Preparation method using polypropiolactone and ionic liquid

Abstract

A method for efficiently making polypropiolactone and related copolymers from betapropiolactone utilizing carboxylate salts of onium cations is disclosed. In another aspect, the present invention provides a polymerization system comprising a combination of initiators and monomers that together enable the efficient production of polypropiolactone and related copolymers. Novel polymer compositions are disclosed that have structural and / or compositional properties that distinguish them from previously produced polymers and polymer compositions.

Description

[Technical Field]

[0001] The present disclosure relates to polymer systems comprising polypropiolactones having a residue of a phosphate anion covalently attached to one end of the polymer chain and one or more onium-based cations at the other end of the chain. The disclosure also relates to polymerizable compositions and methods for preparing such polymer systems utilizing ionic liquids containing phosphate cations. [Background technology]

[0002] Polyester polymers have proven to be versatile materials with a wide range of applications. Polyesters based on petroleum-derived aromatic monomers are among the most widely utilized polymers. For example, polyethylene terephthalate (PET) is produced on a large scale for the production of water bottles, textiles, and other consumer goods. Unfortunately, PET is not biodegradable, making it a major contributor to the growing problem of environmental pollution from post-consumer residual plastic waste, including damage to marine ecosystems. In recent years, there has been growing interest in biodegradable polyesters such as polylactic acid (PLA) and poly-3-hydroxybutyrate (PHB). The high cost and properties of these polymers make it difficult to provide them in large quantities to replace existing bulk polymers. There remains a need for high-performance biodegradable polyesters and methods for producing such polymers from flexible feedstock sources that allow manufacturers to balance the cost and sustainability profiles of their products.

[0003] Although the polymerization of betapropiolactone (BPL) and related substituted beta-lactones has been known for several decades, until now it has not been possible to economically produce very high molecular weight polypropiolactone or related copolymers, nor has it been easy to control the compositional properties and secondary structure of such polymers to optimize them for various applications. The time required for the preparation of polypropiolactone can be long, and a need exists for methods of preparing such polymers that require less processing time.

[0004] What is needed are polymers prepared from beta-lactones with higher, controllable molecular weights. What is needed are polymers prepared from beta-lactones with controllable polydispersities. What is needed are methods for preparing such polymers that allow for the preparation of polymer systems with desired molecular weights and polydispersities. What is needed is a method for preparing polypropiolactone that requires less time and provides control over the molecular weight and polydispersity of the formed polymer. Summary of the Invention

[0005] Disclosed is a polymer comprising one or more polymer chains having units derived from ring-opened beta-lactones and having, at one end of the chain portion, a residue of a phosphate anion covalently bonded to one end of the polymer chain. The polymer may have a mixture of a residue of a carboxylate anion and a residue of a phosphate anion at one end of the polymer. The other end of the chain portion may be one or more onium cations. 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 and phosphorus. The onium cation may include one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations.

[0006] The onium cation may be one or more of a quaternary nitrogen- or quaternary phosphonium-containing cation. The one or more quaternary nitrogen-containing cations may be a quaternary amine, and two or more of the groups attached to the nitrogen may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms. The one or more quaternary nitrogen-containing cations may include one or more ammonium, amidinium, and guanidinium cations, or onium cations based on nitrogen-containing heterocycles. The one or more quaternary nitrogen-containing cations may include one or more onium cations based on nitrogen-containing heterocycles, including optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium. The one or more quaternary nitrogen-containing cations may include one or more optionally substituted imidazolium cations. The one or more quaternary nitrogen-containing cations may be represented by the formula [ka] and one or more ammonium cations corresponding to In the formula, R 1 is, separately in each occurrence, a group containing one or more carbon atoms, and R 1 Two or more of may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms. The one or more quaternary nitrogen-containing cations have the formula: [ka] and may be one or more guanidinium cations corresponding to In the formula, R 1is, independently in each occurrence, a carbon-containing group that may contain one or more heteroatoms. The one or more quaternary ammonium cations may be one or more tetraalkylammonium anions or onium cations based on nitrogen-containing heterocycles such as optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium. The one or more quaternary ammonium cations may be one or more tetraalkylammonium anions or onium cations based on nitrogen-containing heterocycles such as optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium. The one or more quaternary phosphonium cations may be of the formula: [ka] can correspond to In the formula, R 1 is, separately in each occurrence, a carbon-containing group optionally containing one or more heteroatoms, and R 1 Two or more of may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms. The one or more quaternary phosphonium cations may be tetraalkylphosphonium cations.

[0007] One or more polymer chains have residues of an end-capping or quenching agent at some of the ends of the chains. The end-capping agent may include one or more electrophilic organic compounds. The end-capping agent may be an organic halide, an organic sulfonate, a haloalkylsilane, an aniline derivative, a phosphoric acid derivative, or an isophthalic acid derivative.

[0008] The polymer may include a comonomer that polymerizes with the ring-opened beta-lactone. The comonomer may be one or more of caprolactone, lactide, epoxide, oxetane, cyclic anhydride, cyclic ether, lactam, episulfide, aziridine, (meth)acrylate, valerolactone, butyrolactone, glycolide, and substituted glycolides, and may be one or more epoxides.

[0009] Polymerizable compositions are disclosed that include: a) one or more beta-lactones; and b) one or more salts or zwitterions of one or more onium-containing cations and one or more phosphate anions. The one or more salts of the one or more onium-containing cations and one or more phosphate anions may be based on any one or more of the cations and anions disclosed above.

[0010] The one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions have the formula: [ka] may correspond to one of In the formula, R 1 is, separately in each occurrence, a carbon group optionally containing one or more heteroatoms, and R 1 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms, and R 2 is, separately in each occurrence, a carbon group optionally containing one or more heteroatoms.

[0011] The one or more salts of the one or more quaternary nitrogen-containing cations and the one or more phosphate anions have the formula: [ka] can correspond to In the formula, R 1 and R 2 Each occurrence of independently defines a hydrocarbyl group.

[0012] The one or more salts of the one or more quaternary nitrogen-containing cations and the one or more phosphate anions have the formula: [ka] can correspond to In the formula, R 1 and R 2 has been previously defined.

[0013] The disclosed polymerizable compositions can include one or more of a chain transfer agent, a chain extender, a quenching agent, and an end-capping agent. The disclosed polymerizable compositions can exhibit a ratio of one or more of the beta-lactones to one or more salts or zwitterions including one or more onium cations and one or more phosphate anions of about 10 to 1 to about 1,000,000 to 1. The end-capping or quenching agent can be present in an amount less than 10 molar equivalents relative to the amount of one or more salts or zwitterions of one or more onium cations and one or more phosphate anions.

[0014] Disclosed are methods comprising contacting one or more beta-lactones, and optionally comonomers, with one or more salts or zwitterions comprising one or more onium cations and one or more phosphate anions under conditions to prepare one or more polymers comprising one or more polymer chains having ring-opened beta-lactone units. The disclosed onium cations can be any of those disclosed herein. The disclosed one or more phosphate anions can be any of those disclosed herein. The disclosed methods can include contacting the polymerizable composition at about 30°C to about 120°C. The polymerizable composition can be contacted at a pressure of about 1 bar (0.1 MPa) to about 20 bar (2.0 MPa).

[0015] One or more salts or zwitterions containing one or more onium cations and one or more phosphate anions can form ionic liquids that can mix well with the liquid components in the disclosed compositions and function as carriers for certain solid components. Such ionic liquids offer advantages in use due to their liquid properties. Such compounds in liquid form can perform their function when added to a polymerizable composition. Solid components may have an induction period because they need to dissolve in the reaction mixture before they can function. These ionic liquids do not require such an induction period.

[0016] The use of compounds containing phosphorus-based anions can result in higher molar masses in shorter times. These salts are obtained as low-melting solids and can be used as liquid-like initiators for slurry polymerization of beta-lactones. The polymers exhibit controllable molecular weights and polydispersities. The disclosed methods provide a means to control molecular weight and polydispersity. The disclosed polymers can exhibit higher molecular weights than previously known for polymers containing one or more polymer chains with ring-opened beta-propiolactone and / or substituted beta-propiolactone units. [Brief explanation of the drawings]

[0017] [Figure 1] 1 shows the dependence of molar mass [Mn] on the ratio of monobasic ionic liquid equivalents to beta-propiolactone. [Figure 2] Figure 1 shows the molar mass [Mn] dependence on the tribasic ionic liquid equivalent to beta-lactone ratio. [Figure 3a] 1H NMR spectroscopy (500 MHz; CDCl3) of P3HP prepared using octadecyl-trimethylammonium dimethyl phosphate. [Figure 3b] 1H NMR spectroscopy (500 MHz; CDCl3) of P3HP prepared using octadecyl-trimethylammonium dimethyl phosphate. [Figure 4] 1H NMR spectroscopy (500 MHz; CDCl3) of P3HP prepared using tris(tetramethylammonium) phosphate. [Figure 5] Figure 1 shows the molar mass [g / mol] of P3HP using 1H NMR spectroscopy with ODTMA DMP as catalyst and end group analysis by GPC. [Figure 6] Figure 1 shows the temperature dependence of polymer molar mass [Mn] using ODTMA DMP as additive [monomer to ionic liquid ratio = 500:1]. [Figure 7] 1 shows a comparison of beta-lactone conversion versus time with various polymerization additives. DETAILED DESCRIPTION OF THE INVENTION

[0018] Definitions of specific functional groups and chemical terms are described in more detail below. For purposes of the present invention, chemical elements are defined as defined in the Periodic Table of the Elements, CAS version, Handbook of Chemistry and Physics, 75 th (back cover), and specific functional groups are generally defined as described therein. In addition, general principles of organic chemistry, as well as specific functional moieties and reactivities, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999, Smith and March's Advanced Organic Chemistry, 5 th Edition, John Wiley&Sons, Inc., New York, 2001, Larock, Comprehensive Organic Transformations, VCH Publishers, Inc., New York, 1989, Carruthers, Some Modern Methods of Organic Synthesis, 3 rd Edition, Cambridge University Press, Cambridge, 1987, the entire contents of each of which are incorporated herein by reference.

[0019] The disclosed polymers may include one or more crystalline polymorphs and may exist in various crystalline forms. The term "beta-lactone" refers to a substituted or unsubstituted cyclic ester having a four-membered ring containing an oxygen atom, a carbonyl group, and two optionally substituted methylene groups. Unsubstituted beta-lactones are referred to as propiolactones. Substituted beta-lactones include mono-, di-, tri-, and tetra-substituted beta-lactones. Beta-lactones may contain a single lactone moiety. Beta-lactones may contain two or more four-membered cyclic ester moieties. "Substantially all" means that 95 percent or more, 98 percent or more, or 99 percent or more of the referenced parameter or material is present, and the percentage may be by weight or mole percent depending on the context.

[0020] The term "epoxide," as used herein, refers to a substituted or unsubstituted oxirane. Such substituted oxiranes include mono-, di-, tri-, and tetra-substituted oxiranes. Such epoxides may be further optionally substituted as defined herein. An epoxide may contain a single oxirane moiety. An epoxide may contain two or more oxirane moieties.

[0021] As used herein, the term "polymer" refers to a molecule of high relative molecular weight whose structure actually or conceptually comprises multiple repeating units derived from molecules of lower relative molecular weight. Polymers can be composed of or derived from beta-lactone monomers (e.g., polypropiolactone). The disclosed polymers can be copolymers, terpolymers, heteropolymers, block copolymers, or tapered heteropolymers incorporating two or more different monomers.

[0022] As used herein, the terms "halo" and "halogen" refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br), and iodine (iodine, -I). Carbon-containing groups refer to groups having a carbon skeleton commonly referred to as hydrocarbyl groups, including the variations described in this paragraph. The terms "aliphatic" or "aliphatic group," as used herein, refer to a hydrocarbon moiety that may be straight-chain (i.e., unbranched), branched, or cyclic (including fused, bridged, and spiro-fused polycyclics), may be fully saturated, or may contain one or more units of unsaturation, but is not aromatic. Aliphatic groups may contain 1 to 40 carbon atoms, 1 to 20 carbon atoms, 2 to 20 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon atoms, 1 to 5 carbon atoms, 1 to 4 carbon atoms, 1 to 3 carbon atoms, or 1 to 2 carbon atoms. Aliphatic groups include, but are not limited to, straight or branched chain, alkyl, alkenyl, and alkynyl groups, as well as hybrids thereof, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, or (cycloalkyl)alkenyl.

[0023] 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.

[0024] The term "unsaturated," as used herein, means that a moiety has one or more double or triple bonds. The terms "alicyclic," "carbocycle," or "carbocyclic," used alone or as part of a larger moiety, refer to a saturated or partially unsaturated cycloaliphatic monocyclic or polycyclic ring system having 3 to 12 members, as described herein, where the aliphatic ring system is defined below and is optionally substituted as described herein. Alicyclic groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornyl, adamantyl, and cyclooctadienyl. Alicyclic groups can have 3 to 6 carbons. The terms "alicyclic," "carbocycle," or "carbocyclic" also include an aliphatic ring fused to one or more aromatic or non-aromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring. As used herein, the term "alkenyl" refers to a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon double bond by the removal of a single hydrogen atom. As used herein, the term "alkynyl" refers to a monovalent group derived from a straight- or branched-chain aliphatic moiety having at least one carbon-carbon triple bond by the removal of a single hydrogen atom. As used herein, the term "alkoxy" refers to an alkyl group, as previously defined, attached to the parent molecule through an oxygen atom. Examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, and n-hexoxy. The term "acyl," as used herein, refers to a carbonyl-containing functionality, e.g., -C(=O)R', where R' is hydrogen or an optionally substituted aliphatic, heteroaliphatic, heterocyclic, aryl, heteroaryl group, or is substituted (e.g., with hydrogen or an aliphatic, heteroaliphatic, aryl, or heteroaryl moiety) with an oxygen- or nitrogen-containing functionality (e.g., to form a carboxylic acid, ester, or amide functionality).The term "acyloxy," as used herein, refers to an acyl group attached to a parent molecule through an oxygen atom. The term "aryl," used alone or as part of a larger moiety such as "aralkyl," "aralkoxy," or "aryloxyalkyl," refers to monocyclic and polycyclic ring systems having a total of 5 to 20 ring members, in which at least one ring in the system is aromatic and each ring in the system contains 3 to 12 ring members. The term "aryl" may be used interchangeably with the term "aryl ring," which refers to an aromatic ring system, including, but not limited to, phenyl, biphenyl, naphthyl, anthracyl, and the like, which may bear one or more substituents. As used herein, the term "aryl" also includes within its scope groups in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthymidyl, phenanthridinyl, or tetrahydronaphthyl, where the radical or point of attachment is on the aryl ring.

