Manufacturing method of biodegradable polyester

Abstract

A method is disclosed for the efficient production of poly(3-hydroxypropionate) (polypropiolactone) and related copolymers from 3-hydroxypropionate (beta-propiolactone) utilizing zwitterionic polymerization initiators. In another aspect, the present invention provides a polymerization system comprising a combination of initiators and monomers that, together, allow for the efficient production of poly(3-hydroxypropionate) (polypropiolactone) and related copolymers. Novel polymer compositions are disclosed that have structural and / or compositional properties that differentiate them from previously produced polymers and polymer compositions.

Description

[Technical field]

[0001] This application claims priority to U.S. Provisional Patent Application No. 63 / 154,014, filed February 26, 2021, which is incorporated by reference in its entirety for all purposes. [Background technology]

[0002] Polyester polymers have proven to be versatile materials with widespread use. Polyesters based on petroleum-derived aromatic monomers are among the most widely utilized polymers, e.g., polyethylene terephthalate (PET) is produced on a large scale to make water bottles, textiles, and other consumer goods. Unfortunately, PET is not biodegradable and therefore is a major contributor to the growing problem of environmental pollution, including harm to marine ecosystems, caused by post-consumer plastic residual waste. In recent years, there has been growing interest in biodegradable polyesters, examples of which include polylactic acid (PLA) and poly-3-hydroxybutyrate (PHB). Summary of the Invention [Problem to be solved by the invention]

[0003] The high cost and properties of these polymers make them difficult to accommodate mass production applications to replace existing bulk polymers. There remains a need for high performance biodegradable polyesters and methods for producing such polymers from flexible raw material sources that allow manufacturers to balance the cost and sustainability aspects of their products. The present disclosure provides solutions to these and other related problems. [Means for solving the problem]

[0004] Summary of the Invention A process for the polymerization of beta-lactones using zwitterionic initiators for the preparation of high molecular weight biodegradable polyesters and biodegradable polyester copolymers with superior properties is disclosed. Previously it was not possible to economically produce very high molecular weight poly(3-hydroxypropionate (p3HP) or related copolymers, nor was it easy to control the compositional properties and secondary structure of the polymers to optimize them for many applications. A method is disclosed for efficiently producing poly(3-hydroxypropionate) and related copolymers by utilizing zwitterionic polymerization initiators. The polymers produced can have unique properties that suit the desired commercial application and differentiate them from known polyesters produced by other methods. A polymerization system is disclosed that includes a unique combination of initiators, monomers, oligomers, end capping agents, chain extenders, chain transfer agents, and crosslinkers that allows for the production of superior polymer products. Polymer compositions are disclosed that have structure and / or compositional properties that differentiate them from previously produced polymers and polymer compositions.

[0005] Disclosed is a polymer comprising one or more polymer chains of polymers of beta-propiolactone and / or substituted beta-propiolactone, the polymer having a residue of a zwitterion having an anion and a cation at one end of the chain, the anion moiety being covalently attached to one end of the polymer chain. The one or more polymer chains may have a residue of an end-capping agent at the other end of the chain. The end-capping agent may be one or more of an organic halide, an organic sulfonate, a haloalkylsilane, an aniline derivative, a phosphate derivative, and an isophthalic acid derivative. The anion may be an oxygen or sulfur based anion and the cation may be an organic onium cation. The onium cation may include nitrogen, phosphorus, sulfur, antimony, or arsenic. The zwitterion anion and cation may be linked by a bond or a polyvalent organic moiety. The polymer may be of the formula PI or P-II: +ZLX-(A)-H PI +ZLX-(A)-R k P-II wherein A, at each occurrence separately, may be a polymer chain having ring-opened beta-propiolactone and / or substituted beta-propiolactone units; Z, at each occurrence separately, may be a cation derived from a zwitterion; L, at each occurrence separately, may be a bond or a multivalent organic moiety; X, at each occurrence separately, may be an anion derived from a zwitterion; R k may, separately in each occurrence, be the residue of an end-capping agent. A may, at each occurrence separately, be a polymeric chain comprising units derived from 3-hydroxypropionate and / or substituted 3-hydroxypropionate. Z may, at each occurrence separately, be an organic onium cation. L may, at each occurrence separately, be an optionally substituted C1-C 100 X may be, separately at each occurrence, an oxygen or sulfur-based anion. k may be, separately at each occurrence, a residue of an endblocking agent which may be one or more of an organic halide, an organic sulfonate, a haloalkylsilane, an aniline derivative, a phosphate derivative, and an isophthalic acid derivative; Z may be, separately at each occurrence, an organic onium cation containing nitrogen, phosphorus, sulfur, antimony, or arsenic; L may be, separately at each occurrence, an optionally substituted C1-C 40 It may be an aliphatic group.

[0006] Disclosed is a polymerizable composition comprising: a. one or more beta-propiolactones and / or substituted beta-propiolactones; and b. one or more zwitterionic initiators. The polymerizable composition may comprise one or more comonomers that copolymerize with the one or more beta-propiolactones and / or substituted beta-propiolactones. The ratio of the one or more beta-propiolactones and / or substituted beta-propiolactones to the one or more zwitterionic initiators may be from about 100:1 to about 1,000,000:1. The endcapping agent may be present in an amount less than 10 molar equivalents relative to the amount of zwitterionic initiator added. The polymerizable composition may comprise one or more of the comonomers caprolactone, lactide, epoxide, oxetane, cyclic anhydride, lactam, episulfide, aziridine, (meth)acrylate, valerolactone, butyrolactone, and glycolide. The polymerizable composition may include one or more of an endblocking agent, a chain transfer agent, a quenching agent, a chain extender, a branching agent, etc. The polymerizable composition may include one or more of a chain transfer agent, a chain extender, and an endblocking agent.

[0007] Methods are disclosed that include contacting one or more beta-propiolactones and / or substituted beta-propiolactones and comonomers with one or more zwitterionic initiators under conditions to prepare one or more polymers comprising one or more polymer chains having ring-opened beta-propiolactone and / or substituted beta-propiolactone units and having a zwitterionic residue at one end of the chain having an anion and a cation, the anion moiety being covalently attached to one end of the polymer chain. The one or more beta-propiolactones and / or substituted beta-propiolactones and comonomers and the one or more zwitterionic initiators may be contacted at a temperature of from about 0° C. to about 120° C. The one or more beta-propiolactones and / or substituted beta-propiolactones and comonomers and the one or more zwitterionic initiators may be contacted at a pressure of from about 1 bar to about 20 bar. The one or more beta-propiolactones and / or substituted beta-propiolactones and comonomers and the one or more zwitterionic initiators are contacted for a time sufficient to arrive at a desired molecular weight of the one or more beta-propiolactones and / or substituted beta-propiolactones and comonomers. The quenching agent may be one or more mineral acids, organic acids, acidic resins or solids, and end-capping agents. [Brief description of the drawings]

[0008] [Figure 1] 1 shows a comparison of molar mass from betaine and lauryl betaine at various M:I ratios. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] definition Definitions of specific functional groups and chemical terms are described in more detail below. For the purposes of the present invention, chemical elements are identified according to the Periodic Table of the Elements, CAS edition, "Handbook of Chemistry and Physics", 75th edition, inside cover, and specific functional groups are generally defined as described therein. In addition, general principles of organic chemistry, as well as specific functional moieties and reactivities, are described in "Organic Chemistry", Thomas Sorrell, University Science Books, Sausalito, 1999; Smith and March, "March's Advanced Organic Chemistry", 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.

[0010] Certain disclosed polymers may contain one or more asymmetric centers and therefore may exist in various stereoisomeric forms, such as enantiomers and / or diastereomers. The polymers and compositions thereof may be in the form of individual enantiomers, diastereomers or geometric isomers, or may be in the form of a mixture of stereoisomers. The disclosed polymers may be enantiopure compounds. Mixtures of enantiomers or diastereomers are disclosed.

[0011] Certain disclosed polymers may contain monomers capable of linking by reaction at multiple sites, thus creating the possibility of positional isomerism in the resulting polymer chain. Certain disclosed polymers may exist in different positional isomeric forms. The polymers and compositions thereof described herein may be regioregular, or may contain regioirregularity, or may even be substantially positional random. The disclosed polymers may be substantially regioregular. The disclosed polymers may include one or more crystalline polymorphs, and thus may exist in various crystalline forms. The polymers and compositions thereof may be in the form of a β, γ or δ crystalline polymorph, or may be in the form of a mixture of crystalline polymorphs. As described herein, certain polymers may have one or more double bonds that can exist as either Z or E isomers, unless otherwise specified. The polymers are disclosed as individual isomers substantially free of other isomers, or alternatively as mixtures of various isomers, such as racemic mixtures of enantiomers. The aforementioned polymers may themselves include compositions that include one or more polymers. As used herein, the term "isomer" includes all geometric, stereoisomers, and positional isomers. For example, "isomer" includes cis and trans isomers, E- and Z-isomers, R- and S-enantiomers, diastereomers, (D)-isomers, (L)-isomers, racemic mixtures thereof, and other mixtures thereof. For example, in some embodiments, stereoisomers are provided that are substantially free of one or more corresponding stereoisomers, and may be referred to as "stereochemically enriched."

[0012] The term "beta-lactone" as used herein refers to a substituted or unsubstituted cyclic ester having a four-membered ring containing an oxygen atom, a carbonyl group, and two optionally substituted methylene groups. When unsubstituted, the beta-lactone is called propiolactone. Substituted beta-lactones include mono-, di-, tri-, and tetra-substituted beta-lactones. Beta-lactones contain a single lactone moiety. Beta-lactones may contain two or more four-membered ring ester moieties.

[0013] The term "epoxide" as used herein refers to a substituted or unsubstituted oxirane. Such substituted oxiranes include mono-, di-, tri-, and tetra-substituted oxiranes. An epoxide contains a single oxirane moiety. An epoxide contains two or more oxirane moieties.

[0014] The term "polymer" as used herein refers to a relatively high molecular weight molecule, the structure of which actually or conceptually contains multiple repeats of units derived from a relatively low molecular weight molecule. The polymer may be composed of beta-lactone monomers (e.g., polypropiolactone). The disclosed polymers may be copolymers, terpolymers, heteropolymers, block copolymers, or tapered heteropolymers incorporating two or more different monomers. With regard to the structural depiction of such macromolecules, the convention of showing the association of different monomer units or polymer blocks separated by slashes may be used herein. For example, the structure:

[0015] [ka] can be used to represent copolymers of beta-propiolactone and beta-butyrolactone. Such structures are to be interpreted to encompass copolymers incorporating any ratio of the different monomer units depicted, unless otherwise specified. The depiction of the present invention is also intended to represent random, tapered, block copolymers, and any combination of two or more of these all implied, unless otherwise specified.

[0016] The terms "halo" and "halogen" as used herein refer to an atom selected from fluorine (fluoro, -F), chlorine (chloro, -Cl), bromine (bromo, -Br) and iodine (iodo, -I). The terms "aliphatic group" or "aliphatic group" as used herein refer to a hydrocarbon moiety that may be linear (i.e. unbranched), branched or cyclic (including fused, bridged and spiro-fused polycyclic), fully saturated or may not be aromatic but may contain one or more units of unsaturation. An aliphatic group may 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. Exemplary aliphatic groups include, but are not limited to, linear or branched alkyl, alkenyl, and alkynyl groups, and hybrids thereof, such as (cycloalkyl)alkyl, (cycloalkenyl)alkyl, or (cycloalkyl)alkenyl. As used herein, the term "heteroaliphatic" refers to an aliphatic group in which one or more carbon atoms are independently replaced with one or more atoms selected from the group consisting of oxygen, sulfur, nitrogen, or phosphorus. One to six carbon atoms may be independently replaced with one or more of oxygen, sulfur, nitrogen, or phosphorus. Heteroaliphatic groups may be substituted or unsubstituted, branched or unbranched, cyclic or acyclic, and may include saturated, unsaturated, or partially unsaturated groups. As used herein, the term "unsaturated" means that the moiety has one or more double or triple bonds. The terms "alicyclic", "carbocycle" or "carbocyclic" used alone or as part of a larger moiety refer to a saturated or partially unsaturated cycloaliphatic monocyclic or polycyclic ring system having 3 to 12 members, as described herein, where the aliphatic ring system is optionally substituted as defined below and 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 may have 3 to 6 carbons.The terms "alicyclic," "carbocycle," or "carbocyclic" also include an aliphatic ring fused to one or more aromatic or non-aromatic rings, e.g., decahydronaphthyl or tetrahydronaphthyl, where the radical or point of attachment is on the aliphatic ring.

