Polypropiolactone and preparation method using ionic liquid

Abstract

Methods of efficiently preparing polypropiolactone and related copolymers from beta-propiolactone using carboxylate salts of onium cations are disclosed. In another aspect, the present invention provides a polymerization system comprising a combination of an initiator and a monomer that together are effective to produce polypropiolactone and related copolymers. Disclosed are novel polymer compositions having structural and / or compositional characteristics that make them distinct from previously produced polymers and polymer compositions.

Description

Technical Field

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

[0002] Polyester polymers have proven to be versatile materials with a wide range of uses. Polyesters based on petroleum-derived aromatic monomers are among the most widely used polymers, with polyethylene terephthalate (PET) being produced on a large scale for use in water bottles, textiles, and other consumer products. Unfortunately, PET is not biodegradable and has therefore become a major contributor to the growing environmental pollution problem caused by residual post-consumer plastic waste, including damage to marine ecosystems. In recent years, there has been increasing interest in biodegradable polyesters, examples of which include polylactic acid (PLA) and poly-3-hydroxybutyrate (PHB). The high cost and properties of these polymers make them difficult to use in high-volume applications to replace existing bulk polymers. There remains a need for high-performance biodegradable polyesters and methods for preparing such polymers from flexible raw material sources that allow manufacturers to balance the cost and sustainability of their products.

[0003] While the polymerization of β-propiolactone (BPL) and related substituted β-lactones has been known for decades, it has not previously been possible to economically produce very high molecular weight polypropiolactones or related copolymers, nor has it been possible to directly control the compositional properties and secondary structure of such polymers to optimize their range of applications. The preparation of polypropiolactones can be lengthy, and therefore methods for preparing such polymers that require less processing time are desired.

[0004] What is needed are polymers prepared from β-lactones having relatively high and controllable molecular weights. What is needed are polymers prepared from β-lactones having controlled polydispersity. What is needed are methods for preparing such polymers that allow for the preparation of polymer systems having desired molecular weights and polydispersities. What is needed are methods for preparing polypropiolactones that require less time and provide control over the molecular weight and polydispersity of the resulting polymers. Summary of the Invention

[0005] Disclosed are polymers comprising one or more polymer chains having units derived from a ring-opening beta-lactone and having a residue of a phosphate anion covalently bonded to one end of a portion of the chain. The polymer may have a mixture of residues of a carboxylate anion and residues of a phosphate anion at one end of the polymer. The other end of the portion of the chain may be one or more onium cations. The onium cations may contain one or more of nitrogen, phosphorus, sulfur, antimony, or arsenic. The onium cations may contain one or more of nitrogen and phosphorus. The onium cations may include one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations.

[0006] Onium cations can be one or more quaternary nitrogen-containing or quaternary phosphonium cations. The one or more quaternary nitrogen-containing cations can be quaternary amines, wherein two or more groups bonded to the nitrogen can form one or more aromatic or non-aromatic ring structures, and the ring structure can optionally contain one or more heteroatoms. The one or more quaternary nitrogen-containing cations can include one or more ammonium cations, amidino cations and guanidino cations or onium cations based on nitrogen-containing heterocycles. The one or more quaternary nitrogen-containing cations can include one or more onium cations based on nitrogen-containing heterocycles, and the nitrogen-containing heterocycles include optionally substituted pyridinium, imidazolium, pyrrolidinium or piperidinium. The one or more quaternary nitrogen-containing cations can include one or more optionally substituted imidazolium cations. The one or more quaternary nitrogen-containing cations are one or more ammonium cations corresponding to the following formula:

[0007] where R 1 is independently at each occurrence a group containing one or more carbon atoms, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms. One or more quaternary nitrogen-containing cations may be one or more guanidinium cations corresponding to the following formula: where R 1 In each occurrence, independently be a carbon-containing group that can contain one or more heteroatoms. One or more quaternary ammonium cations can be one or more tetraalkylammonium anions or onium cations based on nitrogen-containing heterocycles, for example, pyridinium, imidazolium, pyrrolidinium or piperidinium optionally substituted. One or more quaternary ammonium cations can be one or more tetraalkylammonium anions or onium cations based on nitrogen-containing heterocycles, for example, pyridinium, imidazolium, pyrrolidinium or piperidinium optionally substituted. One or more quaternary phosphonium cations can correspond to the following formula:

[0008] where R 1 is independently at each occurrence a carbon-containing group optionally containing one or more heteroatoms, wherein two or more R 1One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.The one or more quaternary phosphonium cations may be tetraalkylphosphonium cations.

[0009] A polymer is disclosed wherein one or more polymer chains have a residue of an end-capping agent or quencher at a portion of the chain ends. 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 phosphate derivative, or an isophthalic acid derivative.

[0010] The polymer may contain a comonomer that is polymerized with the ring-opening β-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.

[0011] Disclosed is a polymerizable composition comprising: a) one or more β-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 can be based on any one or more of the cations and anions disclosed above.

[0012] The one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions may correspond to one of the following formulae:

[0013]

[0014] where R 1 is independently at each occurrence a carbon-containing group, which optionally contains one or more heteroatoms, wherein two or more R 1 may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms; and wherein R 2 Independently at each occurrence is a carbon-containing group optionally containing one or more heteroatoms.

[0015] The one or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions may correspond to the following formula:

[0016]

[0017] where R 1 and R 2 is independently at each occurrence a hydrocarbyl group as defined above.

[0018] The one or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions may correspond to the following formula:

[0019]

[0020] where R 1 and R 2 As defined above.

[0021] The disclosed polymerizable compositions may include one or more of a chain transfer agent, a chain extender, a quencher, and an end-capping agent. The disclosed polymerizable compositions may exhibit a ratio of one or more β-lactones to one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions of about 10:1 to about 1,000,000:1. The amount of the end-capping agent or quencher relative to the amount of the one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions may be less than 10 molar equivalents.

[0022] A method is disclosed, comprising contacting one or more β-lactones, and, optionally, comonomers, with one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions under certain conditions to produce one or more polymers comprising one or more polymer chains having ring-opening β-lactone units. The disclosed onium cations can be any cation disclosed herein. The disclosed one or more phosphate anions can be any of the ones disclosed herein. The disclosed method can comprise contacting a polymerizable composition at a temperature of 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).

[0023] One or more salts or zwitterions containing one or more onium cations and one or more phosphate anions can form ionic liquids that can be well mixed with the liquid components in the disclosed compositions and can be used as carriers for certain solid components. This type of ionic liquid provides advantages in applications due to its liquid nature. When added to polymerizable compositions, these liquid compounds can perform their functions. Solid components can have an induction period because they need to be dissolved in the reaction mixture before they can function. These ionic liquids do not require such an induction period.

[0024] The use of compounds containing phosphorus-based anions can provide higher molar masses in a shorter time. These salts are obtained as low-melting solids and can be used as liquid initiators for slurry polymerization of β-lactones. The polymers exhibit controllable molecular weight and controllable polydispersity. The disclosed method provides a means for controlling molecular weight and polydispersity. The disclosed polymers can exhibit higher molecular weights than previously known polymers containing one or more polymer chains having ring-opened β-propiolactone and / or substituted β-propiolactone units. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 The dependence of the molar mass [Mn] on the ratio of the monovalent ionic liquid equivalent to β-propiolactone is illustrated.

[0026] Figure 2 The dependence of the molar mass [Mn] on the ternary ionic liquid equivalent to β-lactone ratio is illustrated.

[0027] Figure 3a and 3b The preparation of P3HP using octadecyl-trimethylammonium dimethyl phosphate is described. 1 H NMR spectroscopy (500 MHz; CDCl 3 ).

[0028] Figure 4 The preparation of P3HP using tris(tetramethylammonium)phosphate is described. 1 H NMR spectroscopy (500 MHz; CDCl 3 ).

[0029] Figure 5 The results of GPC and end group analysis are shown. 1 H NMR spectrum, molar mass of P3HP using ODTMADMP as catalyst [g / mol].

[0030] Figure 6 The temperature dependence of the polymer molar mass [Mn] using ODTMA DMP as an additive [monomer to ionic liquid ratio = 500:1,

[0031] Figure 7 The comparison of β-lactone conversion versus time using various polymerization additives is presented. DETAILED DESCRIPTION

[0032] The definitions of specific functional groups and chemical terms are described in more detail below. For purposes of the present invention, chemical elements are determined according to the Periodic Table of the Elements (CAS version, Handbook of Chemistry and Physics, 75th edition, inside cover), and specific functional groups are generally defined as described therein. In addition, the general principles of organic chemistry, as well as specific functional moieties and reactivities, are described in Organic Chemistry, Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March March's Advanced Organic Chemistry, 5th 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, 3rd Edition, Cambridge University Press, Cambridge, 1987; the entire contents of each of which are incorporated herein by reference.

[0033] The disclosed polymers may include one or more crystalline polymorphs and may exist in various crystalline forms. The term "β-lactone" refers to a substituted or unsubstituted cyclic ester having a four-membered ring comprising an oxygen atom, a carbonyl group, and two optionally substituted methylene groups. Unsubstituted β-lactones are known as propiolactones. Substituted β-lactones include monosubstituted, disubstituted, trisubstituted, and tetrasubstituted β-lactones. β-lactones may comprise a single lactone moiety. β-lactones may comprise two or more four-membered ring ester moieties. "Substantially all" refers to the presence of 95% or more, 98% or more, or 99% or more of a reference parameter or material, wherein the percentages may be weight percentages or mole percentages based on the context.

[0034] As used herein, the term "epoxide" refers to a substituted or unsubstituted oxirane. Such substituted oxiranes include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes. Such epoxides may be further optionally substituted as defined herein. An epoxide may contain a single oxirane moiety. An epoxide may contain two or more oxirane moieties.

[0035] As used herein, the term "polymer" refers to a molecule of high relative molecular mass whose structure includes multiple repeating units that are actually or conceptually derived from molecules of low relative molecular mass. A polymer can be composed of or derived from a β-lactone monomer (e.g., polypropiolactone). The disclosed polymers can be copolymers, terpolymers, heteropolymers, block copolymers, or tapered heteropolymers comprising two or more different monomers.

[0036] As used herein, the terms "halo" and "halogen" refer to atoms selected from fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br) and iodine (iodo, -I). A carbon-containing group refers to a group having a carbon backbone, commonly referred to as a hydrocarbon group, and includes the variations described in this paragraph. As used herein, the terms "aliphatic" or "aliphatic group" refer to a hydrocarbon moiety that can be straight chain (i.e., unbranched), branched, or cyclic (including fused, bridged, and spirocyclic polycyclics), and can be fully saturated or can contain one or more unsaturated units, but is not aromatic. An aliphatic group can contain 1-40 carbon atoms, 1-20 carbon atoms, 2-20 carbon atoms, 1-12 carbon atoms, 1-8 carbon atoms, 1-6 carbon atoms, 1-5 carbon atoms, 1-4 carbon atoms, 1-3 carbon atoms, or 1 or 2 carbon atoms. Aliphatic groups include, but are not limited to, straight or branched chain alkyl, alkenyl, and alkynyl groups, and hybrids thereof, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, or (cycloalkyl)alkenyl.

[0037] 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.

[0038] The term "unsaturated" as used herein refers to a portion having one or more double or triple bonds. The terms "alicyclic", "carbocycle" or "carbocyclic" used alone or as part of a larger portion refer to a saturated or partially unsaturated cyclic aliphatic monocyclic or polycyclic ring system with 3 to 12 members as described herein, wherein the alicyclic ring system is optionally substituted as defined below and as described herein. Alicyclic groups include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, norbornyl, adamantyl and cyclooctadienyl. Alicyclic groups can have 3-6 carbons. The terms "alicyclic", "carbocycle" or "carbocyclic" also include alicyclic rings fused to one or more aromatic or non-aromatic rings, such as decahydronaphthyl or tetrahydronaphthyl, wherein the free radical or point of attachment is on the alicyclic ring. As used herein, the term "alkenyl" refers to a monovalent group derived from a straight or branched aliphatic moiety having at least one carbon-carbon double bond by removing a single hydrogen atom. As used herein, the term "alkynyl" refers to a monovalent group derived from a straight or branched aliphatic moiety having at least one carbon-carbon triple bond by removing a single hydrogen atom. As used herein, the term "alkoxy" refers to an alkyl group as previously described attached to the parent molecule through an oxygen atom. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, and n-hexoxy. As used herein, the term "acyl" refers to a carbonyl-containing functional group, such as -C(=O)R', where R' is hydrogen or an optionally substituted aliphatic, heteroaliphatic, heterocyclic, aryl, heteroaryl, or a substituted (e.g., with hydrogen or an aliphatic, heteroaliphatic, aryl, or heteroaryl moiety) oxygen- or nitrogen-containing functional group (e.g., forming a carboxylic acid, ester, or amide functional group). As used herein, the term "acyloxy" refers to an acyl group attached to the parent molecule via an oxygen atom. The term "aryl," used alone or as part of a larger moiety such as "aralkyl," "aralkyloxy," or "aryloxyalkyl," refers to monocyclic and polycyclic ring systems having a total of 5 to 20 ring members, wherein at least one ring in the system is aromatic, and wherein each ring in the system contains 3 to 12 ring members. The term "aryl" can be used interchangeably with the term "aromatic ring," wherein "aryl" refers to an aromatic ring system, including but not limited to phenyl, biphenyl, naphthyl, anthracenyl, and the like, which may bear one or more substituents. Similarly, the term "aryl" as used herein also includes groups in which an aromatic ring is fused to one or more other rings, such as benzofuranyl, indanyl, phthalimidyl, naphthimidyl, phenantriidinyl, or tetrahydronaphthyl, wherein the radical or point of attachment is on the aryl ring.

