Abstract: Supported onium salts used as initiators for the synthesis of polycarbonates by copolymerization of carbon dioxide with epoxides are described. Embodiments of the present disclosure describe initiators comprising an insoluble portion including an onium cation attached to an insoluble support; and an anion, wherein the anion is a counter-ion to the onium cation. Embodiments further describe methods of making polycarbonates using the initiator, methods of making initiators, and the like.

Abstract: The present disclosure features materials and methods for synthesizing polycarbamates via chain-growth copolymerization in the presence of a Lewis acid of a first reactant having a oxirane or thiirane moiety and at least one heteroallene reactant, wherein a first heteroallene reactant is an isocyanate or an isothiocyanate. Also featured are polycarbamate copolymers and terpolymers according to formula (I): (I), wherein An is a halogen atom or a carboxylate or alkoxide moiety; each X and X? is independently an oxygen or a sulfur atom; each R1 and R2 is independently a hydrogen atom or an alkyl group including linear, branched, saturated, unsaturated, aromatic, cyclic alkyl groups, and heteroatom-containing alkyl groups, R3 is an electron deficient group, m and o are independently selected from integers ? 1 and n is 0 or an integer ? 1. Both X and X? can be the same or X and X? can be different.

Abstract: Methods of recovering and/or reusing activators and/or initiators following polycarbonate synthesis may include: contacting an amine compound with a carboxylic acid compound to form a first ammonium salt including a first ammonium cation associated with a carboxylate group; mixing the first ammonium salt with a reaction solution to obtain a first solution comprising a protonated polycarbonate, an activator adduct, and a second ammonium salt in which the second ammonium cation is associated with the carboxylate group from the first ammonium salt; contacting the first solution to precipitate the polycarbonate out of solution; separating the activator adduct from the precipitated polycarbonate and the second ammonium salt to obtain a second solution; separating the precipitated polycarbonate from the second ammonium salt to recover the second ammonium salt; and separating the activator adduct from the second solution to recover an activator capable of being reused for synthesizing additional polycarbonates.

Abstract: Embodiments of the present disclosure describe a method of synthesizing a glycidyl azide homopolymer comprising contacting a glycidyl azide monomer, an initiator, and a Lewis acid sufficient to form the glycidyl azide homopolymer; wherein the glycidyl azide homopolymer is directly polymerized from the glycidyl azide monomer. Embodiments of the present disclosure further describe a method of making a glycidyl azide polymer comprising contacting one or more of a glycidyl azide monomer, an epoxide monomer, carbon dioxide, an initiator, and a Lewis acid in a reaction medium to form a glycidyl azide polymer.

Abstract: Embodiments include degradable polyethers comprising ester units from a cyclic ester or carbonate units from carbon dioxide incorporated into a poly(ethylene oxide) backbone or a multifunctional core of a degradable polyether star. Embodiments include methods of forming a degradable polyether comprising contacting an ethylene oxide monomer with a lactide monomer or carbon dioxide in the presence of an alkyl borane and an initiator. Embodiments include methods of forming degradable polyether stars comprising contacting a diepoxide monomer with carbon dioxide and/or a cyclic ester in the presence of an initiator and a first amount of an alkyl borane to form a multifunctional core comprising degradable carbonate linkages and/or degradable ester linkages, and contacting the multifunctional core with an ethylene oxide monomer in the presence of a second amount of an alkyl borane to form arms of a polyether attached to the degradable multifunctional core.

Abstract: Embodiments of the present disclosure describe polymerization systems for the synthesis of polycarbonate polyols, methods of synthesizing polycarbonate polyols using the polymerization systems, methods of recovering initiators and/or activators for use or re-use in the synthesis of polycarbonate polyol, and the like. The polymerization systems can comprise an initiator including a mono- or multi-functional carboxylate or carbonate salt having an organic cation as a counter-ion; an optional co-initiator including a mono- or multi-functional protic compound selected from acids, alcohols, water, and combinations thereof; and an activator including a borane compound selected from alkyl boranes and aryl boranes; wherein the activator and one or more of the initiator and co-initiator associate to form an ate complex.

