Crafts Polymerization Research Articles

Stable Anion Exchange Membrane Bearing Quinuclidinium for High‐performance Water Electrolysis

AbstractAnion exchange membranes (AEMs) are core components in anion exchange membrane water electrolyzers (AEM‐WEs). However, the stability of functional quaternary ammonium cations, especially under high temperatures and harsh alkaline conditions, seriously affects their performance and durability. Herein, we synthesized a 1‐methyl‐3,3‐diphenylquinuclidinium molecular building unit. Density functional theory (DFT) calculations and accelerated aging analysis indicated that the quinine ring structure was exceedingly stable, and the SN2 degradation mechanism dominated. Through acid‐catalyzed Friedel–Crafts polymerization, a series of branched poly(aryl‐quinuclidinium) (PAQ‐x) AEMs with controllable molecular weight and adjustable ion exchange capacity (IEC) were prepared. The stable quinine structure in PAQ‐x was verified and retained in the ex situ alkaline stability. Furthermore, the branched polymer structure reduces the swelling rate and water uptake to achieve a tradeoff between dimensional stability and ionic conductivity, significantly improving the membrane's overall performance. Importantly, PAQ‐5 was used in non‐noble metal‐based AEM‐WE, achieving a high current density of 8 A cm−2 at 2 V and excellent stability over 2446 h in a gradient constant current test. Based on the excellent alkaline stability of this diaryl‐quinuclidinium group, it can be further considered as a multifunctional building unit to create multi‐topological polymers for energy conversion devices used in alkaline environments.

Effect of POSS Size on the Porosity and Adsorption Performance of Hybrid Porous Polymers

Polyhedral oligomeric silsesquioxanes (POSS), with unique cage-like three-dimensional (3D) structures, have been considered as promising nanoblocks for novel hybrid porous polymers (HPPs). To date, T8 POSS-based HPPs have been extensively studied, while the potential of larger POSS remains elusive and intriguing. Herein, we report the synthesis of a series of T8, T10, and T12 POSS-based HPPs (T8TPM, T10TPM, and T12TPM) and investigate their size-dictated structure–property relationships. These novel HPPs with identical composition yet distinct framework topologies are available through Friedel–Crafts polymerization of octa-, deca-, and dodeca-vinyl POSS with triptycene in a fixed mass ratio. It is found that the structures and properties of these materials are highly related to the POSS type and, more importantly, display an almost linear increase with increasing POSS size. Specifically, the surface area, pore volume, and adsorption capacity of T12TPM are 1214.8 m2 g–1, 1.00 cm3 g–1, and 4462.4 mg g–1 (Rhodamine B), showing an increase of 13.2, 56.3, and 37.9% compared with T8TPM, respectively. These results demonstrate the profound influence of the POSS size on the structure–property relationship of HPPs and could be used to predict the property of larger T14, T16, and T18 POSS-based HPPs. This calls for future endeavors in the exploration of larger POSS-based HPPs.

Tetraphenylethylene-based fluorescent conjugated microporous polymers for fluorescent sensing trinitrophenol

Two tetraphenylethylene-based fluorescent conjugated microporous polymers (TTTPT and TTDAT) were obtained by the Friedel−Crafts polymerization reactions catalysed by CH3SO3H. In virtue of containing tetraphenylethylene, triphenylamine and s-triazine units in their porous skeletons, the resulting TTTPT and TTDAT show excellent fluorescence sensing performance for trinitrophenol (TNP) with high quenching coefficients of 1.66 × 104 and 1.31 × 105 l mol–1, respectively. TTDAT can also sense to dinitrophenol (DNP) with the Ksv of 2.70 × 104 l mol–1. The fluorescent quenching mechanisms of TTTPT and TTDAT for selective detecting TNP attribute to conventional photoinduced electron-transfer mechanism, absorption competition quenching mechanism and/or the resonant energy transfer mechanism.