[0039] The terms "heteroaryl" and "heteroaryl-", used alone or as part of a larger moiety, such as "heteroaralkyl" or "heteroaralkoxy", refer to groups having 5-14 ring atoms, preferably 5, 6 or 9 ring atoms; having 6, 10 or 14 pi electrons shared in a cyclic arrangement; and having from 1 to 5 heteroatoms in addition to carbon atoms. The term "heteroaryl" may be used interchangeably with the terms "heteroaryl ring" and "heteroaryl group", any of which terms include rings that are optionally substituted. The term "heteroatom" refers to nitrogen, oxygen or sulfur, and includes any oxidized form of nitrogen or sulfur, as well as any quaternized form of a basic nitrogen. A heteroaryl group may be monocyclic or bicyclic. "Heteroaralkyl" refers to an alkyl group substituted with a heteroaryl group, wherein the alkyl and heteroaryl portions are independently optionally substituted. The term "partially unsaturated" refers to a ring portion that includes at least one double or triple bond.

[0040] As described herein, disclosed compounds may contain "optionally substituted" moieties. Regardless of whether or not the term "optionally" is present in front, the term "substituted" refers to that one or more hydrogens of a designated moiety are replaced by suitable substituents. Unless otherwise indicated, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and when more than one position in any given structure can be substituted by one or more substituents selected from a specific group, the substituents at each position may be the same or different. The combination of substituents envisioned is that which results in the formation of stable or chemically feasible compounds. The term "stable" as used herein refers to compounds that are substantially unchanged when under conditions that allow their production, detection, and in certain embodiments, their recovery, purification, and use for one or more purposes disclosed herein.

[0041] As used herein, the term "alkoxylated" refers to a molecule to which one or more functional groups (typically, but not strictly limited to, alcohols, amines, or carboxylic acids) have attached a hydroxyl-terminated alkyl chain. Alkoxylated compounds may contain a single alkyl group, or they may be oligomeric moieties, such as hydroxyl-terminated polyethers. Alkoxylated materials may be derived from the parent compound by treating the functional groups with epoxides. Unless otherwise indicated, "a," "an," "the," and "at least one" are used interchangeably and mean one or more than one.

[0042] In some of the disclosed structures, parts of the structure are connected by dashed lines. This suggests that the connected structures are ionically bonded together.

[0043] Disclosed are polymers comprising one or more polymer chains having units derived from ring-opening β-lactones and having a residue of a phosphate anion covalently bonded to one end of a portion of the chain. The polymer may have a mixture of residues of a carboxylate anion and residues of a phosphate anion bound to one end of the polymer chain. The other end of a portion of the chain may be one or more onium cations. Also disclosed is a polymerizable composition comprising: a. one or more β-lactones; and b. one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions. The polymerizable composition can prepare the disclosed polymer. The polymerizable composition can prepare any known polymer derived from one or more β-lactones and optional comonomers, as disclosed herein. Also disclosed are methods for producing one or more polymers by contacting one or more β-lactone-substituted β-propiolactones and optional comonomers with one or more salts or zwitterions under certain conditions, wherein the one or more salts or zwitterions contain one or more onium cations and one or more phosphate anions, the polymers comprising one or more polymer chains having ring-opening β-lactone units. The disclosed onium cations can be any cation disclosed herein. The disclosed one or more phosphate anions can be any of the phosphate anions disclosed herein. The polymers produced from the polymerizable compositions and disclosed methods can exhibit controllable molecular weight and polydispersity. Such polymers can have higher molecular weights than previously produced polymers. Such polymers can exhibit lower polydispersity than previously produced polymers.

[0044] The polymers produced contain monomeric units derived from ring-opening β-lactones. The polymers may also contain units derived from comonomers. The resulting polymers may be capped at one end with one or more quenchers, residues of onium groups, and the like. In the polymer structures described herein, such end-capping groups are represented by Z. Onium groups and chain terminators are described below.

[0045] The polymer may contain a residue of a phosphate anion covalently bound to one end of the polymer chain at one end of a portion of the chain. The polymer may have a mixture of residues of a carboxylate anion and residues of a phosphate anion bound to one end of the polymer chain. The other end of a portion of the chain may be one or more onium cations. The monomer unit derived from a ring-opening β-lactone may correspond to the following formula: where R 3is independently at each occurrence hydrogen or a carbon-containing group, which may have one or more hydrogen or fluorine atoms attached to a carbon atom, which may optionally contain one or more heteroatoms and / or substituents; and x is a real number greater than 1. The variable x can be selected so that the resulting polymer can have a number average molecular weight of about 500 to 2,000,000 g / mol. The variable x can be 3 to 50,000.

[0046] The polymer formed may have the residue of an anionic initiator group at the other end of the polymer chain. Such residue may be based on any known initiator group, which may be added separately to the reaction mixture or generated in situ during the polymerization reaction. The initiator residue may be one or more residues conforming to one of the following formulae: D, Among them, D, R 2 and R 4 As defined herein.

[0047] The prepared polymer may correspond to the following formula Wherein D is the residue of one or more anionic initiators. The prepared polymer may have a portion of the polymer chain with a phosphate ester bound to one end of the chain. Such a polymer may correspond to one of the following formulas:

[0048] where R 2 、R 3 , a, b and x are as described herein; and,

[0049] Z is independently hydrogen, a residue of an onium cation, a residue of a quencher, etc. at each occurrence. A portion of the polymer chains may have carboxylate groups at the ends of some chains. Such a polymer may correspond to the following formula:

[0050] where R 2 、R 3 , Z and x are as described herein; and,

[0051] R 4 is independently at each occurrence a carbon-containing group which may contain heteroatoms or be substituted with functional groups. The polymers prepared may include polymers having a different initiator at one end of the chain as described herein.

[0052] R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms. 1Each occurrence may independently be one or more of alkyl, aryl, alkaryl, aralkyl, which may contain heteroatoms or one or more unsaturated moieties, wherein two or more R 1 R may form a cycloalkyl group or a cyclic ring containing one or more aromatic groups, wherein such groups may contain heteroatoms and / or unsaturated groups. 1 Can be C independently at each occurrence 1-20 Alkyl, C 3-24 Cycloalkyl, C 5-24 Aryl, C 6-24 Alkaryl, C 6-24 One or more of aralkyl groups, which may contain heteroatoms or one or more unsaturated moieties. 1 Can be C independently at each occurrence 1-12 Alkyl, C 3-12 Cycloalkyl, C 5-12 Aryl, C 6-12 Alkaryl, C 6-12 One or more of aralkyl groups, which may contain heteroatoms or one or more unsaturated moieties. 1 Each occurrence can be independently one or more C 1-12 Alkyl groups which may contain heteroatoms or one or more unsaturated moieties. 1 Each time it appears, it can be C 1-4 Alkyl groups which may contain heteroatoms or one or more unsaturated moieties. 1 Each occurrence may independently be one or more of methyl, ethyl, propyl or butyl.

[0053] R 2 R is independently at each occurrence a carbon-containing group which may contain heteroatoms or one or more unsaturated moieties. 2 Each occurrence may independently be one or more of alkyl, aryl, alkaryl, aralkyl, which may contain heteroatoms or one or more unsaturated moieties, wherein two or more R 2 R may form a cycloalkyl group or a cyclic ring containing one or more aromatic groups, wherein such groups may contain heteroatoms and / or unsaturated groups. 2 Can be C independently at each occurrence 1-20 Alkyl, C 3-24 Cycloalkyl, C 5-24 Aryl, C 6-24 Alkaryl, C 6-24 One or more of aralkyl groups, which may contain heteroatoms or one or more unsaturated moieties. 1 Can be C independently at each occurrence 1-12 Alkyl, C 3-12 Cycloalkyl, C 5-12Aryl, C 6-12 Alkaryl, C 6-12 One or more of aralkyl groups, which may contain heteroatoms or one or more unsaturated moieties. 2 Each occurrence can be independently one or more C 1-12 Alkyl groups which may contain heteroatoms or one or more unsaturated moieties. 2 Each time it appears, it can be C 1-4 Alkyl groups which may contain heteroatoms or one or more unsaturated moieties. 2 Each occurrence may independently be one or more of methyl, ethyl, propyl or butyl.

[0054] R 3 One or more can be the carbon-containing group with one or more hydrogen or fluorine atoms bonded to carbon atom, described carbon-containing group can contain unsaturated group, electrophilic group, nucleophilic group, anionic group, cationic group, containing zwitterionic group, hydrophobic group, hydrophilic group, halogen atom, natural mineral, synthetic mineral, carbon-based particle, ultraviolet active group, the polymer with surfactant property, and one or more in polymerization initiator or active heterocycle.Functional group can be connected to ring by linking group (M), and described linking group (M) plays the effect that the functional part of group is connected to ring.Exemplary linking group can be carbon-containing group, ether, thioether, polyether (for example polyolefin ether). R 3 One or more of them can be halogen-substituted alkyl, sulfonic acid-substituted alkoxy; alkylsulfonate alkoxy; alkyl ether-substituted alkyl; polyalkylene oxide-substituted alkyl, alkyl ester-substituted alkyl; alkenyloxy-substituted alkyl; aryl ester-substituted alkyl; alkenyl; cyano-substituted alkyl; alkenyl ester-substituted alkyl; cycloalkyl-substituted alkyl; aryl; heteroatom-containing cycloalkenyl, alkyl ether-substituted alkyl; hydroxyl-substituted alkyl, alicyclic-substituted alkenyl; aryl-substituted alkyl; halogenated aryl-substituted alkyl; aryloxy-substituted alkyl; alkyl ether-substituted alkaryl; heteroatom-containing alicyclic alkyl; heteroatom-containing aryl-substituted alkyl, alkylamide-substituted alkyl, alkenyl-substituted alicyclic group; two R 3 Can form a cyclic ring, which may optionally contain one or more unsaturated groups; an alkyl group substituted with a β-propiolactone group, which may optionally contain one or more ether groups and / or one or more hydroxyl groups; an alkyl group substituted with a glycidyl ether group or a benzocyclobutenyl group optionally substituted with one or more ether groups. β-propiolactone corresponds to the following formula, in which all R 3 is hydrogen. R on a carbon atom 3 They can all be H, and one or two R on the other carbon atom 3 It may be an optionally substituted C 1-40aliphatic, optionally substituted C 1-20 heteroaliphatic, optionally substituted aryl, or two R 3 The groups may be optionally joined together to form an optionally substituted ring, which optionally contains one or more heteroatoms. One or two R 3 can be an alkyl group, and the other can be hydrogen. The alkyl group can be C 1-20 Alkyl, C 1-12 Alkyl, C 1-8 Alkyl, C 1-4 Alkyl, wherein the alkyl group may contain unsaturated groups, heteroatoms or functional groups containing heteroatoms. One or two R on different carbon atoms 3 It can be methyl or ethyl, and the other can be hydrogen. Two R on the same carbon atom 3 It can be methyl, and other R 3 It's hydrogen.

[0055] R 4 is independently at each occurrence a carbon-containing group which may contain heteroatoms or be substituted with functional groups. 4 Each occurrence may independently be one or more of alkyl, aryl, alkaryl, aralkyl, which may contain heteroatoms or one or more unsaturated moieties, wherein two or more R 4 R may form a cycloalkyl group or a cyclic ring containing one or more aromatic groups, wherein such groups may contain heteroatoms and / or unsaturated groups. 4 Each occurrence can be independently one or more C 1-20 Alkyl groups which may contain heteroatoms or one or more unsaturated moieties. 4 Each occurrence can be independently for multiple C 1-12 An alkyl group which may contain heteroatoms or one or more unsaturated moieties. 4 Each occurrence can independently be one or more C 1-12 Alkyl groups which may contain heteroatoms or one or more unsaturated moieties. 4 Can be C independently at each occurrence 1-4 Alkyl groups which may contain heteroatoms or one or more unsaturated moieties. 4 Each occurrence of R may independently be one or more of methyl, ethyl, propyl or butyl. 4 An acrylate group can be formed with the carbonyloxy moiety to which it is bonded.