[0017] The term "alkenyl" as used herein refers to a monovalent group derived from a straight or branched chain aliphatic moiety having at least one carbon-carbon double bond by the removal of a single hydrogen atom. The term "alkynyl" as used herein refers to a monovalent group derived from a straight or branched chain aliphatic moiety having at least one carbon-carbon triple bond by the removal of a single hydrogen atom. The term "alkoxy" as used herein refers to an alkyl group, as defined above, attached to the parent molecule by an oxygen atom. Examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, tert-butoxy, neopentoxy, and n-hexoxy. The term "acyl" as used herein refers to a carbonyl-containing functional group, such as -C(=O)R ’ [In the formula, R ’is hydrogen or an optionally substituted aliphatic, heteroaliphatic, heterocyclic, aryl, heteroaryl group, or is substituted (e.g., with hydrogen or an aliphatic, heteroaliphatic, aryl, or heteroaryl moiety) with oxygen or nitrogen-containing functional groups (e.g., to form carboxylic acid, ester, or amide functional groups). As used herein, the term "acyloxy" refers to an acyl group attached to a parent molecule by an oxygen atom. The term "aryl" used alone or as part of a larger moiety such as in "aralkyl", "aralkoxy" or "aryloxyalkyl" refers to monocyclic and polycyclic ring systems having a total of five to twenty ring members, at least one ring in the system is aromatic, and each ring in the system contains three to twelve ring members. The term "aryl" may be used interchangeably with the term "aryl ring", and "aryl" refers to aromatic ring systems that may have one or more substituents, including, but not limited to, phenyl, biphenyl, naphthyl, anthracyl, and the like. Also included within the scope of the term "aryl" as used herein are groups in which an aromatic ring is fused to one or more additional rings, such as benzofuranyl, indanyl, phthalimidyl, naphthymidyl, phenantriidinyl, or tetrahydronaphthyl, where the group or point of attachment is on the aryl ring. The terms "heteroaryl" and "heteroar-", used alone or as part of a larger moiety, such as "heteroaralkyl" or "heteroaralkoxy", refer to groups that share 6, 10, or 14 pi-electrons in a cyclic arrangement; have 5 to 14 ring atoms, preferably 5, 6, or 9 ring atoms; and have 1 to 5 heteroatoms in addition to the carbon atoms. The term "heteroaryl" may be used interchangeably with the terms "heteroaryl ring" and "heteroaryl group", either of which terms include optionally substituted rings. The term "heteroatom" refers to nitrogen, oxygen, or sulfur, and includes any oxidized form of nitrogen or sulfur, and any quaternized form of a basic nitrogen.Heteroaryl groups include, but are not limited to, thienyl, furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl, purinyl, naphthyridinyl, benzofuranyl, and pteridinyl. As used herein, the terms "heteroaryl" and "heteroar-" also include groups in which a heteroaryl ring is fused to one or more aryl, alicyclic, or heterocyclyl rings, where the group or point of attachment is on the heteroaryl ring. Non-limiting examples include indolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl, indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl, cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and pyrido[2,3-b]-1,4-oxazin-3(4H)-one. Heteroaryl groups may be monocyclic or bicyclic. The term "heteroaralkyl" refers to an alkyl group substituted by a heteroaryl, where the alkyl and heteroaryl portions are independently optionally substituted. In certain embodiments, the term "5- to 10-membered heteroaryl" refers to a 5- to 6-membered heteroaryl ring having 1-3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, or an 8- to 10-membered bicyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur. The term "partially unsaturated" refers to a ring moiety that contains at least one double or triple bond. The term "partially unsaturated" is intended to encompass rings with multiple sites of unsaturation, but is not intended to include aryl or heteroaryl moieties as defined herein.

[0018] The disclosed compounds may include "optionally substituted" moieties. The term "substituted," whether preceded by the term "optionally" or not, means that one or more hydrogens of the specified moiety have been replaced with a suitable substituent. Unless otherwise specified, an "optionally substituted" group may have a suitable substituent at each substitutable position of the group, and if there are multiple positions in a given structure, may be substituted with multiple substituents selected from a specified group, and the substituents may be the same or different at all positions. The combinations of substituents envisioned are those that result in the formation of stable or chemically feasible compounds. As used herein, the term "stable" refers to compounds that remain substantially unchanged when subjected to conditions that allow for their preparation, detection, and in some embodiments, their recovery, purification, and use for one or more purposes disclosed herein. As used herein, the term "alkoxylated" means that one or more functional groups of a molecule (usually, but in no way limited to, functional groups are alcohols, amines, or carboxylic acids) have been added to the molecule with a hydroxy-terminated alkyl chain. The alkoxylated compounds may contain a single alkyl group, or they may be oligomeric moieties such as hydroxyl-terminated polyethers. Unless otherwise specified, "a," "an," "the," and "at least one" are used interchangeably and mean one or more than one.

[0019] method Disclosed is a method for polymerizing beta-propiolactone (BPL) and / or substituted beta-propiolactone, optionally in combination with one or more additional comonomers (collectively monomers), using a zwitterionic polymerization initiator that may or may not be covalently bound in the final polymer product.

[0020] Feed ratio and polymer properties The method includes contacting the monomers with a zwitterionic initiator, where a molar ratio of monomer to initiator is selected to prepare a polymer of a desired molecular weight, for example, the molar ratio may be 10:1 or more, 100:1 or more, 1,000:1 or more, 2,000:1 or more, 3,000:1 or more, 4,000:1 or more, 5,000:1 or more, 7,500:1 or more, 10,000:1 or more, 15,000:1 or more, 20,000:1 or more, 30,000:1 or more, 40,000:1 or more, 50,000:1 or more, 75,000:1 or more, or 100,000:1 or more. The initiator is contacted with the monomers for a time sufficient to prepare a polymer of the desired molecular weight. The method comprises providing a polymer composition having a number average molecular weight M of 50,000 g / mol or more, 75,000 g / mol or more, 100,000 g / mol or more, 150,000 g / mol or more, 200,000 g / mol or more, 250,000 g / mol or more, 300,000 g / mol or more, 400,000 g / mol or more, 500,000 g / mol or more, 600,000 g / mol or more, or 700,000 g / mol or more. n The method may include allowing the initiator to contact the monomer until Mn is formed. The Mn of the polymer composition is as measured by gel permeation chromatography (GPC) using CHCl3 as the solvent and referenced to polymethyl methacrylate standards.

[0021] The GPC chromatogram of the resulting polymer composition may be multimodal and include one or more peaks representing a discrete population of low molecular weight oligomers (e.g., polyester chains) having a molecular weight of about 5,000 g / mole or less, about 4,500 or less, about 4,000 or less, about 3,500 or less, about 3,000 or less, about 2,500 or less, about 2,000 or less, about 1,500 or less, or about 1,000 g / mole or less. In the GPC chromatogram of the resulting polymer composition, the ratio of the area of ​​the peak resulting from polymer chains having a Mn of greater than 50,000 g / mole to the area of ​​the peak representing oligomers having a Mn of less than 5,000 g / mole may be at least 10:1.

[0022] The method includes allowing the zwitterionic initiator to contact the monomers for a predetermined interval of time. The method may include monitoring the progress of the polymerization reaction (e.g., by analyzing an aliquot from the reaction mixture by a suitable technique such as GPC or by utilizing an in situ monitoring technique). The method may include monitoring the increase in molecular weight of the polymer and / or monitoring the decrease in monomer concentration. The method may include stopping the reaction when the molecular weight of the polymer composition (or instead of molecular weight, e.g., the reactant viscosity) reaches a desired value or exceeds a predetermined threshold. The method may include monitoring the depletion of the monomers until their concentration reaches a desired concentration or falls below a predetermined threshold. The method may include stopping the reaction when the concentration of the monomers reaches a desired concentration or falls below a predetermined threshold.

[0023] The formed polymer composition may have low polydispersity, a polydispersity index (PDI) of 3.5 or less, 3.0 or 2.5 or less, or 2.2 or less. The formed polymer composition may have a PDI of 1.05 or more, 1.1 or more, 1.2 or more, 1.5 or more, or 2.0 or more. The PDI values ​​described refer to those measured by GPC. The PDI values ​​may be calculated without including GPC peaks resulting from oligomers having Mn less than about 5,000 g / mol, less than about 4,500, less than about 4,000, less than about 3,500, less than about 3,000, less than about 2,500, less than about 2,000, less than about 1,500, or less than about 1,000 g / mol.

[0024] The method includes the step of: forming a polymer composition having an M N The method may be characterized in that the formed polymer composition has an M of 20,000 g / mole to 50,000 g / mole, and a PDI of less than 1.5. N and a PDI of less than 1.5; an M of 50,000 g / mol to 100,000 g / mol N and a PDI of less than 1.5; an M of 100,000 g / mol to 200,000 g / mol Nand a PDI of less than 1.5; an M of 200,000 g / mol to 500,000 g / mol N and a PDI of less than 1.5; an M of 400,000 g / mol to 800,000 g / mol N and a PDI of less than 1.5; an M of 20,000 g / mol to 50,000 g / mol N and a PDI of less than 2.0; an M of 50,000 g / mol to 100,000 g / mol N and a PDI of less than 2.0; an M of 100,000 g / mol to 200,000 g / mol N and a PDI of less than 2.0; an M of 200,000 g / mol to 500,000 g / mol N and a PDI of less than 2.0; an M of 400,000 g / mol to 800,000 g / mol N and a PDI of less than 2.0; an M of 20,000 g / mol to 50,000 g / mol N and a PDI of less than 2.5; an M of 50,000 g / mol to 100,000 g / mol N and a PDI of less than 2.5; an M of 100,000 g / mol to 200,000 g / mol N and a PDI of less than 2.5; an M of 200,000 g / mol to 500,000 g / mol N and a PDI of less than 2.5; an M of 400,000 g / mol to 800,000 g / mol N and a PDI of less than 2.5; an M of 20,000 g / mol to 50,000 g / mol N and a PDI of less than 3; an M of 50,000 g / mol to 100,000 g / mol N , and a PDI of less than 3; an M of 100,000 g / mol to 200,000 g / mol N , and a PDI of less than 3; M of 200,000 g / mol to 500,000 g / mol N and a PDI of less than 3; or an M of 400,000 g / mol to 800,000 g / mol N and a PDI of less than 3. The PDI of each of the recited examples of molecular weight ranges may be greater than 3.0 up to about 20.0, about 10.0, or about 6.0.

[0025] Reaction conditions The monomers may be contacted with the zwitterionic initiator in a solvent, which may include polar aprotic solvents such as amides, nitriles and sulfoxides, protic liquids such as water or alcohols, ethers, esters, ketones, or aliphatic or aromatic hydrocarbons, halogenated hydrocarbons, or fluorinated hydrocarbons. 4~12 The solvent may comprise an aliphatic hydrocarbon, an ether, or a chlorinated hydrocarbon. The solvent may comprise an ether, petroleum ether, isobutane, pentane, hexane, or heptane, or a higher aliphatic hydrocarbon. The solvent may consist of isobutane or hexane. The solvent may be substantially anhydrous. The solvent may comprise an ether selected from tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, dimethoxyethane, diglyme, triglyme, tetraglyme, 1,3-dioxolane, t-butyl methyl ether, and diethyl ether. The solvent may comprise tetrahydrofuran, which may be anhydrous.

[0026] The method may include contacting the monomer with a zwitterionic initiator without a solvent. The polymerization may be carried out in neat monomer. The monomer may be contacted in a solvent system in which the zwitterionic initiator is not soluble. The method may include contacting the comonomer with a suspension of solid particles comprising the zwitterionic initiator. The method may include contacting the neat monomer with solid particles comprising the zwitterionic initiator that are insoluble in the neat monomer.

[0027] The method may include contacting the monomer with a zwitterionic initiator that forms micelles. The reaction mixture may include micelles formed from a plurality of zwitterionic molecules. The zwitterionic initiator that forms micelles is described in more detail below. The micelles may be suspended in a suitable solvent. A suspension of micelles may be provided to the polymerization mixture. The method may include forming such micelles directly in neat monomer. The zwitterionic initiator used for such methods may include a hydrophobic moiety (described more fully below), and when dispersed in a polar liquid medium, the initiator forms micelles. The method may include contacting the monomer with a composition that includes micelles that include the zwitterionic initiator in a polar solvent.

[0028] A gas containing BPL vapor may be contacted with solid particles containing zwitterionic initiator. The gas containing monomer vapor may comprise a mixture of monomer with air or an inert gas such as nitrogen or argon. The solid particles may be suspended in such a gas stream. The particles are separated from the gas stream as they grow larger due to polymer formation. Additional initiator particles may be added to the gas stream (continuously or in discontinuous installments) to replace particles separated from the stream. The gas stream may be maintained at subatmospheric pressure and / or elevated temperature.