Friedel–Crafts Polymerization Approach to Easily Recyclable Heterogeneous Chiral Phosphoric Acids

Key words organophosphoric acids - Friedel–Crafts reaction - polymerization - transfer hydrogenation

Poly(arylene pyridine)s: New alternative materials for high temperature polymer electrolyte fuel cells

Developing high-performance and low-cost high temperature polymer exchange membranes (HT-PEMs) is a huge challenge to fuel cells. Here, two poly(arylene pyridine)s (PTAP and PBAP) are synthesized through a simple one-step Friedel–Crafts polymerization of 4-acetylpyridine and para-terphenyl/biphenyl. Both PTAP and PBAP exhibit superior organic solubility and excellent thermal stability. Owing to pyridine groups, PBAP and PTAP membranes display excellent phosphoric acid (PA) absorption capability. The PTAP membrane achieves a PA uptake of 220% after immersing in 85 wt% PA solution at 100 °C, and a high conductivity of 0.102 S cm−1 at 180 °C. Specially, PBAP and PTAP also possess remarkable chemical stability. After 450 h Fenton test, the PTAP membrane still exhibits a high PA uptake of 200% and high conductivity of 0.086 S cm−1. A single H2-O2 cell based on the PTAP/220% membrane shows a peak power density of 743 mW cm−2 at 180 °C without any back pressure, which also displays excellent durability under 200 mA cm−2 and 400 mA cm−2 at 160 °C. Thus, this work develops a facile, cost effective and up-scalable synthetic route of alternative HT-PEM under mild conditions, comparing with the state-of-the-art polybenzimidazole (PBI) membrane.

Rosin-based porous heterogeneous catalyst functionalized with hydroxyl groups and triazole groups for CO2 chemical conversion under atmospheric pressure condition

Development of efficient, green and recyclable heterogeneous catalysts for the chemical conversion of CO2 into cyclic carbonates with excellent yields under atmospheric pressure condition is still a very challenging task. Herein, a class of biomass-derived hyper-cross-linked porous heterogeneous catalysts MPAc-Br and MPAc-OH-Br, based on easily available and sustainable rosin, was synthesized by Friedel–Crafts polymerization and the further N-alkylation of triazole groups. Compared with MPAc-Br, the bifunctional catalyst MPAc-OH-Br (bearing triazole IL groups and -OH groups) exhibited higher catalytic activity for direct chemical conversion of CO2 into cyclic carbonates (up to 99% yields) under metal-, solvent-free and atmospheric pressure conditions. The rosin-based porous molecular structure and bifunctional groups on the surface of MPAc-OH-Br played a very important role in the promoting the cycloaddition of CO2 with epoxides under the optimal conditions. Furthermore, MPAc-OH-Br exhibited good stability and reusability (96% yield after 10 recycles).

Multifunctional Polyhedral Oligomeric Silsesquioxane (POSS) Based Hybrid Porous Materials for CO2 Uptake and Iodine Adsorption.

In this study, two different types of hybrid porous organic polymers (POPs), polyhedral oligomeric silsesquioxane tetraphenylpyrazine (POSS-TPP) and tetraphenylethene (POSS-TPE), were successfully synthesized through the Friedel−Crafts polymerization of tetraphenylpyrazine (TPP) and tetraphenylethene (TPE), respectively, with octavinylsilsesquioxane (OVS) as node building blocks, in the presence of anhydrous FeCl3 as a catalyst and 1,2-dichloroethane at 60 °C. Based on N2 adsorption and thermogravimetric analyses, the resulting hybrid porous materials displayed high surface areas (270 m2/g for POSS-TPP and 741 m2/g for POSS-TPE) and outstanding thermal stabilities. Furthermore, as-prepared POSS-TPP exhibited a high carbon dioxide capacity (1.63 mmol/g at 298 K and 2.88 mmol/g at 273 K) with an excellent high adsorption capacity for iodine, reaching up to 363 mg/g, compared with the POSS-TPE (309 mg/g).