[0056] The formed polymer composition can have a low polydispersity, for example, a polydispersity index (PDI) of 3.5 or less, 3.0 or less, 2.5 or less, 2.2 or less, 2.0 or less, 1.8 or less, 1.7 or less, 1.6 or less, 1.5 or less, 1.4 or less, 1.3 or less, 1.2 or less, 1.1 or less, 1.05 or less. The formed polymer composition can have a PDI of 1.05 or greater, 1.1 or greater, 1.2 or greater, 1.5 or greater or 2.0 or greater. The PDI values ​​are measured by GPC (gel permeation chromatography) and calculated using a standard software package. Polydispersity is calculated using formula Mw / Mn by Mn (number average molecular weight) and Mw (weight average molecular weight). PDI values ​​can be calculated excluding GPC peaks resulting from oligomers having Mn less than about 5,000 g / mol, less than about 4,500, less than about 4,000, less than about 3,500, less than about 3,000, less than about 2,500, less than about 2,000, less than about 1,500, or less than about 1,000 g / mol.

[0057] The prepared polymer can have a number average molecular weight of greater than about 500 g / mol, 1,000 g / mol, 5,000 g / mol, 10,000 g / mol, 17,000 g / mol, 20,000 g / mol, 25,000 g / mol, 50,000 g / mol, 100,000 g / mol, 200,000 g / mol, 300,000 g / mol, or 500,000 g / mol, as measured in the present disclosure. The number average molecular weight of the prepared polymer can be 2,000,000 g / mol or less, or 1,000,000 g / mol or less. Measured as the present disclosure, the weight average molecular weight of prepared polymer can be greater than about 500g / mol, 1,000g / mol, 5,000g / mol, 10,000g / mol, 17,000g / mol, 20,000g / mol, 25,000g / mol, 50,000g / mol, 100,000g / mol, 200,000g / mol, 300,000g / mol, 500,000g / mol, 600,000g / mol or 700,000g / mol.Prepared polymer can have 2,000,000g / mol or less or 1,000,000g / mol or less number-average molecular weight.Measure molecular weight by GPC (gel permeation chromatography), and use standard software package to use THF as solvent and calculate with reference to monodisperse polymethyl methacrylate standard.

[0058] Polymers containing β-lactone residues are disclosed. Functional groups on β-lactones can provide functionality to polymers and copolymers prepared from β-lactones. The functional groups can act as polymerization initiators, improve polymer adhesion to certain substrates or polymer systems, improve hydrophobicity or hydrophilicity, improve hardness or scratch resistance, act as polymerization catalysts, and so on. β-lactone polymers and copolymers can be used as intermediate layers in multilayer films, including such films having different polymer layers. β-lactone polymers and copolymers decompose under certain conditions, allowing the other layers to be easily separated for recycling. β-lactone polymers and copolymers can be used as intermediate layers between other polymer coatings and substrates. β-lactone polymers and copolymers decompose under certain conditions, allowing the substrate to be easily separated from the other coatings for reuse during recycling. β-lactone polymers and copolymers can be used as decomposable outer film layers or coatings, or such outer layers can be functionalized to impart a desired set of properties to the structure.

[0059] The polymerizable composition can comprise a. one or more beta-lactones; and b. one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions.

[0060] The β-lactone that may be present in the polymerizable composition and used to prepare the polymer may be any β-lactone that polymerizes under the conditions defined herein. The β-lactone may correspond to the following general formula:

[0061]

[0062] where R 3 As mentioned above.

[0063] Disclosed are homopolymers prepared from the β-lactones. Disclosed are copolymers of more than one β-lactone. Disclosed are compositions comprising copolymers of one or more of the disclosed β-lactones and one or more monomers reactive with the one or more β-lactones. Disclosed are compositions comprising copolymers of one or more of the disclosed β-lactones and one or more monomers reactive with the one or more β-lactones. Such copolymers may include one or more of a glycol, a difunctional polyalkylene oxide, an amine-terminated polyalkylene oxide, one or more difunctional polyesters, a lactam, a lactide, a cyclic lactone, a cyclic anhydride, a cyclic ether epoxide, an episulfide, an aziridine, a (meth)acrylate, a valerolactone, a butyrolactone, a glycolide, a substituted glycolide, or a polyether. Such comonomers may be one or more of an epoxide, an ethylene oxide, a lactam, and a lactide. The comonomer can be one or more cyclic anhydrides, including succinic anhydride, methylsuccinic anhydride, methyldiglycolic anhydride, methylglutaric anhydride, maleic anhydride, phthalic anhydride, citraconic anhydride, and trans-1,2-cyclohexanedicarboxylic anhydride. These copolymers can contain units derived from β-propiolactone. The disclosed copolymers can be block copolymers, random copolymers, or one or more chains can be grafted onto the polymer backbone.

[0064] The one or more β-lactones may be:

[0065] The one or more β-lactones may be: where R 10 Can be used with R 3 The one or more beta lactones may be

[0066]

[0067] wherein Ar is any optionally substituted aryl group, R 12 Selected from the group consisting of: -H, optionally substituted C 1-20 aliphatic groups, optionally substituted C 1-20 heteroaliphatic group and optionally substituted aryl group, and R 13 Is fully or partially unsaturated C 2-20 Straight chain aliphatic groups. The polymer can be prepared from a mixture of β-propiolactone and pivalolactone:

[0068]

[0069] The one or more beta lactones may be:

[0070]

[0071] The polymer can be prepared from β-propiolactone and a β-lactone of one of the following formulas:

[0072] The polymer can be prepared from a mixture of β-lactones, wherein the β-lactones are provided as a mixture of positional isomers. Any of the aforementioned β-lactone comonomers can be provided in combination with their positional isomers. When the β-lactone comonomers are provided as a mixture of positional isomers, the positional isomer having the largest substituent on the carbon adjacent to the ring oxygen atom is present in molar excess relative to the other positional isomers. The major positional isomer is present relative to the minor positional isomer in a ratio of 2:1 or greater, at least 3:1, at least 5:1, at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, or at least 100:1.

[0073] Described polymkeric substance can be prepared by the mixture of beta-lactone and one or more cyclic ethers, and described cyclic ether comprises tetrahydrofuran (THF), substituted tetrahydrofuran (THF) and epoxide.Epoxide can be substituted epoxide.Epoxide can be one or more in oxirane, propylene oxide, butylene oxide, 4-vinyl epoxy cyclohexane, 4-ethyl epoxy cyclohexane, limonene oxide (limonene oxide), glycidyl ether, glycidyl ester or epoxy cyclohexane.Epoxide can correspond to following formula:

[0074] where R 3 As defined herein. One or more substituted epoxides may correspond to the formula: where R 10 As defined above. The one or more substituted epoxides may be:

[0075]

[0076] The one or more substituted epoxides may correspond to one of the following formulae:

[0077]

[0078] Among them, Ar, R 10 、R 12 and R 13 Each is as defined above. The one or more substituted epoxides may correspond to one of the following formulae:

[0079]

[0080] Disclosed are methods for polymerizing β-propiolactone (BPL) and / or substituted β-propiolactones, optionally with one or more other comonomers (collectively referred to as monomers), using an initiator as described herein. The initiator may or may not be covalently attached to the final polymer product.

[0081] The polymerizable composition comprises one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions. The phosphate anions can initiate polymerization of one or more β-lactones and comonomers polymerizable therewith. The presence of one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions can promote the in situ formation of carboxylate anions, which can initiate polymerization of these monomers. The presence of one or more salts or zwitterions containing one or more onium cations and one or more phosphate anions can result in the preparation of polymers in which both the phosphate anion and the carboxylate anion initiate polymer chains. The one or more salts or zwitterions of one or more onium cations and one or more phosphate anions can catalyze or accelerate the polymerization of monomers.

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

[0083] The one or more quaternary nitrogen-containing cations may contain four carbon-containing groups bound to the amine nitrogen, wherein two or more carbon groups may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms. The one or more quaternary nitrogen-containing cations may include one or more nitrogen-containing heterocycles. The one or more nitrogen-containing heterocycles may contain optionally substituted pyridinium, imidazolium, pyrrolidinium or piperidinium moieties. The one or more quaternary nitrogen-containing cations may include one or more optionally substituted imidazolium salts. The one or more quaternary nitrogen-containing cations may include one or more ammonium cations, amidinium cations and guanidinium cations. The one or more quaternary ammonium cations may correspond to the following formula where R 1 As defined herein. The one or more guanidinium cations may correspond to the following formula: where R 1 As defined herein.

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

[0085] One or more quaternary phosphonium cations can be one or more phosphonium cations containing four carbon-containing groups. One or more quaternary phosphonium cations can be one or more tetraalkylphosphonium cations. One or more quaternary phosphonium cations can correspond to the following formula: where R 1 As defined herein.

[0086] The phosphate anion can be any phosphate anion that allows one or more salts, or one or more onium cations and one or more phosphate anion zwitterions to perform the functions disclosed herein. The phosphate anion can have 1-3 onium cations bonded to an oxygen group. The phosphate anion can have 0-2 optionally substituted carbon-containing groups bonded to oxygen. The phosphate anion can correspond to the following formula: where R 2 As defined herein, a is an integer from 1 to 3 and b is an integer from 0 to 2. The variable a may be 1, 2, or 3. The variable b may be 0, 1, or 2. The sum of a and b is 3. The anion may be a mixture of compounds wherein a and b are different in the individual anions in the mixture. The phosphate anion may correspond to the following formula: where R 2 As defined herein.

[0087] The one or more salts of one or more onium cations and one or more phosphate anions can be any such salt that provides the properties disclosed herein. Such salts are formed from the phosphate anions and onium cations disclosed herein, as well as the various anions and cations described herein. The one or more salts of one or more onium cations and one or more phosphate anions can correspond to the following formula where R 2 is independently at each occurrence an optionally substituted hydrocarbyl group; Z′ is independently at each occurrence an onium cation as described herein, including the variations described herein; a is independently at each occurrence 1, 2, or 3; and b is independently at each occurrence 0, 1, or 2; wherein the sum of a and b is 3.

[0088] The one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions correspond to one of the following formulae:

[0089]

[0090] where 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 may correspond to one of the following formulas:

[0091]

[0092] where R 1 and R 2 As defined herein. The one or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions may correspond to the formula:

[0093] where R 1 and R 2 As defined herein. The one or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions may correspond to the formula:

[0094] where R 1 and R 2 As defined herein.

[0095] The polymerizable composition may comprise one or more zwitterions comprising one or more onium cations, one or more phosphate anions, and an optionally substituted carbon group between the anion and the cation, the carbon group being bonded to the anion and the cation. The one or more zwitterions may be any defined zwitterion that provides the properties disclosed herein. Such zwitterions are formed from the phosphate anions and onium cations disclosed herein, as well as the various anions and cations described herein. The one or more zwitterions comprising one or more onium cations, one or more phosphate anions, and an optionally substituted alkylene moiety between the anion and the cation may correspond to the formula

[0096] where R 2 、R 5 , Z', a and b are as defined herein. The zwitterion may correspond to one of the following formulas:

[0097] where R 1 、R 2 、R 5, a and b are as defined herein. The one or more zwitterions of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions may correspond to one of the following formulae:

[0098]

[0099] where R 1 、R 2 and R 5 As defined herein, the one or more zwitterions containing one or more quaternary nitrogen-containing cations and one or more phosphate anions may correspond to the following formula:

[0100] where R 1 、R 2 and R 5 As defined herein, the one or more zwitterions of one or more quaternary nitrogen-containing cations and one or more phosphate anions correspond to the formula:

[0101] where R 1 、R 2 and R 5 As defined herein, the one or more zwitterions of one or more quaternary nitrogen-containing cations and one or more phosphate anions may correspond to the following formula:

[0102] where R 1 、R 2 and R 5 As defined herein. 5 R is independently at each occurrence an optionally substituted carbon-containing moiety. 5 Each occurrence may independently be one or more of alkylene, arylene, alkarylene groups, aralkylene groups which may contain heteroatoms or one or more unsaturated moieties, wherein two or more R 5 A cycloalkylene group or a cyclic ring containing one or more arylene groups may be formed, wherein such groups may contain heteroatoms and / or unsaturated groups. 5 Can be C independently at each occurrence 1-20 Alkylene, C 3-24 Cycloalkylene, C 5-24 Arylene, C 6-24 Alkarylene, C 6-24 One or more of aralkylene groups, which may contain heteroatoms or one or more unsaturated moieties. 5 Can be C independently at each occurrence 1-12 Alkylene, C 3-12 Cycloalkylene, C5-12 Arylene, C 6-12 Alkarylene, C 6-12 One or more of aralkylene groups, which may contain heteroatoms or one or more unsaturated moieties. 5 Each occurrence can be independently one or more C 1-12 Alkyl groups which may contain heteroatoms or one or more unsaturated moieties. 5 Can be C independently at each occurrence 1-4 Alkylene, which may contain heteroatoms or one or more unsaturated moieties. 1 Each occurrence may independently be one or more of methylene, ethylene, propylene or butylene.

