Synthesis and polymerization of vinyl triazolium ionic liquids
Inventors
Luebke, David • Nulwala, Hunaid • Matyjaszewski, Krzysztof • Adzima, Brian
Assignees
Publication Number
US-9969823-B1
Publication Date
2018-05-15
Expiration Date
2031-09-01
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Abstract
Herein, we describe polymerized ionic liquids, demonstrate the synthesis of polymerized ionic liquids, and demonstrate the polymerization of triazolium monomers. One embodiment shows the polymeriazation of the triazolium monomers with bis(trifluoromethanesulfonyl)imide anions. In another embodiment we show the feasibility of copolymerizing with commodity monomers such as styrene using free radical polymerization techniques.
Core Innovation
The invention relates to polymerized ionic liquids and specifically to the synthesis and polymerization of vinyl 1,2,3-triazolium monomers. These monomers can be polymerized themselves as well as copolymerized with commodity monomers such as styrenics and acrylates using free radical polymerization techniques. The ionic monomers described feature the ability to be functionalized at multiple positions, offering improved properties over existing ionic monomers, including improved polymerizability and the ability to copolymerize with common monomers to produce polymerized ionic liquids with tailored properties.
The background identifies a problem with existing ionic liquids which, while possessing desirable characteristics like negligible vapor pressure, thermal stability, and solubility, exist in a liquid state that limits their use in many device-based applications. Poly(ionic liquids) provide a way to process ionic liquids into films or gels and retain their advantageous properties. However, conventional approaches to preparing polymerizable ionic liquid monomers often reduce functional diversity or result in polymers with lower concentrations of ionic groups. Additionally, imidazolium-based monomers polymerize only via vinyl groups on one position of the ring, making polymerization challenging. The invention addresses these problems by introducing a novel class of 4-vinyl-1,2,3-triazolium monomers that can autonomously polymerize and copolymerize with commodity polymers, enabling access to polymers with improved molecular architectures and ionic characteristics.
Claims Coverage
The claims cover a polymerized ionic liquid composition comprising several specific 4-vinyl-1,2,3-triazolium monomers and methods for their polymerization including copolymerization with other monomers. The independent claims introduce the composition, polymerization methods, solvents, and initiators used.
Polymerized ionic liquid composition comprising specific vinyl-triazolium monomers
The composition includes 1-Benzyl-3-methyl-4-vinyl-triazolium bis(trifluoromethanesulfonyl)amide, 1-Hexyl-3-methyl-4-vinyl-triazolium bis(trifluoromethanesulfonyl)amide, 1-decyl-3-methyl-4-vinyl-triazolium bis(trifluoromethanesulfonyl)amide, 2-(3-methyl-4-vinyl-triazolium-1-yl)ethanol bis(trifluoromethanesulfonyl)amide, Tert-butyl N-[2-(4-vinyltriazol-1-yl)ethyl]carbamate, 1-phenyl-3-methyl-4-vinyl-triazolium bis(trifluoromethanesulfonyl)amide, 1-(1-pyridine)-3-methyl-4-vinyl-triazolium bis(trifluoromethanesulfonyl)amide, and 1-TEG-3-methyl-4-vinyl-triazolium bis(trifluoromethanesulfonyl)amide.
Polymerization using monomer and initiator mixtures
The polymerization can be performed using mixtures containing at least one monomer and at least one initiator to yield polymerized ionic liquids.
Polymerization in presence of solvents
Polymerization can occur in mixtures including at least one monomer, at least one initiator, and at least one solvent, with solvent examples encompassing a wide range of polar and nonpolar organic solvents and water.
Use of radical initiators for polymerization
The polymerization initiators are radical initiators, which may be azo-initiators, inorganic initiators, ultraviolet light initiators, or organic peroxides, with extensive specific examples enumerated.
The claimed invention encompasses polymerized ionic liquid compositions of specified vinyl-triazolium compounds and methods for their polymerization using radical initiators in various solvents, enabling versatile polymerization approaches.
Stated Advantages
Polymerizable vinyl-triazolium monomers exhibit improved ability to homopolymerize and copolymerize with commodity monomers such as styrenics and acrylates.
The polymerized ionic liquids maintain desirable ionic liquid properties like high conductivity, low vapor pressure, and thermal stability while being processable into films, cross-linked materials, vesicles, and gels.
The synthetic approach enables functionalization at multiple positions on the triazolium ring, increasing functional diversity and control over molecular architecture compared to existing ionic liquid monomers.
Negligible vapor pressure of the monomers allows straightforward degassing and polymerization without extensive purification steps.
The polymers show varied solubility profiles dependent on pendant groups, facilitating tailored applications.
Documented Applications
Use of polymerized vinyl-triazolium ionic liquids in gas separations.
Use of polymerized vinyl-triazolium ionic liquids as antimicrobial coatings.
Use in water purification.
Use as electrolytes for batteries.
Use in gas separation membrane sensors.
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