Abstract: Embodiments of the present disclosure describe a method of removing an end group from a polymer comprising contacting a polymer having a thiocarbonylthio end group, or a solution containing such a polymer, with an excess of a borane compound in the presence of oxygen. Embodiments of the present disclosure further describe a method of polymerization comprising contacting one or more monomers with an initiator and a chain transfer agent to form a polymer having a thiocarbonylthio end group in a reaction solution and contacting the polymer with a borane compound in the presence of oxygen to remove the thiocarbonylthio end group from the polymer.

Abstract: Degradable ethylene oxide-based copolymers, including random, tapering, and block copolymers are described. For example, the present disclosure describes materials and methods for synthesizing degradable hydrophilic ethylene oxide-based copolymers, degradable amphiphilic ethylene oxide-based block copolymers, degradable hydrophobic polyethers and degradable functionalized polyethers via boron-activated copolymerization of ethylene oxide monomers with carbon dioxide.

Abstract: Supported onium salts used as initiators for the synthesis of polycarbonates by copolymerization of carbon dioxide with epoxides are described. Embodiments of the present disclosure describe initiators comprising an insoluble portion including an onium cation attached to an insoluble support; and an anion, wherein the anion is a counter-ion to the onium cation. Embodiments further describe methods of making polycarbonates using the initiator, methods of making initiators, and the like.

Abstract: Embodiments of the present disclosure describe initiating systems comprising an activator and an initiator, wherein the activator includes an alkyl borane or alkyl aluminum, wherein the initiator includes an organic cation and either an alkali metal or a compound containing an active protic hydrogen. Embodiments of the present disclosure further describe methods of making a polycarbonate comprising contacting a cyclic monomer and carbon dioxide in the presence of an activator and an initiator to form a polycarbonate, wherein the catalyst is one or more of an alkyl borane and alkyl aluminum, wherein the initiator includes an organic cation and either an alkali metal or a compound containing an active protic hydrogen.

Abstract: Embodiments of the present disclosure describe a method of synthesizing a glycidyl azide homopolymer comprising contacting a glycidyl azide monomer, an initiator, and a Lewis acid sufficient to form the glycidyl azide homopolymer; wherein the glycidyl azide homopolymer is directly polymerized from the glycidyl azide monomer. Embodiments of the present disclosure further describe a method of making a glycidyl azide polymer comprising contacting one or more of a glycidyl azide monomer, an epoxide monomer, carbon dioxide, an initiator, and a Lewis acid in a reaction medium to form a glycidyl azide polymer.

Abstract: Embodiments of the present disclosure describe a method of making a polycarbonate, comprising contacting one or more cyclic monomers and carbon dioxide in the presence of one or more of a Lewis acid catalyst, an initiator, and an ionic liquid; and agitating, sufficient to copolymerize the one or more cyclic monomers and carbon dioxide to create a polycarbonate. Embodiments of the present disclosure further describe a method of controlling a polymer composition, comprising contacting one or more cyclic monomers and carbon dioxide; adjusting an amount of one or more of a Lewis acid catalyst, an ionic liquid, and an initiator in the presence of the one or more cyclic monomers and carbon dioxide, sufficient to selectively modify a resulting polycarbonate; and agitating, sufficient to copolymerize the one or more cyclic monomers and carbon dioxide to create the polycarbonate.

Abstract: Embodiments of the present disclosure describe a method of making a polyester compound comprising adding an initiator to a reaction medium, charging the reaction medium with an amount of carbon dioxide, and adding a cyclic ester compound to the reaction medium.