Tunable construction of biphenyl-based porous polymeric nanostructures and their synergistically enhanced performance in pollutant adsorption and energy storage

Morphological diversity and porosity of porous organic polymers (POPs) exert vital influence on their potential applications. Herein, we demonstrate the morphology and porosity design of biphenyl-based hyper-cross-linked porous organic polymers by using a Lewis acid catalyzed Friedel–Crafts polymerization in the presence of formaldehyde dimethyl acetal (FDA) as cross-linker. The chemical composition of POPs is tunable by simply varying monomer to FDA ratio, leading to considerable morphological diversity such as the nanospheres, nanofibers, and flower-like nanostructures. High specific surface areas with mostly microporous nature, stable organic frameworks and tunable morphologies coupled with facile synthetic protocol let the hyper-cross-linked polybiphenyl (HCPbPh) based POPs exhibit the outstanding adsorption capacity and efficiency towards p-cresol based pollutant. The obtained carbon materials by direct pyrolysis of corresponding POPs can be used as the electrode materials for supercapacitors, exhibiting outstanding electrochemical performance with specific capacitance up to 421 F g−1 at 1 A g−1, and capacitance retention of 97% even after 10,000 cycles at 12 A g−1. This methodology delivers a new platform for the fabrication of microporous and mesoporous materials for various potential applications including energy storage, adsorption, and catalysis.

Multifunctional Hypercrosslinked Porous Organic Polymers Based on Tetraphenylethene and Triphenylamine Derivatives for High-Performance Dye Adsorption and Supercapacitor.

We successfully prepared two different classes of hypercrosslinked porous organic polymers (HPPs)—the tetraphenylethene (TPE) and (4-(5,6-Diphenyl-1H-Benzimidazol-2-yl)-triphenylamine (DPT) HPPs—through the Friedel−Crafts polymerization of tetraphenylethene and 4-(5,6-diphenyl-1H-benzimidazol-2-yl)-triphenylamine, respectively, with 1,4-bis(chloromethyl)benzene (Ph-2Cl) in the presence of anhydrous FeCl3 as a catalyst. Our porous materials exhibited high BET surface areas (up to 1000 m2 g−1) and good thermal stabilities. According to electrochemical and dyes adsorption applications, the as-prepared DPT-HPP exhibited a high specific capacitance of 110 F g−1 at a current density of 0.5 A g−1, with an excellent cycling stability of over 2000 times at 10 A g−1. In addition, DPT-HPP showed a high adsorption capacity up to 256.40 mg g−1 for the removal of RhB dye from water.

Hypercrosslinked porous organic polymers based on tetraphenylanthraquinone for CO2 uptake and high-performance supercapacitor

We successfully synthesized two different kinds of hyper-crosslinked porous organic polymers (CPOPs) based on tetraphenylanthraquinone units by a reaction of 9,10-bis(diphenylmethylene)- 9,10-dihydroanthracene (An-4Ph) as the building unit with formaldehyde dimethyl acetal and 2,4,6-trichloro-1,3,5-triazine as two external crosslinkers by using a simple and friendly one-step Friedel−Crafts polymerization in the presence anhydrous FeCl3 as a catalyst to afford An-CPOP-1 and An-CPOP-2 as a black solid with high yield, respectively. Fourier-transform infrared (FTIR) and NMR spectroscopy were confirmed the chemical structures of the synthesized monomers and the corresponding polymers. Both An-CPOP-1 and An-CPOP-2 showed amorphous character, outstanding thermal stability, and high BET surface area (up to 1000 m2/g) with microporosity and mesoporosity architectures based on XRD, TGA analyses and N2 adsorption/desorption measurements. Interestingly, TEM and SEM images revealed that An-CPOP-1 had regular tubular nanotubes structure without using template or surfactant or carbonization at the elevated temperature. The as-prepared An-CPOP-2 exhibited a high specific capacitance of 98.4 F g−1 at a current density of 0.5 A g−1 and excellent cycling stability (95.3% capacitance retention over 2000 cycles), which could be used as good material for energy storage application.

Photocatalytic Suzuki–Miyaura Coupling Reactions over Palladium Anchored on 8‐Hydroxyquinoline‐Based Polymers

AbstractThrough a one‐pot Friedel–Crafts polymerization method, a series of 8‐hydroxyquinoline‐based polymers with excellent light capturing ability is synthesized to support palladium for light‐driven Suzuki–Miyaura reactions (SMRs). The results of X‐ray powder diffractometer and transmission electron microscopy analyses suggest that the 8‐hydroxyquinoline‐based polymers are amorphous in structure and irregular in morphology. According to the data of thermogravimetric analysis and Brunauer‐Emmett‐Teller gas absorption, they are thermally stable up to 340 °C and are large in specific surface area. With palladium anchored securely on the 8‐hydroxyquinoline units of the polymer skeleton, the obtained photocatalysts exhibit excellent activity and reusability in SMRs under blue‐light irradiation.

