactone polymer is formed, it is precipitated from the solvent. Optionally, a surfactant and / or a buffer can be added to control the properties, yield or formation rate of the polypropiolactone polymer. When precipitated from the solvent, the polypropiolactone is substantially free of unreacted starting components, undesirable by-products and / or solvents. Because this technology reacts substantially all β-lactone monomers, the resulting polypropiolactone is safe in products such as beverages and / or food containers that are configured to contact people. In addition, by reacting substantially all β-lactone monomers, the polar protic solvent can be reused.

[0061] The reaction between β-lactone monomers to form the polypropiolactone polymer can be carried out as a polymerization reaction as shown in Scheme 1 below.

[0062] Solution 1 :

[0063]

[0064] The polymer may contain at one end of a portion of the chain the residue of a phosphate or carboxylate anion covalently bonded to the one end of the polymer chain. The polymer may have a mixture of residues of carboxylate anions and residues of phosphate anions bound to the one end of the polymer chain. The other end of a portion of the chain may be one or more onium cations.

[0065] Based on the beta-lactone monomers used, the polypropiolactone polymer can have any structure of repeating beta-hydroxy units. The polypropiolactone can have a structure that is the residue of the beta-lactone monomer used to form the polypropiolactone. The polypropiolactone can have the following structure:

[0066]

[0067] Each R 1 is independently at each occurrence hydrogen, or a carbon-containing group which may have one or more hydrogen or fluorine atoms attached to a carbon atom, which may optionally contain one or more heteroatoms and / or substituents; and

[0068] Wherein x is a real number greater than 1. The variable n can be selected so that the number average molecular weight of the resulting polymer is from about 500 to 2,000,000 g / mol. x can be from 3 to 50,000.

[0069] The polymer formed may have the residue of an anionic initiator group at the other end of the polymer chain. Such residue may be based on any known initiator group, which may be added separately to the reaction mixture or generated in situ during the polymerization reaction. The residue of the initiator may be formed from a phosphorus compound and / or a carboxylate compound. The residue of the initiator may be one or more residues according to one of the following formulae: D,

[0070] wherein D is the residue of one or more anionic initiators,

[0071] where R 2 is independently at each occurrence an optionally substituted group containing one or more carbon atoms;

[0072] where R 4 is independently at each occurrence a group containing one or more carbon atoms, which may contain heteroatoms or be substituted with functional groups.

[0073] The prepared polymer may correspond to the following formula Wherein D is the residue of one or more anionic initiators.The prepared polymer can be part of a polymer chain, which has a phosphate bonded to one end of the chain.Such a polymer can correspond to one of the following formulas:

[0074] wherein a is an integer from 1 to 3, and b is an integer from 0 to 2. The variable a may be 1, 2, or 3. The variable b may be 0, 1, or 2. The sum of a and b is 3.

[0075] where R 1 and R 2 As mentioned in this article;

[0076] where x is as described herein; and

[0077] Z is independently hydrogen, the residue of an onium cation, etc. at each occurrence. A portion of the polymer chains may have carboxylate groups at the ends of some chains. Such polymers may correspond to the formula:

[0078]

[0079] where R 2 、R 1 , Z and x are as described above; and R 4 As described herein. The polymers prepared may comprise polymers with different initiators as described herein.

[0080] R 1One or more of can be carbon-containing groups, it can have one or more hydrogen or fluorine atoms combined with carbon atoms, carbon-containing groups can contain unsaturated groups, electrophilic groups, nucleophilic groups, anionic groups, cationic groups, groups containing zwitterions, hydrophobic groups, hydrophilic groups, halogen atoms, natural minerals, synthetic minerals, carbon-based particles, ultraviolet active groups have one or more of the polymer of surfactant properties and polymerization initiator or active heterocycle. Functional group can be connected to the ring by linking group (M), and the linking group (M) plays the effect that the functional part of the group is connected to the cyclic ring. Exemplary linking group can be carbon-containing groups, ethers, thioethers, polyethers (such as polyalkylene ethers). R 1 One or more of them can be halogen-substituted alkyl, sulfonic acid-substituted alkoxy; alkylsulfonate alkoxy; alkyl ether-substituted alkyl; polyalkylene oxide-substituted alkyl, alkyl ester-substituted alkyl; alkenyloxy-substituted alkyl; aryl ester-substituted alkyl; alkenyl; cyano-substituted alkyl; alkenyl ester-substituted alkyl; cycloalkyl-substituted alkyl; aryl; heteroatom-containing cycloalkenyl, alkyl ether-substituted alkyl; hydroxyl-substituted alkyl, alicyclic-substituted alkenyl; aryl-substituted alkyl; halogenated aryl-substituted alkyl; aryloxy-substituted alkyl; alkyl ether-substituted alkaryl; heteroatom-containing alicyclic alkyl; heteroatom-containing aryl-substituted alkyl, alkylamide-substituted alkyl, alkenyl-substituted alicyclic group; two R 1 can form a cyclic ring, which may optionally contain one or more unsaturated groups; an alkyl group substituted by a β-lactone group, which may optionally contain one or more ether groups and / or one or more hydroxyl groups; an alkyl group substituted by a glycidyl ether group or a benzocyclobutenyl group optionally substituted by one or more ether groups. β-lactone corresponds to a group in which all R 1 It is the general formula under hydrogen. R on a carbon atom 1 They can all be H, and one or both R on the other carbon atom 1 It may be an optionally substituted C 1-40 aliphatic groups, optionally substituted C 1-20 heteroaliphatic group, optionally substituted aryl group, or two R 1 The groups may be optionally joined together to form an optionally substituted ring, which optionally contains one or more heteroatoms. One or two R 1 Can be alkyl, other R 1 Can be hydrogen. Alkyl can be C 1-20 Alkyl, C 1-12 Alkyl, C 1-8 Alkyl, C 1-4 Alkyl, wherein the alkyl group may contain unsaturated functional groups or one or more heteroatoms. One or two R on different carbon atoms 1 It can be methyl or ethyl, other R1 Can be hydrogen. Two R on the same carbon atom 1 It can be methyl, and other R 1 It's hydrogen.

[0081] R 2 Independently in each carbon-containing group, the carbon-containing group may contain heteroatoms or one or more unsaturated moieties. 2 Each occurrence may independently be one or more of alkyl, aryl, alkaryl, aralkyl, which may contain heteroatoms or one or more unsaturated moieties, wherein two or more R 2 R may form a cycloalkyl group or a cyclic ring containing one or more aromatic groups, wherein such groups may contain heteroatoms and / or unsaturated groups. 2 Can be C independently at each occurrence 1-20 Alkyl, C 3-24 Cycloalkyl, C 5-24 Aryl, C 6-24 Alkaryl, C 6-24 One or more of aralkyl groups, which may contain heteroatoms or one or more unsaturated moieties. 2 Can be C independently at each occurrence 1-12 Alkyl, C 3-12 Cycloalkyl, C 5-12 Aryl, C 6-12 Alkaryl, C 6-12 One or more of aralkyl groups, which may contain heteroatoms or one or more unsaturated moieties. 2 Can be C independently at each occurrence 1-12 One or more of an alkyl group, which may contain heteroatoms or one or more unsaturated moieties. 2 Can be C independently at each occurrence 1-4 Alkyl groups which may contain heteroatoms or one or more unsaturated moieties. 2 Each occurrence may independently be one or more of methyl, ethyl, propyl or butyl.

[0082] R 3 is independently at each occurrence a carbon-containing group, wherein two or more R 3 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms. 3 Each occurrence may independently be one or more of alkyl, aryl, alkaryl, aralkyl, which may contain heteroatoms or one or more unsaturated moieties, wherein two or more R 3 R may form a cycloalkyl group or a cyclic ring containing one or more aromatic groups, wherein such groups may contain heteroatoms and / or unsaturated groups. 3Can be C independently at each occurrence 1-20 Alkyl, C 3-24 Cycloalkyl, C 5-24 Aryl, C 6-24 Alkaryl, C 6-24 One or more of aralkyl groups, which may contain heteroatoms or one or more unsaturated moieties. 3 Can be C independently at each occurrence 1-12 Alkyl, C 3-12 Cycloalkyl, C 5-12 Aryl, C 6-12 Alkaryl, C 6-12 One or more of aralkyl groups, which may contain heteroatoms or one or more unsaturated moieties. 3 Each occurrence can be independently one or more C 1-12 Alkyl groups which may contain heteroatoms or one or more unsaturated moieties. 3 Can be C independently at each occurrence 1-4 Alkyl groups which may contain heteroatoms or one or more unsaturated moieties. 3 Each occurrence may independently be one or more of methyl, ethyl, propyl or butyl.