[0029] The zwitterionic initiator and monomer may be contacted at low, ambient or elevated temperatures. The mixture may be maintained at a temperature of about 30° C. or more, about 40° C. or more, about 50° C. or more, about 60° C. or more, about 70° C. or more, about 80° C. or more, about 100° C. or more, or about 120° C. or more. The mixture may be maintained at a temperature of about 100° C. or less, or about 120° C. or less. The mixture may be maintained at a temperature of less than about 20° C., less than about 15° C., less than about 10° C., less than about 5° C., less than about 0° C., less than about −10° C. or less than about −20° C. The method may include removing heat from the mixture to maintain the desired temperature. The method may include varying the temperature of the polymerization mixture during the process. The method may include cooling the mixture to maintain the desired temperature. The method may include varying the temperature of the polymerization mixture over time during the process.

[0030] The polymerization may be carried out at elevated pressure. Elevated pressure may allow the process to be carried out at temperatures above the boiling points of certain reaction mixture components (e.g., solvent and monomer) and / or may aid in the separation of volatile components when a pressurized process stream or reactor is depressurized. The monomer may be contacted with the zwitterionic initiator at a pressure of more than 1 bar, about 2 bar or more, about 3 bar or more, about 5 bar or more, about 10 bar or more, about 15 bar or more, about 20 bar or more, about 30 bar or more, or about 40 bar or more. The pressure may be about 50 bar or less, about 60 bar or less, about 70 bar or less, about 80 bar or less, about 90 bar or less, or about 100 bar or less. Pressure may be applied by pressurization of the reactor headspace adjacent to the reaction mixture (e.g., by introduction of a pressurized inert gas). Pressure may be applied by heating the contained amount of the mixture. Pressure may be controlled by application of a back pressure regulator or other pressure relief system. The pressure may be maintained by applying pressure to a hydrostatically filled reaction vessel. Two or more of these techniques may be used.

[0031] The methods provided herein can be carried out in a batch process, a continuous process, or a hybrid of batch and continuous processes (e.g., a fed batch reaction). The methods may include feeding one or more components to the polymerization mixture over time. Monomers, oligomers, endblockers, chain extenders, chain transfer agents, or crosslinkers may be added to the polymerization mixture over time (continuously or in one or more discontinuous additions). The composition of monomers added to such reactant feeds may be varied over time. The polymer composition produced comprises a tapered copolymer or a block copolymer.

[0032] Quench The disclosed method may include a step of quenching the polymerization reaction. The quenching agent may be added after a predetermined reaction time or when the polymer composition reaches a desired molecular weight (e.g., when the Mn of the formed polymer composition exceeds a predetermined threshold). The quenching agent may be added once a target portion of the monomer has been consumed or once the desired molecular weight has been achieved. If the method includes a continuous process utilizing a plug flow reactor, the quenching agent may be added at a specific location along the length of the reactor. The quenching agent may be one or more mineral acids, organic acids, acidic resins or solids. The quenching agent may be HCl, H2SO4, RSO3H, HBr, H3PO4, acidic resins or acidic inorganic solids. The quenching agent may be a sulfonic acid derivative, boric acid or a boric acid derivative, phosphoric acid or a phosphoric acid derivative. The quenching agent may be a sulfonic acid. The sulfonic acid may be represented by the formula R q SO3H [wherein, R q is a group selected from the group consisting of optionally substituted aliphatic, optionally substituted aryl, optionally substituted heterocyclic, and optionally substituted heteroaryl groups. q is optionally substituted C1 to C 20 Alkyl, C1-C 20The sulfonic acid may be one or more of p-toluenesulfonic acid (also known as pTSA or tosylic acid), methanesulfonic acid, ethanesulfonic acid, 1-propanesulfonic acid, trifluoromethylsulfonic acid, 4-nitrophenylsulfonic acid, sulfoacetic acid, cumenesulfonic acid, xylenesulfonic acid, 3-amino-1-propanesulfonic acid, 2-sulfanylethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, benzenesulfonic acid, 4-hydroxybenzenesulfonic acid, cyclohexanesulfonic acid, 4-ethylbenzenesulfonic acid, 2,5-dimethylbenzenesulfonic acid, 4-methylmethanilic acid, 1-naphthalenesulfonic acid, and perfluorooctane sulfonic acid. The quenching agent may be methanesulfonic acid, p-toluenesulfonic acid, or sulfamic acid. The acid used as the quenching agent is selected from the group consisting of cations bound to the polymer (e.g., covalently bound Z resulting from zwitterionic initiators) and cations bound to the polymer (e.g., covalently bound Z resulting from zwitterionic initiators). + It may act by protonating the active chain ends of the polymer (e.g., forming -OH or CO2H groups) with the anion of the acid acting as a counterion to the -OH or -CO2H group. + (CH2)4CO2 - A polymerization process comprising contacting monomers with a zwitterionic initiator of the structure: MeN, when such reaction is quenched with HCl, + (CH2)4CO2(CH2CH2CO2) n CH2CH2CO2 - and the resulting quenched polymer composition has the formula: [MeN + (CH2)4CO2(CH2CH2CO2) n CH2CH2CO2H]Cl - The acidic quenching agent may be characterized in that the conjugate base of the acid is substantially non-nucleophilic.

[0033] The quenching agent may be a phosphoric acid derivative having at least one acidic hydrogen atom. The phosphoric acid derivative may be selected from phosphoric acid, pyrophosphate, triphosphate, alkyl derivatives of phosphoric acid, pyrophosphate or triphosphate, aryl derivatives of phosphoric acid, pyrophosphate or triphosphate, and mixtures thereof. The quenching agent may be represented by the formula:

[0034] [ka] wherein R1 and R2 are independently hydrogen, monophosphate, diphosphate, optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocycle, an ester derivative of a monophosphate, or an ester derivative of a diphosphate group. The quenching agent may be a phosphoric acid having R, R 1 and R 2 where each of the formulas is as defined above:

[0035] [ka] The quenching agent may be a phosphonic or phosphinic acid having the formula: The quenching agent may be a boron-containing compound. The quenching agent may be a fluoroboric acid.

[0036] The quenching agent may be an acid in combination with a solid support. The solid supported acid may comprise an inorganic solid of silica, alumina, zirconia, titania, zeolite, metal oxide or clay. The quenched composition forms a polymer composite with the inorganic solid quenching agent. The method may include adding a polymer supported acid as a quenching agent. The polymeric support may comprise a polymer derived from at least one of styrene, chloromethylated styrene and divinylbenzene monomers. The polymeric solid support may be selected from polystyrene, polysulfone, nylon, poly(chloromethylstyrene); polyolefins, polyacrylic acid, polymethylmethacrylate and crosslinked ethoxylated acrylic resins. When the quenching agent comprises a solid, the method may include flowing the reaction stream comprising the unquenched polymer through a fixed bed of the solid quenching agent. When the method comprises a continuous process utilizing a plug flow reactor, the quenching agent may be added at one or more locations along the length of the reactor.

[0037] terminal blockade The method includes adding an end-capping agent to quench the polymerization, as disclosed in International Application PTC WO2019241596, the entirety of which is incorporated herein by reference. The monomer may be polymerized such that the end of the formed polymer chain has a carboxylic acid or carboxylate functional group. The end group is reacted with an end-capping agent. The end-capping agent can make the formed polymer more stable. 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, and an isophthalic acid derivative. The electrophilic reagent caps the growing chain end and forms a covalent bond Z. + The compound R-X' can react with the anionic chain end (e.g., to form a -OR, CO2R group), while the free anion X' - is the cation attached to the polymer (e.g., the covalent bond Z resulting from a zwitterionic initiator). + It acts as a counterion to the cation (Me3N+ (CH2)4CO2 - A polymerization process comprising contacting BPL with a zwitterionic initiator of the structure: MeN, which, when such reactants are then quenched with benzyl bromide (BnBr), produces a polymerization product of the structure: MeN + (CH2)4CO2(CH2CH2CO2) n CH2CH2CO2 - and the resulting quenched polymer composition has the formula: [MeN + (CH2)4CO2(CH2CH2CO2) n CH2CH2CO2Bn]Br - It may also contain a chain of

[0038] The end-capping agent may comprise an alkyl halide, such as an aliphatic chloride, bromide, or iodide. The quenching agent may be represented by the formula R n -X h [In the formula, R n is an optionally substituted C 1~40 is an aliphatic group, X h is selected from Cl, Br or I. The end capping agent may include a compound of the formula: p -CH2-X h [In the formula, R p is -H or an optionally substituted group of aliphatic aryl, heterocyclic and heteroaryl groups. The end-capping agent may be one or more of methyl bromide, methyl iodide, allyl chloride, allyl bromide, benzyl chloride or benzyl bromide. The end-capping agent may be a compound of the formula R n OSO2R n [In the formula, R n is defined above. The quenching agent may comprise methyl triflate. The end-capping agent may comprise an organic sulfonate which may correspond to the formula R n OSO2OR n [In the formula, R n is as defined above. The quenching agent may include a dialkyl sulfate, such as dimethyl sulfate or diethyl sulfate.

[0039] The endblocking agent may be a silane or may include a compound containing silyl or siloxy groups, such as those of the formula:

[0040] [ka] [where, X h is as defined above, and each R t is methyl, ethyl or propyl, and each R s is -H, chloro, methyl or ethyl; X h may be -Cl, R t may be methyl or ethyl; R s may be methyl. The endcapping agent may comprise δ-chloropropyltrimethoxysilane.

[0041] The thermally stable aniline derivative may be an endblocker which may include an azole, such as one selected from the group consisting of benzothiazole, benzoxazole, benzimidazole, 2-aminothiophenol, o-phenylenediamine, and 2-aminophenol.

[0042] Exemplary endblockers may further include a phosphate, such as trimethyl phosphate. Exemplary endblockers may further include other additives and stabilizers, such as isophthalic acid.

[0043] The method may include adding a chain extender or crosslinker to the polymerization reaction. The chain extender or crosslinker may be added as a quenching agent. When analogues of the above end-capping agents having two or more suitable reactive functional groups in a single molecule are utilized as quenching agents, they may act as chain extenders or crosslinkers, respectively. Quenching with a bifunctional chain extender results in reaction with the carboxylate ends of two separate polymer chains to form a dimeric chain extension product. It will be understood that bifunctional analogues of any of the above quenching agents may be utilized to achieve the same effect.

[0044] The chain extender may include a compound of the formula X'-L'-X', where X' is independently an anion as defined herein, and L' comprises a divalent moiety. L'- is an optionally substituted C1-C 100 Aliphatic groups, optionally substituted C1-C 40 Aliphatic group; optionally substituted C 1~24 Aliphatic groups, optionally substituted C1-C 20 Aliphatic groups, optionally substituted C1-C 12 Aliphatic groups, optionally substituted C-C 10 Aliphatic groups; optionally substituted C4-C8 aliphatic groups, optionally substituted C4-C6 aliphatic groups, optionally substituted C2-C4 aliphatic groups, optionally substituted C1-C3 aliphatic groups, optionally substituted C6-C 12 It may be an aliphatic group or an optionally substituted C1, C2, C3, C4, C5, C6, C7 or C8 aliphatic group.

[0045] L'- may be an optionally substituted straight chain alkyl chain or an optionally substituted branched alkyl chain. L'- may be -C(R a R b )-[wherein, R a and R b are each independently a C1-C4 alkyl group. 20It may be an alkyl group. L'- may be an aliphatic group having 2-30 carbons containing one or more gem-dimethyl substituted carbon atoms. L'- may contain one or more optionally substituted rings, such as saturated or partially unsaturated carbocycles, saturated or partially unsaturated heterocycles, aryls and heteroaryls. L'- may be a substituted ring (i.e., the X' group is directly connected to an atom that constitutes the ring in -L'-). The ring may be part of the L'- moiety having one or more non-ring heteroatoms or an optionally substituted aliphatic group that separates one or more X' groups from the ring. L'- may contain one or more heteroatoms in its backbone (i.e., separating the attachment sites of the -X' groups in a group of covalently bonded atoms). L'- may be an optionally substituted C4-C 40 One or more sp in the aliphatic moiety 2 Carbon atoms are represented by -O-, -NR 1 -, -S-, -S(O)-, -S(O)2-, -OC(O)-, -OC(O)O-, -NR 1 C(O)-, -NR 1 C(O)O-, -NR 1 C(O)NR 1 -, -N=N-, -NR 1 C(N)NR 1 -, -SC(O)-, -SC(O)S-, -SC(S)S-, -NR 1 C(O)S- and -NR 1 C(S)O-[wherein, R 1is as defined above and in the genus and subgenus herein.], provided that the -L'- moiety resulting from such replacement has a structure consistent with recognized principles that define the structure of stable organic molecules. When multiple such replacements are present, they are separated by at least one aliphatic carbon atom, at least two aliphatic carbon atoms. L'- may include one or more ether, ester, urethane and / or amide linkages. L'- may comprise an oligomer or polymer. The polymer may be one or more of polyolefins, polyethers, polyesters, polycarbonates, polyamides and polyimides. When -L'- comprises a polymer, the X' group may be at the end of a polymer chain.