Synthesis of secondary amine‐based fluorescent porous organic polymers via Friedel–Crafts polymerization reaction for adsorbing and fluorescent sensing iodine

AbstractWe present the preparation and characterization of a novel class of secondary amine‐based porous organic polymers (POPs: TDPA and TTPBTA), and their iodine adsorption, fluorescence sensing properties for the first time. Two secondary amine‐based POPs were synthetized by Friedel−Crafts polymerization reaction catalyzed via methylsulfonic acid with yields of 22.51 and 54.44%. The thermal stability of resulting POPs run up to above 268 and 568°C, and their BET specific surface areas are 56.5 and 2.49 m2 g−1, respectively. Their iodine adsorption and fluorescent sensing properties are comparable to that of triphenylamine (TPA)‐based (tertiary amine) POPs. The resulting POPs display excellent sorption abilities to iodine molecules with the iodine adsorption capacity of about 3.93 and 1.64 g g−1. Adsorbed iodine is easily desorbed by heating or washing with organic solvents, which make them reusable. They can also adsorb iodine from cyclohexane solution. Moreover, the POPs possess excellent fluorescent sensing property for I2 with Ksv of 1.85 × 104 and 6.56 × 104 L mol−1, as well as the limits of detection (LODs) of 1.62 × 10−11 and 6.86 × 10−12 mol L−1. The performance of adsorbing and fluorescence sensing iodine can be explained by electron transfer mechanism.

Synthesis of tetraphenylethylene-based fluorescent conjugated microporous polymers for fluorescent sensing and adsorbing iodine

Abstract Two tetraphenylethylene-based fluorescent conjugated microporous polymers were obtained by the polymerization of a CH3SO3H catalyzed Friedel−Crafts polymerization reaction. The resulting CMPs show high thermal stability with a decomposition temperature above 575 and 487 °C, and have the porosity with BET surface area of 564.8 and 44.1 m2 g−1, respectively. Due to the introduction of tetraphenylethylene units, the CMPs have excellent fluorescence sensing performance for I2 with high Ksv of 1.53 × 105 and 9.07 × 104 L mol−1. Taking advantage of such porosity, effective sorption sites, and charge-transfer interactions, which display excellent I2 adsorption capacity in vapor with the uptake of up to 3.41 and 2.91 g g−1.

Triazine-based conjugated microporous polymers with N,N,N′,N′-tetraphenyl-1,4-phenylenediamine, 1,3,5-tris(diphenylamino)benzene and 1,3,5-tris[(3-methylphenyl)-phenylamino]benzene as the core for high iodine capture and fluorescence sensing of o-nitrophenol

A series of novel triazine-based conjugated microporous polymers were constructed via Friedel–Crafts polymerization.

Cyclopentadithiophene based branched polymer electrets synthesized by friedel–crafts polymerization

ABSTRACTIn this report, the BF3·Et2O catalyzed Friedel–Crafts polymerization of cyclopentadithiophene monomers for branched conjugation‐interrupted polymer electrets with the potential application in OFET memories were demonstrated. Branched polycyclopentadithiophenes with controlled molecular weights (Mn) of approximately 8800 g/mol and narrow polydispersity index (PDI = 1.08–1.49) were obtained through the optimized polymerization temperature and time, and monomer addition strategy. OFET memories by using the synthesized polymers as the electret layers were fabricated and exhibited multilevel flash memory behaviors, wide memory windows, high on/off ratios, and long retention lifetime. Impressively, due to the strong hydrophobic, extended pi‐conjugation and electron‐donating properties, the branched polycyclopentadithiophene based OFET memory exhibited much lower programming voltage than other branched polymer electrets based devices. It is expected that the branched polycyclopentadithiophenes probably have potential application in other organic electronic devices. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3140–3150