[0083] R 4 is independently at each occurrence a carbon-containing group which may contain heteroatoms or be substituted with functional groups. 4 Each occurrence may independently be one or more of alkyl, aryl, alkaryl, and aralkyl, which may contain heteroatoms or one or more unsaturated moieties, wherein two or more R 4 R may form a cycloalkyl group or a cyclic ring containing one or more aromatic groups, wherein such groups may contain heteroatoms and / or unsaturated groups. 4 Can be multiple Cs independently at each occurrence 1-20 An alkyl group which may contain heteroatoms or one or more unsaturated moieties. 4 Each occurrence can be independently for multiple C 1-12 An alkyl group which may contain heteroatoms or one or more unsaturated moieties. 4 Each occurrence can be independently one or more C 1-12 Alkyl groups which may contain heteroatoms or one or more unsaturated moieties. 4 Can be C independently at each occurrence 1-4 Alkyl groups which may contain heteroatoms or one or more unsaturated moieties. 4 Each occurrence of R may independently be one or more of methyl, ethyl, propyl or butyl. 4 An acrylate group can be formed with the carbonyloxy moiety to which it is bonded.

[0084] The polymer composition formed can have a 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, 1.05 or less. The polymer composition formed can have a PDI of 1.05 or greater, 1.1 or greater, 1.2 or greater, 1.5 or greater, or 2.0 or greater. The PDI values ​​refer to values ​​measured by GPC. PDI values ​​can be calculated excluding GPC peaks resulting from oligomers having Mn 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.

[0085] The prepared polymers can 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, as measured by the present disclosure. The number average molecular weight of the prepared polymers can be 2,000,000 g / mol or less, or 1,000,000 g / mol or less. As disclosed herein, the weight average molecular weight of the prepared polymer can be 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. The prepared polymer can have a number average molecular weight of 2,000,000 g / mol or less or 1,000,000 g / mol or less. The number average molecular weight and / or weight average molecular weight of polymer composition refer to the molecular weight measured by gel permeation chromatography (GPC) using THF as solvent and with reference to monodisperse polymethyl methacrylate standards.

[0086] The polypropiolactone polymers described herein can have a glass transition temperature suitable for use in products such as food and / or beverage containers or films, coatings and / or paints. The glass transition temperature can be about -25°C or higher, about -20°C or higher, or about -15°C or higher. The glass transition temperature can be about 0°C or lower, about -5°C or lower, or about -10°C or lower. The glass transition temperature can be measured by any known technique. The glass transition temperature can be measured by differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA).

[0087] Polypropiolactone polymers as herein described can have the melting temperature required for products such as food and / or beverage containers or films, coatings and / or paints.The melting temperature can be approximately 60 degrees Celsius or higher, approximately 70 degrees Celsius or higher or approximately 80 degrees Celsius or higher.The melting temperature can be approximately 120 degrees Celsius or lower, approximately 110 degrees Celsius or lower or approximately 100 degrees Celsius or lower.The melting temperature can be measured by any known technology.The glass transition temperature can be measured by differential scanning calorimetry (DSC) or dynamic mechanical analysis (DMA).

[0088] Polymers containing β-lactone residues are disclosed. Functional groups on β-lactones can provide functionality to polymers and copolymers prepared from β-lactones. The functional groups can act as polymerization initiators, improve polymer adhesion to certain substrates or polymer systems, improve hydrophobicity or hydrophilicity, improve hardness or scratch resistance, act as polymerization catalysts, and the like. β-lactone polymers and copolymers can be used as intermediate layers in multilayer films, including such films having different polymer layers. β-lactone polymers and copolymers decompose under certain circumstances, allowing the other layers to be easily separated for recycling and reuse. β-lactone polymers and copolymers can be used as intermediate layers between other polymer coatings and substrates. β-lactone polymers and copolymers decompose under certain circumstances, allowing the substrate to be easily separated from the other coatings for recycling and reuse. β-lactone polymers and copolymers can be used as outer film layers or coatings that can be decomposed, or such outer layers can be functionalized to provide a desired set of properties to the structure.

[0089] The polymerizable composition can comprise 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.

[0090] The β-lactone that may be present in the polymerizable composition and used to prepare the polymer may be any β-lactone that polymerizes under the conditions defined herein. The β-lactone may correspond to the formula:

[0091]

[0092] where R 1As mentioned above.

[0093] Homopolymers prepared from the β-lactones are disclosed. Copolymers of more than one β-lactone are disclosed. Compositions comprising copolymers of one or more of the disclosed β-lactones and one or more monomers reactive with the one or more β-lactones are disclosed. Compositions comprising copolymers of one or more of the disclosed β-lactones and one or more monomers reactive with the one or more β-lactones are disclosed. Such copolymers may include one or more of a glycol, a difunctional polyalkylene oxide, an amine-terminated polyalkylene oxide, one or more difunctional polyesters, a lactam, a lactide, a cyclic lactone, a cyclic anhydride, a cyclic ether epoxide, an episulfide, an aziridine, a (meth)acrylate, a valerolactone, a butyrolactone, a glycolide, a substituted glycolide, or a polyether. Such comonomers may be one or more of an epoxide, an ethylene oxide, a lactam, and a lactide. The comonomer can 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 can contain units derived from β-propiolactone. The disclosed copolymers can be block copolymers, random copolymers, or one or more chains can be grafted onto the polymer backbone.

[0094] The one or more β-lactones may be:

[0095]

[0096] The one or more β-lactones may be:

[0097]

[0098] where R 10 Can be used with R 1 same.

[0099] The one or more β-lactones may be

[0100]

[0101] wherein Ar is any optionally substituted aryl group, R 12 Selected from the group consisting of: -H, optionally substituted C 1-20 aliphatic groups, optionally substituted C 1-20 heteroaliphatic group and optionally substituted aryl group, and R 13 Is fully or partially unsaturated C 2-20 Straight-chain aliphatic group.

[0102] The polymer can be prepared from a mixture of β-propiolactone and pivalolactone:

[0103]

[0104] The one or more β-lactones may be:

[0105]

[0106] The polymer can be prepared from a mixture of β-propiolactone and a β-lactone of one of the following formulas:

[0107]

[0108] The polymer can be prepared from a mixture of β-lactones, wherein the β-lactones are provided as a mixture of positional isomers. Any of the aforementioned β-lactone comonomers can be provided in combination with their positional isomers. When the β-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 relative to the minor positional isomer in a ratio of 2:1 or greater, 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.

[0109] Described polymkeric substance can be prepared by the mixture of beta-lactone and one or more cyclic ethers, and described cyclic ether comprises tetrahydrofuran (THF), substituted tetrahydrofuran (THF) and epoxide.Epoxide can be substituted epoxide.Epoxide can be one or more in oxirane, propylene oxide, butylene oxide, 4-vinyl epoxy cyclohexane, 4-ethyl epoxy cyclohexane, limonene oxide (limonene oxide), glycidyl ether, glycidyl ester or epoxy cyclohexane.Epoxide can correspond to following formula:

[0110] where R 1 As defined herein. One or more substituted epoxides may correspond to the formula:

[0111] where R 10 Can be used with R 1 The one or more substituted epoxides may be:

[0112]

[0113] The one or more substituted epoxides may correspond to one of the following formulae:

[0114]

[0115] wherein Ar can be any optionally substituted aryl group;

[0116] where R 10 As defined above;

[0117] where R 12 Can be selected from the group consisting of: -H, optionally substituted C 1-20 aliphatic groups, optionally substituted C 1-20 heteroaliphatic group and optionally substituted aryl group, and R 13 Is fully or partially unsaturated C 2-20 a straight-chain aliphatic group, and

[0118] The one or more substituted epoxides may correspond to one of the following formulae:

[0119] Disclosed are methods of polymerizing beta-lactones using an initiator as described herein, optionally in combination with one or more additional comonomers (collectively referred to as monomers).The initiator may or may not be covalently attached to the final polymer product.