[0046] When trifunctional or higher functional end-capping agents are utilized, star or comb polymer compositions may be obtained. Such end-capping agents have the formula X'-L''-X', where X' is as defined above and herein, and L'' has any of the formulas listed for L', but is a polyvalent linker having three or more sites available for covalent attachment of X' functional groups. L'' may have from 3 to about 50 or more X' groups attached. L'' may have 3 or 4-6 X' groups attached. L'' may include polymers having a large number (i.e., tens or hundreds) of X' groups attached (for example, when X' groups are present as substituents on monomers that comprise polymer L'').

[0047] The quenching agent, endblocking agent, crosslinking agent or chain extender may be added to the reaction mixture in an amount less than 10 molar equivalents relative to the amount of zwitterionic initiator added to the polymerization process, for example, 0.1 to 10 molar equivalents, or 0.1 to 2 molar equivalents, or 1 to 2 molar equivalents, or about 1 molar equivalent relative to the amount of zwitterionic initiator.

[0048] Beta-propiolactone and / or functionalized beta-propiolactone Several novel polymer systems containing beta-propiolactone (BPL) and / or functionalized beta-propiolactone are disclosed. Beta-propiolactone is also known as 3-hydroxypropionate. The present disclosure relates to the use of hydroxyalkanoates. Polypropiolactone is also known as poly(3-hydroxypropionate). This disclosure relates to polymers referred to as poly(hydroxyalkanoates). Beta-propiolactone and / or functionalized beta-propiolactone can be used as a tie layer between polymeric layers which may be based on the same polymer or different polymers. The different polymers may be incompatible with each other. Functionalized beta-propiolactone and / or beta-propiolactone may be used as an adhesive layer to bond polymeric structures together or to other substrates. Polymers and copolymers of beta-propiolactone and / or functionalized beta-propiolactone may be used as coatings or free-standing films, or in multilayer coatings or films. The functional groups may react with other monomer systems to form crosslinks between polymer layers, or can polymerize into formed layers of other copolymers. Beta-propiolactone and / or functionalized beta-propiolactone may have functional groups that improve the bonding of the film or coating to the substrate.

[0049] The functional groups from the functionalized beta-propiolactone can impart functionality to polymers and copolymers prepared from the functionalized beta-propiolactone. The functional groups can act as polymerization initiators, improve adhesion of the polymer to certain substrates or polymer systems, improve hydrophobicity or hydrophilicity, improve hardness or scratch resistance, polymerization catalysts, etc. The functionalized beta-propiolactone and / or beta-propiolactone polymers and copolymers may function as intermediate layers in multilayer films, including such films having layers of different polymers. The functionalized beta-propiolactone and / or beta-propiolactone polymers and copolymers may degrade under certain circumstances, allowing other layers to be easily separated for reuse upon recycling. The functionalized beta-propiolactone and / or beta-propiolactone polymers and copolymers may function as intermediate layers between coatings of other polymers and substrates. The functionalized beta-propiolactone and / or beta-propiolactone polymers and copolymers degrade under certain conditions, allowing the substrate to be easily separated for reuse upon recycling. The functionalized beta-propiolactone and / or beta-propiolactone polymers and copolymers can be used as an outer film layer or coating layer that can be degraded, or such outer layers can be functionalized to provide a desired set of properties to the structure.

[0050] General formula:

[0051] [ka] [In the formula, R 4 is independently at each occurrence hydrogen, a hydrocarbyl moiety, or a fluorocarbyl moiety; the hydrocarbyl or fluorocarbyl moiety may optionally contain at least one heteroatom or at least one substituent. The functionalized beta-propiolactone has at least one R present as a hydrocarbyl or fluorocarbyl moiety that can enhance the functionality of the functionalized beta-propiolactone incorporated into a polymer chain useful in coatings or films. 4 At least one R 4 is a hydrocarbyl or fluorocarbyl group and may contain one or more unsaturated groups, electrophilic groups, nucleophilic groups, anionic groups, cationic groups, zwitterionic groups, hydrophobic groups, hydrophilic groups, halogen atoms, natural minerals, synthetic minerals, carbon-based particles, UV-active groups, surface-active polymers and polymerization initiators, or reactive heterocyclic rings. The functional groups may be linked to the ring by a linking group (M) that serves to link the functionality of the group to the cyclic ring. Exemplary linking groups may be hydrocarbylene, fluorocarbylene groups, ethers, thioethers, polyethers (such as polyalkene ethers). One or more R 4 may be a halogen-substituted alkyl group, a sulfonate-substituted alkyloxy group, an alkylsulfonate alkyloxy group, an alkyl ether-substituted alkyl group, a polyalkylene oxide-substituted alkyl group, an alkyl ester-substituted alkyl group, an alkenyloxy-substituted alkyl group, an aryl ester-substituted alkyl group, an alkenyl group, a cyano-substituted alkyl group, an alkenyl ester-substituted alkyl group, a cycloalkyl-substituted alkyl group, an aryl group, a heteroatom-containing cycloalkenyl, an alkyl ether-substituted alkyl group, a hydroxyl-substituted alkyl group, an alicyclic-substituted alkenyl group, an aryl-substituted alkyl group, a haloaryl-substituted alkyl group, an aryloxy-substituted alkyl group, an alkyl ether-substituted alkaryl group, a heteroatom-containing alicyclic-substituted alkyl group, a heteroatom-containing aryl-substituted alkyl group, an alkylamide-substituted alkyl group, or an alkenyl-substituted alicyclic group; 4may form a cyclic ring which may optionally contain one or more unsaturated groups; an alkyl group substituted with a beta-propiolactone group, which may optionally contain one or more ether groups and / or one or more hydroxyl groups; a glycidyl ether group, or a benzocyclobutenyl substituted alkyl group optionally substituted with one or more ether groups. Beta-propiolactone may be represented by R 4 In some embodiments, R on one carbon atom corresponds to the formula 4 are both H, while both R on the other carbon atom are 4 is an optionally substituted C 1~40 Aliphatic, optionally substituted C 1~20 heteroaliphatic, optionally substituted aryl, or both R 4 The groups may optionally be joined together to form an optionally substituted ring that optionally contains one or more heteroatoms. 4 One or two of R may be methyl and the others may be hydrogen. 4 may be methyl, while other R 4 is hydrogen.

[0052] Disclosed are homopolymers prepared from one or more of the described functionalized beta-propiolactones or beta-propiolactones. Disclosed are copolymers of beta-propiolactone and one or more functionalized beta-propiolactones. Disclosed are compositions comprising copolymers of one or more of the disclosed beta-propiolactones and / or functionalized beta-propiolactones with one or more monomers reactive with one or more functionalized beta-propiolactones. Such copolymers include a plurality of one or more diols, difunctional polyalkylene oxides, amine-terminated polyalkylene oxides, one or more difunctional polyesters, cyclic lactones, cyclic anhydrides, or polyethers. These copolymers may include units derived from beta-propiolactone. The disclosed copolymers may be block copolymers, random copolymers, or one or more chains may be grafted onto the polymer backbone.

[0053] Comonomers Disclosed are compositions comprising copolymers of one or more of the disclosed beta-propiolactones and / or functionalized beta-propiolactones with one or more reactive monomers. Disclosed are compositions comprising copolymers of one or more of the disclosed beta-propiolactones and / or functionalized beta-propiolactones with one or more reactive monomers. Such copolymers include a plurality of one or more diols, difunctional polyalkylene oxides, amine-terminated polyalkylene oxides, one or more difunctional polyesters, lactams, lactides, cyclic lactones, cyclic anhydrides, epoxides, episulfides, or polyethers. Such comonomers may be one or more epoxides, oxiranes, lactams, and lactides. The comonomer may be one or more cyclic anhydrides including succinic anhydride, methyl succinic anhydride, methyl diglycolic anhydride, methyl glutaric anhydride, maleic anhydride, phthalic anhydride, citraconic anhydride, trans-1,2-cyclohexanedicarboxylic anhydride. These copolymers may also include units derived from beta-propiolactone. The disclosed copolymers may be block copolymers, random copolymers, or one or more chains may be grafted onto the polymer backbone.

[0054] The one or more substituted beta-lactones may be selected from the group consisting of:

[0055] [ka] wherein Ar is an optionally substituted aryl group and Ph is a phenyl group. may be also possible.

[0056] One or more substituted propiolactones include:

[0057] [ka] [In the formula, R 10represents independently in each occurrence -H, optionally substituted C 1~40 Aliphatic, optionally substituted C 1~20 heteroaliphatic, and optionally substituted aryl groups. may be also possible.

[0058] One or more substituted propiolactones are

[0059] [ka] [wherein Ar is an optionally substituted aryl group. R 12 represents independently in each occurrence -H, optionally substituted C 1~40 Aliphatic, optionally substituted C 1~20 heteroaliphatic and optionally substituted aryl, R 13 represents, independently in each occurrence, a fully or partially unsaturated C 2~20 It is a straight chain aliphatic group. The polymer may have both R 4 is hydrogen, and both R on the other carbon atom 4 The mixture may be prepared from a mixture of BPL and pivalolactone, each of which is substituted with a methyl group. One or more of the substituted propiolactones may be selected from the group consisting of:

[0060] [ka] may be also possible.

[0061] The polymer comprises BPL and a compound of the formula:

[0062] [ka] The lactone may be prepared from a mixture of beta-lactones.

[0063] The polymer may be prepared from a mixture of BPL and one or more substituted propiolactones provided as a mixture of positional isomers. Any of the above substituted beta-lactone comonomers may be provided in combination with their positional isomers. When the substituted beta-lactone comonomers are provided as a mixture of positional isomers, the positional isomer having the largest substituent on the carbon adjacent to the ring oxygen atom is present in molar excess relative to the other positional isomers. The major positional isomer is present in a ratio of 2:1 or greater relative to the minor positional isomer, such as 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.

[0064] The polymer may be prepared from a mixture of BPL and one or more cyclic ethers including tetrahydrofuran, substituted tetrahydrofuran, or epoxides. The epoxides may be substituted epoxides, ethylene oxide, propylene oxide, butylene oxide, 4-vinylcyclohexene oxide, 4-ethylcyclohexene oxide, limonene oxide, glycidol ethers, glycidol esters, or cyclohexene oxide. The epoxides may be represented by the formula:

[0065] [ka] [In the formula, R 4 are as defined herein.] The one or more substituted epoxides may correspond to the formula:

[0066] [ka] [In the formula, R 10 are as defined in the genus and subgenera herein.] The one or more substituted epoxides may correspond to the following:

[0067] [ka] may be also possible. The one or more substituted epoxides have the formula:

[0068] [ka] [In the formula, Ar, R 10 , R 12 and R 13 each of which is as defined above.] It may correspond to one of the following:

[0069] The comonomer may be one or more cyclic anhydrides including succinic anhydride, methyl succinic anhydride, methyl diglycolic anhydride, methyl glutaric anhydride, maleic anhydride, phthalic anhydride, citraconic anhydride, trans-1,2-cyclohexanedicarboxylic anhydride.

[0070] In the method, when a comonomer is present with the BPL, the comonomer may be added at the beginning of the process together with the BPL, for example, a batch polymerization may be carried out using a defined mixture of the BPL and one or more comonomers. The method may include a step of varying the monomer composition over time by the addition of additional monomer to the polymerization mixture. Such addition may include continuous addition of the BPL, the comonomer, or a mixture of the BPL and the comonomer. Such addition may include batchwise addition of the BPL, the comonomer, or a mixture of the BPL and the comonomer. Depending on the reaction conditions provided and the relative polymerization rates of the comonomers under the polymerization conditions, such a method may result in random copolymers, tapered copolymers, or block copolymers.

[0071] Chain Transfer Agents The method includes the use of a chain extender, a chain transfer agent and / or a crosslinker. The method may include contacting beta-propiolactone (and optional comonomers) with a zwitterionic initiator in the presence of one or more chain transfer agents. In the context of the present invention, a chain transfer agent is defined as any substance or reagent capable of terminating the growth of one polymer chain and initiating the polymerization of a new polymer chain. In a living polymerization, this is usually a reversible process, and the net effect is that, on average, all chains grow at a similar rate in the composition. 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 chain ends (e.g., for subsequent crosslinking or chain extension reactions, or to impart physical properties such as hydrophilicity or hydrophobicity), examples of the latter include chain transfer agents with radically polymerizable functional groups such as vinyl groups, perfluoro moieties or siloxy groups.

[0072] The chain transfer agent may include an acidic compound. Such acidic compounds may be characterized in that their conjugate bases are nucleophilic. The conjugate bases of the provided acidic chain transfer agents may be sufficiently nucleophilic to ring-open the beta-propiolactone (or react with the provided comonomer). Exemplary chain transfer agents include carboxylic acids, sulfonic acids, phosphoric acids, phosphonic acids, phosphinic acids, thiocarboxylic acids, dithiocarboxylic acids, thiols, phenols, and the like.