[0103] The polymerizable composition may include one or more of an end-capping agent, a quencher, a chain extender, or a branching agent. The quencher can be any compound that terminates the active ends of the polymer during the polymerization process to stop further polymer growth. The quencher can be one or more of an inorganic acid, an organic acid, and an acidic resin or solid. The quencher can be HCl, H2SO4, RSO3H, HBr, H3PO4, an acidic resin, or an acidic inorganic solid. The quencher can be a sulfonic acid derivative, boric acid or a boric acid derivative, phosphoric acid or a phosphoric acid derivative. The quencher can be a sulfonic acid. The sulfonic acid can be p-toluenesulfonic acid (also known as pTSA or tosylic acid), methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, trifluoromethanesulfonic acid, 4-nitrophenylsulfonic acid, sulfoacetic acid, isopropylbenzenesulfonic acid, xylenesulfonic acid, 3-amino-1-propanesulfonic acid, 2-thioethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, benzenesulfonic acid, 4-hydroxybenzenesulfonic acid, cyclohexanesulfonic acid, 4-ethylbenzenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, 4-methylm-aminobenzenesulfonic acid, 1-naphthalenesulfonic acid or perfluorooctanesulfonic acid. The quencher can be methanesulfonic acid, p-toluenesulfonic acid or a sulfonic acid. The acid used as a quencher can act by protonating the active chain ends of the polymer (e.g., to form -OH or CO2H groups), wherein the anion of the acid acts as a counterion to the polymer-bound cation from the initiator.

[0104] The quencher 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, pyrophosphoric acid, triphosphoric acid, an alkyl or aryl derivative of phosphoric acid, an alkyl or aryl derivative of pyrophosphoric acid, or an alkyl derivative or aryl of triphosphoric acid. The quencher may be a boron-containing compound. The quencher may be fluoroboric acid. The quencher may be an acid bound to a solid support. The solid-supported acid may include an inorganic solid selected from silica, alumina, zirconia, titania, zeolites, metal oxides, and clays. The quenched composition may form a polymer composite with the inorganic solid quencher. The method may include adding a polymer-supported acid as the quencher. The polymer support may include a polymer derived from at least one of styrene, chloromethylated styrene, and divinylbenzene monomers. The polymer solid support may be one or more of polystyrene, polysulfone, nylon, poly(chloromethylstyrene); polyolefin, polyacrylic acid, polymethyl methacrylate, and a cross-linked ethoxylated acrylate resin. When the quencher comprises a solid, the method may include flowing the reactant stream containing the unquenched polymer through a fixed bed of the solid quencher.

[0105] The end-capping agent may include an electrophilic organic compound. The end-capping agent may include one or more of an organic halide, an organic sulfonate, a haloalkylsilane, an aniline derivative, a phosphate derivative, a boric acid derivative as disclosed herein, and an isophthalic acid derivative. 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., to form an -OR or Co2R group), and the released anion X'- acts as a counterion for 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 include a compound of formula R n -X h A compound wherein R n is an optionally substituted C 1-40 aliphatic group, and X h is selected from Cl, Br or I. The capping agent may include R p -CH2-X h , where R p is -H or an optionally substituted group selected from the group consisting of aliphatic groups, aromatic groups, heterocyclic groups and heteroaryl groups. The end-capping agent may be one or more of methyl bromide, methyl iodide, allyl chloride, allyl bromide, benzyl chloride and benzyl bromide. The end-capping agent may include an organic sulfonate. The organic sulfonate may correspond to the formula R n OsO2R q , where R n As defined above, R qis -H or an optionally substituted group selected from the group consisting of aliphatic groups, aromatic groups, heterocyclic groups and heteroaryl groups. The quencher may include methyl trifluoromethanesulfonate. The end-capping agent may include an organic sulfate. The organic sulfate may correspond to the formula R n OsO2OR n , where R n As defined above. The quencher may comprise a dialkyl sulfate, such as dimethyl sulfate or diethyl sulfate.

[0106] The end-capping agent can be a silane, which can include a compound containing a silyl group or a siloxy group. The end-capping agent can be a heat-stable aniline derivative, which can include azoles, such as those selected from the group consisting of benzothiazole, benzoxazole, benzimidazole, 2-aminothiophenol, o-phenylenediamine and 2-aminophenol. Exemplary end-capping agents can further include phosphoric acid esters, such as trimethyl phosphate and triphenyl phosphate. Exemplary end-capping agents can even further include other additives and stabilizers, such as isophthalic acid.

[0107] The polymerizable composition may contain a chain extender or a branching agent. The chain extender or branching agent may be added as a quencher. Analogs of the above-mentioned end-capping agents having two or more suitable reactive functional groups in a single molecule can be used as quenchers, which can act as chain extenders or branching agents, respectively. Quenching with a bifunctional chain extender results in reaction with the carboxylate ends of two separate polymer chains, resulting in the formation of a dimeric extended chain product. It should be understood that bifunctional analogs of any of the above-mentioned quenchers can be used to similar effect. If a trifunctional or higher functional end-capping agent is used, branched, star-shaped, or comb-shaped polymer compositions can be obtained. When the method comprises a continuous process utilizing a plug flow reactor, the quencher can be added at specific points along the length of the reactor.

[0108] The polymer formed is prepared from a ratio of monomer to initiator, such as phosphate and / or carboxylate anions, wherein the molar ratio of monomer to initiator is selected to produce 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 produce a polymer of the desired molecular weight. The method may include contacting the initiator with the monomer until a polymer composition is formed having a number average molecular weight, Mn, as described herein. The Mn of the polymer composition refers to the value measured by gel permeation chromatography (GPC) using THF as solvent and referenced to monodisperse polymethyl methacrylate standards.

[0109] The method includes contacting the initiator with the monomer for a specified time interval. The method may include the step of monitoring the progress of the polymerization reaction (e.g., by analyzing aliquots from the reaction mixture by a suitable technique (e.g., GPC), or by utilizing an in situ monitoring technique). The method may include the step of monitoring the increase in polymer molecular weight and / or the step of monitoring the decrease in monomer concentration. The method may include stopping the reaction when the molecular weight of the polymer composition (or a representative indicator of molecular weight, such as reaction viscosity) reaches a desired value or exceeds a predetermined threshold. The method may include the step of monitoring the consumption of the monomer until its concentration reaches a desired concentration or is below a predetermined threshold. The method may include the step of stopping the reaction when the monomer concentration reaches a desired concentration or is below a predetermined threshold.

[0110] 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. The solvent may include C 4-12 Aliphatic hydrocarbons, ethers or chlorinated hydrocarbons. The solvent may include ether, petroleum ether, isobutane, pentane, hexane or heptane, or higher aliphatic hydrocarbons. 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, tert-butyl methyl ether and diethyl ether. The solvent may include tetrahydrofuran, which may be anhydrous.

[0111] The solvent can be a non-polar solvent. The solvent can be a non-polar ether. The solvent can be a non-cyclic ether. As disclosed above, the solvent can have a polarity of less than 0.2. The solvent can be a dialkyl ether or an alkylcycloalkyl ether. The alkyl group can be branched or straight chain. The alkyl group can contain no unsaturated groups. Exemplary non-polar solvents include methyl tert-butyl ether, dimethyl ether, diethyl ether, cyclopentyl methyl ether, ethyl acetate, and diisopropyl ether.

[0112] The solubility of the initiator in some solvents may be low, and the molecular weight of the resulting polymer may be higher than expected because the effective ratio of monomers in the reaction system may be higher due to a portion of the added initiator being insoluble in the reaction solvent.

[0113] The method may include contacting the monomer with the initiator in the absence of a solvent. The polymerization may be carried out in pure monomer. The method may include contacting the monomer in a solvent system in which the initiator is insoluble. The method may include contacting the comonomer with a suspension of solid particles containing the initiator. The method may include contacting the pure monomer with solid particles containing the initiator, wherein the solid particles are insoluble in the pure monomer. It is desirable to add the initiator, salt, or zwitterion disclosed herein as a liquid or in a liquid carrier. The disclosed initiator, salt, or zwitterion may be heated to a temperature at which it is liquid or soluble in the carrier or solvent, and then the carrier or solvent is added to the reaction mixture. The temperature at which the disclosed initiator, salt, or zwitterion is added to the solvent or carrier or made liquid may be above the process reaction temperature. Adding the initiator in liquid form is advantageous because it reduces the reaction time of the initiation reaction. This reduces or avoids the need for an induction period.

[0114] The initiator and monomer may be contacted at low temperature, ambient temperature, or 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 to about -20°C. The method may include the step of 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 process. The method may include the step of cooling the mixture to maintain the desired temperature. The method may include varying the temperature of the polymerization mixture over time during the process.

[0115] Polymerization can be carried out under elevated pressure. This can allow the process to be carried out at a temperature higher than the boiling point of some reaction mixture components (e.g., solvent, monomer) and / or can contribute to the separation of volatile components when the process stream or reaction vessel under pressurization is decompressed. Monomer can be contacted with the initiator under a pressure higher than 1 bar (0.1 MPa), approximately 2 bar (0.2 MPa) or higher, approximately 3 bar (0.3 MPa) or higher, approximately 5 bar (0.5 MPa) or higher, approximately 10 bar (1.0 MPa) or higher, approximately 15 bar (1.5 MPa) or higher, approximately 20 bar (2.0 MPa) or higher, approximately 30 bar (3.0 MPa) or higher, or approximately 40 bar (4.0 MPa) or higher. The pressure can be about 50 bar (5.0 MPa) or lower, about 60 bar (6.0 MPa) or lower, about 70 bar (7.0 MPa) or lower, about 80 bar (8.0 MPa) or lower, about 90 bar (9.0 MPa) or lower or about 100 bar (10.0 MPa) or lower. Pressure can be applied by pressurizing the reactor head space in contact with the reaction mixture (e.g., by introducing a pressurized inert gas). Pressure can be applied by heating the mixture in a sealed container (contained volume). Pressure can be maintained by applying pressure to a hydrostatically filled reaction vessel. Two or more of these methods can be used. Pressure can be controlled by using a back pressure regulator or other pressure relief system.

[0116] The method disclosed herein can be carried out in a batch process, a continuous process, a mixture of batch and continuous processes (e.g., a batch feed reaction). The method may include the step of adding one or more components to the polymerization mixture over time. Monomers, oligomers, end-capping agents, chain extenders, chain transfer agents, or cross-linking agents can be added to the polymerization mixture over time (continuously or discontinuously one or more times). The composition of the added monomers can change over time. This method is characterized in that the polymer composition produced includes a tapered copolymer or a block copolymer.

[0117] The method may comprise a fed-batch process and includes dissolving or suspending the initiator in the reaction vessel (optionally with an initial charge of solvent and / or monomer) and then adding the monomer, chain extender, chain transfer agent or cross-linking agent to the initial mixture at a controlled rate. Such a method is useful for controlling the exothermic reaction associated with the ring-opening polymerization of some monomers and maintaining safe operating conditions. Certain monomers can be fed at a rate determined at least in part by the exothermic rate observed in the reaction mixture. Monomers can be fed continuously into the process. Monomers can be fed discontinuously (e.g., in a discontinuous addition mode or at a variable rate) into the process. Monomers can be fed over a period of time and then stopped at a certain time interval before the polymerization ends.

[0118] The method may include a continuous flow process and includes a step of continuously adding an initiator to the reactant stream of the monomer. The mixed initiator and monomer stream (monomers stream) may then be directed through a continuous reactor with enough contact times and temperature distributions to produce the required degree of polymerization. The method may include adding more initiators, additional monomers, solvents or other reaction components at a position along the length of the continuous reactor.

[0119] The method may include a continuous flow process and includes the step of contacting a reactant stream comprising an initiator and a monomer in an extruder. The combined initiator monomer stream may be directed through the extruder under sufficient contact time and temperature distribution to consume substantially all of the monomer. The method may include a reactive extruder having a temperature gradient between an inlet and an outlet. The temperature toward the extruder outlet may be higher than the temperature at the extruder inlet. In this process, there may be no solvent in the reactant stream, and the outlet of the extruder includes molten polymer. The molten polymer stream from the extruder may be fed to a pelletizer to produce particles of solid polymer. The method may include a reactive extruder connected to a pre-reactor, the pre-reactor feeding the feed port of the extruder. The pre-reactor may include a plug flow reactor, a batch reactor, or a semi-continuous reactor. Two or more pre-reactors may feed a single extruder. A single pre-reactor may feed two or more reactive extruders.