[0025] The terms "heteroaryl" and "heteroalkoxy," used alone or as part of a larger moiety, e.g., "heteroaralkyl" or "heteroaralkoxy," refer to groups having 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms, in which 6, 10, or 14 pi electrons are shared in a cyclic arrangement, and which have 1 to 5 heteroatoms in addition to carbon atoms. The term "heteroaryl" can be used interchangeably with the terms "heteroaryl ring" and "heteroaryl group," either of which includes optionally substituted rings. The term "heteroatom" refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur and any quaternized form of a basic nitrogen. Heteroaryl groups can be monocyclic or bicyclic. "Heteroaralkyl" refers to an alkyl group substituted by a heteroaryl, where the alkyl and heteroaryl portions are independently optionally substituted. The term "partially unsaturated" refers to a ring moiety that contains at least one double or triple bond.

[0026] As described herein, the disclosed compounds may contain "optionally substituted" moieties. The term "substituted," whether preceded by the term "optionally," means that one or more hydrogens of the specified moiety have been replaced with a suitable substituent. Unless otherwise indicated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and if more than one position in any given structure may be substituted with more than one substituent selected from a specified group, the substituents may be the same or different at all positions. Combinations of substituents envisioned are those that result in the formation of stable or chemically feasible compounds. The term "stable," as used herein, refers to compounds that are substantially unchanged when exposed to conditions that allow for their production, detection, and, in certain embodiments, their recovery, purification, and use for one or more of the purposes disclosed herein.

[0027] As used herein, the term "alkoxylated" means that one or more functional groups on a molecule (typically, the functional groups are, but are not strictly limited to, alcohol, amine, or carboxylic acid) have a hydroxy-terminated alkyl chain attached to it. The alkoxylated compound may contain a single alkyl group or may be an oligomeric moiety such as a hydroxyl-terminated polyether. The alkoxylated material may be derived from a parent compound by treating the functional group with an epoxide. Unless otherwise specified, "a," "an," "the," and "at least one" are used interchangeably and mean one or more than one.

[0028] In certain structures, portions of the disclosed structures are joined by dashed lines indicating that the connected structures are ionically bonded together. [ka] are connected by

[0029] Disclosed are polymers comprising one or more polymer chains having units derived from ring-opened beta-lactones and having, at one end of the chain segment, a residue of a phosphate anion covalently attached to one end of the polymer chain. The polymers can have a mixture of residues of carboxylate anions and residues of phosphate anions attached to one end of the polymer chain. The other end of the chain segment can be one or more onium cations. Also disclosed are polymerizable compositions comprising: (a) one or more beta-lactones; and (b) one or more salts or zwitterions comprising one or more onium cations and one or more phosphate anions. The polymerizable compositions can prepare the disclosed polymers. The polymerizable compositions can prepare any known polymer derived from one or more beta-lactones and, optionally, comonomers, as disclosed herein. Also disclosed are methods of contacting one or more beta-lactone-substituted betapropiolactones, and optionally, comonomers, with one or more salts or zwitterions comprising one or more onium cations and one or more phosphate anions under conditions to prepare one or more polymers comprising one or more polymer chains having ring-opened beta-lactone units. The disclosed onium cations can be any of those disclosed herein. The disclosed one or more phosphate anions can be any of those disclosed herein. Polymers prepared from the polymerizable compositions and disclosed methods can exhibit controllable molecular weights and polydispersities. Such polymers can have higher molecular weights than those previously prepared. Such polymers can exhibit lower polydispersities than those previously prepared.

[0030] The prepared polymer contains monomer units derived from the ring-opened beta-lactone. The polymer may also contain units derived from a comonomer. The formed polymer can be terminated at one end with one or more of a quenching agent, a residue of an onium group, or the like. In the polymer formulas described herein, such end groups are represented by Z. Onium groups and chain terminators are described herein below.

[0031] The polymer may include, at one end of a chain segment, a residue of a phosphate anion covalently attached to one end of the polymer chain. The polymer may have a mixture of residues of carboxylate anions and residues of phosphate anions attached to one end of the polymer chain. The other end of the chain segment may be one or more onium cations. The monomer unit derived from the ring-opened beta-lactone may correspond to the formula: [ka] In the formula, R 3 is independently in each occurrence hydrogen or a carbon-containing group which may have one or more hydrogen or fluorine atoms bonded to a carbon atom, a may optionally include one or more heteroatoms and / or substituents, and x is a real number greater than 1. The variable x may be selected so that the resulting polymer may have a number average molecular weight of about 500 to 2,000,000 g / mol. The variable x may be 3 to 50,000.

[0032] The polymer formed may have the residue of an anionic initiator group at the other end of the polymer chain. Such a residue may be based on any known initiator group, which may be added separately to the reaction mixture during the polymerization reaction or may be generated in situ. The initiator residue may have the formula: D, [ka] wherein D, R 2 and R 4 is as defined herein.

[0033] The prepared polymer has the formula [ka] where D is the residue of one or more anionic initiators. The prepared polymer may have a portion of the polymer chain with a phosphate attached to one end of the chain. Such a polymer may correspond to the formula: [ka] may correspond to one of In the formula, R 2 , R 3 , a, b, and x are as described herein; Z, independently in each occurrence, is hydrogen, a residue of an onium cation, a residue of a quenching agent, etc. Some of the polymer chains may have carboxylate groups at some of the ends of the chains. Such polymers have the formula: [ka] can correspond to In the formula, R 2 , R 3 , Z and x are as described herein; R 4 is independently in each occurrence a carbon-containing group that may contain heteroatoms or may be substituted with a functional group. The polymers prepared may include polymers with different initiators at one end of the chain as described herein.

[0034] R 1 is, separately in each occurrence, a carbon-containing group; R 1 Two or more of R may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms. 1 may, independently in each occurrence, be one or more alkyl, aryl, alkaryl, or aralkyl groups which may contain heteroatoms or one or more unsaturated moieties; R 1 Two or more of R may form a cycloalkyl group or a cyclic ring containing one or more aryl groups, and such groups may contain heteroatoms and / or unsaturated groups. 1 represents, separately in each occurrence, one or more C 1-20 Alkyl group, C 3-24 Cycloalkyl groups, C 5-24 Aryl group, C 6-24 Alkaryl group, C 6-24 R can be an aralkyl group. 1 represents, separately in each occurrence, one or more C1-12 Alkyl group, C 3-12 Cycloalkyl groups, C 5-12 Aryl group, C 6-12 Alkaryl group, C 6-12 R can be an aralkyl group. 1 represents, separately in each occurrence, one or more C 1-12 R can be an alkyl group. 1 is, separately in each occurrence, C, which may contain heteroatoms or one or more unsaturated moieties; 1-4 R can be an alkyl group. 1 may, at each occurrence independently, be one or more of a methyl, ethyl, propyl, or butyl group.

[0035] R 2 R, in each occurrence, is independently a carbon-containing group that may contain heteroatoms or one or more unsaturated moieties. 2 may, independently in each occurrence, be one or more alkyl, aryl, alkaryl, or aralkyl groups which may contain heteroatoms or one or more unsaturated moieties; R 2 Two or more of R may form a cycloalkyl group or a cyclic ring containing one or more aryl groups, and such groups may contain heteroatoms and / or unsaturated groups. 2 represents, separately in each occurrence, one or more C 1-20 Alkyl group, C 3-24 Cycloalkyl groups, C 5-24 Aryl group, C 6-24 Alkaryl group, C 6-24 R can be an aralkyl group. 1 represents, separately in each occurrence, one or more C 1-12 Alkyl group, C 3-12 Cycloalkyl groups, C 5-12 Aryl group, C 6-12 Alkaryl group, C 6-12 R can be an aralkyl group. 2 represents, separately in each occurrence, one or more C 1-12 R can be an alkyl group.2 is, separately in each occurrence, C, which may contain heteroatoms or one or more unsaturated moieties; 1-4 R can be an alkyl group. 2 may, at each occurrence independently, be one or more of a methyl, ethyl, propyl, or butyl group.

[0036] R 3 One or more of the R groups may be carbon-containing groups that may have one or more hydrogen or fluorine atoms bonded to a carbon atom, and the carbon-containing groups may include one or more of unsaturated groups, electrophilic groups, nucleophilic groups, anionic groups, cationic groups, zwitterionic groups, hydrophobic groups, hydrophilic groups, halogen atoms, natural minerals, synthetic minerals, carbon-based particles, UV-active groups, polymers with surfactant properties, and polymerization initiators or reactive heterocyclic rings. The functional groups may be linked to the ring by a linking group (M) that functions to link the functional portion of the group to the cyclic ring. Exemplary linking groups may be carbon-containing groups, ethers, thioethers, polyethers (such as polyalkene ethers), etc. 3 one or more of R may be halogen-substituted alkyl groups; sulfonate-substituted alkyloxy groups; alkylsulfonate alkyloxy groups; alkyl ether-substituted alkyl groups; polyalkylene oxide-substituted alkyl groups; alkyl ester-substituted alkyl groups; alkenyloxy-substituted alkyl groups; aryl ester-substituted alkyl groups; alkenyl groups; cyano-substituted alkyl groups; alkenyl ester-substituted alkyl groups; cycloalkyl-substituted alkyl groups; aryl groups; heteroatoms including cycloalkenyl, alkyl ether-substituted alkyl groups; hydroxyl-substituted alkyl groups; alicyclic-substituted alkenyl groups; aryl-substituted alkyl groups; haloaryl-substituted alkyl groups; aryloxy-substituted alkyl groups; alkyl ether-substituted alkaryl groups; heteroatoms including alicyclic-substituted alkyl groups; aryl-substituted alkyl groups, alkylamido-substituted alkyl groups, alkenyl-substituted alicyclic groups; 3may form a cyclic ring that may optionally contain one or more unsaturated groups; an alkyl substituted betapropiolactone group that may optionally contain one or more ether groups and / or one or more hydroxyl groups; a glycidyl ether group, or a benzocyclobutenyl substituted alkyl group optionally substituted with one or more ether groups. 3 corresponds to a formula where all of the R on one carbon atom are hydrogen. 3 may both be H, and one or both R on the other carbon atom 3 is optionally replaced by C 1-40 Aliphatic, optionally substituted C 1-20 R may be heteroaliphatic, optionally substituted aryl, or both. 3 The groups can optionally be joined together to form an optionally substituted ring, optionally containing one or more heteroatoms. 3 One or two of the groups may be alkyl and the others may be hydrogen. 1-20 Alkyl group, C 1-12 Alkyl group, C 1-8 Alkyl group, C 1-4 The R groups on different carbon atoms can be alkyl groups, and the alkyl groups can contain unsaturation, heteroatoms, or heteroatom-containing functional groups. 3 One or two of the R groups may be methyl or ethyl, and the other may be hydrogen. 3 can be methyl, but other R 3 is hydrogen.

[0037] R 4 R is, independently in each occurrence, a carbon-containing group that may contain heteroatoms or be substituted with functional groups. 4 may, independently in each occurrence, be one or more alkyl, aryl, alkaryl, or aralkyl groups which may contain heteroatoms or one or more unsaturated moieties; R 4 Two or more of R may form a cycloalkyl group or a cyclic ring containing one or more aryl groups, and such groups may contain heteroatoms and / or unsaturated groups. 4represents, separately in each occurrence, one or more C 1-20 R can be an alkyl group. 4 represents, separately in each occurrence, one or more C 1-12 R can be an alkyl group. 4 represents, separately in each occurrence, one or more C 1-12 R can be an alkyl group. 4 is, separately in each occurrence, C, which may contain heteroatoms or one or more unsaturated moieties; 1-4 R can be an alkyl group. 4 R, in each occurrence, can be independently one or more of a methyl, ethyl, propyl, or butyl group. 4 can form an acrylate group with the carbonyloxy moiety to which it is attached.

[0038] The formed polymer compositions may have low polydispersity, for example, a polydispersity index (PDI) of 3.5 or less, 3.0 or less, 2.5 or less, 2.2 or less, 2.0 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, or 1.05 or less. The formed polymer compositions may have a PDI of 1.05 or more, 1.1 or more, 1.2 or more, 1.5 or more, or 2.0 or more. The listed PDI values ​​are measured by GPC (gel permeation chromatography) and calculated using standard software packages. Polydispersity is calculated from Mn (number average molecular weight) and Mw (weight average molecular weight) using the formula Mw / Mn. PDI values ​​can be calculated without including 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.