[0120] The polypropiolactone polymer may include one or more inhibitors configured to reduce the formation of polyacrylic acid before or during the process of forming acrylic acid. One or more inhibitors may be selected so that polyacrylic acid is not formed when forming β-lactone and / or when polypropiolactone is heated to form acrylic acid. The inhibitor may include monomethyl ether hydroquinone, 2-tert-butyl-1,4-benzoquinone, 1,4-benzoquinone, 2,6-di-tert-butylphenol, tert-butylhydroquinone, dibutyldithiocarbamate copper (ii), 2-[1-(2-hydroxy-3,5-di-tert-amylphenyl) ethyl]-4,6-di-tert-amylphenyl acrylate, phenothiazine, 4-methoxyphenol, 4-tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 6-tert-butyl-2,4-xylenol, 1,1-diphenyl-2-picrylphenylhydrazine free radical, 2,6-di-tert-butyl-p-cresol or one or more of its combination.

[0121] The polypropiolactone polymer can further comprise the residue (residue) of phosphorus compound and / or surfactant.Described polypropiolactone polymer can comprise the residue (residue) of phosphorus compound and / or surfactant of any amount that does not hinder described polypropiolactone polymer from using in downstream products such as food and / or beverage products.Based on the gross mass of polymer, polypropiolactone polymer can comprise the mass percent of the residue of phosphorus compound and / or surfactant of about 5% or less, about 3% or less or about 1% or less.Based on the gross mass of polymer, polypropiolactone polymer can comprise the mass percent of the residue of phosphorus compound and / or surfactant of about 0.01% or more, about 0.1% or more or about 0.5% or more.

[0122] The phosphorus compound can support the polymerization of β-lactone in a polar protic solvent to form polypropiolactone. The phosphorus compound can be configured as a surfactant, a promoter, a catalyst, an initiator, or a combination thereof.

[0123] A phosphorus compound can initiate polymerization between β-lactone monomers to form a polypropiolactone polymer. The phosphorus compound can initiate a process in which the β-lactone monomers ring-open to form an intermediate that forms repeating units derived from the ring-opened β-lactone. The phosphorus compound can be any compound known to dissociate or disperse in polar protic solvents and can serve as an initiator. The phosphorus compound can form an anion sufficient to promote the formation of a polymer having repeating units derived from the ring-opened β-lactone.

[0124] The phosphorus compound can be configured as a surfactant having hydrophobic and hydrophilic groups such that the phosphorus compound can reduce the surface tension between the polar protic solvent and the β-lactone monomer. The hydrophobic group can be non-polar. Examples of hydrophobic groups that can be included in the phosphorus compound include C 5-20 The alkyl, aryl or alkyl-aryl groups that can optionally comprise unsaturated structures.The phosphorus compound can comprise one or more, two or more, three or more or four or more hydrophobic groups.The hydrophilic group can have electronegativity, makes the molecule become soluble in polar protic solvents.The example of the hydrophilic group can comprise one or more in oxygen-containing group, phosphorus-containing group and / or nitrogen-containing group.

[0125] The phosphorus compound can be configured as a catalyst or promoter that increases the polymerization rate in polar protic solvents so that the polypropiolactone polymer is formed before an unwanted amount of the β-lactone degrades into other compounds such as hydroxycarboxylic acids. The phosphorus compound can be selected so that the reaction will convert substantially all of the β-lactone monomer in about 3 hours or less.

[0126] The phosphorus compound can have two or more parts with different electronegativity, so that the phosphorus compound promotes and / or improves the rate of polymerization of beta-lactone monomers into polypropiolactone polymers. The phosphorus compound can include at least one part that is a cation and another part that is an anion. The anion and cationic parts can be connected by covalent bonds or ionic bonds. When covalently bound, the phosphorus compound can be configured as or act as a zwitterion. In other words, the phosphorus compound can be a single molecule including a cation and anion parts. When the cation and anion parts are ionically bound, the phosphorus compound can be configured as a salt that dissociates in a polar protic solvent.

[0127] The phosphorus compound can be present in a solution of the method for forming the polymer in a mass percentage sufficient to cause the ring opening of the β-lactone compound to form the polypropiolactone polymer and reduce the formation of by-products. Based on the total mass of the solution equal to 100%, the phosphorus compound can be present in the polypropiolactone polymer at a mass percentage of about 0.01% or more, about 0.1% (mass) or more, or about 0.5% or more. Based on the total mass of the solution equal to 100%, the phosphorus compound can be present in a concentration of about 5% or less, about 3% or less, or about 1% or less.

[0128] The polymerizable composition comprises one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions. The phosphate anions can initiate polymerization of one or more β-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, which can initiate polymerization of these 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 polymers in which both the phosphate anion and the carboxylate anion initiate polymer chains. The one or more salts or zwitterions of one or more onium cations and one or more phosphate anions can catalyze or accelerate the polymerization of monomers.

[0129] The method can include any number of different phosphorus compounds sufficient to cause ring opening of the β-lactone compound to form a polypropiolactone polymer and reduce the formation of by-products. The solution can contain one or more, two or more, three or more, four or more, or a plurality of phosphorus compounds. The method can include a phosphorus compound configured as a zwitterion and a different phosphorus compound, the phosphorus compound including a carboxylate or phosphate anion and an onium cation that ionically combine to form a salt.

[0130] The carboxylate or phosphate anion and the onium cation of the phosphorus compound can include any compound sufficient to promote the ring opening of the β-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 the onium cation can be ionically or covalently bound together.

[0131] The anion of the phosphorus compound can include one or more of a phosphate, carboxylate, carbonate, alkoxy, 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 on the oxygen atom of the carbonyl of a phosphate, carboxylate or carbonate. The anion moiety can be phosphatidic acid.

[0132] Onium cation (omnium cation) can comprise one or more in phosphorus compound, quaternary ammonium compound or its arbitrary combination.At quaternary ammonium compound and / or compound nitrogen and / or phosphorus atom place, onium cation (omnium cation) can have one or more, two or more, three or more or four or more replacements.

[0133] The phosphorus compound comprises a phosphate anion covalently bound to an omnium cation. The omnium cation covalently bound to the phosphate anion may comprise a moiety containing one or more optionally saturated C 1-20 Alkyl or aryl quaternary ammonium, containing one or more C 1-20 The phosphonium cation may further include hydrogen, C 1-20 One or more, two or more, or three or more substitutions of alkyl, aryl, or alkyl-aryl optionally including an unsaturated structure, or any combination thereof. The onium cation may include choline.

[0134] The phosphorus compound may include a compound corresponding to Formula I:

[0135] Formula I:

[0136] Each R 3 is independently at each occurrence a carbon-containing group, wherein two or more R 3 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.

[0137] where R a comprising a phosphate group, a carboxylate group, a carbonate group, a phosphate group, a halide, or any combination thereof;

[0138] The phosphorus compound may include a phosphate compound configured as a zwitterion corresponding to Formula II:

[0139] Formula II: or

[0140] where R 5 are independently a quaternary ammonium group, a phosphonium group, another onium cation, or any combination thereof; and

[0141] where R 2 As defined herein;

[0142] The phosphorus compound may include a phosphate compound configured as a salt and corresponding to Formula III:

[0143] Formula III:

[0144] Each R 2 As defined herein; and

[0145] where R b Contains a quaternary ammonium group, a phosphonium group, another onium cation, or any combination thereof.

[0146] The onium cation may be derived from any onium compound that enhances the formation of the polymer disclosed herein. The onium cation may include one or more of nitrogen, phosphorus, sulfur, antimony, or arsenic. The onium cation may include one or more of nitrogen, phosphorus, or sulfur. The onium cation may include one or more of nitrogen or phosphorus. The onium cation may include one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations. The onium cation may include one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations. The one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations may include one or more tetraalkylammonium anions or tetraalkylphosphonium anions.