[0120] The method may include a continuous flow process and includes a step of contacting a reactant stream comprising an initiator and a monomer in one or more reactors. The method may include a slurry batch reactor, a slurry continuous stirred tank reactor, or a slurry loop reactor. The monomers may be polymerized in a liquid phase polymerization reactor and / or a gas phase polymerization reactor. When polymer chains are formed in the reactor during the polymerization process, solid particles of solid polymer may be produced in the reactor, so that the process stream may constitute a slurry. The polymer particles in the slurry may have one or more melt, physical, rheological and / or mechanical properties of interest, such as density, melt index (MI), melt flow rate (MFR), comonomer content, molecular weight, crystallinity, etc. Depending on the application to which the polymer is to be applied, different properties of the particles may be desirable. The selection and control of reaction conditions in the reactor, such as temperature, pressure, chemical concentration, polymer production rate, initiator type, etc., may affect the properties of the polymer particles.

[0121] The disclosed method may include a step of quenching the polymerization reaction. A quencher may be added after a specified reaction time, or when the polymer composition has reached a desired molecular weight (the Mn of the formed polymer composition exceeds a predetermined threshold). The quencher may be added when substantially all monomer has been consumed. When the method comprises a continuous process utilizing a plug flow reactor, the quencher is added at specific points along the length of the reactor.

[0122] This method involves adding an end-capping agent to quench the polymerization, as disclosed in PCT application WO2019241596A1, the entire contents of which are incorporated herein by reference. Monomers can be polymerized such that the ends of the resulting polymer chains have carboxyl or carboxylate functional groups. The end groups react with the end-capping agent. The end-capping agent can make the resulting polymer more stable.

[0123] The quencher, end-capping agent, cross-linking agent or chain extender can be added to the reaction mixture in an amount of 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.

[0124] In methods where a comonomer is present along with the β-lactone, the comonomer can be added at the beginning of the process along with the β-lactone. For example, a batch polymerization can be performed using a specific mixture of β-lactone and one or more comonomers. The methods can include varying the monomer composition over time by adding additional monomer to the polymerization mixture. This addition can include continuous addition of the BPL β-lactone, comonomer, or a mixture of β-lactone and comonomer. This addition can include batch addition of the β-lactone, comonomer, or a mixture of β-lactone and comonomer. Depending on the reaction conditions provided and the relative polymerization rates of the comonomers under the polymerization conditions, these methods can produce random, tapered, or block copolymers.

[0125] The method may include the use of chain extenders, chain transfer agents, and / or crosslinking agents. The method may include contacting β-propiolactone (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 agent that is 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, and the net effect is 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 polymer composition produced, to optimize the amount of catalyst used, and / or to control the polydispersity of the polymer composition produced. Chain transfer agents can also be used to introduce additional functional groups at the ends of the chains (e.g., for subsequent crosslinking or chain extension reactions, or to impart specific physical properties, such as hydrophilicity or hydrophobicity, etc.). Examples of the latter include chain transfer agents having free radical polymerizable functional groups, such as vinyl groups, perfluorinated moieties, or siloxyl groups.

[0126] Chain transfer agents (CTA) may include acidic compounds. Such acidic compounds are characterized in that their conjugate bases are nucleophilic. The conjugate bases of the provided acidic chain transfer agents may have sufficient nucleophilicity to be able to ring-open β-propene lactone (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, mercaptans, phenols, and the like. Chain transfer agents may include compounds of the formula Y'-T-(Y') r Compounds wherein each Y' is independently an acidic functional group (or a salt formed by deprotonation of such a group), -T- is a multivalent moiety, and r is an integer between 0 or 1-10. Y' can be independently selected from carboxylic acids, sulfonic acids, phosphoric acids, phosphonic acids, phosphinic acids, thiocarboxylic acids, dithiocarboxylic acids, mercaptans, and phenol-OH groups (or anions formed by deprotonation of any of these groups). Chain transfer agents can include molecules (dicarboxylic acids, tricarboxylic acids) having more than one functional group capable of acting as a chain transfer agent. Chain transfer agents can include carboxylic acids such as formic acid, acetic acid, propionic acid, 3-hydroxypropionic acid, 3-hydroxybutyric acid, lactic acid, benzoic acid, acrylic acid, and methacrylic acid. Chain transfer agents can include phenols, mercaptans, or derivatives thereof.

[0127] The CTA can be present at the start of the reaction or added during the polymerization process (continuously at a constant or variable rate, or in batches). The addition of the CTA can be used to control the molecular weight distribution of the polymer composition. The CTA can be added in batches at one or more time points in the reaction to provide a polymer composition with a bimodal or multimodal molecular weight distribution. The CTA can 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 start of the polymerization reaction, the result is a polymer composition with a narrow PDI. The chain transfer agent can be provided at a molar ratio of about 1:1 to about 10,000:1 relative to the polymerization initiator, or at a molar ratio of about 1:1 to about 10:1, such as 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 8:1, or 10:1, or at a molar ratio of 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).

[0128] The polymerization method can be integrated into a process for producing β-lactone. This integrated process offers advantages in energy efficiency due to reduced introduction of water, oxygen, or other impurities, and can produce a higher quality polymer product. The method can include reacting ethylene oxide with carbon monoxide to form β-propiolactone. Exemplary catalysts and methods for this process are described in published patent applications: WO2013 / 063191, WO2014 / 004858, WO2003 / 050154, WO2004 / 089923, WO2012 / 158573, WO2010 / 118128, WO2013 / 063191, and WO2014 / 008232; in U.S. Pat. Nos. 10,662,283, 5,359,081, and 5,310,948, and in the publication "Synthesis of beta-lactones" J. Am. Chem. Soc., Vol. 124, 2002, pp. 1174-1175, the entire contents of each of which are incorporated herein by reference. The process may include the steps of contacting ethylene oxide with carbon monoxide in the presence of a carbonylation catalyst and a solvent to provide a reactant stream comprising β-propiolactone; separating a product stream comprising β-lactone from the reactant stream; and feeding the reactant stream comprising β-lactone into a polymerization reactor for contact with an anionic initiator to provide a second reactant stream comprising a biodegradable polyester. This combined carbonylation / polymerization process is characterized in that substantially all of the carbonylation catalyst is removed from the reactant stream comprising β-propiolactone prior to feeding the reactant stream into the polymerization reactor. This combined carbonylation / polymerization process is characterized in that at least a portion of the solvent used in the carbonylation process is present in the reactant stream comprising β-propiolactone and is fed into the polymerization reactor. The process may include separating the solvent from the second reactant stream comprising the polymer. The process may include recycling the separated solvent back into the carbonylation reaction. The process is characterized in that the reactant stream comprising β-propiolactone contains residual ethylene oxide, and a β-propiolactone-ethylene oxide mixture is fed into the polymerization reactor. Ethylene oxide may comprise a comonomer in the BPL polymerization.

[0129] The method described herein comprises the step of contacting the β-lactone and an optional comonomer with a polymerization initiator, which is one or more salts of one or more onium cations and one or more phosphate anions, one or more zwitterions having one or more phosphate anions and onium cations, or one or more carboxylates of onium cations, which can be generated in situ. The carboxylates of the cations can include any compound having an onium cation residue and a carboxylate group in salt form. The carboxylate moiety can have a hydrocarbon group bonded to a carbonyl group, and it can be optionally substituted. The hydrocarbon group can be an alkyl, aryl, or alkaryl group. The alkyl group can be C1至20 Straight or branched chain, optionally substituted with substituents that do not interfere with the ability of the salt to act as an anionic initiator. The hydrocarbon group may be an optionally substituted C 1至8 Straight-chain or branched alkyl, C 1至4 Straight or branched alkyl, methyl or ethyl or methyl. The onium cation can be any cation that forms a salt with a carboxylate that does not interfere with the carboxylate forming an anion that can initiate anionic polymerization. Exemplary oniums include one or more cations containing nitrogen, phosphorus, sulfur, antimony or arsenic. Exemplary oniums contain one or more of nitrogen, phosphorus or sulfur. The onium can contain one or both of nitrogen and phosphorus. The onium can contain nitrogen. The carboxylate of the onium ion can correspond to the following formula:

[0130] where R 20 R is independently at each occurrence an optionally substituted hydrocarbyl group, w is independently at each occurrence 1 or greater, and Z is an onium cation as described herein. 20 It may be a multivalent body having a valence of W. 20 It can be an alkyl, aryl or alkaryl group. 20 It may be C optionally substituted by a substituent 1至20 Straight or branched chain, said substituents do not interfere with the ability of said salt to function as an anionic initiator. 20 It may be optionally substituted C 1-8 Straight-chain or branched alkyl, C 1-4 A may be a straight or branched alkyl group, a methyl group, an ethyl group, or a methyl group. A, at each occurrence, may independently be a polymer chain comprising units derived from a ring-opened beta lactone. W, at each occurrence, may independently be 2 or greater. W may be from 1 to 6. W may be from 2 to 6 or from 2 to 3. The initiator may include an organic "onium cation" as described herein. The disclosed salts and zwitterions may be used as initiators, generating an initiator and acting to accelerate polymerization.

[0131] The disclosed method can include contacting the monomer with an initiator in the presence of a complexing agent. Adding a complexing agent can improve the method by increasing the polymerization rate, increasing the yield of the polymer, or can improve the properties of the polymer by controlling properties such as molecular weight or polydispersity. Exemplary complexing agents include crown ethers and other macropolyheterocycles containing rings with multiple -O-, -NR-, and -S-heteroatoms. Complexing agents include crown ethers. Exemplary crown ethers include, but are not limited to, those described in the paper entitled "APPLICATIONS OF CROWN ETHERS IN INDUSTRIAL ANIONIC POLYMERIZATIONS" (Thomas Newton Montgomery, Jr.; Georgia Institute of Technology, December, 1977), the entire contents of which are incorporated herein by reference. 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), dibenzo-18-crown-6, 21-crown-7, and derivatives or mixtures of any of these. Complexing agents may include 15-crown-5 or 12-crown-4. Crown ethers may be selected based on their ability to effectively form complexes with the cationic functional groups present in the zwitterionic polymerization initiator used in the method. Complexing agents include macrocyclic heterocycles containing heteroatoms other than oxygen. Complexing agents may include crown ethers in which one or more oxygen atoms are substituted by nitrogen or sulfur atoms. Complexing agents may include azacrown ethers, such as 4,7,13,16,21-pentaoxa-1,10-diazabicyclo[8.8.5]tricosane; 1,4,8,12-tetraazacyclopenta-decane; and 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane. 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 thiacrown ethers.

[0132] 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 into the reaction as described above to add the initiator. The complexing agent can be used in an amount of about 1:100 to about 100:1 molar ratio relative to the polymerization initiator, and in an amount of 1:10 to 10:1, or 1:2 to 2:1 molar ratio relative to the zwitterionic polymerization initiator. A chain transfer agent can be used in the process, and the complexing agent can be provided in a molar ratio of 1:10 to 10:1, 1:5 to 5:1, or 1:2 to 2:1 molar ratio relative to the CTA.

[0133] When w is 2 or greater, the formed polymer can be chain extended by a compound having two or more epoxide and / or lactone groups. Chain extension and / or crosslinking can be carried out under conditions of ring opening of the epoxide and / or lactone groups as disclosed herein.

[0134] Implementation Plan

[0135] 1. A polymer comprising one or more polymer chains having ring-opening β-lactone units, having at one end of a portion of the polymer chains a residue of a phosphate anion covalently bound to the one end of the polymer chain, and at the other end of a portion of the polymer chains one or more onium-containing cations.

[0136] 2. The polymer of embodiment 1, wherein the onium cation contains one or more of nitrogen, phosphorus, sulfur, antimony, or arsenic.

[0137] 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.

[0138] 4. A polymer according to any of the preceding embodiments, wherein the one or more quaternary nitrogen-containing cations are amines having four carbon groups, two or more of which may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms.

[0139] 5. The polymer according to any one of the preceding embodiments, wherein the one or more nitrogen-containing cations include one or more ammonium cations, amidinyl cations, and guanidinyl cations, or onium cations based on nitrogen-containing heterocycles.

[0140] 6. A polymer according to any one of the preceding embodiments, wherein the one or more nitrogen-containing cations comprises one or more nitrogen-containing heterocycle-based onium cations comprising optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium.

[0141] 7. The polymer according to any of the preceding embodiments, wherein the one or more nitrogen-containing cations comprises one or more optionally substituted imidazolium salts.

[0142] 8. The polymer according to any of the preceding embodiments, wherein the one or more nitrogen-containing cations comprises one or more of one or more quaternary ammonium cations or one or more guanidinium cations.

[0143] 9. The polymer according to any one 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.

