Nanoporous hypercrosslinked polymers containing Tg enhancing comonomers

• Hypercrosslinked polymers HCPs containing Tg enhancing alternating copolymer sequences were prepared.
• The HCPs containing alternating copolymer sequences exhibit BET surface areas up to 1058 m2/g.
• Experimental results are consistent with simulation results.
• The correlation between surface area versus comonomer content serves as a model system for designing functionalized hypercrosslinked polymers.

Hypercrosslinked polymers containing functionalized alternating copolymer sequences of substituted stilbene or styrene and N-aryl substituted maleimides have been synthesized. Alternating copolymers containing these comonomers possess semi-rigid structures, and incorporation of these units into the precursor polymer particles for hypercrosslinking leads to a systematic increase in Tg and chain stiffness of these materials as the concentration of the comonomers is increased. Surface area and porosity of the subsequent hypercrosslinked polymers were investigated using nitrogen adsorption/desorption isotherms at 77 K. These hypercrosslinked polymers exhibit BET surface areas ranging from 1058 m2/g at 25 mol% alternating copolymer incorporation down to loss of measurable surface area at ca. 60% incorporation. The experimental surface area results correlate with predictions from simulations and serve as model systems for future studies on specifically functionalized hypercrosslinked polymer particles.

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