A new generation of porous polymer networks has been obtained in quantitative yield by reacting two rigid trifunctional aromatic monomers (1,3,5-triphenylbenzene and triptycene) with two ketones having electron-withdrawing groups (trifluoroacetophenone and isatin) in superacidic media. The resulting amorphous networks are microporous materials, with moderate Brunauer-Emmett-Teller surface areas (from 580 to 790 m g), and have high thermal stability. In particular, isatin yields networks with a very high narrow microporosity contribution, 82% for triptycene and 64% for 1,3,5-triphenylbenzene. The existence of favorable interactions between lactams and CO molecules has been stated. The materials show excellent CO uptakes (up to 207 mg g at 0 °C/1 bar) and can be regenerated by vacuum, without heating. Under postcombustion conditions, their CO/N selectivities are comparable to those of other organic porous networks. Because of the easily scalable synthetic method and their favorable characteristics, these materials are very promising as industrial adsorbents.

A set of mixed matrix membranes (MMMs) has been prepared by incorporating a triptycene-isatin porous polymer network (PPN) to three aromatic polyimides (one commercial, Matrimid, and two synthesized by us: 6FDA–6FpDA and 6FDA–TMPD) covering a wide range of performances for gas separation. The triptycene-isatin PPN is a highly microporous network having a high CO2 uptake and high chemical and thermal stability. The good compatibility between the components (PPN content of 15 and 30% w/w) was supported by the increase in the glass transition temperature of MMMs relative to the pure polyimide membranes. The addition of the PPN particles improved the permeability of all the gases tested, by increasing diffusivity and, in some cases, gas solubility. The improvements were particularly noticeable in Matrimid-based MMMs, where gas permeability increased by 700%, whereas CO2/N2 and CO2/CH4 ideal selectivities decreased by a mere 4% and 12%, respectively.

Mixed matrix membranes, MMMs, consisting of variable loads of a porous polymer network, PPN, within an o-hydroxipolyamide, HPA (6FCl-APAF, made from the reaction between 2,2-bis[4-chlorocarbonylphenyl)hexafluoropropane, 6FCl, and 2,2bis(3-amino-4-hydroxyphenyl)hexafluoropropane, APAF), have been thermally treated to induce the rearrangement of HPA to a polybenzoxazole (β-TR-PBO). HPA is 6FCl-APAF was loaded with a PPN synthetized, by us, by combining triptycene (TRP) and trifluoroacetophenone (TFAP). Mechanical, thermal and morphological properties of the membranes have been determined.CO2/CH4 selectivity of MMMs decreased slightly both when the PPN load was augmented and when thermal rearrangement took place. The changes in selectivity can be attributed mostly to solubility effects for β-TR-MMMs and to diffusive effects for the © YYYY Elsevier. This manuscript version is made available under the CC-BY-NC-ND 4.0 MMM from neat HPA. CO2 and CH4 permeabilities increased to the 2008 Robeson´s upper bond for an optimal 30 % PPN load both before and after thermal rearrangement.These relatively good permselectivities are explained in terms of compaction, rigidity, fractional free volumes and filling-matrix interactions.

A novel series of linear, high-molecular-weight polymers and copolymers were synthesized by one-pot, metal-free superacid-catalyzed polymerization of aliphatic 1,2-diketones (2,3-butanedione (1a), 2,3-hexadione (1b), 3,4-hexadione (1c), 2,3-butanedione monoxime (1d), pyruvic acid (1e), 1,4-dibromo-2,3-butanedione (1f), 2-bromopyruvic acid (1g), and methyl-3,3,3-trifluoropyruvate (1h) with linear, nonactivated, multiring aromatic hydrocarbons terphenyl (A), biphenyl (B), fluorene (C), and N-ethyl carbazole (D). Depending on the reaction system, the polymerizations were carried out as stoichiometric or non stoichiometric, with direct or inverse monomer addition. Copolymers were obtained by polymerization of 1,2-diketones with a mixture of aromatic hydrocarbons. In the course of the polymerization only one carbonyl group of a 1,2-diketone reacts to form C−C bonds with aromatic fragments while the other functional groups (including the second carbonyl group) are incorporated unchanged into polymer chain. The polymerizations performed at room temperature in the Brønsted superacid CF 3 SO 3 H (TFSA) and in a mixture of TFSA with methylene chloride or trifluoroacetic acid (TFA) tolerant of carbonyl, acetyl, N-oxime, carboxy, methoxy, and bromomethyl groups. The polymers obtained were soluble in most common organic solvents, and flexible transparent, colorless films could be cast from the solutions. 1 H and 13 C NMR analyses of the polymers synthesized revealed high regio-selectivity of the polymerizations and yielded linear structures with para-substitution in the phenylene fragments of the main chains. An electron affinity (EA) of the carbonyl component and the heterolytic C−O bond dissociation energy (DE) in carbinol 3 (correlating with the activation energy of carbocation 4 formation) have been used to rationalize the reactivity of carbonyl components. The calculations show the following reactivity order of the diketones. 1f > 1g ≈ 1e> 1a> 1d > 1h> 1b>1c which is totally in agreement with the experimental data. The new functional polymers obtained demonstrate good processability, high T g and thermal stability. Unexpected white light emission was observed for polymer 2gA.