Dynamic covalent polymerizations with elemental sulfur and sulfur prepolymers
AssigneeArizona Board of Regents on Behalf of the University of Arizona
InventorsDong-Chul Pyun, Yueyan Zhang
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Abstract
An iterative approach to dynamic covalent polymerizations of elemental sulfur with functional comonomers to prepare sulfur prepolymers that can further react with other conventional, commercially available comonomers to prepare a wider class of functional sulfur polymers. This iterative method improves handling, miscibility and solubility of the elemental sulfur, and further enables tuning of the sulfur polymer composition. The sulfur polymers may be a thermoplastic or a thermoset for use in elastomers, resins, lubricants, coatings, antioxidants, cathode materials for electrochemical cells, and polymeric articles such as polymeric films and free-standing substrates.
Claims20
An iterative method of synthesizing a sulfur polymer, said method comprising:
- a. providing elemental sulfur;
- b. heating the elemental sulfur to form a molten sulfur comprising dynamic sulfur-sulfur (S—S) bonds, wherein heating enables thermal activation and scission of the dynamic S—S bonds from said molten sulfur to form sulfur radicals;
- c. adding one or more first comonomers to the molten sulfur, wherein each first comonomer comprises at least one reactive functional group, wherein the one or more first comonomers and molten sulfur copolymerize by a reaction of the sulfur radicals with the reactive functional groups of the one or more first comonomers to form a sulfur prepolymer;
- d. heating the sulfur prepolymer to form a molten sulfur prepolymer comprising the dynamic S—S bonds, wherein heating enables thermal activation and scission of the dynamic S—S bonds from said molten sulfur prepolymer to form sulfur-containing radical species;
- and
- e. adding one or more second comonomers to the molten sulfur prepolymer, wherein each of the one or more second comonomers comprises at least one reactive functional group, wherein the one or more second comonomers and the molten sulfur prepolymer copolymerize by a reaction of the sulfur-containing radical species with the reactive functional groups of the one or more second comonomers to form the sulfur polymer;
- wherein the iterative method improves processability of the elemental sulfur in producing the desired sulfur polymer by initially copolymerizing the elemental sulfur with the one or more first comonomers to prepare the sulfur prepolymer that is tailored to be miscibly or solubly compatible with the one or more second comonomers.
An iterative method of synthesizing a sulfur polymer, said method comprising:
- a. providing elemental sulfur;
- b. heating the elemental sulfur to form a molten sulfur comprising dynamic sulfur-sulfur (S—S) bonds, wherein heating enables thermal activation and scission of the dynamic S—S bonds from said molten sulfur to form sulfur radicals;
- c. adding one or more unsaturated comonomers to the molten sulfur, wherein each unsaturated comonomer comprises at least one alkenyl functional group, wherein the one or more unsaturated comonomers and molten sulfur copolymerize by a reaction of the sulfur radicals with the alkenyl functional groups to form a sulfur prepolymer;
- d. heating the sulfur prepolymer to form a molten sulfur prepolymer comprising the dynamic S—S bonds, wherein heating enables thermal activation and scission of the dynamic S—S bonds from said molten sulfur prepolymer to form sulfur-containing radical species;
- and
- e. adding one or more second comonomers to the molten sulfur prepolymer, wherein each of the one or more second comonomers comprises at least one reactive functional group, wherein the one or more second comonomers and the molten sulfur prepolymer copolymerize by a reaction of the sulfur-containing radical species with the reactive functional groups of the one or more second comonomers to form the sulfur polymer;
- wherein the iterative method improves processability of the elemental sulfur in producing the desired sulfur polymer by initially copolymerizing the elemental sulfur with the one or more unsaturated comonomers to prepare the sulfur prepolymer that is tailored to be miscibly or solubly compatible with the one or more second comonomers.
An iterative method of synthesizing a sulfur polymer, said method comprising:
- a. providing elemental sulfur;
- b. heating the elemental sulfur to form a molten sulfur comprising dynamic sulfur-sulfur (S—S) bonds, wherein heating enables thermal activation and scission of the dynamic S—S bonds from said molten sulfur to form sulfur radicals;
- c. adding one or more first comonomers to the molten sulfur, wherein each first comonomer comprises at least one reactive functional group, wherein the one or more first comonomers and molten sulfur copolymerize by a reaction of the sulfur radicals with the reactive functional groups of the one or more first comonomers to form a sulfur prepolymer;
- d. dissolving the sulfur prepolymer in an organic solvent;
- and
- e. adding one or more second comonomers to the dissolved sulfur prepolymer, wherein each of the one or more second comonomers comprises at least one reactive functional group, wherein the sulfur prepolymer is miscible with the one or more second comonomers, wherein the one or more second comonomers and the sulfur prepolymer copolymerize to form the sulfur polymer;
- wherein the one or more first comonomers are selected to form the sulfur prepolymer having a tunable composition that enables miscibility or solubility of the sulfur prepolymer with the one or more second comonomers, and wherein the second comonomers are selected such that the second comonomers are soluble in the sulfur prepolymer, wherein the second comonomers are different from the first comonomers,
- wherein the iterative method improves processability of the elemental sulfur in producing the desired sulfur polymer by initially copolymerizing the elemental sulfur with the one or more first comonomers to prepare the sulfur prepolymer that is tailored to be miscibly or solubly compatible with the one or more second comonomers.
Dependencies are inferred from the claim text.