[0144] 10. The polymer according to any one of the preceding embodiments, wherein the one or more quaternary ammonium cations correspond to the formula

[0145]

[0146] where R 1 is independently a carbon-containing group at each occurrence, and wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.

[0147] 11. A polymer according to any one of the preceding embodiments, wherein the one or more guanidinium cations correspond to the formula

[0148] where R 1 is independently a carbon-containing group at each occurrence, and wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.

[0149] 12. A polymer according to any one of the preceding embodiments, wherein the one or more imidazolium cations corresponds to the formula

[0150] where R 1 is independently at each occurrence a carbon-containing group.

[0151] 13. The polymer according to any one of the preceding embodiments, wherein the one or more quaternary ammonium cations is one or more tetraalkylammonium anions or N-alkyl substituted imidazolium.

[0152] 14. The polymer according to any one of the preceding embodiments, wherein the one or more phosphorus-containing cations are one or more quaternary phosphonium anion cations.

[0153] 15. The polymer of any one of the preceding embodiments, wherein the one or more quaternary phosphonium cations correspond to the formula:

[0154] where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.

[0155] 16. The polymer of any one of the preceding embodiments, wherein the phosphate anion corresponds to the formula: where R 2 is independently at each occurrence an optionally substituted carbon-containing group;

[0156] a is independently 1, 2 or 3 at each occurrence; and b is independently 0, 1 or 2 at each occurrence;

[0157] The sum of a and b is 3.

[0158] 17. A polymer according to any one of the preceding embodiments, wherein the phosphate anion corresponds to the formula where R 2 is independently at each occurrence a carbon-containing group.

[0159] 18. The polymer according to any one of the preceding embodiments, wherein the one or more polymer chains have the residue of an end-capping agent or a quencher on a portion of the ends of the chain.

[0160] 19. The polymer according to any one of the preceding embodiments, wherein the terminal end-capping agent is an organic halide, an organic sulfonate, a haloalkylsilane, an aniline derivative, a phosphate derivative, and an isophthalic acid derivative.

[0161] 20. The polymer according to any one of the preceding embodiments, wherein the polymer contains a comonomer polymerized with the ring-opening β-propiolactone and / or substituted β-propiolactone.

[0162] 21. The polymer according to 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 glycolides.

[0163] 22. The polymer of any preceding embodiment, wherein the comonomer is one or more epoxides.

[0164] 23. The polymer of any one of the preceding embodiments, wherein the polymer corresponds to one of the following formulae:

[0165] where R 2 is independently at each occurrence an optionally substituted carbon-containing group,

[0166] R 3is independently at each occurrence hydrogen, a carbon-containing group; which may optionally contain one or more heteroatoms and / or substituents

[0167] a is independently 1, 2, or 3 at each occurrence;

[0168] b is independently 0, 1, or 2 at each occurrence;

[0169] x is independently approximately a real number greater than 1 at each occurrence; and,

[0170] Z is independently at each occurrence hydrogen, the residue of an onium cation, the residue of a quencher, a capping agent, or hydrogen.

[0171] 24. The polymer according to any one of the preceding embodiments, wherein a portion of the polymer chains may have carboxylate groups at the ends of some of the chains.

[0172] 25. The polymer according to any one of the preceding embodiments, wherein a portion of the polymer chains may have carboxylate groups at the ends of some chains corresponding to the formula:

[0173]

[0174] where R 2 is independently at each occurrence an optionally substituted carbon-containing group,

[0175] R 3 is independently at each occurrence hydrogen, a carbon-containing group; which may optionally contain one or more heteroatoms and / or substituents,

[0176] R 4 is independently at each occurrence a carbon-containing group, which may contain heteroatoms or be substituted with functional groups;

[0177] a is independently 1, 2, or 3 at each occurrence;

[0178] b is independently 0, 1, or 2 at each occurrence;

[0179] x is independently a real number greater than 1 at each occurrence; and,

[0180] Z is independently at each occurrence hydrogen, the residue of an onium cation, the residue of a quencher, a capping agent, or hydrogen.

[0181] 26. A polymerizable composition comprising:

[0182] a. one or more β-propiolactones and / or substituted β-propiolactones; and

[0183] b. 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.

[0184] 27. The polymerizable composition of embodiment 26, wherein the onium cation comprises one or more of nitrogen, phosphorus, sulfur, antimony, or arsenic.

[0185] 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.

[0186] 29. The polymerizable composition of any one of embodiments 26 to 28, wherein the one or more quaternary nitrogen-containing cations or quaternary phosphonium-containing cations are one or more tetraalkylammonium anions or tetraalkylphosphonium anions.

[0187] 30. A polymerizable composition according to any one of embodiments 26 to 28, wherein the one or more quaternary nitrogen-containing cations are tetrahydrocarbyl amines, wherein two or more of the hydrocarbyl groups can form one or more aromatic or non-aromatic ring structures, which ring structures can optionally contain one or more heteroatoms.

[0188] 31. The polymerizable composition of any one of embodiments 26 to 30, wherein the one or more quaternary nitrogen-containing cations include one or more ammonium cations, amidinyl cations, and guanidinyl cations, or onium cations based on nitrogen-containing heterocycles.

[0189] 32. A polymerizable composition according to any one of embodiments 26 to 31, wherein the one or more quaternary nitrogen-containing cations include one or more nitrogen-containing heterocyclic-based onium cations, wherein the nitrogen-containing heterocyclic onium cations include optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium.

[0190] 33. The polymerizable composition of any one of embodiments 26 to 32, wherein the one or more quaternary nitrogen-containing cations comprise one or more optionally substituted imidazoliums.

[0191] 34. The polymerizable composition of any one of embodiments 26 to 32, wherein the one or more quaternary nitrogen-containing cations are one or more quaternary ammonium cations corresponding to the formula

[0192] where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.

[0193] 35. The polymerizable composition of any one of embodiments 26 to 34, wherein the one or more quaternary nitrogen-containing cations are one or more guanidinium cations corresponding to the formula:

[0194] where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.

[0195] 34b. The polymerizable composition of any one of embodiments 25 to 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.

[0196] 35b. The polymerizable composition of any one of embodiments 25 to 34, wherein the one or more imidazolium cations corresponds to the formula

[0197] where R 1 and is independently at each occurrence a carbon-containing group which may contain heteroatoms.

[0198] 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.

[0199] 37. The polymerizable composition of any one of embodiments 26 to 36, wherein the one or more quaternary phosphonium anion cations are one or more tetraalkylphosphonium cations.

[0200] 38. The polymerizable composition of any one of embodiments 26 to 34, wherein the one or more quaternary phosphonium cations corresponds to the formula: where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.

[0201] 39. The polymerizable composition of any one of embodiments 26 to 38, wherein the one or more quaternary phosphonium cations are tetraalkylphosphonium cations.

[0202] 40. The polymerizable composition of any one of embodiments 26 to 39, wherein the phosphate anion corresponds to the formula: where R 2is independently at each occurrence an optionally substituted carbon-containing group;

[0203] a, at each occurrence, is independently 1, 2, or 3; and b, at each occurrence, is independently 0, 1, or 2; wherein the sum of a and b is 3.

[0204] 41. The polymerizable composition of any one of embodiments 26 to 40, wherein the one or more salts of one or more onium cations and one or more phosphate anions correspond to the formula where R 2 is independently at each occurrence an optionally substituted carbon-containing group; Z′ is independently at each occurrence an onium cation; a is independently at each occurrence 1, 2, or 3; and b is independently at each occurrence 0, 1, or 2; wherein the sum of a and b is 3.

[0205] 42. The polymerizable composition of any one of embodiments 26 to 41, wherein the one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions correspond to one of the following formulas

[0206] where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms; and wherein R 2 is independently at each occurrence an optionally substituted carbon-containing group; a is independently at each occurrence 1, 2 or 3; and b is independently at each occurrence 0, 1 or 2; wherein the sum of a and b is 3.

[0207] 43. The polymerizable composition of any one of embodiments 26 to 42, wherein the one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions correspond to one of the following formulas

[0208] where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms; and wherein R 2 is independently at each occurrence a carbon-containing group.

[0209] 44. The polymerizable composition of any one of embodiments 26 to 43, wherein the one or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions correspond to the formula

[0210] where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms; and R 2 and independently at each occurrence is an optionally substituted carbon-containing group.

[0211] 45. The polymerizable composition of any one of embodiments 26 to 44, wherein the one or more zwitterionic salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions correspond to the formula where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms; and R 2 and independently at each occurrence is an optionally substituted carbon-containing group.

[0212] 46. ​​The polymerizable composition of any one of embodiments 26 to 45, wherein the one or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions correspond to the formula where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms; and R 2 and independently at each occurrence is optionally substituted hydrocarbyl.

[0213] 47. The polymerizable composition of any one of embodiments 26 to 46, wherein the zwitterion corresponds to the formula where R 2 is independently an optionally substituted carbon-containing group at each occurrence; R5 is independently an optionally substituted carbon-containing moiety; Z′ is independently an onium cation at each occurrence; a is independently 1, 2 or 3 at each occurrence; and b is independently 0, 1 or 2 at each occurrence; wherein the sum of a and b is 3.

[0214] 48. The polymerizable composition of any one of embodiments 26 to 47, wherein the zwitterion corresponds to one of the formula

[0215] where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms; and wherein R 2 is independently at each occurrence an optionally substituted carbon-containing group; R 5 is independently an optionally substituted carbon-containing moiety; a is 1, 2, or 3 at each occurrence; and b is 0, 1, or 2 at each occurrence, wherein the sum of a and b is 3.

[0216] 49. The polymerizable composition of any one of embodiments 26 to 48, wherein the one or more zwitterions of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions correspond to one of the formula

[0217] where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms; wherein R 2 is independently at each occurrence an optionally substituted carbon-containing group; and, R 5 is independently an optionally substituted carbon-containing moiety.

[0218] 50. The polymerizable composition of any one of embodiments 26 to 49, wherein the one or more zwitterions containing one or more quaternary nitrogen-containing cations and one or more phosphate anions correspond to the formula: where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms; and R 2 is independently at each occurrence an optionally substituted hydrocarbyl group, and R 5 is independently an optionally substituted carbon-containing moiety.

[0219] 51. The polymerizable composition of any one of embodiments 26 to 50, wherein the one or more zwitterions of one or more quaternary nitrogen-containing cations and one or more phosphate anions correspond to the formula: where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms; and R 2 is independently at each occurrence an optional carbon-containing group, and R 5 is independently an optionally substituted carbon-containing moiety.

[0220] 52. The polymerizable composition of any one of embodiments 26 to 51, wherein the one or more zwitterions of one or more quaternary nitrogen-containing cations and one or more phosphate anions correspond to the formula: where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms; and R 2 is independently at each occurrence an optionally substituted carbon-containing group, and R 5 is independently an optionally substituted carbon-containing moiety.

[0221] 53. The polymerizable composition of any one of embodiments 26 to 52, comprising one or more comonomers copolymerized with one or more β-lactones.

[0222] 54. The polymerizable composition of any one of embodiments 26 to 53, comprising one or more of a chain transfer agent, a chain extender, a quencher, and an end-capping agent.

[0223] 55. The polymerizable composition of any one of embodiments 26 to 54, wherein the molar ratio of the one or more β-lactones to the one or more salts of the one or more onium cations and the one or more phosphate anions or the one or more zwitterions having the one or more phosphate anions and the onium cations is from about 10 to 1 to about 1,000,000 to 1.

[0224] 56. The polymerizable composition according to any one of embodiments 26 to 55, wherein the end-capping agent is an organic halide, an organic sulfonate, a haloalkylsilane, an aniline derivative, a phosphate derivative, a boric acid derivative, and an isophthalic acid derivative.

[0225] 57. A polymerizable composition according to any one of embodiments 26 to 56, wherein the amount of the capping agent or quencher present is 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.

[0226] 58. The polymerizable composition of any one of embodiments 26 to 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 glycolides.

[0227] 59. The polymerizable composition of any one of embodiments 26 to 58, wherein the comonomer is one or more epoxides.

[0228] 60. A method comprising contacting the components of the polymerizable composition of any of embodiments 26 to 59 under conditions to produce one or more polymers comprising one or more polymer chains having ring-opening β-lactone units.

[0229] 61. The method of embodiment 60, wherein the components are contacted at a temperature of about 30°C to about 120°C.

[0230] 62. The method of embodiment 60 or 61, wherein the components are contacted at a pressure of about 1 bar (0.1 MPa) to about 20 bar (2.0 MPa).

[0231] 63. The method of any one of embodiments 60 to 62, wherein the components are contacted for a sufficient time to consume substantially all of the one or more of the β-lactone and the comonomer.

[0232] 64. The method according to any one of embodiments 60 to 63, wherein after a specified reaction time, or when the polymer composition reaches a desired molecular weight, a quencher is added to terminate the polymerization reaction.