[0073] The chain transfer agent (CTA) has the formula Y'-T-(Y') rwhere each Y' is independently an acidic functional group (or a salt formed by deprotonation of such a group), -T- is a polyvalent moiety, and r is 0 or an integer from 1 to 10. Y' may be independently selected from carboxylic acid, sulfonic acid, phosphoric acid, phosphonic acid, phosphinic acid, thiocarboxylic acid, dithiocarboxylic acid, thiol, and phenolic -OH groups (or anions formed by deprotonation of any of these). The chain transfer agent may include a molecule having multiple functional groups (e.g., dicarboxylic acid, tricarboxylic acid, etc.) capable of acting as a chain transfer agent. The chain transfer agent may include a carboxylic acid, such as formic acid, acetic acid, propionic acid, 3-hydroxypropionic acid, 3-hydroxybutanoic acid, lactic acid, benzoic acid, acrylic acid, and methacrylic acid. The chain transfer agent may include a phenol, a thiol, or a derivative thereof.

[0074] The CTA may be present at the beginning of the reaction or may be added during the polymerization process (continuously at a constant or variable rate, or by portioned addition). The CTA may be added portionwise at one or more points during 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 broad molecular weight distribution. When the CTA is added at the beginning of the polymerization reaction, the result is a polymer composition with a narrow PDI. The chain transfer agent may be provided in a molar ratio to the zwitterionic polymerization initiator of from about 1:1 to about 10,000:1, or from 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 from about 10:1 to about 100:1, such as 20:1, 30:1, 40:1, 50:1, 75:1 or 100:1, from about 100:1 to about 1,000:1, such as 200:1, 300:1, 400:1, 500:1, 750:1, 1000:1.

[0075] The polymerization method may be integrated into a process for the manufacture of beta-lactone. Such an integrated process may have advantages in terms of energy efficiency and may result in a higher quality polymer product due to reduced introduction of water, oxygen or other impurities. The method may include the step of reacting carbon monoxide with ethylene oxide to form beta-propiolactone. Exemplary catalysts and methods for such processes are described in published WO 2013 / 063191, WO 2014 / 004858, WO 2003 / 050154, WO 2004 / 089923, WO 2012 / 158573, WO 2010 / 118128, WO 2013 / 063191 and WO 2014 / 008232; U.S. Pat. Nos. 10,662,283, 5,359,081 and 5,310,948, as well as 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 method may include the steps of contacting ethylene oxide with carbon monoxide in the presence of a carbonylation catalyst and a solvent to provide a reaction stream comprising beta-propiolactone; separating a product stream comprising beta-lactone from the reaction stream and feeding the beta-lactone-containing reaction stream to a polymerization reactor and contacting it with a zwitterionic catalyst (optionally in the presence of one or more comonomers) to provide a second reaction stream comprising a biodegradable polyester. Such an integrated carbonylation / polymerization process may be characterized in that substantially all of the carbonylation catalyst is removed from the reaction stream comprising beta-propiolactone prior to feeding the stream to the polymerization reactor. Such an integrated carbonylation / polymerization process is characterized in that at least a portion of the solvent in which the carbonylation process is carried out is present in the reaction stream comprising beta-propiolactone and fed to the polymerization reactor. The method may include the step of separating the solvent from the second reaction stream comprising the polymer. The method may include the step of recycling the separated solvent to the carbonylation reaction.The process may be characterized in that the beta-propiolactone containing reaction stream contains residual ethylene oxide, and the beta-propiolactone ethylene oxide mixture is fed to a polymerization reactor. Ethylene oxide may be a comonomer in BPL polymerization.

[0076] Zwitterionic Initiators The methods described herein include contacting the BPL and optional comonomers with a polymerization initiator that is zwitterionic--e.g., a polymerization initiator that has at least one cation and at least one anion both covalently bound to a single molecule. Such zwitterions may be small molecules, or they may include oligomers or polymers. Zwitterionic initiators may be small molecules with a single covalently bound cation and a single covalently bound anion, or they may include two or several covalently bound cations, two or several covalently bound anions. Zwitterionic initiators may include polymers that include multiple covalently bound cations and anions. Zwitterionic initiators have an overall neutral charge (e.g., the charges of the bound cations and bound anions are equal and cancel each other out), but in certain embodiments, a given zwitterionic initiator may have an overall positive or negative charge balanced by free (e.g., non-covalently bound) anions or cations, respectively. The zwitterionic initiator may comprise an essentially pure chemical or a mixture of molecules capable of functioning as a zwitterionic initiator, since where the zwitterionic initiator comprises an oligomeric or polymeric structure--such a composition comprises, for example, a statistical mixture of related molecules.

[0077] The zwitterionic initiator has the formula: + ) a -L-(X - ) b [In the formula, each Z + is a cation, and each X - is an anion, -L- is a bond, or each Z + and X -a and b are each an integer from 1 to 20. The term multivalent in the context of the present invention means that the structure of the moiety -L-, taken in isolation, has multiple positions at which Z+ and X- ions can be suitably attached by covalent bonds to form a stable molecular structure. For example, using this convention, a compound of the formula Me3N + CH2CH2CH2CO2 - Zwitterionic initiators having the formula (Z + ) a -L-(X - ) b [In the formula, Z + is trimethylammonium, and X - is a carboxylate, -L- is a divalent moiety -CH2CH2CH2-, and a and b are each 1.

[0078] Cationic group (Z + ) The zwitterionic initiator may comprise an organic "onium cation." Such onium cations most commonly contain a heteroatom, nitrogen, phosphorus, or sulfur (or a combination of two or more of these), however, less common organic cations such as stibonium or arsonium cations are also applicable.

[0079] Zwitterionic initiators may include ammonium, amidinium, and guanidinium cations, nitrogen-containing heterocycles, such as nitrogen-based onium cations that may be optionally substituted pyridinium, imidazolium, pyrrolidinium, or piperidinium. The onium cation may be:

[0080] [ka] [In the formula, R 1 , R 2 and R 3 independently for each occurrence, C 1~40 Aliphatic;C 1~40heteroaliphatic; phenyl; 3-8 membered saturated or partially unsaturated or aromatic monocyclic carbocycle; 7-14 carbon saturated, partially unsaturated or aromatic polycyclic carbocycle; 5- or 6-membered monocyclic heteroaryl ring having 1-4 heteroatoms independently selected from nitrogen, oxygen or sulfur; 3-8 membered saturated or partially unsaturated heterocyclic ring having 1-3 heteroatoms independently selected from nitrogen, oxygen and sulfur; 6-12 membered polycyclic saturated or partially unsaturated heterocycle having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur; 8-10 membered bicyclic heteroaryl ring having 1-5 heteroatoms independently selected from nitrogen, oxygen or sulfur; and any two or more of R 1 , R 2 and R 3 R is an optionally substituted group selected from the group consisting of polymer chains which, optionally together with the intervening atoms, form one or more optionally substituted, optionally unsaturated rings, optionally containing one or more additional heteroatoms; 5 is independently at each occurrence hydrogen or C 1~40 Aliphatic;C 1~40 Heteroaliphatic; 3- to 8-membered saturated or partially unsaturated monocyclic carbocyclic ring; 7- to 14-membered saturated or partially unsaturated polycyclic carbocyclic ring; 5- to 6-membered monocyclic heteroaryl ring having 1 to 4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 8- to 14-membered polycyclic heteroaryl ring having 1 to 5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 3- to 8-membered saturated or partially unsaturated monocyclic heterocyclic ring having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur; 6- to 14-membered saturated or partially unsaturated polycyclic heterocyclic ring having 1 to 5 heteroatoms independently selected from nitrogen, oxygen, or sulfur; phenyl; 8- to 14-membered polycyclic aryl ring; and two R 5 Group or R 5 and one or more R 1 and / or R 2group is an optionally substituted group selected from the group consisting of polymer chains which, together with the intervening atoms, can form one or more optionally substituted carbocyclic, heterocyclic aryl or heteroaryl rings; and Ring A is an optionally substituted 5- to 10-membered ring, optionally containing one or more additional heteroatoms and / or sites of unsaturation.

[0081] The cation has the formula:

[0082] [ka] [In the formula, R 1 , R 2 and R 3 each of which is as defined above.] R may be a quaternary ammonium cation that may correspond to 1 , R 2 and R 3 Each is independently C 1~20 aliphatic group, C 1~12 aliphatic group, C 1~8 aliphatic group, C 1~9 Aliphatic group or C 1~4 Aliphatic groups, or methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, 2-ethylhexyl and C 8~20 R may be alkyl. 1 , R 2 and R 3 At least one of R is methyl; 1 , R 2 and R 3 Two of the groups are methyl and the third group is C 2~20 Contains an alkyl chain, or R 1 , R 2 , R 3 are methyl. 1 , R 2 and R 3 One of the R may include a polymer chain or a hydrophobic moiety. 1 , R 2 and R 3The groups taken together form a ring, for example a five- or six-membered saturated or unsaturated ring, optionally containing one or more additional heteroatoms. The ammonium cation

[0083] [ka] [In the formula, R 20 is an optionally substituted C 2~40 is selected from aliphatic, optionally substituted aryl, optionally substituted benzyl, and polymer chains. may be also possible.

[0084] The zwitterionic initiator may include a phosphorus-based cation. The zwitterionic initiator may include a phosphonium cation. The zwitterionic initiator has the formula:

[0085] [ka] [In the formula, R 1 , R 2 and R 3 each as defined above.] R 1 , R 2 and R 3 At least one or all of R may be an aryl group, e.g., phenyl. 1 , R 2 and R 3 may be a polymer chain, and the polymer chain may be linked to the phosphorus atom via an aryl ring of the phosphonium cation, and the phosphonium cation may be

[0086] [ka] [Wherein, Ar and R 20 are as defined above and in the genera and subgenera herein; may be optionally substituted aryl, optionally substituted heteroaryl, and polymeric chains. It could be.

[0087] The cation may be an amidinium cation. The amidinium cation may be linked to the -L- moiety via either the carbon atom or the two nitrogen atoms that make up the amidinium group. All resonance forms of such cations are included. The cation may be:

[0088] [ka] In the formula, R 1 , R 2 and R 5 Each of the is as defined. R 1 , R 2 and R 3 Each of the following is independently 1~12 aliphatic group, C 1~8 aliphatic group, C 1~9 Aliphatic group or C 1~4 R may be an aliphatic group. 1 , R 2 and R 3 is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, 2-ethylhexyl and C 8~20 R may be independently selected from alkyl. 1 , R 2 and R 3 At least one of R may be methyl. 1 and R 2 The groups may together form a ring, such as a five- or six-membered saturated or unsaturated ring. The cation may be a bicyclic amidinium group, which may have one nitrogen atom with three non-hydrogen substituents and a second nitrogen atom with bonds to four non-hydrogen substituents. Such non-hydrogen substituents may be aliphatic substituents or the ring of the bicyclic amidinium group.

[0089] The amidinium cation is:

[0090] [ka] [In the formula, R 1 is as defined above.] may be also possible.

[0091] The cation may be a guanidinium cation in any of the resonance forms of such a cation.

[0092] [ka] [In the formula, R 1 , R 2 and R 5 each is as defined above, and C and D represent a 5- to 8-membered saturated or partially unsaturated ring. may be also possible.

[0093] The cations are

[0094] [ka] [In the formula, R 1 is as defined above.] R 1 , R 2 and R 3 Each of the following is independently 1~12 aliphatic group, C 1~8 aliphatic group, C 1~9 Aliphatic group or C 1~4 R may be an aliphatic group. 1 , R 2 and R 3 are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, 2-ethylhexyl and C 8~20 R may be independently selected from the group consisting of alkyl. 1 , R 2 and R 3 At least one of R may be methyl. 1 and R 2The groups may be joined together to form a ring, such as a five- or six-membered saturated or unsaturated ring. The cation may be a bicyclic amidinium group, which may have one nitrogen atom with three non-hydrogen substituents and a second nitrogen atom with bonds to four non-hydrogen substituents. The non-hydrogen substituents may be an aliphatic group or the ring of the bicyclic amidinium group.

[0095] The cation may include a sulfur-based onium salt, such as a sulfonium salt.

[0096] [ka] wherein each of them is as defined above. R 1 and R 2 may each be methyl. The cations are

[0097] [ka] [In the formula, R 1 , R 2 , R 3 and R 5 each of which is as defined above.] R may be a sulfoxonium cation. 1 and R 2 may be methyl, and / or each of R 5 may be methyl. In this context, R 3 and R 5 At least one of may be an optionally substituted aryl group.

[0098] The cation may contain both nitrogen and phosphorus atoms, such as a phosphazenium cation, which is:

[0099] [ka] [In the formula, R 1 , and R 2 each of which is as defined above.] Each R 1 and R 2 The group may be methyl. The cation is:

[0100] [ka] may be also possible.

