Hydrogen storage remains a major technological barrier to the widespread adoption of hydrogen as an energy source. Organic polymers offer one potential route to useful hydrogen storage materials. Recently, Frechet and his coworkers described a series of hypercrosslinked polymers with high surface area and studied their surface properties and hydrogen storage capacities. McKeown and his coworkers studied a class of materials termed Polymers of Intrinsic Microporosity (PIMs) which are also based on a "hypercrosslinked" concept. We enchained N-substituted maleimide and functionalized stilbene alternating copolymers into a "hypercrosslinked system" to achieve high rigidity, high surface areas, high aromatic content and good thermal stability. Hypercrosslinked copolymers of N-(3-methylphenyl)maleimide (3MPMI), 4-methyl stilbene (4MSTBB), vinylbenzyl chloride (VBC) and divinyl benzene (DVB) were synthesized. Scanning electron micrographs (SEM) show the copolymers are porous and some examples have shown surface areas over 1200 m²/g. We have also found the incorporation of 3MPMI and 4MSTBB improves the thermal stability and raises the glass transition temperature of the copolymer. However, the incorporation of 3MPMI and 4MSTBB decreases the hypercrosslinking density and therefore causes a decrease in the copolymer surface area. The systematic study of styrene (STR) – vinylbenzyl chloride (VBC) – divinyl benzene (DVB) networks indicates that a low density of chloromethyl groups leads to a decrease in surface area. Therefore, we are continuing to investigate other monomers, such as N-substituted maleimide and functionalized stilbene containing chloromethyl groups, in order to enhance thermal stability while maintaining surface area. In order to increase the enthalpy of hydrogen adsorption and thus raise the temperature of hydrogen storage, the monomer N,N-dimethyl-N',N'-diethyl-4,4'-diaminostilbene (4,4'DASTB-3MPMI) which contains electron donating groups was incorporated into hypercrosslinked polymer particles. Hypercrosslinked polymer (4,4'DASTB-3MPMI)1.0(VBC)98.5(DVB).50 exhibits a surface area of 3257 m²/g. / Master of Science

Nanoporous organic polymers, including hypercrosslinked polymers (HCPs), covalent organic frameworks (COFs), polymers of intrinsic microporosity (PIMs), and conjugated microporous polymers (CMPs) etc., are considered good candidates for potential gas storage and gas separation applications. Porosities and surface areas of a series of semirigid alternating copolymers, which contained tert-butyl carboxylate-functionalized stilbene or tert-butyl carboxylate-functionalized styrene, and maleic anhydride or tert-butyl carboxylate-functionalized phenyl maleimide, were investigated using nitrogen sorption/desorption isotherms at 77 K and molecular simulations. These alternating copolymers were found to have Brunauer-Emmett-Teller (BET) surface areas in the range of 20-40 m2/g. Surface areas of these alternating copolymers increased as the steric crowding of the polymer backbone increased, which was the result of introducing extra phenyl rings and/or N-phenyl substituent maleimide units. Surface areas were found to increase as the persistence length increased. A series of HCPs containing functionalized stilbene and N-substituted phenyl maleimide were synthesized via free radical suspension polymerization. The incorporation of these functionalized, chain stiffening, Tg enhancing comonomers raised the Tgs of precursor polymers before they were crosslinked. Surface areas of these HCPs, obtained from nitrogen adsorption/desorption isotherms at 77 K, were up to 1058 m2/g. However, the surface areas of these HCPs were systematically lower than the controls. The high rigidity of the polymer backbone, which was the result of incorporating Tg enhancing comonomer, likely affected the chain mobility of the precursor polymer, decreased the efficiency of post-crosslinking reactions, and thus resulted in lower surface areas. Amine-functionalized styrene/stilbene polymers were prepared via free radical polymerization or post-modification. Amine-containing silica-based sorbents were prepared using the impregnation method. Sorption of CO2 by these materials was tested using TGA and compared with control samples. Both high amine content and certain levels of surface area were found to be important for a sorbent to achieve high CO2 uptake. Highest CO2 uptake (12 wt%) under our testing condition in these materials was achieved by an amine-containing silica sorbent. / Ph. D.