Abstract: Embodiments of the present disclosure describe a method of making a polycarbonate, comprising contacting one or more cyclic monomers and carbon dioxide in the presence of one or more of a Lewis acid catalyst, an initiator, and an ionic liquid; and agitating, sufficient to copolymerize the one or more cyclic monomers and carbon dioxide to create a polycarbonate. Embodiments of the present disclosure further describe a method of controlling a polymer composition, comprising contacting one or more cyclic monomers and carbon dioxide; adjusting an amount of one or more of a Lewis acid catalyst, an ionic liquid, and an initiator in the presence of the one or more cyclic monomers and carbon dioxide, sufficient to selectively modify a resulting polycarbonate; and agitating, sufficient to copolymerize the one or more cyclic monomers and carbon dioxide to create the polycarbonate.

Abstract: Embodiments of the present disclosure describe initiating systems comprising an activator and an initiator, wherein the activator includes an alkyl borane or alkyl aluminum, wherein the initiator includes an organic cation and either an alkali metal or a compound containing an active protic hydrogen. Embodiments of the present disclosure further describe methods of making a polycarbonate comprising contacting a cyclic monomer and carbon dioxide in the presence of an activator and an initiator to form a polycarbonate, wherein the catalyst is one or more of an alkyl borane and alkyl aluminum, wherein the initiator includes an organic cation and either an alkali metal or a compound containing an active protic hydrogen.

Abstract: Provided herein are methods for synthesizing cyclic carbonates, glycocarbonates, and polyglycocarbonates by reacting polyol glycans with carbon dioxide. Synthesis can include selective polycondensation of polyol glycan hydroxyl moieties.

Abstract: Embodiments of the present disclosure describe a method of making a polycarbonate, comprising contacting one or more cyclic monomers and carbon dioxide in the presence of one or more of a Lewis acid catalyst, an initiator, and an ionic liquid; and agitating, sufficient to copolymerize the one or more cyclic monomers and carbon dioxide to create a polycarbonate. Embodiments of the present disclosure further describe a method of controlling a polymer composition, comprising contacting one or more cyclic monomers and carbon dioxide; adjusting an amount of one or more of a Lewis acid catalyst, an ionic liquid, and an initiator in the presence of the one or more cyclic monomers and carbon dioxide, sufficient to selectively modify a resulting polycarbonate; and agitating, sufficient to copolymerize the one or more cyclic monomers and carbon dioxide to create the polycarbonate.

Abstract: Embodiments of the present disclosure describe initiating systems comprising an activator and an initiator, wherein the activator includes an alkyl borane or alkyl aluminum, wherein the initiator includes an organic cation and either an alkali metal or a compound containing an active protic hydrogen. Embodiments of the present disclosure further describe methods of making a polycarbonate comprising contacting a cyclic monomer and carbon dioxide in the presence of an activator and an initiator to form a polycarbonate, wherein the catalyst is one or more of an alkyl borane and alkyl aluminum, wherein the initiator includes an organic cation and either an alkali metal or a compound containing an active protic hydrogen.

Abstract: Embodiments of the present disclosure describe a method of making a polycarbonate, comprising contacting one or more cyclic monomers and carbon dioxide in the presence of one or more of a Lewis acid catalyst, an initiator, and an ionic liquid; and agitating, sufficient to copolymerize the one or more cyclic monomers and carbon dioxide to create a polycarbonate. Embodiments of the present disclosure further describe a method of controlling a polymer composition, comprising contacting one or more cyclic monomers and carbon dioxide; adjusting an amount of one or more of a Lewis acid catalyst, an ionic liquid, and an initiator in the presence of the one or more cyclic monomers and carbon dioxide, sufficient to selectively modify a resulting polycarbonate; and agitating, sufficient to copolymerize the one or more cyclic monomers and carbon dioxide to create the polycarbonate.

Abstract: Provided herein are methods for synthesizing cyclic carbonates, glycocarbonates, and polyglycocarbonates by reacting polyol glycans with carbon dioxide. Synthesis can include selective polycondensation of polyol glycan hydroxyl moieties.