[0039] The prepared polymers may have a number average molecular weight of greater than about 500 g / mol, 1,000 g / mol, 5,000 g / mol, 10,000 g / mol, 17,000 g / mol, 20,000 g / mol, 25,000 g / mol, 50,000 g / mol, 100,000 g / mol, 200,000 g / mol, 300,000 g / mol, or 500,000 g / mol, when measured as disclosed herein. The prepared polymers may have a number average molecular weight of up to 2,000,000 g / mol or up to 1,000,000 g / mol. The prepared polymers may have weight average molecular weights of greater than about 500 g / mol, 1,000 g / mol, 5,000 g / mol, 10,000 g / mol, 17,000 g / mol, 20,000 g / mol, 25,000 g / mol, 50,000 g / mol, 100,000 g / mol, 200,000 g / mol, 300,000 g / mol, 500,000 g / mol, 600,000 g / mol, or 700,000 g / mol, when measured as disclosed herein. The prepared polymers may have number average molecular weights of 2,000,000 g / mol or less, or 1,000,000 g / mol or less. Molecular weights are measured by GPC (gel permeation chromatography) and calculated using standard software packages using THF as the solvent and referencing monodisperse polymethyl methacrylate standards.

[0040] Polymers containing beta-lactone residues are disclosed. Functional groups on the beta-lactone can provide functionality to polymers and copolymers prepared from the beta-lactone. The functional groups can act as polymerization initiators, improve adhesion of the polymer to a particular substrate or polymer system, improve hydrophobic or hydrophilic properties, improve hardness or scratch resistance, polymerization catalysts, and the like. Beta-lactone polymers and copolymers can function as intermediate layers in multilayer films, including those films having layers of different polymers. Beta-lactone polymers and copolymers can degrade under certain conditions, allowing the other layers to be easily separated for reuse in recycling. Beta-lactone polymers and copolymers can function as intermediate layers between other polymer coatings and substrates. Beta-lactone polymers and copolymers can degrade under certain conditions, allowing the substrate to be easily separated from other coating layers for reuse in recycling. Beta-lactone polymers and copolymers can be used as outer film or coating layers that can be degraded, or such outer layers can be functionalized to provide a desired set of properties to the structure.

[0041] The polymerizable composition may include: a. one or more beta-lactones; and b. one or more salts or zwitterions comprising one or more onium cations and one or more phosphate anions.

[0042] The beta-lactone that may be in the polymerizable composition and that may be used to prepare the polymer may be any beta-lactone that polymerizes under the conditions defined in this application. The beta-lactone may have the general formula: [ka] where R 3 is as mentioned above.

[0043] Homopolymers prepared from the disclosed beta-lactones are disclosed. Copolymers of two or more beta-lactones are disclosed. Compositions are disclosed that include copolymers of one or more of the disclosed beta-lactones with one or more monomers reactive with one or more of the beta-lactones. Compositions are disclosed that include copolymers of one or more of the disclosed beta-lactones with one or more monomers reactive with one or more of the beta-lactones. Such copolymers may include a plurality of one or more diols, difunctional polyalkylene oxides, amine-terminated polyalkylene oxides, one or more difunctional polyesters, lactams, lactides, cyclic lactones, cyclic anhydrides, cyclic ether epoxides, episulfides, aziridines, (meth)acrylates, valerolactones, butyrolactones, glycolides, substituted glycolides, or polyethers. Such comonomers may be one or more of epoxides, oxiranes, lactams, and lactides. The comonomer may be one or more cyclic anhydrides, including succinic anhydride, methylsuccinic anhydride, methyldiglycolic anhydride, methylglutaric anhydride, maleic anhydride, phthalic anhydride, citraconic anhydride, and trans-1,2-cyclohexanedicarboxylic anhydride. These copolymers may contain units derived from beta-propiolactone. The disclosed copolymers may be block copolymers, random copolymers, or one or more chains that may be grafted onto the polymer backbone.

[0044] One or more beta-lactones [ka] The one or more beta-lactones may be [ka] wherein R 10 is R 3 The one or more beta-lactones may be the same as [ka] It can be, where Ar is any optionally substituted aryl group and R 12 -H, optionally substituted C 1-20 Aliphatic, optionally substituted C 1-20 heteroaliphatic and optionally substituted aryl, R 13 is a fully or partially unsaturated C 2-20 It is a straight chain aliphatic group. The polymer can be prepared from a mixture of beta-propiolactone and pivalolactone. [ka]

[0045] One or more beta-lactones [ka] It could be. The polymer has the formula: [ka] It can be prepared from beta propiolactone and beta lactone.

[0046] The polymer can be prepared from a mixture of beta-lactones, where the beta-lactones are provided as a mixture of positional isomers. Any of the above-mentioned beta-lactone comonomers may be provided in combination with their positional isomers. When the beta-lactone comonomers are provided as a mixture of positional isomers, the positional isomer having the largest substituent on the carbon adjacent to the ring oxygen atom is present in molar excess relative to the other positional isomers. The major positional isomer is present in a ratio of 2:1 or greater relative to the minor positional isomer, at least 3:1, at least 5:1, at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, or at least 100:1 relative to the minor positional isomer.

[0047] The polymer may be prepared from a mixture of beta-lactone and one or more cyclic ethers, including tetrahydrofuran, substituted tetrahydrofuran, and epoxides. The epoxides may be substituted epoxides. The epoxides may be one or more of ethylene oxide, propylene oxide, butylene oxide, 4-vinylcyclohexene oxide, 4-ethylcyclohexene oxide, limonene oxide, glycidol ethers, glycidol esters, or cyclohexene oxide. The epoxides may be represented by the formula: [ka] where R 3 is as defined herein. The one or more substituted epoxides may be of the formula: [ka] where R 10 is as defined above. The one or more substituted epoxides are [ka] The one or more substituted epoxides may be of the formula: [ka] may correspond to one of In the formula, Ar, R 10 , R 12 , and R 13 wherein each of the is as defined above. The one or more substituted epoxides have the formula: [ka] It may correspond to one of the following:

[0048] Disclosed are methods for polymerizing betapropiolactone (BPL) and / or substituted betapropiolactones using the initiators described herein, optionally in combination with one or more additional comonomers (collectively, monomers), which may or may not be covalently bound in the final polymer product.

[0049] The polymerizable composition includes one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions. The phosphate anions can initiate the polymerization of one or more beta-lactones and comonomers polymerizable therewith. The presence of one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions can promote the in situ formation of carboxylate anions that can initiate the polymerization of such monomers. The presence of one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions can result in the preparation of a polymer, where both the phosphate anions and the carboxylate anions initiate the polymer chain. The one or more salts or zwitterions of one or more onium cations and one or more phosphate anions can function to catalyze or accelerate the polymerization of the monomers.

[0050] The onium cation can be derived from any onium compound that enhances the formation of the polymer disclosed herein. The onium cation can include one or more of nitrogen, phosphorus, sulfur, antimony, or arsenic. The onium cation can include one or more of nitrogen, phosphorus, or sulfur. The onium cation can include one or more of nitrogen or phosphorus. The onium cation can include one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations. The onium cation can include one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations. The one or more quaternary nitrogen-containing cations or quaternary phosphonium cations can include one or more tetraalkylammonium anions or tetraalkylphosphonium anions.

[0051] The one or more quaternary nitrogen-containing cations may contain four carbon-containing groups bonded to the amine nitrogen, and two or more of the carbon groups may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms. The one or more quaternary nitrogen-containing cations may contain one or more nitrogen-containing heterocycles. The one or more nitrogen-containing heterocycles may contain optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium moieties. The one or more quaternary nitrogen-containing cations may contain one or more optionally substituted imidazolium. The one or more quaternary nitrogen-containing cations may include one or more ammonium, amidinium, and guanidinium cations. The one or more quaternary ammonium cations may be represented by the formula [ka] can correspond to R 1 is as defined herein. The one or more guanidinium cations are of the formula: [ka] can correspond to R 1 is as defined herein.

[0052] The one or more quaternary ammonium cations may be one or more tetraalkylammonium anions or onium cations based on nitrogen-containing heterocycles, such as optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium. The one or more quaternary ammonium cations may be one or more tetraalkylammonium or N-alkyl-substituted imidazolium cations. The one or more tetraalkylammonium cations may contain one or more of methyl, ethyl, propyl, or butyl groups. The butyl group may be n-butyl or tert-butyl. The one or more tetraalkylammonium cations may be tetramethylammonium, tetraethylammonium, or tetratert-butylammonium.

[0053] The one or more quaternary phosphonium cations can be one or more phosphonium cations containing four carbon-containing groups. The one or more quaternary phosphonium cations can be one or more tetraalkylphosphonium cations. The one or more quaternary phosphonium cations can be represented by the formula: [ka] where R 1 is as defined herein.

[0054] The phosphate anion can be any phosphate anion that allows one or more onium cations and one or more salts or zwitterions of the one or more phosphate anions to perform the functions disclosed herein. The phosphate anion can have 1 to 3 onium cations attached to oxygen groups. The phosphate anion can have 0 to 2 optionally substituted carbon-containing groups attached to oxygen groups. The phosphate anion has the formula: [ka] where R 2 are as defined herein, a is an integer from 1 to 3, and b is an integer from 0 to 2. The variable a can be 1, 2, or 3. The variable b can be 0, 1, or 2. The sum of a and b is 3. The anion can be a mixture of compounds where a and b are different for each anion in the mixture. The phosphate anion has the formula: [ka] where R 2 is as defined herein.

[0055] The one or more salts of one or more onium cations and one or more phosphate anions can be any such salt that provides the properties disclosed herein. Such salts are formed from the phosphate anions and onium cations disclosed herein, as well as the various anions and cations described herein. The one or more salts of one or more onium cations and one or more phosphate anions can be represented by the formula: [ka] can correspond to In the formula, R 2 is, separately in each occurrence, an optionally substituted hydrocarbyl group; Z' is, separately in each occurrence, an onium cation as described herein, including the mutations as described herein; a is, separately in each occurrence, 1, 2, or 3; b is, separately in each occurrence, 0, 1, or 2; and the sum of a and b is 3.

[0056] The one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions have the formula: [ka] corresponds to one of In the formula, R 1 , R 2 , a, and b are as defined herein. The one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions have the formula: [ka] may correspond to one of In the formula, R 1 and R 2 is as defined herein. The one or more salts of the one or more quaternary nitrogen-containing cations and the one or more phosphate anions have the formula: [ka] where R 1 and R2 is as defined herein. The one or more salts of the one or more quaternary nitrogen-containing cations and the one or more phosphate anions have the formula: [ka] where R 1 and R 2 is as defined herein.

[0057] The polymerizable composition may include 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 having bonds to the anion and the cation. The one or more zwitterions may be any of the defined zwitterions that provide the properties disclosed herein. Such zwitterions may be 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 hydrocarbylene moiety between the anion and the cation may be represented by the formula: [ka] can correspond to In the formula, R 2 , R 5 , Z′, a, and b are as defined herein. Zwitterions have the formula: [ka] may correspond to one of In the formula, R 1 , R 2 , R 5 , a, and b are as defined herein. The one or more zwitterions of the one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and the one or more phosphate anions are represented by the formula: [ka] may correspond to one of In the formula, R 1 , R 2 , and R 5 is as defined herein. The one or more zwitterions comprising one or more quaternary nitrogen-containing cations and one or more phosphate anions have the formula: [ka] where R 1 , R 2 , and R 5 is as defined herein. The one or more zwitterions of the one or more quaternary nitrogen-containing cations and the one or more phosphate anions have the formula: [ka] where R 1 , R 2 , and R 5 is as defined herein. The one or more zwitterions of the one or more quaternary nitrogen-containing cations and the one or more phosphate anions have the formula: [ka] where R 1 , R 2 , and R 5 is as defined herein. 5 R is, separately in each occurrence, a carbon-containing moiety that may be optionally substituted. 5 may, independently in each occurrence, be one or more alkylene, arylene, alkarylene, or aralkylene groups which may contain heteroatoms or one or more unsaturated moieties; R 5 Two or more of R may form a cycloalkylene group or a cyclic ring containing one or more arylene groups, and such groups may contain heteroatoms and / or unsaturated groups. 5 represents, separately in each occurrence, one or more C 1-20 Alkylene group, C 3-24 Cycloalkylene group, C 5-24Arylene group, C 6-24 Alkalylene group, C 6-24 R may be an aralkylene group. 5 represents, separately in each occurrence, one or more C 1-12 Alkylene group, C 3-12 Cycloalkylene group, C 5-12 Arylene group, C 6-12 Alkalylene group, C 6-12 R can be an aralkyl group. 5 represents, separately in each occurrence, one or more C 1-12 R can be an alkyl group. 5 is, separately in each occurrence, C, which may contain heteroatoms or one or more unsaturated moieties; 1-4 R can be an alkylene group. 1 may, at each occurrence independently, be one or more of a methylene, ethylene, propylene, or butylene group.

[0058] The polymerizable composition may include one or more of an end-capping agent, a quenching agent, a chain extender, or a branching agent. The quenching agent may be any compound that terminates the active end of a polymer during polymerization to stop the continued growth of the polymer. The quenching agent may be one or more of an inorganic acid, an organic acid, and an acidic resin or solid. Quenching agents include HCl, H 2The quenching agent may be SO4, RSO3H, HBr, H3PO4, an acidic resin, or an acidic inorganic solid. The quenching agent may be a sulfonic acid derivative, boric acid or a boric acid derivative, or phosphoric acid or a phosphoric acid derivative. The quenching agent may be a sulfonic acid. The sulfonic acid may be one or more of p-toluenesulfonic acid (also known as pTSA or tosylic acid), methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, trifluoromethylsulfonic acid, 4-nitrophenylsulfonic acid, sulfoacetic acid, cumenesulfonic acid, xylenesulfonic acid, 3-amino-1-propanesulfonic acid, 2-sulfanylethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, benzenesulfonic acid, 4-hydroxybenzenesulfonic acid, cyclohexanesulfonic acid, 4-ethylbenzenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, 4-methylmetanilic acid, 1-naphthalenesulfonic acid, or perfluorooctane sulfonic acid. The quenching agent can be methanesulfonic acid, p-toluenesulfonic acid, or sulfamic acid. The acid used as the quenching agent can act by protonating the active chain end of the polymer (e.g., forming an -OH or COH group), with the anion of the acid acting as a counterion to the polymer-bound cation from the initiator.