[0101] R 1 , R 2 and R 3 is C 1~40 an aliphatic or optionally substituted phenyl group, C 1~40 aliphatic group, C 1~20 Fluorinated aliphatic and optionally substituted aryl, C 1~40 aliphatic group, C 1~20 aliphatic group, C 1~12 Aliphatic or phenyl group, C 1~12 aliphatic group, C 1~8 aliphatic group, C 1~6 Aliphatic group or C 1~4 R is independently selected from the group consisting of aliphatic groups. 1 , R 2 and R 3 Each of R may be methyl, ethyl, butyl, an optionally substituted phenyl group, phenyl, or trifluoromethyl. 1 and R 2 may each be methyl; R 3 is C 2~20 R may be an aliphatic group or an optionally substituted phenyl group. 1 , R 2 and R 3 At least one of the following is C 1~20 Fluorinated aliphatic groups, C 1~12 aliphatic group, C 1~8 Fluorinated aliphatic groups, C 1~6 Fluorinated aliphatic groups, or C 1~4 The fluorinated aliphatic group may be trifluoromethyl.

[0102] Anionic group (X-) Zwitterionic initiators contain one or more covalently bound anions (e.g., X - The anion may be an oxygen or sulfur based anion. The oxygen based anion is an anion of the formula -QO - [wherein Q contains sulfur, phosphorus, boron or a carbonyl group.] - -CO2 - , -SO3 - , -OPORO2 - , -PORO2 - -OPRO2 - or -PRO2 -

[0023] wherein R is -H, optionally substituted C 1~40 The anion may include a -CO2 - , -SO3 - , -OP(O)ORO - (phosphate anion), or -PR(O)O - (phosphinate anion). The anion may be a sulfur anion and X is S. The anion may be a dithiocarboxylate anion. X is (-C(S)S - )-(S) n S - [wherein n is an integer of 1 to 20].

[0103] Linker group (-L-) The zwitterionic initiator has the formula: + ) a -L-(X - ) b where -L- is a bond or a polyvalent organic moiety to which a cation and an anion are covalently attached. The present invention places no limitations on the structure of -L-, which may be any carbon-containing moiety. For example, a cation Z + But X - When it contains one or more carbon atoms that can be a site of attachment of a group (or vice versa), L- may be considered to contain a covalent bond. L- is as defined above.

[0104] L- may be an optionally substituted ring (i.e., -Z + and -X - The group is directly linked to an atom that constitutes the ring by -L-, and the ring may be joined by one or more Z + Or X - The group may have one or more non-ring heteroatoms or optionally substituted aliphatic groups separating the ring. Structural constraints may be incorporated into the moieties -L- to bind the Z + and X - The structural constraints may be cyclic, bicyclic, bridged and tricyclic moieties. When -L- comprises a polymer, Z + and X - The group may be present on a monomer that is incorporated into the polymer.

[0105] Ammonium Carboxylate Zwitterionic Initiators The zwitterionic initiator may comprise a nitrogen-containing cation and a carboxylate anion, which can be represented by the formula R 1 R 2 R 3 N + -L-CO2 - [In the formula, R 1 , R 2 , R 3 and -L- are each as defined above. Such zwitterionic initiators may correspond to Me3N + -L-CO2 - , Et3N + -L-CO2 - , i-PrEt2N + -L-CO2 - , n-Bu3N + -L-CO2 - or R 20 Me2N + -L-CO2 - [Wherein, -L- and R 20 wherein each of is as defined above.

[0106] Zwitterionic initiators have the formula R 1 R 2R 3 N + -L a -CO2 - [In the formula, L a is C 1~100 and R may be an optionally substituted divalent aliphatic radical of 1 , R 2 and R 3 is as defined above. a is C 1~40 an optionally substituted divalent aliphatic radical of 1~40 a branched or unbranched divalent alkyl group of C 1~20 a branched or unbranched divalent alkyl group of C 1~12 a branched or unbranched divalent alkyl group of C 1~8 or a branched or unbranched divalent alkyl group of C 1~6 A branched or unbranched divalent alkyl group of C 1~20 Straight chain divalent alkyl group, C 1~12 Straight chain divalent alkyl group, C 1~8 Straight chain divalent alkyl group, C 1~8 Straight chain divalent alkyl group or C 1~6 The zwitterionic initiator may be a linear divalent alkyl group. + -L a -CO2 - , Et3N + -L a -CO2 - , i-PrEt2N + -L a -CO2 - , n-Bu3N + -L a -CO2 - or R 20 Me2N + -L a -CO2 - [-L a - and R 20 wherein each of the above is defined. Zwitterionic initiators may be derived from the reaction of a tertiary amine with chloroacetic acid, bromoacetic acid, and the like. Zwitterionic initiators may have the formula:

[0107] [ka] [In the formula, R 1 , R 2 , and R 3 is as defined above.] has.

[0108] Zwitterionic initiators are

[0109] [ka] may be also possible.

[0110] Zwitterionic initiators may be derived from amino acids. Such reagents may be obtained by treating an amino acid with an alkylating agent capable of quaternizing the amine group; such zwitterionic initiators are

[0111] [ka] [R 1 , R 2 , and R 3 each of which is as defined above and in the genus and subgenera herein.

[0112] The zwitterionic initiator may be a betaine of an amino acid, which is:

[0113] [ka] may be also possible.

[0114] Zwitterionic initiators include those containing an amidinium cation and a carboxylate anion, e.g.,

[0115] [ka] [In the formula, R 1 and R 2 each of which is as defined above.] may be also possible.

[0116] Zwitterionic initiators are

[0117] [ka] [In the formula, L, L a , R 1 R 2 , R 3 and R 5 each of which is as defined above.] may be also possible.

[0118] Zwitterionic initiators include those containing a guanidinium cation and a carboxylate anion, e.g.

[0119] [ka] [In the formula, R 1 , R 2 and L are each as defined above. The zwitterionic initiator may include

[0120] [ka] [In the formula, L, L a and R 1 each of which is as defined above.] may be also possible.

[0121] Phosphonium Carboxylate Zwitterionic Initiators The zwitterionic initiator may include a phosphorus-containing cation and a carboxylate anion. Such zwitterionic initiators have the formula R 1 R 2 R 3 P + -L-CO2 - or R 1 R 2 R 3 P + -L a -CO2- [In the formula, L, L a , R 1 , R 2 and R 3 Each of the above is as defined above and in the genus and subgenus herein. The zwitterionic initiator may have the formula Me3P + -L a -CO2 - , Et3P + -L a -CO2 - , i-PrEt2P + -L a -CO2 - , n-Bu3P + -L a -CO2 - , Ar3P + -L a -CO2 - , Ph3P + -L a -CO2 - or R 20 Ph2P + -L a -CO2 - [In the formula, -L a -, Ar and R 20 each of which is as defined above.

[0122] Ammonium Sulfonate Zwitterionic Initiator The zwitterionic initiator may include a nitrogen-containing cation and a sulfonate anion. The zwitterionic initiator may be represented by the formula R 1 R 2 R 3 N + -L-SO3 - or R 1 R 2 R 3 N + -L a -SO3 - [In the formula, L a , R 1 , R 2 and R 3 is as defined above. Such zwitterionic initiators may include Me3N + -L a -SO3- , Et3N + -L a -SO3 - , i-PrEt2N + -L a -SO3 - , n-Bu3N + -L a -SO3 - or R 20 Me2N + -L a -SO3 - [In the formula, -L a - and R 20 wherein each of is as defined above.

[0123] The zwitterionic initiator has the formula:

[0124] [ka] [In the formula, R 1 , R 2 , R 3 , R 5 and L are each as defined above. and a sulfonate anion.

[0125] The zwitterionic initiator has the formula:

[0126] [ka] [In the formula, L, L a and R 1 each of which is as defined above.]

[0043]

[0127] The zwitterionic initiator has the formula:

[0128] [ka] [In the formula, R 1 , R 2and L are each as defined above. Such zwitterionic initiators may include a guanidinium cation and a sulfonate anion, which may have the formula:

[0129] [ka] [In the formula, L, L a and R 1 each of which is as defined above.]

[0043]

[0130] Phosphonium Sulfonate Zwitterionic Initiators The zwitterionic initiator may include a phosphorus-containing cation and a sulfonate anion. Such zwitterionic initiators have the formula R 1 R 2 R 3 P + -L-SO3 - or R 1 R 2 R 3 P + -L a -SO3 - [In the formula, L, L a , R 1 , R 2 and R 3 Each of is as defined above. Such zwitterionic initiators may include Me3P + -L a -SO3 - , Et3P + -L a -SO3 - , i-PrEt2P + -L a -SO3 - , n-Bu3P + -L a -SO3 - , Ar3P + -L a -SO3 - , Ph3P + -L a -SO3 - or R 20 Ph2P+ -L a -SO3 - [In the formula, -L a -, Ar and R 20 wherein each of is as defined above.

[0131] Ammonium Phosphate Zwitterionic Initiator Zwitterionic initiators include those having a nitrogen-containing cation and a phosphate anion, such as those having the formula:

[0132] [ka] [In the formula, R 1 , R 2 , R 3 , R, L and L a each of which is as defined above.] Such zwitterionic initiators may include

[0133] [ka] [In the formula, L a , R and R 20 each of which is as defined above.] It may have the formula:

[0134] Zwitterionic initiators include, for example,

[0135] [ka] [In the formula, R 1 , R 2 , R 5 , R and L are as defined above. Such initiators may include an amidinium cation and a phosphate anion having the formula:

[0136] [ka] [In the formula, R1 , R and L are as defined above. It may have the formula:

[0137] Zwitterionic initiators include guanidinium cations and phosphate anions, for example, those of the formula:

[0138] [ka] [In the formula, R 1 , R 2 , and L are each defined above. Such initiators may include those of the formula:

[0139] [ka] [In the formula, R 1 , R 2 and L are each as defined above. It may be of the following type.

[0140] Zwitterionic initiators may include a nitrogen-based cation in combination with a phosphonate (O- or P-linked) or phosphinate anion. Zwitterionic initiators include phosphonate or phosphinate analogs of any of the phosphate zwitterions described above. Such initiators have the formula:

[0141] [ka] [In the formula, R 1 , R 2 and L a each of which is as defined above.]

[0043]

[0142] The zwitterionic initiator may comprise a nitrogen-containing cation and a phosphonate or phosphinate anion. The zwitterionic initiator may be an ammonium phosphonate or ammonium phosphinate, such as:

[0143] [ka] [In the formula, R, R 1 , R 2 , R 3 , R and L are as defined above. Includes.

[0144] The zwitterionic initiator has the formula:

[0145] [ka] [In the formula, R, R 1 , R 2 , R 3 , R and L are as defined above. The compound may comprise an amidinium phosphonate or an amidinium phosphinate which may correspond to one of the following:

[0146] The zwitterionic initiator has the formula:

[0147] [ka] [In the formula, R, R 1 , R 2 , R 3 , R and L are as defined above. The compound may comprise a guanidinium phosphonate or a guanidinium phosphinate which may correspond to one of the following:

[0148] Phosphonium Phosphate Zwitterionic Initiators The zwitterionic initiator may include a phosphorus-containing cation and a phosphorus-containing anion, which may be represented by the formula: R 1 R 2 R 3 P + -L-OPORO2 - , R 1 R 2 R 3 P+ -L-OPRO2 - , R 1 R 2 R 3 P + -L-PRO2 - and R 1 R 2 R 3 P + -L-PORO2 - [In the formula, L, R, R 1 , R 2 and R 3 is as defined above.]

[0149] The zwitterionic initiator may include a phosphonium phosphate, which has the formula R 1 R 2 R 3 P + -L a -OPORO2 - [In the formula, L a , each of R is as defined above.] or Me3P + -L a -OPORO2 - , Et3P + -L a -OPORO2 - , i-PrEt2P + -L a -OPORO2 - , n-Bu3P + -L a -OPORO2 - , Ar3P + -L a -OPORO2 - , Ph3P + -L a -OPORO2 - and R 20 Ph2P + -L a -OPORO2 - [In the formula, -L a -, Ar, R, R 1 , R 2 , R 3 and R 20 is as defined].

[0150] The zwitterionic initiator may include an oxygen (O-) linked phosphonium phosphonate, which is represented by R 1 R 2 R 3 P + -L a -OPRO2 - , or Me3P + -L a -OPRO2 - , Et3P + -L a -OPRO2 - , i-PrEt2P + -L a -OPRO2 - , n-Bu3P + -L a -OPRO2 - , Ar3P + -L a -OPRO2 - , Ph3P + -L a -OPRO2 - , and R 20 Ph2P + -L a -OPRO2 - [In the formula, -L a -, Ar, R, R 1 , R 2 and R 3 and R 20 is as defined above.]

[0151] The zwitterionic initiator may include a P-linked phosphonium phosphonate, which has the formula R 1 R 2 R 3 P + -L a -PORO2 - , or Me3P + -L a -PORO2 - , Et3P + -L a -PORO2 - , i-PrEt2P + -L a -PORO2 -, n-Bu3P + -L a -PORO2 - , Ar3P + -L a -PORO2 - , Ph3P + -L a -PORO2 - and R 20 Ph2P + -L a -PORO2 - [In the formula, -L a -, Ar, R, R 1 , R 2 , R 3 and R 20 is as defined above.]