[0233] 65. The method of any one of embodiments 60 to 64, wherein the quencher is one or more of an inorganic acid, an organic acid, or an acidic resin or a solid.

[0234] 66. The method of any one of embodiments 60 to 65, wherein an end-capping agent is added after a specified reaction time, or when the polymer composition reaches a desired molecular weight.

[0235] 67. The method of embodiment 66, wherein the capping agent comprises one or more electrophilic organic compounds.

[0236] 68. The method according to embodiment 66 or 67, wherein the capping agent comprises one or more of an organic halide, an organic sulfonate, a haloalkylsilane, an aniline derivative, a phosphate derivative, a boric acid derivative, and an isophthalic acid derivative.

[0237] 69. The method of any one of embodiments 66 to 68, wherein the capping agent is present in an amount less than 10 molar equivalents relative to the amount of the one or more salts of the one or more onium cations and the one or more phosphate anions.

[0238] 70. The method of any one of embodiments 60 to 69, wherein the components are contacted in a solvent that is a non-polar solvent or a polar solvent.

[0239] 71. The method of embodiment 70, wherein the solvent is a non-polar ether, an alkanol, or an acetate.

[0240] 72. The method according to embodiments 70 to 72, wherein the solvent exhibits a polarity of less than 0.2.

[0241] 73. The method of any one of embodiments 70 to 73, wherein the solvent is an acyclic ether, or a cyclic ether, a lower alkanol, or an alkyl acetate.

[0242] 74. The method according to any one of embodiments 70 to 73, wherein the solvent is methyl tert-butyl ether, dimethyl ether, diethyl ether, cyclopentyl methyl ether, ethyl acetate, diisopropyl ether.

[0243] 75. The method of any one of embodiments 60 to 74, wherein the formed polymer is contacted with a polyepoxide or polylactone under conditions such that the polymer is crosslinked through the terminal groups of the polymer.

[0244] 75. The method according to any one of embodiments 60 to 75, wherein the polymer formed has a carboxylate group and / or a phosphate group at one end of the formed chain.

[0245] 76. The method of any one of embodiments 60 to 75, wherein a portion of the end groups are phosphate groups.

[0246] 77. The method of any one of embodiments 60 to 76, wherein a portion of the terminal groups is one or more nitrogen-containing cations or phosphorus-containing cations.

[0247] Example

[0248] The following examples are illustrative only and are not intended to limit any aspect of the present disclosure in any way.

[0249] Phosphate used in the examples:

[0250]

[0251] Bio-based phosphate zwitterions used in the examples

[0252]

[0253] Synthesis of salts of trimethyl phosphate and tertiary amines.

[0254] Synthesis of dimethylisopropyltrimethylammonium phosphate [iPTMA DMP]. In a 100 mL round bottom flask equipped with a stir bar, dimethylisopropylamine [DMIPA; 20 mL; 164 mmol] and trimethyl phosphate [TMP; 19.1 mL; 164 mmol] were combined. 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 h, 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 that was quickly filtered and dried under vacuum overnight to give a hygroscopic colorless / white semisolid, 31 g [90%] [T m =21℃].

[0255] 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. The reaction is heated to 150°C overnight (13 h) to yield a yellow liquid (12.7 g) in quantitative yield. This ionic liquid is used directly without further treatment.

[0256] Synthesis of Tetramethylammonium Diphenyl Phosphate [TMADPP]. Tetramethylammonium hydroxide in water [approximately 25% in water; 2.5 mL] was added to a 50-mL two-necked round-bottom flask equipped with a stir bar. The flask was then cooled to 0°C in an ice bath, and 1.7 g of diphenyl phosphate dissolved in a small amount of water [~10 mL] was added dropwise. Once all the acid was added, the solution was allowed to warm to room temperature. After 1 hour, the flask was placed in an oil bath at 35°C with low air flow overnight to evaporate the water, yielding a white powder, approximately 2 g [TMADPP]. m =78℃].

[0257] Table 1. Properties of ionic liquids

[0258]

[0259] a. Determined by differential scanning calorimetry [DSC; 10°C / min]

[0260] b. By thermogravimetric analysis [TGA; 2(g) 10℃ / min]

[0261] c. Solubility was tested at room temperature at a concentration of 1 mg / mL.

[0262] Tertiary amines readily react with trimethyl phosphate in bulk to produce quaternary ammonium phosphates. These solids are isolated as low-melting solids [Table 1]. With the exception of octadecyltrimethylammonium dimethylphosphate [ODTMADMP], which also dissolves in tetrahydrofuran [THF] solutions, the quaternary ammonium phosphates are soluble only in water and alcohol solutions.

[0263] Imidazolium-based ionic liquids are also prepared using the same methods as quaternary ammonium phosphates. Unlike tertiary amines, imidazolium derivatives can react with tris(2-ethylhexyl)phosphate to form the corresponding imidazolium phosphates, such as 1-butyl, 3-(2-ethylhexyl)imidazolium, and bis(2-ethylhexyl)phosphate (behim DEHP). These salts exhibit solubility similar to that of quaternary ammonium phosphates. Surprisingly, behim DEHP is insoluble in water but readily soluble in methyl tert-butyl ether (MTBE), an ideal solvent for β-lactone polymerization. 1,3-Disubstituted imidazolium phosphates are liquids at room temperature, a desirable characteristic for polymerization additives and also facilitates the addition of reagents without the need for heat or solvents.

[0264] Finally, phosphates are prepared through acid / base reactions. This is a conventional method for preparing tetraalkylammonium salts using phosphoric acid or carboxylic acids by dehydrating tetramethylammonium hydroxide with an organic acid. This can be used to prepare monobasic ammonium phosphate salts, such as tetramethyldiphenylammonium phosphate [TMADPP], or tribasic ammonium phosphate salts, such as tris(tetramethylammonium)phosphate [TTMAP]. These salts precipitate as white solids that do not melt but decompose before melting.

[0265] Examples of polymerization using ionic liquids:

[0266] Example 1 The ionic liquid, ODTMADMP [155 mg; 0.32 mmol], was added to a 20 mL scintillation vial equipped with a stir bar. A solution of 1 mL of β-propiolactone [bPL; 16 mmol] in 10 mL of methyl tert-butyl ether [MTBE] was then added to the vial. The reaction was heated at 40°C, and a white powder precipitated from the solution in less than 20 minutes. After 1 hour, GC-TCD analysis of the reaction solvent showed that the β-propiolactone was consumed by greater than 99%. To stimulate the reaction, the solid was filtered, collected, and vacuum dried overnight to yield a white, fluffy solid, 1.01 g [89%; M n (GPC)=45800g / mol, PDI=2.2].

[0267] Ionic liquids as polymerization agents for the preparation of polypropiolactone from bPL

[0268] To test the validity of the structure-property relationship of phosphate-based ionic liquids as polymerization agents for β-propiolactone, reactions were performed under uniform solvent conditions (1.6 M bPL in MTBE at 40°C) over a range of monomer-to-ionic liquid ratios. In this context, a "polymerization agent" can be defined as a catalyst, initiator, or both, acting through a reversible reaction that does not completely consume the phosphate catalyst. Methyl tert-butyl ether (MTBE) was chosen based on the efficacy of β-propiolactone in MTBE solvent under similar conditions using tetramethylammonium acetate as an initiator.

[0269] Table 2. Conditions and results of polymerization of bPL with phosphate ionic liquids

[0270] Ionic liquids [ILs] <![CDATA[M:IL a ]]> <![CDATA[Time b [h]]]> <![CDATA[Mn c [g / mol]]]> <![CDATA[Mw c [g / mol]]]> <![CDATA[PDI c Mw / Mn]]> ODTMADMP 50 1 45800 100800 2.2 250 1 47900 115000 2.4 1000 1 54500 120000 2.2 MmimDMP 50 24 11300 56900 3.0 250 24 32600 93700 2.9 1000 24 55800 172500 3.1 TTMAP 50 3 4200 17100 4.0 250 3 8100 43600 5.4 1000 3 days 53200 262400 4.2 <![CDATA[K3PO4]]> 50 24 92800 681500 7.4 250 24 118400 405000 3.4 1000 6 days 135600 364500 2.7 a-phosphatidylcholine 50 24 33600 299300 8.9 250 24 52900 348900 6.6 1000 24 108000 341500 3.1

[0271] a Molar ratio of monomer [bPL] to ionic liquid in MTBE solvent [~1.6 M].

[0272] b Time to reach a conversion of greater than 99.9% of bPL.

[0273] c Number average molar mass [Mn], weight average molar mass [Mw] and polydispersity index [PDI] determined by GPC in CHCl3 relative to PMMA standards.

[0274] Ammonium phosphates are highly effective additives for the polymerization of β-propiolactone. The most active phosphate is ODTMA DMP, achieving >99% conversion of bPL and producing high-molecular-weight P3HP in less than 1 hour [Mw = >120,000 g / mol; PDI = 2.2]. Imidazolium salts, such as mmim DMP, are also effective, producing high-molecular-weight polymers at high conversions after 24 hours of reaction [Mw = >172,500 g / mol; PDI = 3.1]. Ternary salts have also been used for the polymerization of bPL [TTMAP and tribasic potassium phosphate; K3PO4]. The ternary salts were nearly insoluble in the MTBE / bPL reaction mixture; however, these salts produced very different results for P3HP synthesis; TTMAP produced low molar masses in a relatively fast reaction time (3 h; Mw = 17,100 g / mol; PDI = 4.0), while K3PO4 produced high molar masses after stirring overnight (24 h; Mw = 681,500 g / mol; PDI = 7.4). The low solubility of the salts likely contributed to the slow reaction, especially considering that the basicity of the ternary phosphates is much higher than that of the monophosphates. Nevertheless, K3PO4 was an effective additive to produce high molar mass P3HP in a relatively fast reaction time (24 h) and without the need for any ammonium additives.

[0275] Analysis of the monomer to ionic liquid ratio [M:IL] can provide mechanistic insight into the effects of phosphate. In general, when ODTMA DMP is used in the polymerization of bPL, the molar mass of the resulting polymer is independent of the M:IL ratio [ Figure 1 This suggests that the DMP anion is not the primary initiator of bPL polymerization, but rather reacts in a different manner, such as as a base or in a reversible initiation event. The salt likely does not act as a catalyst alone, as higher ODTMA DMP loadings did not result in faster reaction times. Conversely, lower ODTMA DMP loadings (M:IL ratio = 1000:1) resulted in the fastest complete bPL conversion. Figure 1 Shows the molar mass [M n ] on the ratio of monovalent ionic liquid equivalents to β-lactone. Reactions were performed at 40°C in MTBE [~1.6 M] with ODTMA DMP ionic liquid. The dotted line represents the theoretical molar mass [Theo].

[0276] The tribasic phosphate TTMAP showed the expected trend in the polymerization control of bPL. That is, when more phosphate was used, the polymerization was faster and produced polymers with lower molar mass, such as Figure 2 This is likely due to the increased nucleophilicity of the tribasic phosphate anion, which increases the potency of the initiator. 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 molar mass [M n ] on the ratio of ternary ionic liquid equivalents to β-lactone. Reactions were performed at 40°C using TTMAP ionic liquid in MTBE [~1.6 M]. The dashed line represents the theoretical molar mass [Theo].

[0277] pass 1 End group analysis by H NMR spectroscopy indicated that the major initiator group was the acrylate anion [Figures 3 and 4]. The molar mass using acrylate as the end group closely matched the molar mass of the polymer determined by GPC analysis [Tables 3 and Figure 5 Analysis of the dimethyl phosphate signals and the methyl groups on the ammonium groups indicated that they were not covalently attached to the polymers, but rather that acrylate was the predominant terminal group in these polymers.

[0278] Figure 3a and 3b The results show that P3HP prepared using octadecyl-trimethylammonium dimethyl phosphate [ODTMADMP] 1H NMR spectrum (500 MHz; CDCl3). Top: Integration of acylate [CHH=CH-CO-] set to 1. Bottom: Integration of octadecyl-CH3 set to 3. Reaction conditions [at 40°C, in MTBE solvent (1.6 M), M:IL = 50:1]. Figure 4 The results show that P3HP prepared using tris(tetramethylammonium)phosphate [TTMAP] 1 H NMR spectrum (500 MHz; CDCl3). Reaction conditions [at 40°C, in MTBE solvent (1.6 M), M:IL = 50:1]

[0279] Table 3. End group analysis of monobasic and ternary phosphate ionic liquids used for P3HP polymerization.