[0059] The quenching agent may be a phosphoric acid derivative having at least one acidic hydrogen atom. The phosphoric acid derivative may be one or more of phosphoric acid, pyrophosphate, triphosphate, alkyl or aryl derivatives of phosphoric acid, alkyl or aryl derivatives of pyrophosphate, or alkyl or aryl derivatives of triphosphate. The quenching agent may be a boron-containing compound. The quenching agent may be fluoroboric acid. The quenching agent may be an acid associated with a solid support. The solid-supported acid may include an inorganic solid selected from silica, alumina, zirconia, titanium, zeolite, metal oxide, and clay. The quenched composition may form a polymer complex with the inorganic solid quenching agent. The method may include adding a polymer-supported acid as the quenching agent. The polymer support may include a polymer derived from at least one of styrene, chloromethylated styrene, and divinylbenzene monomer. The polymeric solid support can be one or more of polystyrene, polysulfone, nylon, poly(chloromethylstyrene), polyolefin, polyacrylic acid, polymethyl methacrylate, and cross-linked ethoxylate acrylate resin. When the quenching agent comprises a solid, the method can include flowing the reaction stream containing the unquenched polymer through a fixed bed of the solid quenching agent.

[0060] The end-capping agent may include an electrophilic organic compound. The end-capping agent may include one or more of organic halides, organic sulfonates, haloalkylsilanes, aniline derivatives, phosphoric acid derivatives, boric acid derivatives, and isophthalic acid derivatives as disclosed herein. The electrophilic organic compound caps the growing chain end and releases an anion that satisfies the charge of the covalently bound cationic group. The compound R-X' can react with the anionic chain end (e.g., form an -OR or CO2R group), while the free anion X'- acts as a counterion to the polymer-bound cation. The end-capping agent may include an alkyl halide, such as an aliphatic chloride, bromide, or iodide. The end-capping agent may be a group of the formula R n -X h wherein R n is an optionally substituted C 1-40is an aliphatic group, and X h is selected from Cl, Br, or I. The end-capping agent is R p -CH2-X h wherein R p is -H or an optionally substituted radical selected from the group consisting of aliphatic, aryl, heterocyclic, and heteroaryl. The end-capping agent can be one or more of methyl bromide, methyl iodide, allyl chloride, allyl bromide, benzyl chloride, and benzyl bromide. The end-capping agent can include an organic sulfonate. The organic sulfonate can be a compound of the formula R n OSO2R q where R n is as defined above, and R q is -H or an optionally substituted radical selected from the group consisting of aliphatic, aryl, heterocyclic, and heteroaryl. The quenching agent may include methyl triflate. The end-capping agent may be comprised of an organic sulfate. The organic sulfate may be represented by the formula R n OSO2OR n where Rn is as defined above. The quenching agent may include a dialkyl sulfate, such as dimethyl sulfate or diethyl sulfate.

[0061] The end-capping agent may be a silane, which may include a compound containing a silyl or siloxy group. The end-capping agent may be a thermally stable aniline derivative, which may include an azole, such as one selected from the group consisting of benzothiazole, benzoxazole, benzimidazole, 2-aminothiophenol, o-phenylenediamine, and 2-aminophenol. Exemplary end-capping agents may further include phosphates, such as trimethyl phosphate and triphenyl phosphate. Exemplary end-capping agents may also further include other additives and stabilizers, such as isophthalic acid.

[0062] The polymerizable composition may include a chain extender or branching agent. The chain extender or branching agent may be added as a quenching agent. Analogs of the above-described end-capping agents, which have two or more suitable reactive functional groups within a single molecule, can be used as quenching agents, and they can act as chain extenders or branching agents, respectively. Quenching with a difunctional chain extender results in reaction with the carboxylate ends of two separate polymer chains, leading to the formation of a dimeric chain-extended product. It should be understood that difunctional analogs of any of the above-described quenching agents can be used with similar effect. When a trifunctional or higher functionality end-capping agent is used, branched, star-shaped, or comb-shaped polymer compositions can be obtained. When the method involves a continuous process using a plug flow reactor, the quenching agent can be added at specific points along the length of the reactor.

[0063] The formed polymer is prepared from a ratio of monomer to initiator, such as phosphate anion and / or carboxylate anion, where the molar ratio of monomer to initiator is selected to prepare a polymer of the desired molecular weight. For example, the molar ratio can be 10:1 or greater, 100:1 or greater, 1,000:1 or greater, 2,000:1 or greater, 3,000:1 or greater, 4,000:1 or greater, 5,000:1 or greater, 7,500:1 or greater, 10,000:1 or greater, 15,000:1 or greater, 20,000:1 or greater, 30,000:1 or greater, 40,000:1 or greater, 50,000:1 or greater, 75,000:1 or greater, or 100,000:1 or greater. The initiator is contacted with the monomer for a sufficient time to prepare a polymer of the desired molecular weight. The method can include allowing the initiator to contact the monomer until a polymer composition having a number average molecular weight Mn described herein is formed. The Mn of the polymer composition is referred to as measured by gel permeation chromatography (GPC) using THF as the solvent and referenced to monodisperse polymethyl methacrylate standards.

[0064] The method may include allowing the initiator to contact the monomer for a predetermined time interval. The method may include monitoring the progress of the polymerization reaction (e.g., by analyzing an aliquot from the reaction mixture by a suitable technique such as GPC or by utilizing an in situ monitoring technique). The method may include monitoring the increase in molecular weight of the polymer and / or monitoring the decrease in monomer concentration. The method may include stopping the reaction when the molecular weight of the polymer composition (or a proxy for molecular weight, such as reaction viscosity) reaches a desired value or exceeds a predetermined threshold. The method may include monitoring the depletion of monomer until the concentration of monomer reaches a desired concentration or falls below a predetermined threshold. The method may include stopping the reaction when the concentration of monomer reaches a desired concentration or falls below a predetermined threshold.

[0065] The monomers may be contacted with the initiator in a solvent. The solvent may include polar aprotic solvents such as amides, nitriles, and sulfoxides, protic liquids such as water or alcohols, ethers, esters, ketones, or aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, or fluorinated hydrocarbons. 4-12 The solvent may include an aliphatic hydrocarbon, an ether, or a chlorinated hydrocarbon. The solvent may include ether petroleum ether, isobutane, pentane, hexane, or heptane, or a higher aliphatic hydrocarbon. The solvent may include isobutane or hexane. The solvent may be substantially anhydrous. The solvent may include an ether selected from tetrahydrofuran, 1,4 dioxane, 1,3-dioxane, dimethoxyethane, diglyme, triglyme, tetraglyme, 1,3 dioxolane, t-butyl methyl ether, and diethyl ether. The solvent may include tetrahydrofuran, which may be anhydrous.

[0066] The solvent may be a non-polar solvent. The solvent may be a non-polar ether. The solvent may be an acyclic ether. The solvent may have a polarity of less than 0.2, as disclosed above. The solvent may be a dialkyl ether or an alkylcycloalkyl ether. The alkyl group may be branched or straight-chain. The alkyl group may not contain unsaturated groups. Exemplary non-polar solvents include methyl tert-butyl ether, dimethyl ether, diethyl ether, cyclopentyl methyl ether, ethyl acetate, and diisopropyl ether.

[0067] The initiator may have low solubility in some solvents, and the resulting polymer may exhibit a higher molecular weight than expected, since the effective ratio of monomers in the reaction system may be higher due to some of the charged initiator not being soluble in the reaction solvent.

[0068] The method may include contacting the monomer with the initiator without a solvent. Polymerization may be carried out with neat monomer. The method may include contacting the monomer in a solvent system in which the initiator is not soluble. The method may include contacting the comonomer with a suspension of solid particles comprising the initiator. The method may include contacting the neat monomer with solid particles comprising the initiator, the solid particles being insoluble in the neat monomer. It is desirable to add the initiator, salt, or zwitterion disclosed herein as a liquid or in a liquid carrier. The initiator, salt, or zwitterion disclosed herein can be heated to a temperature at which it is liquid, or dissolved in a carrier or solvent and then added to the reaction mixture. The temperature at which the initiator, salt, or zwitterion disclosed herein is added to the solvent or carrier, or the temperature at which it becomes liquid, may be higher than the process reaction temperature. To reduce the time to initiate the reaction, it is advantageous to add the initiator as a liquid. This reduces or eliminates the need for an induction period.

[0069] The initiator and monomer may be contacted at low ambient temperature or at elevated temperature. The mixture may be maintained at a temperature of about 30°C or higher, about 40°C or higher, about 50°C or higher, about 60°C or higher, about 70°C or higher, about 80°C or higher, or about 100°C or higher. The mixture may be maintained at a temperature of about 120°C or lower or about 100°C or lower. The mixture may be maintained at a temperature of about 20°C or lower, about 15°C or lower, about 10°C or lower, about 5°C or lower, about 0°C or lower, about -10°C or lower, or about -20°C. The method may include removing heat from the mixture to maintain the desired temperature. The method may include varying the temperature of the polymerization mixture over time during the course of the process. The method may include cooling the mixture to maintain the desired temperature. The method may include varying the temperature of the polymerization mixture over time during the course of the process.

[0070] Polymerization can be carried out at elevated pressures. This can allow the process to be carried out at temperatures above the boiling points of certain reaction mixture components (e.g., solvent, monomer) and / or can aid in the separation of volatile components when the pressurized process stream or reaction vessel is depressurized. The monomers may be contacted with the initiator at pressures greater than 1 bar (0.1 MPa), about 2 bar (0.2 MPa) or greater, about 3 bar (0.3 MPa) or greater, about 5 bar (0.5 MPa) or greater, about 10 bar (1.0 MPa) or greater, about 15 bar (1.5 MPa) or greater, about 20 bar (2.0 MPa) or greater, about 30 bar (3.0 MPa) or greater, or about 40 bar (4.0 MPa) or greater. The pressure may be about 50 bar (5.0 MPa) or less, about 60 bar (6.0 MPa) or less, about 70 bar (7.0 MPa) or less, about 80 bar (8.0 MPa) or less, about 90 bar (9.0 MPa) or less, or about 100 bar (10.0 MPa) or less. The pressure may be applied by pressurizing the headspace of the reactor in contact with the reaction mixture (e.g., by introducing pressurized inert gas). The pressure may be applied by heating the mixture in a limited volume. The pressure may be maintained by applying pressure to a hydrostatically filled reaction vessel. Two or more of these approaches may be used. The pressure may be controlled by application of a backpressure regulator or other pressure relief system.

[0071] The methods disclosed herein can be carried out in a batch process, a continuous process, or a hybrid of a batch and continuous process (e.g., a fed-batch reaction). The method can include feeding one or more components to a polymerization mixture over time. Monomers, oligomers, end-capping agents, chain extenders, chain transfer agents, or crosslinkers can be added to the polymerization mixture over time (either continuously or in one or more separate additions). The composition of the added monomers can vary over time. Such methods can be characterized in that the produced polymer composition comprises a tapered copolymer or a block copolymer.

[0072] The method may include a fed-batch process, which may involve dissolving or suspending an initiator in a reaction vessel (optionally with a solvent and / or an initial charge on the monomer) and then feeding the monomer, chain extender, chain transfer agent, or crosslinker to the initial mixture at a controlled rate. Such a method may be useful for controlling the exotherm associated with the ring-opening polymerization of some of the monomers and maintaining safe operating conditions. The particular monomer may be fed at a rate determined, at least in part, by the rate of exotherm observed in the reaction mixture. The monomer may be fed continuously to the process. The monomer may be fed discontinuously to the process (e.g., by separate addition or at varying rates). The monomer may be fed for a period of time and then stopped at an interval prior to the end of the polymerization.

[0073] The method may include a continuous flow process and may include continuously adding an initiator to a reaction stream of monomer. The combined initiator and monomer stream may then be directed through a continuous reactor with a contact time and temperature profile sufficient to produce the desired degree of polymerization. The method may include adding more initiator, additional monomer, solvent, or other reaction components at locations along the length of the continuous reactor.

[0074] The method may include a continuous flow process and may include contacting a reaction stream containing an initiator and a monomer in an extruder. The combined initiator-monomer stream may be directed through the extruder with a contact time and temperature profile sufficient to consume substantially all of the monomer. The method may include a reactive extruder having a temperature gradient between its inlet and outlet. The temperature toward the extruder outlet may be higher than the temperature at the extruder inlet. In such a process, no solvent is present in the reaction stream, and the outlet from the extruder contains molten polymer. The molten polymer stream from the extruder may be fed to a pelletizer to produce solid polymer pellets. The method may include a reactive extruder coupled to a pre-reactor that feeds an inlet to the extruder. The pre-reactor may include a plug flow reactor, a batch reactor, or a fed-batch reactor. Additionally, two pre-reactors may feed a single extruder. A single pre-reactor may feed two or more reactive extruders.

[0075] The method may include a continuous flow process and may involve contacting a reaction stream containing an initiator and a monomer in one or more reactors. The method may include a slurry batch reactor, a slurry continuously stirred tank reactor, or a slurry loop reactor. The monomer may be polymerized in a liquid-phase polymerization reactor and / or a gas-phase polymerization reactor. As polymer chains develop during polymerization in the reactor, solid particles of solid polymer may be produced in the reactor, thereby forming a slurry. The polymer particles in the slurry may have one or more desired melting, physical, rheological, and / or mechanical properties, such as density, melt index (MI), melt flow rate (MFR), comonomer content, molecular weight, and crystallinity. Depending on the application to which the polymer is to be applied, different particle properties may be desirable. Selection and control of reaction conditions in the reactor, such as temperature, pressure, chemical concentration, polymer production rate, and initiator type, may affect the properties of the polymer particles.