[0147] The one or more quaternary nitrogen-containing cations may contain four carbon-containing groups bound to the amine nitrogen, wherein two or more carbon groups may form one or more aromatic or non-aromatic ring structures, which ring structures may optionally contain one or more heteroatoms. The one or more quaternary nitrogen-containing cations may include 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 include one or more optionally substituted imidazoliums. The one or more quaternary nitrogen-containing cations may include one or more ammonium cations, amidinium cations and guanidinium cations. The one or more quaternary ammonium cations may correspond to the following formula where R 3 As defined herein. The one or more guanidinium cations may correspond to the following formula: where R 3 As defined herein.

[0148] The one or more quaternary ammonium cations can 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 can be one or more tetraalkylammonium or N-alkyl-substituted imidazolium cations. The one or more tetraalkylammonium cations can contain one or more of methyl, ethyl, propyl, or butyl. The butyl group can be n-butyl or tert-butyl. The one or more tetraalkylammonium cations can be tetramethylammonium, tetraethylammonium, or tetra-tert-butylammonium cations.

[0149] One or more quaternary phosphonium cations can be one or more phosphonium cations containing four carbon-containing groups. One or more quaternary phosphonium cations can be one or more tetraalkylphosphonium cations. One or more quaternary phosphonium cations can correspond to the following formula: where R 3 As defined herein.

[0150] The phosphate anion can be any phosphate anion that allows the one or more salts or zwitterions of the one or more onium cations and the one or more phosphate anions to perform the functions disclosed herein. The phosphate anion can have 1-3 onium cations bonded to an oxygen group.

[0151] The phosphate anion may have 0-2 optionally substituted groups containing nitrogen atoms bound to oxygen. The phosphate anion may correspond to the formula: where R 2 As defined herein, a is an integer from 1 to 3 and b is an integer from 0 to 2. The variable a may be 1, 2, or 3. The variable b may be 0, 1, or 2. The sum of a and b is 3. The anion may be a mixture of compounds wherein a and b are different in the individual anions in the mixture. The phosphate anion may correspond to the following formula: where R 2 As defined herein.

[0152] 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 and 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 correspond to the following formula

[0153] where R 2 is independently at each occurrence an optionally substituted group containing one or more carbon atoms; Z′ is independently at each occurrence an onium cation as described herein, including the variations described herein; a is independently at each occurrence 1, 2, or 3; and b is independently at each occurrence 0, 1, or 2; wherein the sum of a and b is 3.

[0154] The one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions correspond to one of the following formulae:

[0155]

[0156] where 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 may correspond to one of the following formulas:

[0157]

[0158] where R 3 and R 2 As defined herein. The one or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions correspond to the formula: where R 3 and R 2 As defined herein. The one or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions may correspond to the following formula:

[0159] where R 1 and R 2 As defined herein.

[0160] The polymerizable composition may comprise one or more zwitterions comprising one or more onium cations, one or more phosphate anions, and an optionally substituted carbon group between the anion and the cation, the carbon group being bonded 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 comprising one or more onium cations, one or more phosphate anions, and an optionally substituted alkylene moiety between the anion and the cation may correspond to the formula

[0161] where R 2 、R 3 , Z', a and b are as defined herein, and wherein R 7 is independently an optionally substituted carbon-containing moiety. The zwitterion may correspond to one of the following formulas:

[0162] The zwitterion may correspond to one of the following formulas:

[0163] where R 3 、R 2 、R 7, a and b are as defined herein. The one or more zwitterions of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions may correspond to one of the following formulae:

[0164] where R 3 、R 2 、R 7 As defined herein, the one or more zwitterions containing one or more quaternary nitrogen-containing cations and one or more phosphate anions may correspond to the following formula:

[0165] where R 3 、R 2 、R 7 As defined herein, the one or more zwitterions of one or more quaternary nitrogen-containing cations and one or more phosphate anions correspond to the formula:

[0166] where R 3 、R 2 、R 7 As defined herein, the one or more zwitterions of one or more quaternary nitrogen-containing cations and one or more phosphate anions may correspond to the following formula:

[0167] where R 3 、R 2 、R 7 As defined herein.

[0168] The carboxylate compound can be any compound that is enough to disperse or dissociate in polar protic solvent and promotes that propiolactone polymer forms.The carboxylate compound can comprise any carboxylate radical group that is enough to promote the polymerization of one or more beta-lactones, so that polypropiolactone is formed into the residue with the repeating unit and the carboxylate compound derived from ring-opening beta-lactone.The carboxylate compound can comprise the carboxylate radical group that is bound with enough counter ion ions, so that carboxylate can dissociate or can be dispersed in polar protic solvent.The counter ion can be alkaline earth metal, alkali metal, phosphonium group, quaternary ammonium group, another onium group or its arbitrary combination.The carboxylate compound can have following structure:

[0169] where R 2 and R b As defined herein, dashed lines are as defined herein.

[0170] 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 as high as or lower than that of water. The polar protic solvent can be any solvent that can dissolve the β-lactone and is insoluble in polypropiolactone having a number average molecular weight greater than about 2000 g / mol. The polar protic solvent can have any saturation point of the β-lactone monomer such that at least about 5% of the total mass of the solution can be β-lactone monomer.

[0171] When the beta-lactone monomer and the phosphorus compound contact, the solution can contain any amount of polar protic solvent that is enough to promote the formation of polypropiolactone. Based on the total mass of the solution amounting to 100%, the polar protic solvent can be present with a mass percentage of about 70% or more, about 80% or more, or about 90% or more. The polar protic solvent can be present with a mass percentage of about 98% or less, about 95% or less, or about 92% or less.

[0172] The polar protic solvent can have a boiling point such that the polar protic solvent can be separated from the polypropiolactone polymer without degrading the polypropiolactone due to heating. The boiling point of the polar protic solvent is selected so that the precipitated polypropiolactone polymer can be separated from the polar protic solvent and applied as a film, coating, and / or paint.

[0173] The polar protic solvent can be a solvent comprising acidic protons. The polar protic solvent can include one or more amines and / or hydroxyls. Polar protic solvents can be selected based on whether the solvent can dissolve the polypropiolactone, because it is desirable that the polypropiolactone polymer be precipitated from solution after the polymerization reaction begins. Examples of polar protic solvents can include one or more of water, methanol, ethanol, acetic acid, isopropyl alcohol, n-butyl alcohol, formic acid, or any combination thereof.

[0174] The surfactant can act to reduce the surface tension between the beta-lactone monomer, the phosphorus compound, the polar protic solvent, or any combination thereof. The surfactant can be at least partially miscible with the beta-lactone monomer and the polar protic solvent simultaneously. The surfactant can act in combination with the phosphorus compound to reduce the surface tension between the beta-lactone monomer and the polar protic solvent. When the phosphorus compound has multiple functions as a surfactant and a promoter, a catalyst, and / or an initiator, the surfactant may not be present.

[0175] The surfactant includes hydrophobic and hydrophilic groups to enhance the polymerization of the β-lactone monomer in a polar protic solvent. The surfactant may include the same or different hydrophobic and / or hydrophilic groups as the phosphorus compound. The hydrophobic group may be non-polar. Examples of hydrophobic groups that may be included in the phosphorus compound include C 5-20Alkyl, aryl or alkyl-aryl groups which may optionally include unsaturated structures. The hydrophilic group may have electronegativity, such that the molecule becomes soluble in polar protic solvents. Examples of hydrophilic groups may include one or more oxygen-containing, phosphorus-containing and / or nitrogen-containing groups.

[0176] When the β-lactone monomers are polymerized to form a polypropiolactone polymer, any surfactant that reduces the surface tension between the β-lactone monomers and the polar protic solvent can be used. The surfactant can include one or more polymers having repeating groups of alkylene ethers and one or more terminal hydroxyl groups. The surfactant can include one or more alkylene ethers, including one or more of ethylene ether, propylene ether, butylene ether, or any combination thereof. The surfactant can include a nonionic 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 different surfactants or a combination of different surfactants.

[0177] The surfactant may be present in a mass percentage sufficient to stabilize the solution.The surfactant may be present in a mass percentage sufficient to reduce the surface tension between the β-lactone monomer or its derivative and the polar protic solvent.