[0280] Ionic liquids [ILs] <![CDATA[M:IL a ]]> <![CDATA[Mn b [g / mol]]]> <![CDATA[Mn c [g / mol]]]> <![CDATA[Mn d [g / mol]]]> <![CDATA[Mn e [g / mol]]]> ODTMADMP 50 3600 45800 53700 1300 250 18000 47900 43700 11700 1000 72000 54500 64800 64800 TTMAP 50 3600 4200 2000 2000 250 18000 8100 7200 7400 1000 72000 53200 44900 <![CDATA[265000 f ]]>

[0281] a Molar ratio of monomer [bPL] to ionic liquid [IL].

[0282] bTheoretical molar mass based on the M:IL ratio [ratio × 72 g / mol]

[0283] c Molar mass determined by gel permeation chromatography [GPC; CHCl3 @ 1.0 mL / min compared to PMMA standards]

[0284] d Using acrylic acid end groups in CDCl3 according to 1 molar mass determined by HNMR spectroscopy; Figure 4 ]

[0285] e using ammonium end groups in CDCl3 according to 1 Molar mass determined by HNMR spectroscopy; Figure 3]

[0286] The reaction required >3 days to complete. The tetramethylammonium peak became broadened, indicating that a side reaction may have occurred.

[0287] Figure 5 .Based on GPC and end group analysis 1 H NMR spectrum, molar mass of P3HP using ODTMADMP as catalyst [g / mol].

[0288] The formation of acrylates by elimination chemistry during bPL polymerization is highly dependent on the reaction temperature, i.e., increasing temperature produces more acrylates. This means that adjusting the reaction temperature is an effective way to change the molar mass of P3HP [Table 4 and Figure 6 ].

[0289] Table 4. Temperature dependence of polymerization of bPL and ODTMADMP

[0290]

[0291] a Monomer [bPL] to ionic liquid molar ratio.

[0292] b Time to reach bPL conversion greater than 99.9%.

[0293] c Number average molar mass [Mn], weight average molar mass [Mw] and polydispersity index [PDI] determined by GPC in CHCl3 relative to PMMA standards.

[0294] Figure 6 The polymer molar mass [M n The dotted line shows the theoretical molar mass [MTheo].

[0295] The reaction solvent is another means of producing polymers of various molar masses.

[0296] Table 5. Solvent dependence of polymerization of bPL and ODTMADMP

[0297] solvent <![CDATA[M:IL a ]]> <![CDATA[Time b [h]]]> <![CDATA[Mn c [g / mol]]]> <![CDATA[Mw c [g / mol]]]> <![CDATA[PDI c Mw / Mn]]> MTBE 500:1 2 33600 114200 3.4 THF 500:1 24 15000 46500 3.1 EtOAc 500:1 24 17000 59500 3.5 IPA 500:1 6 days 900 2100 2.3

[0298] a Monomer [bPL] to ionic liquid molar ratio.

[0299] b Time to reach bPL conversion greater than 99.9%.

[0300] c Number average molar mass [Mn], weight average molar mass [Mw] and polydispersity index [PDI] determined by GPC in CHCl3 relative to PMMA standards.

[0301] Figure 7 Shown is the β-lactone conversion versus time when various polymerization additives are used.

[0302] Table 6. Salt dependence of β-lactone polymerization

[0303] Salt <![CDATA[M:IL a ]]> <![CDATA[Time b [h]]]> <![CDATA[Mn c [g / mol]]]> <![CDATA[Mw c [g / mol]]]> <![CDATA[PDI c Mw / Mn]]> TEMADMP 2000 2 95500 238800 2.5 TEAA 2000 2 56100 106600 1.9 TMAA 2000 24 46000 101200 2.2

[0304] a Molar ratio of monomer [bPL] to salt in MTBE solvent [~1.6 M].

[0305] b Time to reach bPL conversion greater than 99.9%.

[0306] c Number average molar mass [Mn], weight average molar mass [Mw] and polydispersity index [PDI] determined by GPC in CHCl3 relative to PMMA standards.

[0307] The foregoing is a description of certain non-limiting embodiments of the present invention. It should be understood, therefore, that the embodiments of the invention described herein are merely illustrative of the application of the principles of the invention. Reference herein to details of the illustrated embodiments is not intended to limit the scope of the claims, which themselves recite those features considered essential to the invention.

Claims

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

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

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. A polymer according to 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 may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms.

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

6. The polymer of any one of the preceding claims, wherein the one or more nitrogen-containing cations comprises one or more nitrogen-containing heterocyclic ring-based onium cations comprising an optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium.

7. A polymer according to any one of the preceding claims, wherein the one or more quaternary ammonium cations corresponds to the formula where R 1 is independently a carbon-containing group at each occurrence, and wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.

8. A polymer according to any one of the preceding claims, wherein the one or more guanidinium cations correspond to the formula where R 1 is independently a carbon-containing group at each occurrence, and wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.

9. A polymer according to any one of the preceding claims, wherein the one or more imidazolium cations corresponds to the formula where R 1 is independently at each occurrence a carbon-containing group.

10. The polymer of any preceding claim, wherein the one or more phosphorus-containing cations are one or more quaternary phosphonium cations.

11. A polymer according to any one of the preceding claims, wherein the one or more quaternary phosphonium cations correspond to the formula: where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.

12. The polymer of any preceding claim, wherein the phosphate anion corresponds to the formula: where R 2 is independently at each occurrence an optionally substituted carbon-containing group; a is independently 1, 2, or 3 at each occurrence; and b is independently 0, 1, or 2 at each occurrence; The sum of a and b is 3.

13. A polymer according to any one of the preceding claims, wherein the phosphate anion corresponds to the formula where R 2 is independently at each occurrence a carbon-containing group.

14. The polymer of any preceding claim, wherein the one or more polymer chains have residues of an end-capping agent or quencher on a portion of the chain ends.

15. The polymer according to any one of the preceding claims, wherein the polymer contains a comonomer polymerized with the ring-opening β-propiolactone and / or substituted β-propiolactone.

16. The polymer of any preceding claim, 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. The polymer of any preceding claim, wherein the comonomer is one or more epoxides.

18. The polymer of any one of the preceding claims, wherein the polymer corresponds to one of the following formulae: or where R 2 is independently at each occurrence an optionally substituted carbon-containing group, R 3 is independently at each occurrence hydrogen, a carbon-containing group; which may optionally contain one or more heteroatoms and / or substituents, a is independently 1, 2, or 3 at each occurrence; b is independently 0, 1, or 2 at each occurrence; x is independently approximately a real number greater than 1 at each occurrence; and, Z is independently at each occurrence hydrogen, the residue of an onium cation, the residue of a quencher, a capping agent, or hydrogen.

19. A polymer according to any preceding claim, wherein a portion of the polymer chains may have carboxylate groups at the ends of some of the chains.

20. A polymer according to any one of the preceding claims, wherein a portion of the polymer chains may have carboxylate groups at the ends of some chains corresponding to the formula: where R 2 is independently at each occurrence an optionally substituted carbon-containing group, R 3 is independently at each occurrence hydrogen, a carbon-containing group; which may optionally contain one or more heteroatoms and / or substituents, R 4 is independently at each occurrence a carbon-containing group, which may contain heteroatoms or be substituted with functional groups; a is independently 1, 2, or 3 at each occurrence; b is independently 0, 1, or 2 at each occurrence; x is independently a real number greater than 1 at each occurrence; and, Z is independently at each occurrence hydrogen, the residue of an onium cation, the residue of a quencher, a capping agent, or hydrogen.

21. A polymerizable composition comprising: a. one or more of β-propiolactone and / or substituted β-propiolactone; and b. 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.

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

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

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

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 cations, amidinyl cations, and guanidinyl cations, or onium cations based on nitrogen-containing heterocycles.

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 nitrogen-containing heterocyclic-based onium cations comprising optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium.

28. The polymerizable composition of any one of claims 21 to 27, wherein the one or more quaternary nitrogen-containing cations are one or more quaternary ammonium cations corresponding to the formula where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.

29. The polymerizable composition of any one of claims 21 to 27, wherein the one or more quaternary nitrogen-containing cations are one or more guanidinium cations corresponding to the formula: , where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms.

30. The polymerizable composition of any one of claims 21 to 29, wherein the one or more imidazolium cations correspond to the formula where R 1 and independently at each occurrence is a carbon-containing group which may contain 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 polymerizable composition of any one of claims 21 to 30, wherein the one or more quaternary phosphonium cations correspond to the formula: where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed and may optionally contain .

33. The polymerizable composition of any one of claims 21 to 32, wherein the phosphate anion corresponds to the formula: where R 2 is independently at each occurrence an optionally substituted carbon-containing group; a is independently 1, 2, or 3 at each occurrence; and b is independently 0, 1, or 2 at each occurrence; The sum of a and b is 3.

34. The polymerizable composition of any one of claims 21 to 33, wherein the one or more salts of the one or more onium cations and the one or more phosphate anions correspond to the formula where R 2 is independently at each occurrence an optionally substituted carbon-containing group; Z′ is independently an onium cation at each occurrence; a is independently 1, 2, or 3 at each occurrence; and b is independently 0, 1, or 2 at each occurrence; The sum of a and b is 3.

35. The polymerizable composition of any one of claims 21 to 33, wherein the one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions correspond to one of the following formulae: where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms; and, wherein R 2 is independently at each occurrence an optionally substituted carbon-containing group; a is independently 1, 2, or 3 at each occurrence; and b is independently 0, 1, or 2 at each occurrence; The sum of a and b is 3.

36. The polymerizable composition of any one of claims 21 to 35, wherein the one or more salts of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions correspond to one of the following formulae: where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms; and, where R 2 is independently at each occurrence a carbon-containing group.

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

38. The polymerizable composition of any one of claims 21 to 37, wherein the one or more salts of one or more quaternary nitrogen-containing cations and one or more phosphate anions correspond to the formula: where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms; and, R 2 and independently at each occurrence is an optionally substituted carbon-containing group.

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

40. The polymerizable composition of any one of claims 21 to 38, wherein the zwitterion corresponds to the formula where R 2 is independently at each occurrence an optionally substituted carbon-containing group; R 5 are independently optionally substituted carbon-containing moieties; Z′ is independently an onium cation at each occurrence; a is independently 1, 2, or 3 at each occurrence; and b is independently 0, 1, or 2 at each occurrence; The sum of a and b is 3.

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

42. The polymerizable composition of any one of claims 21 to 38, wherein the one or more zwitterions of one or more quaternary nitrogen-containing cations or quaternary phosphonium cations and one or more phosphate anions correspond to one of the following formulae: where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms; wherein R 2 is independently at each occurrence an optionally substituted carbon-containing group; and, R 5 is independently an optionally substituted carbon-containing moiety.

43. The polymerizable composition of any one of claims 21 to 38, wherein the one or more zwitterions comprising one or more quaternary nitrogen-containing cations and one or more phosphate anions correspond to the formula: where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 One or more aromatic or non-aromatic ring structures may be formed, which may optionally contain one or more heteroatoms; R 2 is independently at each occurrence an optionally substituted hydrocarbyl group, and R 5 is independently an optionally substituted carbon-containing moiety.

44. The polymerizable composition of any one of claims 21 to 43, wherein the one or more zwitterions of one or more quaternary nitrogen-containing cations and one or more phosphate anions correspond to the formula: where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms; and, R 2 is independently at each occurrence an optional carbon-containing group, and R 5 is independently an optionally substituted carbon-containing moiety.

45. The polymerizable composition of any one of claims 21 to 38, wherein the one or more zwitterions of one or more quaternary nitrogen-containing cations and one or more phosphate anions correspond to the formula: where R 1 is independently at each occurrence a carbon-containing group, wherein two or more R 1 may form one or more aromatic or non-aromatic ring structures, which may optionally contain one or more heteroatoms; and, R 2 is independently at each occurrence an optionally substituted carbon-containing group, and R 5 is independently an optionally substituted carbon-containing moiety.

46. ​​The polymerizable composition of any one of claims 21 to 45, comprising one or more comonomers copolymerized with the one or more β-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 quencher, and an end-capping agent.

48. The polymerizable composition of any one of claims 21 to 47, wherein the molar ratio of one or more β-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.

49. The polymerizable composition of any one of claims 21 to 48, wherein the end-capping agent is an organic halide, an organic sulfonate, a haloalkylsilane, an aniline derivative, a phosphate derivative, a boric acid derivative, and an isophthalic acid derivative.

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

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. A method comprising contacting the components of the polymerizable composition of any one of claims 21 to 52 under conditions to produce one or more polymers comprising one or more polymer chains having ring-opening β-lactone units.

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

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

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

57. A method according to any one of claims 53 to 56, wherein after a specified reaction time, or when the polymer composition has reached a desired molecular weight, a quencher is added to terminate the polymerisation reaction.

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

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

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

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

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

63. The process according to 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. 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 cross-linked through the end groups of the polymer.

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 formed chain.

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

67. The method of any one of claims 53 to 66, wherein a portion of the terminal groups is one or more nitrogen-containing cations or phosphorus-containing cations.

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