[0076] The disclosed method may include a step of quenching the polymerization reaction. The quenching agent may be added after a specified reaction time or when the polymer composition reaches a desired molecular weight (the Mn of the formed polymer composition exceeds a predetermined threshold). The quenching agent may be added when substantially all of the monomer has been consumed. If the method includes a continuous process utilizing a plug flow reactor, the quenching agent is added at a specific point along the length of the reactor.

[0077] The method includes adding an end-capping agent to quench the polymerization, as disclosed in PCT Application WO 2019 / 241596 A1, the entirety of which is incorporated herein by reference. The monomers can be polymerized so that the ends of the formed polymer chains have carboxylic acid or carboxylate functional groups. The end groups react with the end-capping agent. The end-capping agent can make the formed polymer more stable.

[0078] The quenching, end-capping, crosslinking, or chain extender may be added to the reaction mixture in an amount less than 10 molar equivalents relative to the amount of initiator added to the polymerization process, for example, 0.1 to 10 molar equivalents, 0.1 to 2 molar equivalents, or 1 to 2 molar equivalents, or about 1 molar equivalent relative to the amount of initiator.

[0079] In processes in which a comonomer is present with the beta-lactone, the comonomer may be added with the beta-lactone at the beginning of the process; for example, a batch polymerization may be carried out using a defined mixture of beta-lactone and one or more comonomers. The process may include varying the monomer composition over time by adding additional monomers to the polymerization mixture. Such addition may include continuous addition of BPL beta-lactone, a comonomer, or a mixture of beta-lactone and comonomer. Such addition may include batchwise addition of beta-lactone, a comonomer, or a mixture of beta-lactone and comonomer. Depending on the relative polymerization rates of the comonomers under the provided reaction and polymerization conditions, such processes may result in random, tapered, or block copolymers.

[0080] The method may include the use of a chain extender, chain transfer agent, and / or crosslinker. The method may include contacting betapropiolactone (and optional comonomers) with an initiator in the presence of one or more chain transfer agents. A chain transfer agent is defined as any substance or reagent capable of terminating the growth of one polymer chain and initiating the polymerization of a new polymer chain. In living polymerization, this may be a reversible process, with the net effect being that, on average, all chains in the composition grow at a similar rate. Chain transfer agents can be used to control the molecular weight of the resulting polymer composition, optimize the amount of catalyst used, and / or control the polydispersity of the resulting polymer composition. Chain transfer agents can also be used to introduce additional functional groups at the chain ends (e.g., for subsequent crosslinking or chain extension reactions, or to impart specific physical properties such as hydrophilicity or hydrophobicity), examples of the latter including chain transfer agents with radically polymerizable functional groups such as vinyl groups, perfluorinated moieties, or siloxyl groups.

[0081] The chain transfer agent (CTA) may include an acidic compound. Such acidic compounds may be characterized by their conjugate base being nucleophilic. The conjugate base of the provided acidic chain transfer agent may be sufficiently nucleophilic to ring-open the beta-propiolactone (or react with the provided comonomer). Exemplary chain transfer agents include carboxylic acids, sulfonic acids, phosphoric acids, phosphonic acids, phosphinic acids, thiocarboxylic acids, dithiocarboxylic acids, thiols, phenols, and the like. The chain transfer agent may be represented by the formula Y'-T-(Y') rwhere each Y' is independently an acidic functional group (or a salt formed by deprotonation of such a group), -T- is a polyvalent moiety, and r is 0 or an integer from 1 to 10. Y' may be independently selected from carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid, phosphinic acid, thiocarboxylic acid, dithiocarboxylic acid, thiol, and phenolic -OH groups (or anions formed by deprotonation of any of these). Chain transfer agents may include molecules with two or more functional groups capable of acting as chain transfer agents (dicarboxylic acid, tricarboxylic acid). Chain transfer agents may include carboxylic acids such as formic acid, acetic acid, propionic acid, 3-hydroxypropionic acid, 3-hydroxybutanoic acid, lactic acid, benzoic acid, acrylic acid, and methacrylic acid. Chain transfer agents may include phenols, thiols, or derivatives thereof.

[0082] The CTA may be present at the beginning of the reaction or may be added during the polymerization process (continuously at a constant or variable rate, or in small increments). The addition of the CTA may be used to control the molecular weight distribution of the polymer composition. The CTA may be added in small increments at one or more points in the reaction to provide a polymer composition with a bimodal or polymodal molecular weight distribution. The CTA may be added continuously during at least a portion of the polymerization process to provide a polymer composition with a broadened molecular weight distribution. When the CTA is added at the beginning of the polymerization reaction, the result is a polymer composition with a narrow PDI. The chain transfer agent can be provided in a molar ratio relative to the polymerization initiator of from about 1:1 to about 10,000:1, or from about 1:1 to about 10:1, e.g., 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 8:1, or 10:1, or from about 10:1 to about 100:1 (20:1, 30:1, 40:1, 50:1, 75:1, or 100:1), or from about 100:1 to about 1,000:1 (200:1, 300:1, 400:1, 500:1, 750:1, or 1000:1).

[0083] The polymerization method can be incorporated into a process for producing beta-lactone. Such an integrated process can have advantages in terms of energy efficiency and can result in a higher quality polymer product due to reduced introduction of water, oxygen, or other impurities. The method can include reacting ethylene oxide with carbon monoxide to form beta-propiolactone. Exemplary catalysts and methods for such processes are described in published patent applications: WO2013 / 063191, WO2014 / 004858, WO2003 / 050154, WO2004 / 089923, WO2012 / 158573, WO2010 / 118128, WO2013 / 063191, and WO2014 / 008232; U.S. Pat. Nos. 10,662,283, 5,359,081, and 5,310,948; and the publication "Synthesis of beta-Lactones," J. Am. Chem. Soc., vol. 124, 2002, pages 1174-1175, the entire contents of each of which are incorporated herein by reference. The method may include contacting ethylene oxide with carbon monoxide in the presence of a carbonylation catalyst and a solvent to provide a reaction stream containing beta-propiolactone, separating a product stream containing beta-lactone from the reaction stream, feeding the beta-lactone-containing reaction stream to a polymerization reactor, and contacting it with an anionic initiator to provide a second reaction stream containing the biodegradable polyester. Such an integrated carbonylation / polymerization process may be characterized in that substantially all of the carbonylation catalyst is removed from the reaction stream containing beta-propiolactone before feeding the stream to the polymerization reactor. Such an integrated carbonylation / polymerization process may be characterized in that at least a portion of the solvent in which the carbonylation process is carried out is present in the reaction stream containing beta-propiolactone and fed to the polymerization reactor. The method may include separating the solvent from the second reaction stream containing the polymer. The method may include returning the separated solvent to the carbonylation reaction. The process may be characterized in that the reaction stream comprising betapropiolactone contains residual ethylene oxide, and the betapropiolactone ethylene oxide mixture is fed to a polymerization reactor.Ethylene oxide may comprise a comonomer in BPL polymerization.

[0084] The methods described herein include contacting a beta-lactone and optional comonomer with one or more polymerization initiators, which may be generated in situ, that are one or more salts of one or more onium cations and one or more phosphate anions, zwitterions having one or more phosphate anions and one or more onium cations, or carboxylate salts of one or more onium cations. The carboxylate salts of onium cations may include any compound having the residue of an onium cation and a carboxylate group in salt form. The carboxylate moiety may have a hydrocarbyl group attached to a carbonyl group, which may be optionally substituted. The hydrocarbyl group may be an alkyl, aryl, or alkaryl group. The alkyl group may be optionally substituted with a substituent that does not interfere with the ability of the salt to function as an anionic initiator. 1-20 The hydrocarbyl group may be a C group which may be optionally substituted. 1-8 Straight or branched alkyl group, C 1-4 The onium cation may be a straight-chain or branched alkyl group, a methyl or ethyl group, or a methyl group. The onium cation may be any onium cation that forms a salt with the carboxylate, provided that the carboxylate does not prevent the carboxylate from forming an anion capable of initiating anionic polymerization. Exemplary oniums include one or more of onium cations containing nitrogen, phosphorus, sulfur, antimony, or arsenic. Exemplary oniums include one or more of nitrogen, phosphorus, or sulfur. The onium may contain one or both of nitrogen and phosphorus. The onium may contain nitrogen. Carboxylate salts of onium ions have the formula: [ka] Possible, In the formula, R 20 R is, independently in each occurrence, an optionally substituted hydrocarbyl group, w is, independently in each occurrence, a number greater than or equal to 1, and Z is an onium cation as described herein. 20R can be multivalent, having a valence of w. 20 R can be an alkyl, aryl, or alkaryl group. 20 is optionally substituted with substituents that do not interfere with the ability of the salt to function as an anionic initiator. 1-20 It can be straight or branched chain. 20 may be optionally replaced by C 1-8 Straight or branched alkyl group, C 1-4 A can be a linear or branched alkyl group, a methyl or ethyl group, or a methyl group. A, in each occurrence, can be a polymer chain containing units derived from a ring-opened beta-lactone. w, in each occurrence, can be a number greater than or equal to 2. W can be 1 to 6. W can be 2 to 6 or 2 to 3. The initiator can include an organic "onium cation" disclosed herein. The disclosed salts and zwitterions can function as initiators, generate initiators, and accelerate polymerization.

[0085] The disclosed method may include contacting a monomer with an initiator in the presence of a complexing agent. The addition of a complexing agent may improve the method by increasing the polymerization rate, improving polymer yield, or may result in improved polymer properties through control of properties such as molecular weight or polydispersity. Exemplary complexing agents include crown ethers and other macropolyheterocycles containing rings with multiple heteroatoms, such as -O-, -NR-, and -S-. Complexing agents include crown ethers. Exemplary crown ethers include, but are not limited to, those described in the paper "APPLICATIONS OF CROWN ETHERS IN INDUSTRIAL ANIONIC POLYMERIZATIONS" (Thomas Newton Montgomery, Jr.; Georgia Institute of Technology, December 1977). Exemplary complexing agents include 1,4,7,10,13,16-hexaoxacyclooctadecane (18-crown-6), 1,4,7,10,13-pentaoxacyclopentadecane (15-crown-5), 1,4,7,10-tetraoxacyclododecane (12-crown-4), dibenzo18-crown-6,21-crown-7, and derivatives or mixtures of any of these. The complexing agent may include 15-crown-5 or 12-crown-4. Crown ethers may be selected based on their ability to effectively complex with cationic functional groups present in the zwitterionic polymerization initiator used in the process. Complexing agents include macroheterocycles containing heteroatoms other than oxygen. Complexing agents may include crown ethers in which one or more oxygen atoms are replaced by nitrogen or sulfur atoms. Complexing agents may include aza-crown ethers such as 4,7,13,16,21-pentaoxa-1,10-diazabicyclo[8.8.5]tricosane, 1,4,8,12-tetraazaicyclopentadecane, and 1,4,10,13-tetraoxa-7,16-diazaicyclooctadecane. Complexing agents may include those described in U.S. Pat. No. 3,890,278, the entire contents of which are incorporated herein by reference. Complexing agents may include thia-crown ethers.

[0086] The complexing agent can be introduced at the beginning of the polymerization process or at any later time. The complexing agent can be added simultaneously with the initiator. The complexing agent can be provided as a mixture or solution with the polymerization initiator, and the mixture can be fed to the reaction as described above to add the initiator. The complexing agent can be used in an amount ranging from about 1:100 to about 100:1 molar ratio relative to the polymerization initiator, and in an amount ranging from 1:10 to 10:1, or 1:2 to 2:1 relative to the zwitterionic polymerization initiator. A chain transfer agent may also be utilized in the process, and the complexing agent can be provided in a molar ratio ranging from 1:10 to 10:1, 1:5 to 5:1, or 1:2 to 2:1 relative to the CTA.

[0087] When w is 2 or greater, the polymer formed may be chain extended with compounds having two or more epoxide and / or lactone groups. Chain extension and / or crosslinking may be carried out under conditions that result in ring opening of the epoxide and / or lactone groups, as disclosed herein.

[0088] Embodiment 1. A polymer comprising one or more polymer chains having ring-opened beta-lactone units, one end of a portion of the chain having a residue of a phosphate anion covalently attached to one end of the polymer chain, and one or more onium-containing cations at the other end of the portion of the chain.

[0089] 2. The polymer of embodiment 1, wherein the onium cation comprises one or more of nitrogen, phosphorus, sulfur, antimony, or arsenic.

[0090] 3. The polymer of embodiment 1 or 2, wherein the onium cation comprises one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations.

[0091] 4. The polymer of any of the preceding embodiments, wherein the one or more quaternary nitrogen-containing cations are amines having four carbon groups, and two or more of the carbon groups can form one or more aromatic or non-aromatic ring structures, which can optionally contain one or more heteroatoms.

[0092] 5. The polymer of any of the preceding embodiments, wherein the one or more nitrogen-containing cations comprise one or more of ammonium, amidinium, and guanidinium cations, or onium cations based on nitrogen-containing heterocycles.

[0093] 6. The polymer of any of the preceding embodiments, wherein the one or more nitrogen-containing cations comprise one or more onium cations based on a nitrogen-containing heterocycle, including optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium.

[0094] 7. The polymer of any preceding embodiment, wherein the one or more nitrogen-containing cations comprise one or more optionally substituted imidazoliums.

[0095] 8. The polymer of any preceding embodiment, wherein the one or more nitrogen-containing cations comprise one or more of one or more quaternary ammonium cations or one or more guanidinium cations.

[0096] 9. The polymer of any of the preceding embodiments, wherein the one or more quaternary ammonium cations are one or more tetraalkylammonium anions or N-alkyl substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium cations.

[0097] 10. One or more quaternary ammonium cations have the formula [ka] Corresponding to, In the formula, R 1 is, separately in each occurrence, a carbon-containing group; R 1 may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms.

[0098] 11 One or more guanidinium cations are represented by the formula [ka] where R corresponds to 1 is, separately in each occurrence, a carbon-containing group; R 1 may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms.