[0152] The zwitterionic initiator may include an oxygen (O-) linked phosphonium phosphinate, which has the formula R 1 R 2 R 3 P + -L a -PRO2 - or Me3P + -L a -PRO2 - , Et3P + -L a -PRO2 - , i-PrEt2P + -L a -PRO2 - , n-Bu3P + -L a -PRO2 - , Ar3P + -L a -PRO2 - , Ph3P + -L a -PRO2 - , and R 20 Ph2P + -L a -PRO2 - [In the formula, -L a -, Ar, R, R 1 , R 2 , R 3 and R 20is as defined above.]

[0153] Zwitterionic initiators may contain a dithiocarboxylate anion and any of the cationic groups and linker moieties described herein. Such dithiocarboxylate zwitterions can be obtained from 2-methylpyridinium-, quinolinium-, and pyrimidinium salts according to the methods described in Journal of Pharmaceutical Sciences, Vol. 67, No. 7, 1978, pp. 962-964 (1978), which is incorporated herein by reference. Such zwitterionic initiators include:

[0154] [ka] may be also possible.

[0155] Complexing Agent The disclosed method may include contacting the monomer with the zwitterionic initiator in the presence of a complexing agent. The addition of a complexing agent may improve the process by increasing the rate of polymerization and increasing the yield of polymer, or may result in improved polymer properties through control of properties such as molecular weight or polydispersity. Exemplary complexing agents include crown ethers and other macropolyheterocycle-containing rings having multiple heteroatoms of -O-, -NR-, and / or -S-. Complexing agents include crown ethers, such as those described in a dissertation 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 any derivative or mixture thereof. The complexing agent may include 15-crown-5 or 12-crown-4. The crown ether may be selected based on its ability to effectively complex with the cationic functional groups present in the zwitterionic polymerization initiator used in the process. The complexing agent may include macroheterocycles containing heteroatoms other than oxygen; crown ethers in which one or more oxygen atoms are replaced with nitrogen or sulfur atoms; azacrown ethers such as 4,7,13,16,21-pentaoxa-1,10-diazabicyclo[8.8.5]tricosane, 1,4,8,12-tetraazacyclopentadecane, and 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane; or thiacrown ethers. The complexing agent may include those described in U.S. Pat. No. 3,890,278, the entirety of which is incorporated herein by reference. The complexing agent may be introduced at the beginning of the polymerization process or at any subsequent time.The complexing agent may be added simultaneously with the zwitterionic polymerization initiator. The complexing agent may be provided as a mixture or solution with the zwitterionic polymerization initiator and the mixture may be fed to the reaction as described above for initiator addition. The complexing agent may be used in an amount ranging from about 1:100 to about 100:1 relative to the zwitterionic polymerization initiator, 1:10 to 10:1, 1:2 to 2:1 molar ratio relative to the zwitterionic polymerization initiator. A chain transfer agent may be utilized in the process and the complexing agent may be provided in a molar ratio relative to the CTA ranging from 1:10 to 10:1, 1:5 to 5:1, or 1:2 to 2:1.

[0156] Polymer Composition A polymer composition is disclosed. The polymer composition has the formula PI: + ZLX-(A)-H [wherein, Z + each of -L- is as defined above, and -X- is an anion X- as defined above. - in the covalently bonded form; -(A)- is a polymer chain comprising poly(3-hydroxypropionate) or a copolymer comprising poly(3-hydroxypropionate) with one or more comonomers incorporated into the chain, where -H is a proton. The polymer composition may comprise a polymer chain of the formula P-II: + ZLX-(A)-R k or formula P-IIa: + ZLX-(A)-CH2R p [In the formula, Z + , -L-, X and -(A)- are as defined above; R k is R n or a silicon-containing functional group.

[0157] A is a group represented by the formula:

[0158] [ka] The poly(3-hydroxypropionate) (polypropiolactone) chain may be represented by:

[0159] A- may include copolymers of beta-propiolactone with one or more comonomers as disclosed herein as (A)-, having the formula:

[0160] [ka] [In the formula, R 10 and R 13 is as defined above.] The semiconductor device may have one of the following:

[0161] When -(A)- comprises a copolymer of beta-propiolactone and one or more substituted beta-lactones, the substituted beta-lactone monomers may be present as a mixture of positional isomers. Such copolymers have the formula:

[0162] [ka] [In the formula, R 10 is as defined above.]

[0043]

[0163] The copolymer may be a polymer of propiolactone with a positional isomeric mixture of any of the substituted beta-lactones described above and herein. A is a compound of the formula:

[0164] [ka] The copolymer may include a copolymer of beta-propiolactone and one or more epoxides, which may correspond to:

[0165] A is a group represented by the formula:

[0166] [ka] [In the formula, R 10 , R 12 and R 14 each of which is as defined above.] The polymer may include a beta-propiolactone epoxide copolymer represented by one of the following:

[0167] A is the formula

[0168] [ka] The copolymer may include a copolymer of beta-propiolactone and lactide, which may correspond to one of:

[0169] A is a group represented by the formula:

[0170] [ka] The copolymer may be a copolymer of beta-propiolactone and caprolactone, which may correspond to:

[0171] A may comprise beta-propiolactone and two or more additional comonomers, such as any two or more epoxide comonomers, any two or more substituted beta-propiolactone comonomers, at least one epoxide and at least one substituted beta-propiolactone, at least one epoxide and lactide, at least one epoxide and caprolactone, at least one substituted beta-propiolactone and lactide, at least one substituted beta-propiolactone and caprolactone, or a copolymer of lactide and caprolactone.

[0172] The polymer composition may be any of the formulas PI, P-II, or P-IIa, + ZLX- is a group of the formula: R 1 R 2 R 3 N + -LC(O)O-, -L-, R 1 , R 2 and R 3 Each of the above is defined as above. + ZLX-Me3N +-LC(O)O-, Et3N + -LC(O)O-, i-PrEt2N + -LC(O)O-, n-Bu3N + -LC(O)O- or R 20 Me2N + -LC(O)O- [wherein -L- and R 20 wherein each of is as defined above.

[0173] portion + ZLX- is a formula R 1 R 2 R 3 N + -L a -C(O)O-[wherein, L a is Me3N + -L a -C(O)O-, Et3N + -L a -C(O)O-, i-PrEt2N + -L a -C(O)O-, n-Bu3N + -L a -C(O)O- or R 20 Me2N + -L a -C(O)O-, -L a - and R 20 each of which is as defined above. + ZLX- is a group represented by the formula:

[0174] [ka] TIFF2024507947000060.tif204166TIFF2024507947000061.tif55166 [where R 1 , R 2 , R 3 , R 5 , L a and L are each as defined above. may correspond to one of the following:

[0175] The polymer composition may include polymer chains having any of the formulas PI, P-II, or P-IIa, where the moiety + ZLX- is a group of the formula: R 1 R 2 R 3 P + -L a -C(O)O-[wherein, L a , R 1 , R 2 and R 3 each of which is as defined above.], or Me3P + -L a -C(O)O-, Et3P + -L a -C(O)O-, i-PrEt2P + -L a -C(O)O-, n-Bu3P + -L a -C(O)O- - , Ar3P + -L a -C(O)O-, Ph3P + -L a -C(O)O- or R 20 Ph2P + -L a -C(O)O-[wherein, -L a -, Ar and R 20 as defined above and in the genus and subgenera herein.

[0176] The polymer composition includes polymer chains having any of the formulas PI, P-II, or P-IIa, where the moiety + ZLX- is a group of the formula: R 1 R 2 R 3 N + -LS(O)2O- or R 1 R 2 R 3 N + -L a -SO3-, [where L, L a , R 1 , R 2 and R 3 is as defined above. +ZLX is Me3N + -L a -SO3-, Et3N + -L a -SO3-, i-PrEt2N + -L a -SO3-, n-Bu3N + -L a -SO3- or R 20 Me2N + -L a -SO3,

[0177] [ka] [In the formula, R 1 , R 2 , R 3 , R 5 , L, L a - and R 20 each of which is as defined above.] may be also possible.

[0178] The polymer composition includes polymer chains having any of the formulas PI, P-II, or P-IIa, where the moiety + ZLX- is a group of the formula: R 1 R 2 R 3 P + -L a -S(O)2O-[where L a , R 1 , R 2 and R 3 each of which is as defined above.], or Me3P + -L a -S(O)2O-, Et3P + -L a -S(O)2O-, i-PrEt2P + -L a -S(O)2O-, n-Bu3P + -L a -S(O)2O- - , Ar3P + -L a -S(O)2O-, Ph3P + -L a -S(O)2O- or R20 Ph2P + -L a -S(O)2O-[wherein, -L a -, Ar and R 20 Each of the formulas is as defined above. The polymer composition may include polymer chains having any of the formulas PI, P-II, or P-IIa, where the moiety + ZLX- is a group represented by the formula:

[0179] [ka] TIFF2024507947000064.tif89166[where, R 1 , R 2 , R 3 , R, R 20 L and L a each of which is as defined above.] has.

[0180] + ZLX- may include an amidinium phosphonate or an amidinium phosphinate. + ZLX- is a group represented by the formula:

[0181] [ka] [In the formula, R, R 1 , R 2 , R 3 , R and L are as defined above. may correspond to one of the following:

[0182] + ZLX- may include a guanidinium phosphonate or a guanidinium phosphinate. + ZLX is a group represented by the formula:

[0183] [ka] [In the formula, R, R 1 , R 2, R 3 , R and L are as defined above. may correspond to one of the following:

[0184] portion + ZLX- may include a phosphorus-containing cation and a phosphorus-containing anion, and has the formula R 1 R 2 R 3 P + -L-OPORO2-, R 1 R 2 R 3 P + -L-OPRO2-, R 1 R 2 R 3 P + -L-PRO2- and R 1 R 2 R 3 P + -L-PORO2-[where L, R, R 1 , R 2 and R 3 is as defined above.]

[0185] + ZLX- is a formula R 1 R 2 R 3 P + -L a -OPORO2-, Me3P + -L a -OPORO2-, Et3P + -L a -OPORO2-, i-PrEt2P + -L a -OPORO2-, n-Bu3P + -L a -OPORO2-, Ar3P + -L a -OPORO2-, Ph3P + -L a -OPORO2- and R 20 Ph2P + -L a -OPORO2-[wherein, -L a -, Ar, R, R 1 , R2 , R 3 and R 20 is as defined above.

[0186] + ZLX- is a formula R 1 R 2 R 3 P + -L a -OPRO2Me3P + -L a -OPRO2-, Et3P + -L a -OPRO2-, i-PrEt2P + -L a -OPRO2-, n-Bu3P + -L a -OPRO2-, Ar3P + -L a -OPRO2-, Ph3P + -L a -OPRO2- and R 20 Ph2P + -L a -OPRO2-[wherein, -L a -, Ar, R, R 1 , R 2 , R 3 and R 20 is as defined above.

[0187] + ZLX- is a formula R 1 R 2 R 3 P + -L a -PORO2Me3P + -L a -PORO2-, Et3P + -L a -PORO2-, i-PrEt2P + -L a -PORO2-, n-Bu3P + -L a -PORO2-, Ar3P + -L a-PORO2-, Ph3P + -L a -PORO2- and R 20 Ph2P + -L a -PORO2-[wherein, -L a -, Ar, R, R 1 , R 2 , R 3 and R 20 is as defined above.

[0188] + ZLX- is a formula R 1 R 2 R 3 P + -L a -PRO2-, Me3P + -L a -PRO2-, Et3P + -L a -PRO2-, i-PrEt2P + -L a -PRO2-, n-Bu3P + -L a -PRO2-, Ar3P + -L a -PRO2-, Ph3P + -L a -PRO2- and R 20 Ph2P + -L a -PRO2-[wherein, -L a -, Ar, R, R 1 , R 2 , R 3 and R 20 wherein each of is as defined above.

