Synthesis of Fluorinated and Hydrocarbon Ester Functionalized Poly(p-phenylenes) and Their Solubility in Supercritical Fluids

Abstract

Monomers of the structure 2,5-dichloro-1,4-(RO2C)2benzene, where R ) CH2CF2CF3 (1a), -(CH2)2CH3 (1b), -CH2CH2(CF2)5CF3 (1c), and -(CH2)7CH3 (1d), were prepared and characterized in the study. Polymerization by the Ni-catalyzed/Zn-mediated homocoupling methodology afforded poly(pphenylenes) 2a-2d. The polymers obtained after precipitation into methanol showed molecular weights (Mn, relative to polystyrene standards) in the range 7000-13 000. The regiochemistry in the polymer was deduced to be approximately 70% head-to-tail with the remainder head-to-head. The polymers displayed excellent solubility in common polar organic solvents such at THF and chloroform. The poly-

Impact of hexafluoroisopropylidene on the solubility of aromatic‐based polymers in supercritical fluids

“…Hence, fluorinating a polymer enhances its solubility in supercritical CO 2 although the polymer also must have a measurable polar moment to ensure that the polymer dissolves at low pressures and at low temperatures. [7][8][9][10] In fact, Sarbu and co-workers synthesized poly(ether-carbonate) copolymers containing carbonyl groups to demonstrate that polymer polarity can be a controlling factor that determines whether the polymer dissolves in CO 2 .…”

Synthesis of Conducting Organic Polymeric Materials Mediated by Metals: How the Organic Chemists Make Some of the Most Advanced Polymeric Materials

“…(21)). These activated compounds react with the stoichiometric amount of zinc in the presence of a catalytic amount of NiCl 2 and PPh 3 or directly with the catalytic amount of the pre-formed [Ni(PPh 2 ) 2 Cl 2 ] complex to give the polymers 79 with a high variety of yields and molecular weights up to 10 3 D. Most recently, 1,4-dichlorobenzenes have been polymerized by a similar way [109].…”

2,5-Dichloro-1-(ROSO2)benzene [R=C6H5, C6F5, and CH2(CF2)4H]: Synthesis, molecular structure, and solubility in supercritical CO2

“…For example, partially or fully fluorinating a hydrocarbon polymer, such as poly(ethylene-co-propylene) (EP), renders the resultant fluorinated EP polymer soluble in CO 2 [5]. Although it is also important to note that the polymer must have a measurable polar moment to ensure that it dissolves in CO 2 at low pressures and temperatures [4][5][6][7]. Specific CO 2 -fluorocarbon interactions that lead to enhanced solubility have been elucidated with high-pressure, fluorine NMR for mixtures of low molecular weight fluorocarbons with CO 2 [8] and for mixtures of fluorinated polymers and copolymers with CO 2 [9].…”

“…Recently we published a study that reported on the pronounced effect of fluorination on the solubility and phase behavior of rigid-rod polymers in supercritical fluids [7]. As a part of that polymer study we also determined the effect of www.elsevier.com/locate/fluor Journal of Fluorine Chemistry 127 (2006) [330][331][332][333][334][335][336] fluorination on the solubility of the monomers [12] and related aromatic dimers of these rigid-rod polymers [13].…”