[0099] 12. One or more imidazolium cations have the formula [ka] Corresponding to, In the formula, R 1 is, separately in each occurrence, a carbon-containing group.

[0100] 13. The polymer of any preceding embodiment, wherein the one or more quaternary ammonium cations are one or more tetraalkylammonium anions or N-alkyl substituted imidazoliums.

[0101] 14. The polymer of any preceding embodiment, wherein the one or more phosphorus-containing cations are one or more quaternary phosphonium anion cations.

[0102] 15. One or more quaternary phosphonium cations have the formula: [ka] Corresponding to, In the formula, R 1 is, separately in each occurrence, a carbon-containing group; R 1 may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms.

[0103] 16. The phosphate anion has the formula; [ka] where R corresponds to 2 is, separately in each occurrence, an optionally substituted carbon-containing group; a is, separately in each occurrence, 1, 2, or 3; b is, separately in each occurrence, 0, 1, or 2; and the sum of a and b is 3.

[0104] 17. The phosphate anion is represented by the formula [ka] where R corresponds to 2 is, separately in each occurrence, a carbon-containing group.

[0105] 18. A polymer according to any one of the preceding embodiments, wherein one or more polymer chains have residues of an end-capping or quenching agent at some of the ends of the chains.

[0106] 19. The polymer of any of the preceding embodiments, wherein the end-capping agent is an organic halide, an organic sulfonate, a haloalkylsilane, an aniline derivative, a phosphoric acid derivative, and an isophthalic acid derivative.

[0107] 20. The polymer of any one of the preceding embodiments, wherein the polymer comprises a comonomer that polymerizes with the ring-opened betapropiolactone and / or substituted betapropiolactone.

[0108] 21. The polymer of any one of the preceding embodiments, wherein the comonomer is one or more of caprolactone, lactide, epoxide, oxetane, cyclic anhydride, cyclic ether, lactam, episulfide, aziridine, (meth)acrylate, valerolactone, butyrolactone, glycolide, and substituted glycolide.

[0109] 22. The polymer of any one of the preceding embodiments, wherein the comonomer is one or more epoxides.

[0110] 23. A polymer having the formula: [ka] corresponds to one of In the formula, R 2 is, separately in each occurrence, an optionally substituted carbon-containing group; R 3

[0023] The polymer of any one of the preceding embodiments, wherein x is, separately in each occurrence, hydrogen, carbon-containing which may optionally include one or more heteroatoms and / or substituents; a is, separately in each occurrence, 1, 2, or 3; b is, separately in each occurrence, 0, 1, or 2; x is, separately in each occurrence, a real number greater than 1; and Z is, separately in each occurrence, hydrogen, a residue of an onium cation, a quenching agent, a capping agent, or hydrogen.

[0111] 24. The polymer of any one of the preceding embodiments, wherein some of the polymer chains may have carboxylate groups at some ends of the chains.

[0112] 25. A portion of a polymer chain has the formula: [ka] and may have carboxylate groups at the ends of some of the chains corresponding to In the formula, R 2 is, separately in each occurrence, an optionally substituted carbon-containing group; R 3 is, separately in each occurrence, hydrogen, carbon-containing which may optionally contain one or more heteroatoms and / or substituents; R 4 is, independently in each occurrence, a carbon-containing group which may contain heteroatoms or be substituted with a functional group; a is, independently in each occurrence, 1, 2, or 3; b is, independently in each occurrence, 0, 1, or 2; x is, independently in each occurrence, a real number greater than 1; and Z is, independently in each occurrence, hydrogen, a residue of an onium cation, a quenching agent, an end-capping agent, or hydrogen.

[0113] 26. A polymerizable composition comprising: a. one or more of betapropiolactone and / or substituted betapropiolactone; b. one or more salts of one or more zwitterions having one or more onium cations and one or more phosphate anions or one or more phosphate anions and one or more onium cations.

[0114] 27. The polymerizable composition of embodiment 26, wherein the onium cation comprises one or more of nitrogen, phosphorus, sulfur, antimony, or arsenic.

[0115] 28. The polymerizable composition of embodiment 26 or 27, wherein the onium cation comprises one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations.

[0116] 29. The polymerizable composition of any one of embodiments 26 to 28, wherein the one or more quaternary nitrogen-containing cations or quaternary phosphonium cations are one or more tetraalkylammonium anions or tetraalkylphosphonium anions.

[0117] 30. The polymerizable composition of any one of embodiments 26-28, wherein the one or more quaternary nitrogen-containing cations are tetrahydrocarbylamines and two or more of the hydrocarbyl groups can form one or more aromatic or non-aromatic ring structures, which can optionally contain one or more heteroatoms.

[0118] 31. The polymerizable composition of any one of embodiments 26-30, wherein the one or more quaternary nitrogen-containing cations comprise one or more ammonium, amidinium, and guanidinium cations, or onium cations based on nitrogen-containing heterocycles.

[0119] 32. The polymerizable composition of any one of embodiments 26-31, wherein the one or more quaternary nitrogen-containing cations comprise one or more onium cations based on a nitrogen-containing heterocycle, including optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium.

[0120] 33. The polymerizable composition of any one of embodiments 26-32, wherein the one or more quaternary nitrogen-containing cations comprise one or more optionally substituted imidazoliums.

[0121] 34. One or more quaternary nitrogen-containing cations have the formula [ka] and one or more quaternary ammonium cations corresponding to In the formula, R 1 is, separately in each occurrence, a carbon-containing group; R 1 33. The polymerizable composition of any one of embodiments 26-32, wherein two or more of:

[0122] 35. One or more quaternary nitrogen-containing cations have the formula: [ka] and one or more guanidinium cations corresponding to In the formula, R 1 is, separately in each occurrence, a carbon-containing group; R 1 35. The polymerizable composition of any one of embodiments 26-34, wherein two or more of:

[0123] 34b. The polymerizable composition of any one of embodiments 25-33, wherein the one or more quaternary ammonium cations are one or more tetraalkylammonium anions or N-alkyl substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium cations.

[0124] 35b. One or more imidazolium cations are represented by the formula [ka] Corresponding to, In the formula, R 1 35. The polymerizable composition of any one of embodiments 25-34, wherein: is independently at each occurrence a carbon-containing group that may include heteroatoms.

[0125] 36. The polymerizable composition of any one of embodiments 26 to 35, wherein the one or more quaternary ammonium cations are one or more tetraalkylammonium or N-alkyl-substituted imidazolium cations.

[0126] 37. The polymerizable composition of any one of embodiments 26-36, wherein the one or more quaternary phosphonium anion cations are one or more tetraalkylphosphonium cations.

[0127] 38. One or more quaternary phosphonium cations have the formula: [ka] where R corresponds to 1 is, separately in each occurrence, a carbon-containing group; R 1 35. The polymerizable composition of any one of embodiments 26-34, wherein two or more of:

[0128] 39. The polymerizable composition of any one of embodiments 26 to 38, wherein the one or more quaternary phosphonium cations is a tetraalkylphosphonium cation.

[0129] 40 Phosphate anion has the formula; [ka] where R corresponds to 2 is, separately in each occurrence, an optionally substituted carbon-containing group; a is, independently in each occurrence, 1, 2, or 3; 40. The polymerizable composition of any one of embodiments 26-39, wherein b is independently in each occurrence 0, 1, or 2, and the sum of a and b is 3.

[0130] 41. One or more salts of one or more onium cations and one or more phosphate anions are represented by the formula [ka] where R corresponds to 2 41. The polymerizable composition of any one of embodiments 26-40, wherein Z′ is, separately in each occurrence, an optionally substituted carbon-containing group; Z′ is, separately in each occurrence, an onium cation; a is, separately in each occurrence, 1, 2, or 3; b is, separately in each occurrence, 0, 1, or 2; and the sum of a and b is 3.

[0131] 42. One or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions are represented by the formula [ka] where R 1 is, separately in each occurrence, a carbon-containing group; R 1 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms, and R 2 42. The polymerizable composition of any one of embodiments 26-41, wherein: is independently in each occurrence an optionally substituted carbon-containing group; a is independently in each occurrence 1, 2, or 3; b is independently in each occurrence 0, 1, or 2; and the sum of a and b is 3.

[0132] 43. One or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions are represented by the formula [ka] where R 1is, separately in each occurrence, a carbon-containing group; R 1 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms, and R 2 43. The polymerizable composition of any one of embodiments 26-42, wherein is independently at each occurrence a carbon-containing group.

[0133] 44. One or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions are represented by the formula [ka] where R corresponds to 1 but separately in each occurrence, R 1 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms, and R 2 44. The polymerizable composition of any one of embodiments 26-43, wherein each occurrence is independently an optionally substituted carbon-containing group.

[0134] 45. One or more zwitterionic salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions are represented by the formula [ka] where R corresponds to 1 but separately in each occurrence, R 1 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms, and R 2 45. The polymerizable composition of any one of embodiments 26-44, wherein each occurrence is independently an optionally substituted carbon-containing group.

[0135] 46. ​​One or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions are represented by the formula [ka] where R corresponds to 1is, separately in each occurrence, a carbon-containing group; R 1 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms, and R 2 46. ​​The polymerizable composition of any one of embodiments 26 through 45, wherein each occurrence is independently an optionally substituted hydrocarbyl group.

[0136] 47. A zwitterion has the formula [ka] where R corresponds to 2 is, in each occurrence, separately an optionally substituted carbon-containing group; R5 is, in each occurrence, separately an optionally substituted carbon-containing moiety; Z' is, in each occurrence, separately an onium cation; a is, in each occurrence, separately 1, 2, or 3; b is, in each occurrence, separately 0, 1, or 2; and the sum of a and b is 3.

[0137] 48. A zwitterion has the formula [ka] where R 1 is, separately in each occurrence, a carbon-containing group; R 1 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms, and R 2 is, separately in each occurrence, an optionally substituted carbon-containing group; R 5 48. The polymerizable composition of any one of embodiments 26-47, wherein: is independently an optionally substituted carbon-containing moiety; a is independently in each occurrence 1, 2, or 3; b is independently in each occurrence 0, 1, or 2; and the sum of a and b is 3.

[0138] 49. One or more zwitterions of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions are represented by the formula [ka] where R 1 is, separately in each occurrence, a carbon-containing group; R 1 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms, and R 2 is, separately in each occurrence, an optionally substituted carbon-containing group; R 5 49. The polymerizable composition of any one of embodiments 26-48, wherein: are independently an optionally substituted carbon-containing moiety.

[0139] 50. One or more zwitterions comprising one or more quaternary nitrogen-containing cations and one or more phosphate anions are represented by the formula: [ka] where R corresponds to 1 is, separately in each occurrence, a carbon-containing group; R 1 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms, and R 2 is, independently in each occurrence, an optionally substituted hydrocarbyl group; R 5 50. The polymerizable composition of any one of embodiments 26-49, wherein: are independently an optionally substituted carbon-containing moiety.

[0140] 51. One or more zwitterions of one or more quaternary nitrogen-containing cations and one or more phosphate anions are represented by the formula: [ka] where R corresponds to 1 is, separately in each occurrence, a carbon-containing group; R 1 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms, and R 2 is, separately in each occurrence, an optionally carbon-containing group; R5 51. The polymerizable composition of any one of embodiments 26-50, wherein: are independently an optionally substituted carbon-containing moiety.

[0141] 52. One or more zwitterions of one or more quaternary nitrogen-containing cations and one or more phosphate anions have the formula: [ka] where R corresponds to 1 is, separately in each occurrence, a carbon-containing group; R 1 two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms, and R 2 is, separately in each occurrence, an optionally substituted carbon-containing group; R 5 52. The polymerizable composition of any one of embodiments 26-51, wherein: are independently an optionally substituted carbon-containing moiety.

[0142] 53. The polymerizable composition of any one of embodiments 26-52, comprising one or more comonomers that copolymerize with one or more of the beta-lactones.

[0143] 54. The polymerizable composition of any one of embodiments 26-53, comprising one or more of a chain transfer agent, a chain extender, a quenching agent, and an end-capping agent.

[0144] 55. The polymerizable composition of any one of embodiments 26 to 54, wherein the molar ratio of one or more of the beta-lactones to one or more salts of one or more onium cations and one or more phosphate anions or one or more zwitterions having one or more phosphate anions and onium cations is from about 10 to 1 to about 1,000,000 to 1.

[0145] 56. The polymerizable composition of any one of embodiments 26-55, wherein the end-capping agent is an organic halide, an organic sulfonate, a haloalkylsilane, an aniline derivative, a phosphoric acid derivative, a boric acid derivative, and an isophthalic acid derivative.

[0146] 57. The polymerizable composition of any one of embodiments 26-56, wherein the end-capping or quenching agent is present in an amount less than 10 molar equivalents relative to the amount of one or more salts of one or more onium cations and one or more phosphate anions, or one or more phosphate anions and one or more zwitterions having an onium cation.

[0147] 58. The polymerizable composition of any one of embodiments 26-57, wherein the comonomer is one or more of caprolactone, lactide, epoxide, oxetane, cyclic anhydride, cyclic ether, lactam, episulfide, aziridine, (meth)acrylate, valerolactone, butyrolactone, glycolide, and substituted glycolide.

[0148] 59. The polymerizable composition of any one of embodiments 26-58, wherein the comonomer is one or more epoxides.

[0149] 60. A method comprising contacting the elements of the polymerizable composition of any one of embodiments 26-59 under conditions to prepare one or more polymers comprising one or more polymer chains having ring-opened beta-lactone units.

[0150] 61. The method of embodiment 60, wherein the elements are contacted at a temperature of about 30°C to about 120°C.

[0151] 62. The method of embodiment 60 or 61, wherein the elements are contacted at a pressure of about 1 bar (0.1 MPa) to about 20 bar (2.0 MPa).

