Noncoplanar rigid‐rod aromatic polyhydrazides containing Tröger's base

Abstract

A new Trö ger's base-containing aromatic dihydrazide, 2,8-bis(carboxylic)-6H, 12H-5,11-methanodibenzo-[b,f] [1,5]-diazocine dihydrazide, was prepared by the condensation of ethyl p-aminobenzoate with hexamethylenetetramine in the presence of trifluoroacetic acid, followed by converting to the dihydrazide with a high yield and high purity. A series of novel aromatic polyhydrazides were prepared from the Trö ger's unit containing dihydrazide and various aromatic diacyl chlorides via low-temperature solution polycondensation in quantitative yields. All the polyhydrazides were amorphous and readily soluble at room temperature in polar organic solvents such as N,N-dimethylacetamide and N-methyl-2-pyrrolidone. These polymers could be solution cast into transparent, tough, and flexible films with good mechanical properties. They had useful levels of thermal stability associated with good glass transition temperatures (163-172 C), 10% weight-loss temperatures in excess of 460 C, and char yields at 800 C in nitrogen higher than 39%.

The synthesis of microporous polymers using Tröger's base formation

“…Polymers with promisingly high average molecular masses were obtained. In addition, a 13 C solid state NMR spectrum consistent with the ideal structure was obtained for each polymer. For monomers 4 and 5, which both possess additional sites adjacent to the amine groups activated towards electrophilic substitution, a high concentration of monomer or a prolonged reaction time resulted in insoluble gel formation presumably due to cross-linking via further reaction involving the excess dimethoxymethane.…”

“…Commercially available reagents were used without further purication. 1 H NMR spectra were recorded in the solvent stated using an Avance Bruker DPX 400 (400 MHz) or DPX 500 (500 MHz) instruments, with 13 C NMR spectra recorded at 100 MHz or 125 MHz respectively. Matrix Assisted Laser Desorption Ionisation (MALDI) mass spectroscopic analysis was performed with a Waters MALDI Micro MX spectrometer.…”

“…[7][8][9][10][11][12] In addition, TB-containing polymers have been prepared by linking together preformed TB monomers using well-established polymerisation reactions. 13,14 However, despite its long history, the TB-forming reaction has only very recently been used to make polymers (e.g. PIM-EA-TB; Fig.…”

Intrinsically Microporous Soluble Polyimides Incorporating Tröger’s Base for Membrane Gas Separation

“…Taking into consideration the above-mentioned performance advantages of microporous polyimides, incorporating TB units into polyimides are expected to provide rigid PIs with intrinsic microporosity, which we anticipated would have high permeability and good permselectivity for membrane gas separation. TB units have been incorporated into aromatic polyhydrazides, insoluble PIM networks for CO 2 capture applications, , as well as solution-processable PIMs for membrane-based gas separations. ,, However, polyimides incorporating TB units have not been reported to date.…”

The use of a star-shaped trifunctional acyl chloride for the preparation of polyamide thin film composite membranes

“…Thirdly, the reactivity of the acyl groups of 3 is lower as compared to that of TMC due to the electron donating ether groups that render the acyl chloride groups of 3 less electrophilic. However, the polymerization of the bifunctional 4,4′-oxybis(benzoyl chloride) (COCl-Ph-O-Ph-COCl) with various aromatic diamines yields high molecular weight polyamides [28][29][30].…”