Preparation of Poly(ether ketone)s Derived from 2,5-Furandicarboxylic Acid by Polymerization in Ionic Liquid

Aromatic poly(ether ketone)s were synthesized by the Friedel–Crafts polymerization of 2,5-furandicarbonyl dichloride prepared from biomass and petroleum-based aromatic ethers such as diphenyl ether and 1,4-diphenoxybenzene with aluminum chloride (AlCl3). The polymerizations in common molecular solvents such as 1,2-dichloroethane and nitrobenzene did not afford polymers. The Friedel–Crafts polymerization usually undergoes in the swollen gel of the oligomer–AlCl3 complexes; the precipitated physical gels had not been enough swollen. The polymerizations were carried out in various ionic liquids to form swollen gels. The polymerizations proceeded in specific ionic liquid such as 1-butyl-3-methylimidazolium chloride ([C4mim]Cl), and high molecular weight polymers were obtained with good yield. The gels formed in [C4mim]Cl were more highly swollen, and additionally the rate constant estimated by the model reaction of 2,5-furandicarbonyl dichloride and anisole was higher in [C4mim]Cl than that in 1,2-dichloroethane. The obtained poly(ether ketone)s exhibited good thermal stability and chemical resistance comparable to common poly(ether ketone)s.

BF3·Et2O-mediated Friedel–Crafts C–H bond polymerization to synthesize π-conjugation-interrupted polymer semiconductors

C–H bond functionalization offers a chance to develop a new concept of polymerization. In this article, a family of diarylfluorene-based π-conjugation-interrupted polymers (CIPs) with nonlinear or hyperbranched frameworks have been explored by BF3·Et2O-mediated Friedel–Crafts polymerization of AB, AB2 and AB4-type tertiary alcohol monomers at room temperature. Their chemical structures and optoelectronic properties have been characterized and the existence of strong intermolecular π-stacked aggregates have been observed. CIP semiconductors afford a new platform to explore novel functionality of organic devices in organic electronics or spinelectronics.

New polymer syntheses XII. Polyketones based on diarylidenecycloalkanones

Two new series of polyketones containing diarylidene links was synthesized by the Friedel–Crafts polymerization of diarylidenecyclopentanone or diarylidenecyclohexanone with aromatic diacid chlorides, azodibenzoyl chlorides, or aliphatic diacid chlorides. The resulting polymers had inherent viscosities in the range 0.76–1.18 dl/g and showed poor solubilities to common organic solvents excepts strong acids. The thermal stabilities of these polymers were evaluated and correlated to their structural units by thermogravimetric analysis (TGA), DTG and DSC measurements. The TGA data revealed 10% weight losses at 190–300 °C. Moreover, the crystallinity of some polymers were tested by X-ray analyses and the UV–visible spectra showed characteristic absorption bands in the range 240–350 nm.

Symposium on Friedel–Crafts catalysts and polymerization

On 15 September 1945, Michael Polanyi, F.R.S., Professor of Physical Chemistry at the University of Manchester, convened there a one–day meeting entitled ‘Symposium on Friedel–Crafts Catalysts and Polymerization’. The morning was devoted to Friedel-Crafts catalysts and the afternoon to polymerization.

Crosslinkable aromatic polyketones with maleimide pendent groups

AbstractA novel class of crosslinkable aromatic polyketones with maleimide pendent groups were synthesized by Friedel–Crafts polymerization from 5‐maleimido‐isophthaloylchloride and various aromatic reagents. The synthesized polyketones showed a poor solubility. They were characterized by inherent viscosity measurements and infrared (IR) spectroscopy. Differential thermal analysis (DTA) revealed that their crosslinking occurred at relatiively lower temperatures (167–253°C) than did thermal polymerization of ordinary bismaleimides. The thermal‐and thermooxidative stability of crosslinked resins were evaluated by dynamic thermogravimetric analysis (TGA) as well as by isothermal gravimetric analysis (IGA). They were stable in N2 up to 303–329°C and formed anaerobic char yield 50–62% at 800–C. The thermal stability of crosslinkable polyketones was significantly increased after curing.