[0152] 63. The method of any one of embodiments 60-62, wherein the elements are contacted for a time sufficient to consume substantially all of the one or more beta-lactones and comonomers.

[0153] 64. The method of any one of embodiments 60-63, wherein a quenching agent is added to terminate the polymerization reaction after a specified reaction time or when the polymer composition reaches a desired molecular weight.

[0154] 65. The method of any one of embodiments 60-64, wherein the quenching agent is one or more of an inorganic acid, an organic acid, or an acidic resin or solid.

[0155] 66. The method of any one of embodiments 60-65, wherein the end-capping agent is added after a specified reaction time or when the polymer composition reaches a desired molecular weight.

[0156] 67. The method of embodiment 66, wherein the end-capping agent comprises one or more electrophilic organic compounds.

[0157] 68. The method of embodiment 66 or 67, wherein the end-capping agent comprises one or more of an organic halide, an organic sulfonate, a haloalkylsilane, an aniline derivative, a phosphoric acid derivative, a boric acid derivative, and an isophthalic acid derivative.

[0158] 69. The method of any one of embodiments 66-68, wherein the end-capping agent is present in an amount less than 10 molar equivalents relative to the amount of one or more salts of one or more onium cations and one or more phosphate anions.

[0159] 70. The method of any one of embodiments 60-69, wherein the elements are contacted in a solvent that is a non-polar solvent or a polar solvent.

[0160] 71. The method of embodiment 70, wherein the solvent is a non-polar ether, alkanol, or acetate.

[0161] 72. The method of any one of embodiments 70 to 72, wherein the solvent exhibits a polarity of less than 0.2.

[0162] 73. The method of any one of embodiments 70-73, wherein the solvent is an acyclic or cyclic ether, a lower alkanol, or an alkyl acetate.

[0163] 74. The method of any one of embodiments 70-73, wherein the solvent is methyl tert-butyl ether, dimethyl ether, diethyl ether, cyclopentyl methyl ether, ethyl acetate diisopropyl ether.

[0164] 75. The method of any one of embodiments 60-74, wherein the formed polymer is contacted with a polyepoxide or polylactone under conditions such that the polymer is crosslinked through the end groups of the polymer.

[0165] 75. The method of any one of embodiments 60-75, wherein the polymer formed has a carboxylate group and / or a phosphate group at one end of the formed chain.

[0166] 76. The method of any one of embodiments 60-75, wherein some of the terminal groups are phosphate groups.

[0167] 77. The method of any one of embodiments 60-76, wherein some of the terminal groups are one or more nitrogen-containing or phosphorus-containing cations. [Example]

[0168] The following examples are illustrative only and are not intended to limit any aspect of the present disclosure in any way.

[0169] Phosphates used in the examples: [ka]

[0170] Bio-based phosphate zwitterions utilized in the examples [ka]

[0171] Synthesis with salts of trimethyl phosphate and tertiary amines. Synthesis of isopropyl-trimethylammonium dimethyl phosphate [iPTMA DMP]. Dimethylisopropylamine [DMIPA; 20 mL; 164 mmol] and trimethyl phosphate [TMP; 19.1 mL; 164 mmol] were combined in a 100 mL round-bottom flask equipped with a stir bar. The flask was equipped with a reflux condenser and heated to 110°C overnight. The reaction was complete when the solution no longer refluxed. After heating for 14 hours, the solution was cooled to room temperature to give a white solid. The solution was recrystallized from acetone at -20°C to give a white solid, which was quickly filtered and vacuum dried overnight to give 31 g [90%][T] of a water-absorbent, colorless / white semi-solid. m =21°C].

[0172] Synthesis of 1-butyl,3-(2-ethylhexyl)imidazolium bis(2-ethylhexyl)phosphate [behim DEHP]. In a 50 mL round-bottom flask, combine 10 g of tris(2-ethylhexyl)phosphate and 2.8 g of 1-butylimidazole. Heat the reaction to 150 °C overnight [13 h] to obtain a yellow liquid, 12.7 g, quantitative yield. The ionic liquid is used directly without further purification.

[0173] Synthesis of tetramethylammonium diphenyl phosphate [TMA DPP]. Tetramethylammonium hydroxide in water [approximately 25% in water; 2.5 mL] is added to a two-neck 50 mL round-bottom flask equipped with a stir bar. The flask is then cooled to 0 °C in an ice bath, and 1.7 g of diphenyl phosphate dissolved in minimal water [approximately 10 mL] is then added dropwise. Once all the acid has been added, the solution is allowed to warm to room temperature. After 1 hour, the flask is placed in a 35 °C oil bath with low airflow overnight to evaporate the water and leave approximately 2 g of a white powder [T m =78°C]. [Table 1]

[0174] Tertiary amines react readily with bulk trimethyl phosphate to prepare quaternary ammonium phosphates. These solids are isolated as low-melting solids [Table 1]. Quaternary ammonium phosphates are soluble only in water and alcohol solutions, except for octadecyl-trimethylammonium dimethyl phosphate [ODTMA DMP], which also dissolves in tetrahydrofuran [THF] solution.

[0175] Imidazolium-based ionic liquids have also been prepared using the same methodology for quaternary ammonium phosphates. Unlike tertiary amines, imidazolium derivatives can be reacted with tris(2-ethylhexyl)phosphate to produce the corresponding imidazolium phosphates, such as 1-butyl,3-(2-ethylhexyl)imidazolium and bis(2-ethylhexyl)phosphate [behim DEHP]. These salts exhibit similar solubility to quaternary ammonium phosphates. Surprisingly, behim DEHP is insoluble in water but readily dissolves in methyl tert-butyl ether [MTBE], an ideal solvent for beta-lactone polymerization. 1,3-Disubstituted imidazolium phosphates are liquids at room temperature, making them ideal for polymerization additives, as they allow for easy addition of the reagent without the need for heat or solvents.

[0176] Finally, phosphate salts are prepared by acid / base reaction. This is a conventional method for preparing tetraalkylammonium salts using phosphoric acid or carboxylic acid by dehydration of tetramethylammonium hydroxide and an organic acid. This can be used to prepare monobasic ammonium phosphate salts, such as tetramethylammonium diphenyl phosphate [TMA DPP], or tribasic ammonium phosphate salts, such as tris(tetramethylammonium) phosphate [TTMAP]. These salts are isolated as white solids that do not melt and decompose before melting.

[0177] Examples of polymerization with ionic liquids: Example 1 Ionic liquid ODTMA DMP [155 mg; 0.32 mmol] is added to a 20 mL scintillation vial equipped with a stir bar. 1 mL of beta-propiolactone [bPL; 16 mmol] in 10 mL of methyl tert-butyl ether [MTBE] is then added to the vial. The reaction is heated to 40°C, and a white powder precipitates from the solution in less than 20 minutes. After 1 hour, GC-TCD analysis of the reaction solvent indicates that >99% of the beta-propiolactone is consumed. To work up the reaction, the solid is filtered, collected, and dried under vacuum overnight to yield 1.01 g of a white fluffy solid [89%; M n (GPC) = 45800 g / mol, PDI = 2.2].

[0178] Ionic liquids as polymerization agents for polypropiolactone from bPL To test the effectiveness of the structure-property relationship of phosphate-based ionic liquids as polymerization agents for beta-propiolactone, reactions are carried out under homogeneous conditions [1.6 M bPL in MTBE at 40 °C] over a range of monomer-to-ionic liquid ratios. A "polymerization agent" in this context can be defined as a catalyst, initiator, or both via a reversible reaction that does not completely consume the phosphoric acid catalyst. Methyl t-butyl ether (MTBE) is chosen based on its effectiveness in polymerization of beta-propiolactone in MTBE solvent using tetramethylammonium acetate as the initiator under similar conditions. [Table 2]

[0179] Ammonium phosphate salts are highly effective additives for the polymerization of beta-propiolactone. The most active phosphate salts are ODTMA DMP, which yields >99% conversion of bPL and produces high molar mass P3HP in less than one hour (MW = >120,000 g / mol; PDI = 2.2). Imidazolium salts, such as mmim DMP, are similarly effective, producing high molar mass polymers and reaching high conversions (MW = >172,500 g / mol; PDI = 3.1) after 24 hours of reaction. Tribasic salts have also been used in the polymerization of bPL (TTMAP and tribasic potassium phosphate; K3PO4). Tribasic salts were virtually insoluble in the MTBE / bPL reaction mixture; however, these salts produced very different results for P3HP synthesis. TTMAP produced low molar masses with a relatively fast reaction time [3 h; Mw = 17,100 g / mol; PDI = 4.0], whereas K3PO4 produced high molar masses after overnight stirring [24 h; Mw = 681,500 g / mol; PDI = 7.4]. The low solubility of the salts may be the cause of the slow reactivity, especially considering that the basicity of tribasic phosphate salts is much higher than that of their monobasic counterparts. Nevertheless, K3PO4 is an effective additive for producing high molar mass P3HP without ammonium additives at a relatively fast reaction time [24 h].

[0180] Analysis of the monomer-to-ionic liquid ratio [M:IL] can provide mechanistic insight into the effect of phosphate salts. In general, the molar mass of the resulting polymer is independent of the M:IL ratio when using ODTMA-DMP for the polymerization of bPL (Figure 1). This suggests that the DMP anion is not the primary initiator for the polymerization of bPL but reacts in a different manner, such as via a base or a reversible invitation event. Because higher loadings of ODTMA-DMP did not result in faster reaction times, the salt likely does not function solely as a catalyst. Conversely, a lower ODTMA-DMP [M:IL ratio = 1000:1] resulted in the fastest complete conversion of bPL. Figure 1 shows the relationship between the molar mass [M] and the monobasic ionic liquid equivalent to beta-lactone ratio. nThe reaction was carried out in ODTMA DMP ionic liquid in MTBE [approximately 1.6 M] at 40°C. The dashed line represents the theoretical molar mass [Theo].

[0181] The tribasic phosphate, TTMAP, showed the expected trend in controlling the polymerization of bPL. That is, when more phosphate was used, the polymerization was faster, resulting in a lower molar mass polymer, as shown in Figure 2. This is likely due to the increased nucleophilicity of the tribasic phosphate anion and increased initiator effectiveness. As a result, the theoretical molar mass based on the monomer-to-initiator ratio is closer to the measured molar mass of the final polymer. Figure 2 shows the relationship between molar mass [M] and the tribasic ionic liquid equivalents to beta-lactone ratio. n The reaction was carried out in TTMAP ionic liquid in MTBE [approximately 1.6 M] at 40°C. The dashed line represents the theoretical molar mass [Theo].

[0182] 1 End-group analysis by H NMR spectroscopy reveals that the predominant initiator group is an acrylate anion [Figures 3 and 4]. The molar masses using acrylate as the end group closely match the measured molar masses of the polymers by GPC analysis [Table 3 and Figure 5]. Analysis of the dimethyl phosphate signal and the methyl groups on the ammonium groups suggests that they are not covalently attached to the polymer, but rather that acrylate is the predominant end group of these polymers.

[0183] Figure 3a and b show the P3HP prepared using octadecyl-trimethylammonium dimethyl phosphate [ODTMA DMP]. 1 H NMR spectroscopy (500 MHz; CDCl3) is shown. Top: Integration of acrylate [CHH=CH-CO-] was set to 1. Bottom: Integration of octadecyl-CH3 was set to 3. Reaction conditions [M:IL=50:1 in MTBE solvent (1.6 M) at 40 °C]. Figure 4 shows the results of P3HP prepared using tris(tetramethylammonium) phosphate [TTMAP]. 1H NMR spectroscopy (500 MHz; CDCl3) is shown. Reaction conditions [M:IL=50:1 in MTBE solvent (1.6 M) at 40 °C] [Table 3]

[0184] The generation of acrylates via elimination chemistry during bPL polymerization is highly dependent on the reaction temperature; increasing the temperature leads to more acrylates. Adjusting the reaction temperature is therefore an effective way to vary the molar mass of P3HP [Table 4 and Figure 6]. [Table 4]

[0185] Figure 6 shows the polymer molar mass [M n The dashed line represents the theoretical molar mass [MTheo].

[0186] Reaction solvents are another means of producing polymers of various molar masses. [Table 5]

[0187] FIG. 7 shows a comparison of beta-lactone conversion versus time with various polymerization additives. [Table 6]

[0188] The foregoing is a description of certain non-limiting embodiments of the present invention. Accordingly, it is to be understood that the embodiments of the present invention described herein are merely illustrative of the application of the principles of the present invention. Reference herein to details of the illustrated embodiments is not intended to limit the scope of the claims, which themselves recite those features regarded as essential to the invention.

Claims

1. 1. A polymer comprising one or more polymer chains having ring-opened beta-lactone units, a portion of said chains having at one end a residue of a phosphate anion covalently bonded to said one end of said polymer chain, and at the other end of said portion of said chains one or more onium-containing cations.

2. 10. The polymer of claim 1, wherein the onium cation comprises one or more of nitrogen, phosphorus, sulfur, antimony, or arsenic.

3. 3. The polymer of claim 1 or 2, wherein the onium cation comprises one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations.

4. 10. The polymer of any one of the preceding claims, wherein the one or more quaternary nitrogen-containing cations are amines having four carbon groups, two or more of which can form one or more aromatic or non-aromatic ring structures that can optionally contain one or more heteroatoms.

5. 10. The polymer of any one of the preceding claims, wherein the one or more nitrogen-containing cations comprise one or more of ammonium, amidinium, and guanidinium cations, or onium cations based on nitrogen-containing heterocycles.

6. 10. The polymer of any one of the preceding claims, wherein the one or more nitrogen-containing cations comprise one or more onium cations based on nitrogen-containing heterocycles, including optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium.