[0178] The solution may include a buffer mixed with a polar protic solvent before, after, or during contact with the beta-lactone, phosphate buffer, and / or surfactant. The buffer may serve to maintain the pH of the solution containing the polar protic solvent at a value above 7.0, thereby reducing undesirable by-products. Any single or combined buffer sufficient to maintain a 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 at a value above 7.0 may be used. The buffer may include one or more of phosphate buffered saline, bicarbonate, citric acid, boric acid, diethyl barbituric acid, monobasic phosphate, or any combination thereof.

[0179] In a polar solvent, the β-lactone can reach a saturation point at about 50% by mass or less, based on the total mass of the solution. When contacted with the phosphorus compound, the β-lactone monomer can be present in the polar protic solvent at any mass percentage sufficient to form a polypropiolactone polymer. Based on the total mass of the solution, the β-lactone monomer can be present at a mass percentage of about 2% or more, about 5% or more, or about 7% or more. Based on the total mass of the solution, the β-lactone monomer can be present at a concentration of about 35% or less, about 30% or less, about 20% or less, or about 10% or less.

[0180] After isolating the polypropiolactone polymer from solution, the polypropiolactone polymer can be substantially free of by product, because by product and unreacted reactant (i.e. beta-lactone monomer and / or hydroxy carboxylic acid) remain in the solution. Because some by products and reactant may be harmful to the human, so from solution, separate the polypropiolactone polymer, for example, by precipitation, reduce or avoid having undesirable by product or unreacted reactant in the polypropiolactone polymer, and increase the purposes of polymer, for example, for beverage and / or food container or packaging. When reaction was carried out, phosphorus compound, buffer agent and / or surfactant can reduce the amount of the by product formed, so that the pH of solution can not be changed to below 7.0, improved the productive rate of polypropiolactone polymer, and / or improved the performance of polypropiolactone polymer, for example melting temperature, second order transition temperature, number-average molecular weight, weight-average molecular weight or its any combination. By product comprises one or more in acrylic acid compound, crotonaldehyde, 3-hydroxybutanone, tetrahydrofuran (THF) or its any combination. By product and / or reactant (i.e. beta-lactone monomer) can be present in the polypropiolactone polymer with the amount to human body contact safety.By product and / or reactant can be substantially free of polypropiolactone polymer.Based on the total number of polypropiolactone polymer, by product and / or reactant can exist with approximately 100 parts per million or still less, approximately 500 parts per billion or still less or approximately 50 parts per billion or still less amount.By product and / or reactant can exist with approximately 1 part per billion or more, approximately 10 parts per billion or more or approximately 25 parts per billion or more amount.

[0181] The present technology provides a method for forming a polypropiolactone polymer by contacting a β-lactone monomer, a phosphorus compound, and a polar protic solvent. The polar protic solvent and the phosphorus compound can be first contacted under conditions that form a solution. Then, secondly, the β-lactone is contacted with a solution of the polar protic solvent and the phosphorus compound. The β-lactone monomer is first contacted with the polar protic solvent to form a solution, and then the phosphorus compound is contacted with the solution of the β-lactone monomer and the polar protic solvent. The β-lactone monomer, the phosphorus compound, and the polar protic solvent are contacted simultaneously. Optionally, a surfactant and / or a buffer can be added to the solution containing the polar protic solvent before, after, or simultaneously with the phosphorus compound and / or the β-lactone monomer.

[0182] After phosphorus compound, beta-lactone monomer and polar protic solvent contact, the polypropiolactone polymer of initial quantity can precipitate rapidly with approximately 2,000g / mol or higher number-average molecular weight subsequently.The time of reactant reaction is the required time of polymer precipitation.The polypropiolactone polymer of initial quantity can precipitate in approximately 30 seconds or longer time, approximately 5 minutes or longer time or approximately 30 minutes or longer time.The polypropiolactone polymer of initial quantity can precipitate in approximately 24 hours or still less, approximately 12 hours or still less or approximately 3 hours or still less time.

[0183] The β-lactone may have a half-life in a polar protic solvent that allows the formation of polypropiolactone in the presence of a phosphorus compound before significant by-products are produced from the β-lactone. The half-life of the β-lactone in a polar protic solvent may be about 160 minutes or longer, about 190 minutes or longer, or about 220 minutes or longer. The half-life of the β-lactone in a polar protic solvent may be about 300 minutes or shorter, about 270 minutes or shorter, or about 240 minutes or shorter.

[0184] In order that before beta-lactone monomer degradation, substantially all beta-lactone monomers are converted into polypropiolactone polymer, the solution of phosphorus compound, beta-lactone monomer and polar protic solvent can be stirred for a period of time.Stirring can be carried out in the mixed process of polar protic solvent and phosphorus compound, in the combined process of beta-lactone monomer and the solution that contains polar protic solvent and phosphorus compound and / or in the whole reaction process that forms polypropiolactone.This time period can be about 24 hours or shorter, about 12 hours or shorter or about 3 hours or shorter.This time period can be about 30 minutes or longer, about 1 hour or longer or about 2 hours or longer.Can form polypropiolactone polymer by any known technology stirring solution to promote beta-lactone monomer reaction, for example, use stirring blade, impeller, rocking bar, roller, magnetic stirring bar, vortex mixer, stirring rod, stirring scraper or its any combination.

[0185] The method can be carried out in any vessel sufficient to promote the reaction under conditions that reduce undesirable by-products. As described herein, the vessel can be equipped with a heating mechanism to control the temperature of the reaction; a stirring device; or a device to reduce or prevent oxygen contact in the reaction vessel.

[0186] The method of contacting the β-lactone monomer, the polar protic solvent, and the phosphorus compound can be carried out in an oxygen-free environment to avoid degradation of the β-lactone monomer. The method can be carried out in a glove box under a stream of nitrogen or argon or using a Schlenk line. The solution of the polar protic solvent and the phosphorus compound can be formed outside the oxygen-free environment and then contacted with the β-lactone monomer in the oxygen-free environment.

[0187] Beta-lactone monomer can be contacted with the solution containing polar protic solvent and phosphorus compound at a temperature higher than, lower than or equal to ambient temperature (i.e. 25 degrees Celsius). The reaction can be carried out at any temperature sufficient to allow the reaction to proceed at a reasonable rate so that the polypropiolactone polymer precipitates before the half-life of the beta-lactone monomer ends. Beta-lactone monomer can be contacted with the solution containing polar protic solvent and phosphorus compound at a temperature of about 0 degrees Celsius or higher, about 15 degrees Celsius or higher, or about 25 degrees Celsius or higher. Beta-lactone monomer can be contacted with the solution containing polar protic solvent and phosphorus compound at a temperature of about 60 degrees Celsius or lower, about 45 degrees Celsius or lower, or about 30 degrees Celsius or lower.

[0188] After substantially all of the β-lactone has reacted in the polar protic solvent, the polar protic solvent can be separated from the polypropiolactone polymer that has precipitated 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 performed by decantation, evaporation, drying, filtration, sedimentation, or any combination thereof.

[0189] Two or more techniques for separating the polar protic solvent from the polypropiolactone polymer can be used sequentially to reduce the presence of undesirable compounds that may come into contact with the polypropiolactone polymer. The polar protic solvent can be decanted from the polypropiolactone polymer; the polypropiolactone polymer can then be washed with the same or a different polar protic solvent; and the polypropiolactone polymer can be dried to remove the same or a different polar protic solvent used for washing.

[0190] The technology disclosed herein includes contacting a beta-lactone monomer, a phosphorus compound, and a polar protic solvent to form and precipitate a polypropiolactone polymer. Subsequently, the solvent can be separated from the polypropiolactone polymer so that the polypropiolactone polymer is applied or configured to be applied in the form of a coating, film, and / or paint. An example of an application technology is to heat the solution so that the solvent evaporates from the polypropiolactone polymer. The heating can be performed at any temperature sufficient to evaporate the solvent. Heat can be applied at a temperature of about 80 degrees Celsius or higher, about 85 degrees Celsius or higher, or about 90 degrees Celsius or higher. Heat can be applied at a temperature of about 100 degrees Celsius or lower, about 95 degrees Celsius or lower, or about 90 degrees Celsius or lower. The heat of any amount of time sufficient to remove all or substantially all of the solvent from the contact with the polypropiolactone polymer can be applied. The heat application can last for about 1 minute or longer, about 5 minutes or longer, or about 20 minutes or longer. The application of heat may last for about 60 minutes or less, about 45 minutes or less, or about 30 minutes or less.