[0189] + ZLX- is a dithiocarboxylate anion and a cation of the formula

[0190] [ka] The cationic group may comprise any of the cationic groups and linker moieties described above, including one of:

[0191] Formula P-II: + ZLX-(A)-R k [In the formula, Z + , -L-, X, -(A)- and R k wherein each of the formulas is as defined above. Such polymer compositions are disclosed having an end capping agent at one end of the polymer chain, which may correspond to the formula: + ZLX-(A)-OCH3, + ZLX-(A)-OCH2CH3, + ZLX-(A)-OCH2CH2CH3, + ZLX-(A)-OCH2CH=CH2, + ZLX-(A)-OCH2Ar and + ZLX-(A)-OCH2Ph ​​[wherein, Z + , -L-, X, -(A)- and Ar are each as defined above. Exemplary polymer compositions may correspond to one of the formulas:

[0192] [ka] [In the formula, Z + ,L,-X-,(A),R t , R s and m are each defined above. The polymer composition comprises polymer chains corresponding to one of the formulas: + ZLX-(A)-L'-(A)-XLZ + [In the formula, Z + Each of -L-, -X, -(A)- and L' is as defined above and in the genus and subgenus herein. Such polymer compositions may include polymer chains that were extended chains that may correspond to the formula:

[0193] [ka] [In the formula, Z + , -L-, X and -(A)- are as defined above. The polymer chain may include

[0194] The polymer composition including the multifunctional chain extender has the formula: + ZLX-(A)-L''-[(A)-XLZ + ] g [In the formula, g is an integer of 2 to about 50; Z + , -L-, X, -(A)- and L″ are each as defined above. The polymer composition may be characterized as comprising two or more distinct populations of polymer chains distinguished by the initiator groups present on the chains. Such compositions may arise, for example, when a mixture of different zwitterionic initiators is used or when a chain transfer agent is present during polymerization. In the former case, the resulting mixture comprises two or more different polymer chains and has a structure conforming to formula PI or P-II described above. Such mixtures are specifically contemplated and disclosed herein. Mixtures of the type of the present invention may be useful when the polymer-bound zwitterionic initiator confers a particular property (e.g., hydrophilicity, hydrophobicity, affinity for some surfaces, antimicrobial properties, etc.) and it is desired to optimize or modify such property.

[0195] The second category of mixed polymer compositions obtained herein (i.e. resulting from chain transfer) includes a population of polymer chains that do not possibly conform to formula PI or P-II, for example when the CTA corresponds to the formulas described herein. The polymer composition may contain polymer chains of formula PI and polymer chains of formula Y'-T(-Y') g :T-[Y'-(A)-H] g+1 wherein T, Y', (A) and g are as defined above (-H is a proton), resulting from the action of a chain transfer agent of formula PI C It contains a mixture of chains of formula PI C For example, when g is 0, a polymer composition comprising a polymer chain of formula PI in combination with a polymer chain of formula PI is disclosed.C The polymer chain of formula PI has the structure T-CO2-(A)-H, T-SO3-(A)-H, TS-(A)-H (where S is a sulfur atom), T-CS2-(A)-H TC(S)O-(A)-H. C For example, when g is greater than 0, a polymer composition comprising a polymer chain of the formula PI in combination with a polymer chain of the formula PI is disclosed. C The polymer chain has the structure T[-CO2-(A)-H] g , T[-SO3-(A)-H] g , T[-S-(A)-H] g or T[-CS2-(A)-H] g wherein each S is a sulfur atom and g is 2, 3, 4, 5 or greater than 5.

[0196] Formula P-II C :T-[Y'-(A)-R k ] g+1 [In the formula, T, Y', (A), R k and g are each as defined above. The disclosed polymer composition comprises a polymer chain of formula P-II C In combination with the polymer chain of formula P-II, for example, when g is 0, T-CO2-(A)-R k , T-SO3-(A)-R k , TS-(A)-R k (wherein S is a sulfur atom), T-CS2-(A)-R k or TC(S)O-(A)-R k ) may be a mixture containing polymer chains of formula P-II C For example, when g is greater than 0, T[-CO2-(A)-R k ] g In one embodiment, a polymer composition is disclosed that includes a mixture comprising a polymer chain of formula P-II in combination with a polymer chain of formula P-II. C The polymer chain has the structure T[-SO3-(A)-R k ] g , T[-S-(A)-R k ] g or T[CS2-(A)-R k ]g wherein each S is a sulfur atom and g is 1, 2, 3, 4, 5 or greater than 5.

[0197] The polymer composition has the formula PI and PI C , or P-II and P-II C The composition may comprise a mixture of chains of PI:PI. C or P-II:P-II C The ratio is in the range of about 1:1 to about 1:10000. The disclosed polymer compositions include a polymer having formula PI present in a ratio of about 1:1 to about 10:1 (e.g., 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 8:1 or 10:1), about 10:1 to about 100:1 (e.g., 20:1, 30:1, 40:1, 50:1, 75:1 or 100:1), about 100:1 to about 1,000:1 (e.g., 200:1, 300:1, 400:1, 500:1, 750:1 or 1000:1), or about 1,000:1 to about 10,000:1 (e.g., 2,000:1, 3,000:1, 4,000:1, 5,000:1, 7,500:1 or 10,000:1). C The disclosed polymer compositions include a mixture of chains of formula P-II and PI, present in a ratio of about 1:1 to about 10:1 (e.g., 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 8:1, or 10:1), about 10:1 to about 100:1 (e.g., 20:1, 30:1, 40:1, 50:1, 75:1, or 100:1), about 100:1 to about 1,000:1 (e.g., 200:1, 300:1, 400:1, 500:1, 750:1, or 1000:1), or about 1,000:1 to about 10,000:1 (e.g., 2,000:1, 3,000:1, 4,000:1, 5,000:1, 7,500:1, or 10,000:1). C and P-II chains.

[0198] In embodiments where a given polymer composition comprises a mixture of different polymer types, the composition may be determined directly by analytical techniques applied to the composition. Sensitive spectroscopic techniques capable of identifying polymer structures or polymer end groups (i.e., nuclear magnetic spectroscopy or mass spectroscopy) are particularly useful in this regard. Alternatively, the composition may be inferred from knowledge of the feedstocks used to prepare the polymer composition (i.e., the identity and ratio of the zwitterionic initiator, chain transfer agent, and monomers used). In some cases, fractionation or decomposition of the polymer composition may also be used (alone or in combination with other analytical techniques) to determine structural characteristics. EXAMPLES

[0199] The following examples are merely illustrative and are not intended to limit any aspect of the present disclosure in any way. The addition of a strong base generates a zwitterionic initiator in situ. Exemplary strong bases include:

[0200] [ka]

[0201] [Example 1] Betaine (2.1 mg; 0.015 mmol), beta-propiolactone (1.15 g; 16 mmol), and THF (solvent; 13 mL) were combined in a glass vial to give a white polymer of P3HP that precipitated from solution with 100% of the bPL consumed in 24 h (Mn 62,400 g / mol by GPC, PDI 3.4).

[0202] [Example 2] Betaine (1.1 mg; 0.008 mmol), beta-propiolactone (1.15 g; 16 mmol), and 13 mL of THF were combined in a glass vial to give a white polymer of P3HP that precipitated out of solution with 100% of the bPL consumed in 6 h (Mn 108,500 g / mol by GPC, PDI 2.9).

[0203] [Example 3] P3HP can be prepared as described above in Example 2, except that lauryl betaine is used instead of betaine, and the reaction is complete in 24 hours to give a white polymer (Mn by GPC is 51,300 g / mol; PDI is 3.7).

[0204] [Example 4] P3HP can be prepared as described above in Example 1, but using dimethylaminopyridine (DMAP) instead of betaine, and the reaction is complete in 18 hours to give a white polymer (Mn by GPC is 32,600 g / mol; PDI is 3.5). The addition of DMAP generates a zwitterionic initiator in situ.

[0205] [Example 5] P3HP can be prepared as described in Example 1, but using DBU instead of betaine, and the reaction is complete in 12 hours to give a white polymer (M by GPC). n is 19,000 g / mol; PDI is 3.2.) The addition of DBU generates a zwitterionic initiator in situ.

[0206] [Example 6] P3HP can be prepared as described above in Example 1, but using TBD instead of betaine acetate, and the reaction is complete in 18 hours to give a white polymer (M by GPC). n is 40,100 g / mol; PDI is 5.6. The addition of TBD generates a zwitterionic initiator in situ.

[0207] [Example 16] P3HP can be prepared as described above in Example 1, but using MTBD instead of betaine, and the reaction is complete in 18 hours to give a white polymer (M by GPC). nis 48,400 / mol; PDI is 3.0. The addition of MTBD generates a zwitterionic initiator in situ.

[0208] A summary of the polymer molar masses from the polymerization of beta-propiolactone with various initiators is shown in Table 1.

[0209] [Table 1]

[0210] The structure of the zwitterionic compound can affect the polymerization efficiency [Figure 1]. Long alkyl chains produce polymers with lower than target but controllable molar masses, as shown for lauryl betaine. In contrast, betaine produces polymers with high molar masses independent of the M:I ratio of the reaction. This is likely a solubility limited process. However, in some examples, betaine can be used to produce high molecular weight poly(3-hydroxypropionic acid) (Mn=108,500 g / mol) in less than 24 hours.

[0211] Other embodiments The above describes certain non-limiting embodiments of the present invention. It is therefore to be understood that the embodiments of the present invention described herein are merely illustrative of the application of the principles of the present invention. Reference to the details of the illustrative embodiments herein is not intended to limit the scope of the claims, which in themselves recite features considered essential to the invention.

Claims

1. 1. A polymer comprising one or more polymer chains of polymers of beta-propiolactone and / or substituted beta-propiolactone having a zwitterionic residue at one end of the chain, the zwitterionic residue having an anion and a cation, wherein an anionic moiety is covalently attached to the one end of the polymer chain, and the ratio of the one or more beta-propiolactones and / or substituted beta-propiolactones to the one or more zwitterionic initiators is from 100:1 to 1,000,000:

1.

2. 2. The polymer of claim 1, wherein the one or more polymer chains have a residue of an end-capping agent at the other end of the chain, the end-capping agent being one or more of an organic halide, an organic sulfonate, a haloalkyl silane, an aniline derivative, a phosphate derivative, and an isophthalic acid derivative.

3. 3. The polymer of claim 1 or 2, wherein the anion is an oxygen or sulfur based anion and the cation is an organic onium cation, the onium cation comprising nitrogen, phosphorus, sulfur, antimony or arsenic, and the anion and the cation of the zwitterion are linked by a bond or a polyvalent organic moiety.

4. The polymer of claim 1, wherein the ratio of the one or more beta-propiolactones and / or substituted beta-propiolactones to the one or more zwitterionic initiators is from 500:1 to 1,000,000:

1.

5. a. one or more beta-propiolactone and / or substituted beta-propiolactones, and b. one or more zwitterionic initiators Including, A polymerizable composition wherein the ratio of the one or more beta-propiolactones and / or substituted beta-propiolactones to the one or more zwitterionic initiators is from 100:1 to 1,000,000:

1.

6. 6. The polymerizable composition of claim 5, comprising one or more comonomers that copolymerize with the one or more beta-propiolactones and / or substituted beta-propiolactones.

7. 7. The polymerizable composition of claim 5 or 6, comprising one or more of a chain transfer agent, a chain extender, and an endblocking agent.

8. 6. The polymerizable composition of claim 5, wherein the ratio of the one or more beta-propiolactones and / or substituted beta-propiolactones to the one or more zwitterionic initiators is from 500:1 to 1,000,000:

1.

9. 8. The polymerizable composition of claim 7, wherein the endblocking agent is one or more of an organic halide, an organic sulfonate, a haloalkylsilane, an aniline derivative, a phosphate derivative, and an isophthalic acid derivative.

10. 9. The polymerizable composition of claim 5 or 8, wherein the zwitterion has an anion and a cation, the anion is an oxygen or sulfur based anion, the cation is an organic onium cation, the onium cation comprises nitrogen, phosphorus, sulfur, antimony, or arsenic, and the anion and the cation of the zwitterion are linked by a bond or a polyvalent organic moiety.

11. 1. A method comprising the steps of contacting one or more beta-propiolactones and / or substituted beta-propiolactones and comonomers with one or more zwitterionic initiators under conditions to prepare one or more polymers comprising one or more polymer chains having ring-opened beta-propiolactone and / or substituted beta-propiolactone units and having a zwitterionic residue at one end of the chain having an anion and a cation, wherein the anionic moiety is covalently attached to one end of the polymer chain, wherein the ratio of the one or more beta-propiolactones and / or substituted beta-propiolactones to the one or more zwitterionic initiators is from 100:1 to 1,000,000:

1.

12. 12. The method of claim 11, wherein the ratio of the one or more beta-propiolactones and / or substituted beta-propiolactones to the one or more zwitterionic initiators is from 500:1 to 1,000,000:

1.

13. 13. The method of claim 11 or 12, wherein the one or more beta-propiolactones and / or substituted beta-propiolactones and comonomers and one or more zwitterionic initiators are contacted at a pressure from 1 bar to 20 bar.

14. 13. The method of claim 11 or 12, wherein the one or more beta-propiolactones and / or substituted beta-propiolactones and comonomers and one or more zwitterionic initiators are contacted for a time sufficient to obtain a desired molecular weight of the one or more beta-propiolactones and / or substituted beta-propiolactones and comonomers.

15. 13. The method of claim 11 or 12, wherein after a predetermined reaction time or when the polymer composition reaches a desired molecular weight, a quenching agent is added to stop the polymerization reaction, the quenching agent being one or more of a mineral acid, an organic acid, and an acidic resin or solid.

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