7. The one or more quaternary ammonium cations are represented by the formula 【Chemistry 1】 Corresponding to, In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ 5. A polymer according to any one of the preceding claims, wherein two or more of:

8. The one or more guanidinium cations are represented by the formula 【Chemistry 2】 Corresponding to, In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ 5. A polymer according to any one of the preceding claims, wherein two or more of:

9. One or more imidazolium cations are of the formula 【Transformation 3】 Corresponding to, In the formula, R １ 5. The polymer of any one of the preceding claims, wherein, in each occurrence, is separately a carbon-containing group.

10. 10. A polymer according to any one of the preceding claims, wherein the one or more phosphorus-containing cations are one or more quaternary phosphonium cations.

11. The one or more quaternary phosphonium cations have the formula: 【Chemistry 4】 Corresponding to, In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ 5. A polymer according to any one of the preceding claims, wherein two or more of:

12. The phosphate anion has the formula: 【Transformation 5】 Corresponding to, In the formula, R ２ is, separately in each occurrence, an optionally substituted carbon-containing group; a is, independently in each occurrence, 1, 2, or 3; b is independently in each occurrence 0, 1, or 2; 10. The polymer of any one of the preceding claims, wherein the sum of a and b is 3.

13. The phosphate anion is represented by the formula 【Transformation 6】 where R ２ 5. The polymer of any one of the preceding claims, wherein, in each occurrence, is separately a carbon-containing group.

14. 10. A polymer according to any one of the preceding claims, wherein one or more of the polymer chains have residues of an end-capping or quenching agent at some of the ends of the chains.

15. 10. The polymer of any one of the preceding claims, wherein the polymer comprises a comonomer that polymerizes with ring-opened betapropiolactone and / or substituted betapropiolactone.

16. 10. The polymer of any one of the preceding claims, wherein the comonomer is one or more of caprolactone, lactide, epoxide, oxetane, cyclic anhydride, cyclic ether, lactam, episulfide, aziridine, (meth)acrylate, valerolactone, butyrolactone, glycolide, and substituted glycolides.

17. 10. The polymer of any one of the preceding claims, wherein the comonomer is one or more epoxides.

18. The polymer has the formula: 【Transformation 7】 corresponds to one of In the formula, R ２ is, separately in each occurrence, an optionally substituted carbon-containing group; R ３ is, independently in each occurrence, hydrogen, a carbon-containing group which may optionally contain one or more heteroatoms and / or substituents; a is, independently in each occurrence, 1, 2, or 3; b is independently in each occurrence 0, 1, or 2; x is, in each occurrence separately, a real number greater than 1; 10. The polymer of any one of the preceding claims, wherein Z, in each occurrence, is independently hydrogen, a residue of an onium cation, a quenching agent, a capping agent, or hydrogen.

19. 10. A polymer according to any one of the preceding claims, wherein some of the polymer chains may have carboxylate groups at some ends of the chains.

20. A portion of the polymer chain has the formula: 【Transformation 8】 and may have carboxylate groups at the ends of some of said chains corresponding to In the formula, R ２ is, separately in each occurrence, an optionally substituted carbon-containing group; R ３ is, separately in each occurrence, hydrogen, carbon-containing which may optionally include one or more heteroatoms and / or substituents; R ４ is independently in each occurrence a carbon-containing group which may contain heteroatoms or be substituted with functional groups; a is, independently in each occurrence, 1, 2, or 3; b is independently in each occurrence 0, 1, or 2; x, in each occurrence separately, is a real number greater than 1; 10. The polymer of any one of the preceding claims, wherein Z, in each occurrence, is independently hydrogen, a residue of an onium cation, a quenching agent, an end-capping agent, or hydrogen.

21. 1. A polymerizable composition comprising: a. one or more of betapropiolactone and / or substituted betapropiolactone; b. one or more salts of one or more zwitterions having one or more onium cations and one or more phosphate anions or one or more phosphate anions and one or more onium cations.

22. 22. The polymerizable composition of claim 21, wherein the onium cation comprises one or more of nitrogen, phosphorus, sulfur, antimony, or arsenic.

23. 23. The polymerizable composition of claim 21 or 22, wherein the onium cation comprises one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations.

24. 24. The polymerizable composition of any one of claims 21 to 23, wherein the one or more quaternary nitrogen-containing cations or quaternary phosphonium cations are one or more tetraalkylammonium anions or tetraalkylphosphonium anions.

25. 24. The polymerizable composition of any one of claims 21 to 23, wherein the one or more quaternary nitrogen-containing cations are tetrahydrocarbyl amines, and two or more of the hydrocarbyl groups can form one or more aromatic or non-aromatic ring structures that can optionally contain one or more heteroatoms.

26. 26. The polymerizable composition of any one of claims 21 to 25, wherein the one or more quaternary nitrogen-containing cations comprise one or more ammonium, amidinium, and guanidinium cations, or onium cations based on nitrogen-containing heterocycles.

27. 27. The polymerizable composition of any one of claims 21 to 26, wherein the one or more quaternary nitrogen-containing cations comprise one or more of onium cations based on nitrogen-containing heterocycles, including optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium.

28. The one or more quaternary nitrogen-containing cations are represented by the formula 【Chemistry 9】 and one or more quaternary ammonium cations corresponding to In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ can form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms.

29. The one or more quaternary nitrogen-containing cations have the formula: 【Chemistry 10】 and one or more guanidinium cations corresponding to In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ can form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms.

30. One or more imidazolium cations are of the formula 【Chemistry 11】 Corresponding to, In the formula, R １ The polymerizable composition of any one of claims 21 to 29, wherein, in each occurrence, is independently a carbon-containing group which may include heteroatoms.

31. The polymerizable composition of any one of claims 21 to 30, wherein the one or more quaternary phosphonium cations are one or more tetraalkylphosphonium cations.

32. The one or more quaternary phosphonium cations have the formula: 【Chemistry 12】 Corresponding to, In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ The polymerizable composition according to any one of claims 21 to 30, wherein two or more of

33. The phosphate anion has the formula: 【Chemistry 13】 Corresponding to, In the formula, R ２ is, separately in each occurrence, an optionally substituted carbon-containing group; a is, independently in each occurrence, 1, 2, or 3; b is independently in each occurrence 0, 1, or 2; The polymerizable composition according to any one of claims 21 to 32, wherein the sum of a and b is 3.

34. The one or more salts of one or more onium cations and one or more phosphate anions are represented by the formula 【Chemistry 14】 Corresponding to, In the formula, R ２ is, separately in each occurrence, an optionally substituted carbon-containing group; Z' is, independently for each occurrence, an onium cation; a is, independently in each occurrence, 1, 2, or 3; b is independently in each occurrence 0, 1, or 2; The polymerizable composition according to any one of claims 21 to 33, wherein the sum of a and b is 3.

35. The one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions have the formula: 【Chemistry 15】 corresponds to one of In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; R ２ is, separately in each occurrence, an optionally substituted carbon-containing group; a is, independently in each occurrence, 1, 2, or 3; b is independently in each occurrence 0, 1, or 2; The polymerizable composition according to any one of claims 21 to 33, wherein the sum of a and b is 3.

36. The one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions have the formula: 【Chemistry 16】 corresponds to one of In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; R ２ The polymerizable composition of any one of claims 21 to 35, wherein, in each occurrence, is a carbon-containing group.

37. The one or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions have the formula: 【Chemistry 17】 Corresponding to, In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; R ２ The polymerizable composition of any one of claims 21 to 36, wherein each occurrence is independently an optionally substituted carbon-containing group.

38. The one or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions have the formula: [Chemistry 18] Corresponding to, In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; R ２ The polymerizable composition of any one of claims 21 to 37, wherein, in each occurrence, is separately an optionally substituted carbon-containing group.

39. The one or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions have the formula: 【Chemistry 19】 Corresponding to, In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; R ２ The polymerizable composition of any one of claims 21 to 38, wherein each occurrence is independently an optionally substituted hydrocarbyl group.

40. The zwitterion has the formula: 【Chemistry 20】 Corresponding to, In the formula, R ２ is, separately in each occurrence, an optionally substituted carbon-containing group; R ５ are separately optionally substituted carbon-containing moieties; Z' is, independently for each occurrence, an onium cation; a is, independently in each occurrence, 1, 2, or 3; b is independently in each occurrence 0, 1, or 2; The polymerizable composition according to any one of claims 21 to 38, wherein the sum of a and b is 3.

41. The zwitterion has the formula: 【Chemistry 21】 corresponds to one of In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; R ２ is, separately in each occurrence, an optionally substituted carbon-containing group; R ５ are separately optionally substituted carbon-containing moieties; a is, independently in each occurrence, 1, 2, or 3; b is independently in each occurrence 0, 1, or 2; The polymerizable composition according to any one of claims 21 to 38, wherein the sum of a and b is 3.

42. The one or more zwitterions of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions have the formula: 【Chemistry 22】 corresponds to one of In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; R ２ is, separately in each occurrence, an optionally substituted carbon-containing group; R ５ The polymerizable composition of any one of claims 21 to 38, wherein: are independently optionally substituted carbon-containing moieties.

43. The one or more zwitterions comprising one or more quaternary nitrogen-containing cations and one or more phosphate anions have the formula: 【Chemistry 23】 Corresponding to, In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ two or more of R may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; ２ is independently in each occurrence an optionally substituted hydrocarbyl group; R ５ The polymerizable composition of any one of claims 21 to 38, wherein: are independently optionally substituted carbon-containing moieties.

44. The one or more zwitterions of one or more quaternary nitrogen-containing cations and one or more phosphate anions have the formula: 【Chemistry 24】 Corresponding to, In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; R ２ is, separately in each occurrence, optionally a carbon-containing group; R ５ The polymerizable composition of any one of claims 21 to 43, wherein are independently optionally substituted carbon-containing moieties.

45. The one or more zwitterions of one or more quaternary nitrogen-containing cations and one or more phosphate anions have the formula: 【Chemistry 25】 Corresponding to, In the formula, R １ is, separately in each occurrence, a carbon-containing group; R １ two or more of may form one or more aromatic or non-aromatic ring structures which may optionally contain one or more heteroatoms; R ２ is, separately in each occurrence, an optionally substituted carbon-containing group; R ５ The polymerizable composition of any one of claims 21 to 38, wherein: are independently optionally substituted carbon-containing moieties.

46. 46. ​​The polymerizable composition of any one of claims 21 to 45, comprising one or more comonomers that copolymerize with one or more of the beta-lactones.

47. The polymerizable composition of any one of claims 21 to 46, comprising one or more of a chain transfer agent, a chain extender, a quenching agent, and an end-capping agent.

48. 48. The polymerizable composition of any one of claims 21 to 47, wherein the molar ratio of one or more of the beta-lactones to one or more of the one or more salts of one or more onium cations and one or more phosphate anions or one or more zwitterions having one or more phosphate anions and onium cations is from about 10 to 1 to about 1,000,000 to 1.

49. 49. The polymerizable composition of claim 21, wherein the end-capping agent is an organic halide, an organic sulfonate, a haloalkylsilane, an aniline derivative, a phosphoric acid derivative, a boric acid derivative, and an isophthalic acid derivative.

50. 50. The polymerizable composition of any one of claims 21 to 49, wherein the end-capping or quenching agent is present in an amount less than 10 molar equivalents relative to the amount of one or more salts of one or more onium cations and one or more phosphate anions, or one or more zwitterions having one or more phosphate anions and onium cations.

51. 51. The polymerizable composition of any one of claims 21 to 50, wherein the comonomer is one or more of caprolactone, lactide, epoxide, oxetane, cyclic anhydride, cyclic ether, lactam, episulfide, aziridine, (meth)acrylate, valerolactone, butyrolactone, glycolide, and substituted glycolides.

52. The polymerizable composition of any one of claims 21 to 51, wherein the comonomer is one or more epoxides.

53. 53. A method comprising contacting elements of the polymerizable composition of any one of claims 21 to 52 under conditions to prepare one or more polymers comprising one or more polymer chains having ring-opened beta-lactone units.

54. 54. The method of claim 53, wherein the elements are contacted at a temperature of from about 30°C to about 120°C.

55. 55. The method of claim 53 or 54, wherein the elements are contacted at a pressure of from about 1 bar (0.1 MPa) to about 20 bar (2.0 MPa).

56. 56. The method of any one of claims 53 to 55, wherein the elements are contacted for a time sufficient to consume substantially all of the one or more beta-lactones and comonomers.

57. 57. The method of any one of claims 53 to 56, wherein a quenching agent is added to terminate the polymerization reaction after a designated reaction time or when the polymer composition reaches a desired molecular weight.

58. 58. The method of any one of claims 53 to 57, wherein an end-capping agent is added after a specified reaction time or when the polymer composition reaches a desired molecular weight.

59. 59. The method of claim 58, wherein the end-capping agent comprises one or more electrophilic organic compounds.

60. 60. The method of any one of claims 53 to 59, wherein the elements are contacted in a solvent that is a non-polar solvent or a polar solvent.

61. 61. The method of claim 60, wherein the solvent is a non-polar ether, alkanol, or acetate.

62. 62. The method of claim 60 or 61, wherein the solvent is an acyclic or cyclic ether, a lower alkanol, or an alkyl acetate.

63. 63. The method of any one of claims 60 to 62, wherein the solvent is methyl tert-butyl ether, dimethyl ether, diethyl ether, cyclopentyl methyl ether, ethyl acetate diisopropyl ether.

64. 64. The method of any one of claims 53 to 63, wherein the formed polymer is contacted with a polyepoxide or polylactone under conditions such that the polymer is crosslinked through the end groups of the polymer.

65. 65. A method according to any one of claims 53 to 64, wherein the polymer formed has a carboxylate group and / or a phosphate group at one end of the chain formed.

66. The method according to any one of claims 53 to 64, wherein some of the terminal groups are phosphate groups.

67. 67. The method of any one of claims 53 to 66, wherein some of the end groups are one or more nitrogen-containing or phosphorus-containing cations.

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