[0191] The beta-lactone for forming the polypropiolactone polymer can be formed by contacting epoxide and carbon monoxide under the conditions that are enough to form beta-lactone compounds. The example of the process conditions and solvent for forming beta-lactone can be found in at least U.S. Patent No. 8,445,703, which is incorporated herein by reference. Epoxide and carbon monoxide can contact in the presence of a carbonylation catalyst and / or a suitable solvent. The carbonylation catalyst can have any structure including enough Lewis acids, and the Lewis acid has a metal center and a metal carbonyl cation combined with a Lewis acid ion. The example of the carbonylation catalyst can include porphyrin-metal carbonyl catalyst, Schiff base (salen)-metal carbonyl catalyst or a combination of the two. The example of the carbonylation catalyst can also be found in U.S. Patent Nos. 6,852,865, 8,481,756, 10,221,278 and 8,445,703, the entire contents of which are incorporated herein by reference.

[0192] Listed implementation plans

[0193] The following examples are provided to illustrate the present invention but are not intended to limit the scope of the invention. Unless otherwise indicated, all parts and percentages are by weight.

[0194] Embodiment 1. A method comprising:

[0195] a) contacting one or more β-propiolactone monomers and one or more phosphorus compounds and optionally one or more carboxylate compounds in solution under conditions such that a polypropiolactone polymer is formed,

[0196] wherein the solution comprises one or more polar protic solvents and one or more phosphorus compounds and optionally one or more carboxylate compounds, and

[0197] The phosphorus compound comprises phosphorus in ionic form, and the phosphorus in ionic form is either covalently bound to another compound to form a zwitterion, or ionically bound to another compound to form a salt.

[0198] Embodiment 2. The method of embodiment 1, wherein the phosphorus compound comprises a phosphonium compound or an anionic phosphate compound.

[0199] Embodiment 3. The method of embodiment 1, wherein the phosphorus compound comprises one or more of formula I, II and / or III:

[0200] Formula I:

[0201] Each R 3 is independently a hydrocarbon group at each occurrence, wherein two or more R 3One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.

[0202] where R a comprising a phosphate group, a carboxylate group, a carbonate group, an alkoxide group, a halide, or any combination thereof; or

[0203] Formula II:

[0204] where R 5 are independently a quaternary ammonium group, a phosphonium group, another onium cation, or any combination thereof; and

[0205] where R 2 as defined herein; or

[0206] Formula III:

[0207] Each R 2 As defined herein; and

[0208] The solid lines represent covalent bonds, and the dashed lines represent ionic bonds.

[0209] where R b Contains a quaternary ammonium group, a phosphonium group, another onium cation, or any combination thereof.

[0210] Embodiment 4. The method according to embodiment 1-3, wherein the phosphorus compound comprises a cationic phosphine compound and an anionic carboxylate having an anionic carboxylate group, wherein the anionic carboxylate group has C 5-20 alkyl.

[0211] Embodiment 5. The method of embodiments 1-3, wherein the phosphorus compound comprises an anionic phosphate and a cationic quaternary ammonium compound.

[0212] Embodiment 6. The method according to any one of embodiments 1-5, wherein the phosphorus compound comprises one or more C 5-20 alkyl.

[0213] Embodiment 7. The method of any one of Embodiments 1 to 6, wherein the phosphorus compound comprises a cation and an anion covalently bonded to each other.

[0214] Embodiment 8. The method of any one of Embodiments 1 to 7, wherein the phosphorus compound comprises a cation and an anion ionically associated with each other.

[0215] 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 are soluble or dispersible in the polar protic solvent.

[0216] Embodiment 10. The method according to any one of the preceding embodiments, wherein the one or more carboxylate compounds comprise the formula:

[0217]

[0218] where R 2 and R b As defined herein, and dashed line is as defined herein.

[0219] Embodiment 11. The method of any one of the preceding embodiments, wherein when the β-lactone monomer is contacted with the solution, the mass percentage of the one or more polar protic solvents is greater than about 90% based on the total mass of the solution.

[0220] Embodiment 12. A method according to any 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.

[0221] Embodiment 13. The method of any one of the preceding embodiments, wherein the one or more polar protic solvents comprises water.

[0222] Embodiment 14. The method of any one of the preceding embodiments, wherein when the β-propiolactone monomer is contacted with the solution, the β-lactone monomer is present in the solution at a mass percentage of about 5% to about 35% based on the total mass of the solution.

[0223] Embodiment 15. The method of any one of the preceding embodiments, wherein when the β-propiolactone monomer is contacted with the solution, the β-lactone monomer is present in the solution at a mass percentage of about 5% to about 25% based on the total mass of the solution.

[0224] Embodiment 16. The method of any one of the preceding embodiments, wherein when the β-propiolactone monomer is contacted with the solution, the β-propiolactone monomer is present in the solution at a mass percentage of about 5% to about 20% based on the total mass of the solution.

[0225] Embodiment 17. The method according to any of the preceding embodiments, further comprising:

[0226] a) contacting one or more phosphorus compounds with one or more polar protic solvents to form a solution before contacting the β-lactone monomer with the solution.

[0227] Embodiment 18. The method according to any of the preceding embodiments, further comprising:

[0228] a) contacting one or more phosphorus compounds, one or more buffers, and one or more polar protic solvents to form a solution before the β-lactone monomer is contacted with the solution.

[0229] Embodiment 19. The method according to any of the preceding embodiments, further comprising:

[0230] a) contacting one or more phosphorus compounds, one or more surfactants, and one or more polar protic solvents to form a solution before the β-lactone monomer is contacted with the solution.

[0231] Embodiment 20. The method according to any of the preceding embodiments, further comprising:

[0232] 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 the β-lactone monomer is contacted with the solution.

[0233] Embodiment 21. The method of any one of the preceding embodiments, wherein the β-lactone compound is contacted with the solution comprising one or more buffers configured to maintain a pH of the solution greater than 7.0.

[0234] Embodiment 22. The method of any one of the preceding embodiments, wherein the β-lactone monomer is contacted with a solution comprising one or more surfactants.

[0235] Embodiment 23. The method of any one of the preceding embodiments, wherein the β-lactone monomer is contacted with a solution comprising one or more buffers and one or more surfactants.

[0236] Embodiment 24. The method of any one of the preceding embodiments, wherein the one or more surfactants are at least partially miscible with the β-lactone monomer.

[0237] Embodiment 25. The method of any one of the preceding embodiments, wherein the β-lactone and the solution are contacted at a temperature of about 0 degrees Celsius to about 60 degrees Celsius.

[0238] Embodiment 26. The method of any one of the preceding embodiments, wherein the step of contacting the β-lactone monomer with the compound in solution is performed with stirring for a period of time from about 12 hours to about 24 hours.

[0239] Embodiment 27. The method of any one of the preceding embodiments, wherein substantially all of the β-lactone monomer is converted to polypropiolactone polymer or byproduct in about 3 hours or less.

[0240] Embodiment 28. The method according to any of the preceding embodiments, further comprising:

[0241] a) prior to the step of contacting the β-lactone monomer with the compound in solution, contacting the compound with water to form a solution.

[0242] Embodiment 29. The method according to any one of the preceding embodiments, wherein the step of contacting the β-lactone monomer with the compound in the solution is performed in an oxygen-free environment.

[0243] Embodiment 30. The method according to any of the preceding embodiments, further comprising:

[0244] a) Isolating the polypropiolactone polymer from the solution.

[0245] Embodiment 31. The method according to any of the preceding embodiments, further comprising:

[0246] a) precipitating a polypropiolactone polymer from the solution; and

[0247] b) separating the polypropiolactone polymer from the by-products.

[0248] Embodiment 32. The method of any one of the preceding embodiments, wherein the step of separating the polypropiolactone polymer from the solution comprises:

[0249] a) precipitating the polypropiolactone polymer from the solution;

[0250] b) decanting the solution from the polypropiolactone polymer;

[0251] c) washing the polypropiolactone polymer with alcohol to remove residues of the solution; and

[0252] d) Drying the polypropiolactone polymer under vacuum to remove residues of the solution.

[0253] Embodiment 33. The method of any one of the preceding embodiments, wherein the phosphorus compound is present in an amount sufficient to cause ring opening of the β-lactone compound to form a polypropiolactone polymer and reduce by-product formation.

[0254] Embodiment 34. The method of any one of the preceding embodiments, wherein the phosphorus compound is present in the solution in an amount from 10 ppm to about 200,000 ppm.

[0255] 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.

[0256] 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.

[0257] 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.

[0258] Embodiment 38. The method of any one of the preceding embodiments, wherein the one or more buffers are present in an amount of about 0.1 g / L to about 10.0 g / L.

[0259] Embodiment 39. The method of any one of the preceding embodiments, wherein the byproduct is present in the polypropiolactone polymer in an amount of about 10 ppm to about 10,000 ppm.

[0260] Embodiment 40. The method of any one of the preceding embodiments, wherein the presence of the byproduct does not change the pH of the solution below 7.0.

[0261] Embodiment 41. The method of any one of the preceding embodiments, wherein the phosphorus compound comprises a disubstituted phosphate group.

[0262] Embodiment 42. The method according to any of the preceding embodiments, wherein the phosphorus compound comprises 5-20 Cationic quaternary ammonium of an alkyl group.

[0263] Embodiment 43. A method according to any of the preceding embodiments, wherein the cationic quaternary ammonium is covalently bound to the disubstituted phosphate group.

[0264] Embodiment 44. The method of any one of the preceding embodiments, wherein the phosphorus compound comprises choline covalently bound to phosphatidic acid.

[0265] Embodiment 45. The method of any one of the preceding embodiments, wherein the phosphorus compound comprises phosphatidylcholine.

[0266] Embodiment 46. The method of any one of the preceding embodiments, wherein the cationic quaternary ammonium is ionically associated with the disubstituted phosphate group.

[0267] Embodiment 47. The method according to any of the preceding embodiments, wherein the phosphorus compound comprises one or more C 5-20 alkyl.

[0268] Embodiment 48. The method according to any of the preceding embodiments, wherein the phosphorus compound comprises two or more C 5-20 alkyl.

[0269] Embodiment 49. The method according to any of the preceding embodiments, wherein the phosphorus compound comprises three or more C 5-20 alkyl.

[0270] Embodiment 50. The method according to any one of the preceding embodiments, wherein the phosphorus compound comprises four or more C 5-20 alkyl.

[0271] Embodiment 51. A method according to any one of the preceding embodiments, wherein the phosphorus compound comprises a C 1-20 Anionic carboxylate compounds of alkyl groups.

[0272] Embodiment 52. The method of any one of the preceding embodiments, wherein the phosphorus compound comprises an ionically bound phosphorus cation and an anionic carboxylate compound.

[0273] Embodiment 53. The method according to any of the preceding embodiments, wherein the phosphorus compound is in the one or more C 5-20 The alkyl group includes at least some unsaturation.

[0274] Embodiment 54. The method of any one of the preceding embodiments, wherein the one or more surfactants comprises a polymer having repeating groups of an alkylene ether and one or more terminal hydroxyl groups.

[0275] Embodiment 55. The method according to 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.

[0276] Embodiment 56. The method of any one of the preceding embodiments, wherein the one or more surfactants comprises a nonionic polymer.

[0277] Embodiment 57. The method of any one of the preceding embodiments, wherein the one or more surfactants comprises one or more triblock copolymers.

[0278] Embodiment 58. The method of any one of the preceding embodiments, wherein the one or more surfactants comprises a poloxamer, a fatty salt, or any combination thereof.

[0279] Embodiment 59. The method of any one of the preceding embodiments, wherein the one or more buffering agents comprises a monoacid, a polyacid, or a combination of both.

[0280] 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, monobasic phosphate, or any combination thereof.

[0281] Embodiment 61. The method of any one of the preceding embodiments, wherein the byproduct comprises acrylic acid, acrylic acid dimer, 3-hydroxypropionic acid, or any combination thereof.

[0282] 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.

[0283] 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.

[0284] Embodiment 64. The method of any one of the preceding embodiments, wherein the polypropiolactone polymer has a number average molecular weight of about 1 kg / mol to about 1000 kg / mol.

[0285] Embodiment 65. The method of any one of the preceding embodiments, wherein the polypropiolactone polymer has a weight average molecular weight of about 1 kg / mol to about 2000 kg / mol.

[0286] Embodiment 66. The method of any one of the preceding embodiments, wherein the polypropiolactone polymer is substantially free of β-lactone monomers and / or acrylic acid.

[0287] 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.

[0288] Embodiment 68. The method of any one of the preceding embodiments, wherein the polypropiolactone polymer has a crystallization temperature of about 0 degrees Celsius to about 100 degrees Celsius.

[0289] Embodiment 69. The method of any one of the preceding embodiments, wherein the polypropiolactone polymer has a repeating structure according to:

[0290]

[0291] Each R 1 independently selected from hydrogen, methyl, C 2-10 One or more of alkyl or any combination thereof; and

[0292] Where x is a real number greater than 1 and ranging from 50,000.

[0293] Embodiment 70. The method according to any one of the preceding embodiments, wherein the β-lactone monomer has the following structure:

[0294]

[0295] Each R 1 independently selected from hydrogen, methyl, C 2-10 one or more of alkyl or any combination thereof.

[0296] Embodiment 71. The method according to any of the preceding embodiments, further comprising:

[0297] a) contacting carbon monoxide with an epoxy compound to form a β-lactone monomer.

[0298] Embodiment 72. A method according to Embodiment 71, wherein carbon monoxide and the epoxide are contacted in the presence of a carbonylation catalyst.

[0299] Embodiment 73. The method of embodiment 71 or 72, wherein the epoxide compound has a structure according to:

[0300]

[0301] Each R 1 independently selected from hydrogen, methyl, C 2-10 one or more of alkyl or any combination thereof.

[0302] Embodiment 74. A polymer composition according to any one of the preceding embodiments, comprising a polypropiolactone polymer having:

[0303] a) a number average molecular weight of about 1000 g / mol to about 200,000 g / mol;

[0304] b) a PDI of greater than 1 to about 3.5; and

[0305] c) By-products present in amounts of 50 parts per billion or less.

[0306] Example

[0307] The following examples are provided to illustrate the present disclosure but are not intended to limit its scope.

[0308] GPC was performed on an Agilent 1260 Infinity II HPLC system equipped with two PLgel 300x7.5 mm (PL111-6500) size exclusion columns and multiple detectors [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 by monodisperse polymethyl methacrylate ("PMMA") polymer standards. PMMA standards ranged from 500 g / mol to 2,000,000 g / mol (Agilent EasiVial; part number: PL2020-0201). The polypropiolactone polymer was dissolved in HPLC grade chloroform [~5 mg / mL] and then filtered through a 0.2 mm PVDF filter.

[0309] The spectrometer was used to analyze the 1 H NMR spectroscopy analysis. The spectra were referenced to normal chloroform (7.26 ppm). The polypropiolactone polymer sample was dissolved in CDCl3 (99.8% deuterated; Cambridge Isotopes) at a concentration of 10 mg / mL.

[0310] Differential Scanning Calorimetry (DSC) was performed on a TA Instruments Q20 series differential scanning calorimeter at N 2(g) 10℃×min -1 The thermal history of the polymer was as follows: the polymer was melted at 130 °C to erase the thermal and solvent memory and heated at a rate of 10 °C × min -1 The sample was cooled to -30°C at a rate of 10°C x min -1 The polymer was heated to 130°C at a heating rate of 10°C × min and then rapidly cooled to -30°C [melt quenching]. The polymer was then heated to 130°C at a heating rate of 10°C × min -1 ].

[0311] Example 1

[0312] In a glove box, 100 μL of β-propiolactone monomer was added to a 2 mL snap-cap gas chromatography vial. The vial was sealed under a nitrogen atmosphere. Outside the glove box, an aqueous solution containing α-phosphatidylcholine [125 mg; 0.12 mass %] and pluronic [300 mg; 0.3 mass %] was prepared in 100 mL of phosphate-buffered saline [PBS]. Under a nitrogen atmosphere, approximately 900 μL of this solution was added to the β-propiolactone monomer and gently stirred. A white solid precipitated within minutes. The solution was stirred overnight to completely consume the β-propiolactone monomer. The water was decanted, and the polymer was washed three times with isopropanol [1 mL x 3]. The resulting solid was vacuum dried overnight to yield 95 mg of polypropiolactone polymer [95%; Mn(GPC) = 98,000 g / mol, PDI = 1.5].

[0313] Example 2

[0314] In a glove box, 200 μL of β-propiolactone monomer was added to a 2 mL press-cap vial. The vial was sealed under a nitrogen atmosphere. Outside the glove box, an aqueous solution containing octadecyltrimethylammonium dimethylphosphate [ODTMADMP] [150 mg; 0.15 mass %] and pluronic [300 mg; 0.3 mass %] was prepared in 100 mL of deionized water. Under a nitrogen atmosphere, approximately 800 μL of this solution was added to the β-propiolactone monomer and the solution was gently stirred. A white solid precipitated within minutes. The solution was stirred overnight to completely consume the β-propiolactone monomer. The water was decanted and the polymer was washed three times with isopropanol [1 mL x 3]. The resulting solid was vacuum dried overnight to yield 53 mg of polypropiolactone polymer [27%; Mn(GPC) = 218,000 g / mol, PDI = 1.2].

[0315] Example 3

[0316] In the glove box, 200 μL of β-propiolactone monomer was added to a 2 mL press-capped vial. The vial was sealed under a nitrogen atmosphere. Outside the glove box, an aqueous solution containing trihexyl (tetradecyl) phosphonium decanoate [THTDPD] [150 mg; 0.15 mass %] was prepared in 100 mL of deionized water. Under a nitrogen atmosphere, approximately 800 μL of the solution was added to the β-propiolactone monomer and the solution was gently stirred. A white solid precipitated within a few minutes. The solution was stirred overnight to completely consume the β-propiolactone monomer. The water was decanted and the polymer was washed three times with isopropanol [1 mL×3]. The resulting solid was vacuum dried overnight to obtain 13 mg [7%; Mn(GPC)=59,300 g / mol, PDI=1.5].

[0317] result

[0318] Figure 1is a gel permeation chromatography ("GPC") trace of the polypropiolactone from Example 1.

[0319] Figure 2 is the GPC trace of polypropiolactone from Example 2.

[0320] Figure 3 is the GPC trace of polypropiolactone from Example 3.

[0321] Figure 4 It is polypropiolactone in CDCl3 1 HNMR spectrum.

[0322] Figure 5 Figure 1 is a differential scanning calorimetry curve of a polypropiolactone polymer prepared by aqueous polymerization in the presence of PEO-PPO-PEO. First thermal cycle [line A; 10°C / min under N2(g)]. Cooling cycle [line B; 10°C / min under N2(g). Second thermal cycle [line C; 10°C / min under N2(g).

[0323] Examples 1-3 [see above for experimental setup and preliminary results] describe the aqueous polymerization of β-propiolactone monomer. The structures of each compound used in the polymerization of β-propiolactone monomer are shown in Scheme 1 below. Table 1 shows the results for each example. In general, the yields ranged from low to high [7-95%]. Surprisingly, the isolated polymers were of high molar mass, low dispersity [M n >50 kDa, PDI <1.5; Figure 1 ]. 1 HNMR spectroscopy confirmed the structure of poly(3-hydroxypropionic acid)[ Figure 3-4 ]. Thermal properties indicate that the surfactant used plasticizes the polymer as a depression in the melting point of the final polymer was observed [ Figure 5 ].

[0324] Solution 1. Phosphorus compounds and surfactants used in the polymerization of β-propiolactone in water.

[0325]

[0326] Table 1. Aqueous polymerization of β-propiolactone

[0327]

[0328] a. The mass percentage of the initiator in the aqueous solution is 0.15

[0329] b. Pluronic [0.3% by mass in water or PBS solution]

[0330] c. Mass percentage of bPL in solution

[0331] d. Mass yield of P3HP solid

[0332] e. Number average molar mass [M n ] and dispersion index [PDI=M w / M n ], which was determined by GPC [CHCl3@1.0mL / min with PMMA standard]

[0333] f. Melting point [T m ] and crystallization temperature [T c ] was determined by differential scanning calorimetry [DSC; 2(g) below 10℃ / min].

Claims

1. A method comprising: a) contacting one or more β-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, wherein the solution comprises one or more polar protic solvents and one or more phosphorus compounds and optionally one or more carboxylate compounds, and The phosphorus compound comprises phosphorus in ionic form, and the ionic form of phosphorus is 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 method of claim 1, wherein the phosphorus compound comprises one of formula I, II and / or III: Formula I: Each R 3 is independently a hydrocarbon group at each occurrence, wherein two or more R 3 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms; where R a comprising a phosphate group, a carboxylate group, a carbonate group, an alkoxide group, a halide, or any combination thereof; or Formula II: where R 5 are independently a quaternary ammonium group, a phosphonium group, another onium cation, or any combination thereof; and where R 2 as defined herein; or Formula III: Each R 2 As defined herein; and Wherein the solid lines represent covalent bonds, and the dashed lines represent ionic bonds; where R b Contains a quaternary ammonium group, a phosphonium group, another onium cation, or any combination thereof.

4. The method according to claim 1-3, wherein the phosphorus compound comprises the cationic phosphine compound and a 5-20 Anionic carboxylates of alkyl compounds.

5. The method of claims 1-3, wherein the phosphorus compound comprises anionic phosphates and cationic quaternary ammonium compounds.

6. The method according to any one of claims 1 to 5, wherein the phosphorus compound comprises one or more C 5-20 alkyl.

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

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

10. The method of any one of the preceding claims, wherein the one or more carboxylate compounds comprise the formula: where R 2 and R b As defined herein, and dashed line is as defined herein.

11. The method of any one of the preceding claims, wherein when the β-lactone monomer is contacted with the solution, the one or more polar protic solvents are present in a mass percentage greater than about 90% based on the total mass of the solution.

12. 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. The method of any one of the preceding claims, wherein the one or more polar protic solvents comprises water.

14. The method of any one of the preceding claims, wherein when the β-propiolactone monomer is contacted with the solution, the β-lactone monomer is present in the solution at a mass percentage of about 5% to about 35% based on the total mass of the solution.

15. The method according to any one of the preceding claims, 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 the solution prior to contacting the β-lactone monomer with the solution.

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

0.

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

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

19. The method of any one of the preceding claims, wherein substantially all of the β-lactone monomer is converted to polypropiolactone polymer or byproduct in about 3 hours or less.

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

21. The method of any one of the preceding claims, wherein the step of contacting the β-lactone monomer with the compound in the solution is performed in an oxygen-free environment.

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

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

24. The method of any one of the preceding claims, wherein the step of separating the polypropiolactone polymer from the solution comprises: 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; and d) drying the polypropiolactone polymer under vacuum to remove residues of the solution.

25. The method of any preceding claim, wherein the phosphorus compound is present in an amount sufficient to cause ring opening of the β-lactone compound to form the polypropiolactone polymer and to reduce by-product formation.

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

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

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

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

30. The method of any preceding claim, wherein the presence of the by-product does not change the pH of the solution below 7.

0.

31. The method of any one of the preceding claims, wherein the one or more buffering agents comprises a monoacid, a polyacid, or a combination of both.

32. The method of any one of the preceding claims, wherein the byproduct comprises acrylic acid, acrylic acid dimer, 3-hydroxypropionic acid, or any combination thereof.

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

7.

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

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

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

37. The method of any one of the preceding claims, wherein the polypropiolactone polymer has a repeating structure according to: Each R 1 independently selected from hydrogen, methyl, C 2-10 One or more of alkyl or any combination thereof; and Where x is a real number greater than 1 and ranging from 50,000.

38. The method according to any one of the preceding claims, further comprising: a) contacting carbon monoxide with an epoxy compound to form a β-lactone monomer.

39. The polymer composition of the method of any one of the preceding claims, comprising a polypropiolactone polymer having: 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 c) By-products present in amounts of 50 parts per billion or less.

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