Synthesis and Properties of p-Polyphenyl Derivatives<sup>1</sup>

Kovacic, Peter; Marchionna, Vincent J.; Koch, Fred W.; Oziomek, James

doi:10.1021/jo01346a008

Cited by 36 publications

(21 citation statements)

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“…: ELECTROCHEMICAL SCIENCE AND TECHNOLOGY July 1985 longer conjugation lengths (fewer defects) than are produced by thermal isomerization (11). Poly(p-phenylene) electrodes were fabricated from powdered polyphenylene synthesized from benzene with an A1C1JCuCI~ catalyst in accordance wth the method of Kovacic (12). These electrodes were composed of 80 weight percent (w/o) PPP, 10 w/o carbon black (Shawinigan Black| and I0 wlo poly(ethylene-chlprotrifluoroethylene) (Halar| They were compressed and cured at 175~ Such PPP electrodes were typically 0.025 cm thick and had a densitY of ca.…”

Section: Methodsmentioning

confidence: 99%

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Polyacetylene and Polyphenylene as Anode Materials for Nonaqueous Secondary Batteries

Shacklette

Toth

Murthy

et al. 1985

J. Electrochem. Soc.

212

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The conjugated polymers polyacetylene (PA) and poly(p-phenylene) (PPP) have been examined for their possible use as negative electrode materials in nonaqueous secondary batteries. Cathodically stable electrolytes have been identified which allow high reduction levels for these polymers, and charge-storage capacities of 0.34 Ah/g for PA and 0.15 Ah/g for PPP have been demonstrated. Structural evolution of these polymers during cation insertion and extraction has been shown to have a significant influence on their electrochemical behavior. Several new stoichiometric phases have been identified.Polyacetylene (PA) (1) and poly(p-phenylene) (PPP) (2, 3) are crystalline conjugated polymers which can be either partially oxidized or reduced electrochemically. This process results in the formation of a highly conducting complex between the reduced or oxidized polymer and the appropriate counterion from the electrolyte. The electrochemical reaction which occurs in a cell containing PA or PPP electrodes involves the removal or addition of electrons through the external circuit and the insertion of ions from the electrolyte into the polymer lattice.Polyacetylene (1), polyphenylene (2, 3), and other conjugated polymers have been considered for application to nonaqueous-electrolyte secondary batteries, where they may function as either anode or cathode. Recently, the prospects for a particular cell employing polyacetylene as a cathode have been reviewed (4). In this paper, we will discuss the characteristics of polyacetylene and polyphenylene as they relate to the potential use of these polymers as anodes. In this case, we will only be concerned with partially reduced polymers for which the ioninsertion reaction may be represented by-xy e where P denotes the polymer compositional repeat unit, C ~ the inserted cation, y the fractional charge per repeat unit (frequently called the doping level), and x the degree of polymerization. In this paper, P denotes --CH--for PA and --C6H4--for PPP. Two of the most important considerations relating to use in batteries concern the charge storage capacity (maximum value of y) and the operating voltage of the polymer. To date, there has been a discrepancy in the reported values of y obtainable with Li + for polyacetylene by chemical means (5) (y = 0.3) and by electrochemical means (6) (y = 0.08). We have been able to resolve this discrepancy by performing electrochemical reductions in more cathodically stable electrolytes.Having found a stable electrochemical system, we have been able to study the intrinsic properties of polyacetylene and polyphenylene at varying degrees of reduction. ExperimentalAs we will detail in the following sections, we have found that a variety of organoborate salts offer superior stability to the reduced polymers. Some of these salts, lithium tetraphenyl borate (LiBPh4), lithium tetrabutyl borate (LiBBu4), and sodium tetraethyl borate (NaBEt4), were purchased from Atfa Products. Others, which included lithium tetramethyl borate (LiBMe4) and potassium tributyl(N-pyrro...

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Section: Methodsmentioning

confidence: 99%

“…This was Paper 619 presented at the New Orleans, Louisiana, Meeting of the Society, Oct. [7][8][9][10][11][12] 1984.…”

Section: Acknowledgmentmentioning

confidence: 99%

Polyacetylene and Polyphenylene as Anode Materials for Nonaqueous Secondary Batteries

Shacklette

Toth

Murthy

et al. 1985

J. Electrochem. Soc.

212

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“…Earlier work using phthaloyl peroxide describes the stability and proper handling of these compounds. [1][2][3][4][5][6] 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 ing the substrate to a final concentration of 0.1 M. In some cases, when noted, CHCl 3 ...…”

Section: Methodsmentioning

confidence: 99%

“…J = 8 6. Hz, 1H), 4.12 (t, J = 6.6 Hz, 2H),3.90 (s, 3H),3.89 (s, 3H), 2.61 (t, J = 7.1 Hz, 2H), 2.54 (q, J = 7.4 Hz, 4H), 1.99 (m, 2H), 1.01 (t, J = 7.4 Hz, 6H); 13 C NMR (100 MHz, CDCl 3 ) δ 166.9, 152.5, 148.8, 123.5, 122.4, 112.3, 111.5, 67.4, 56.0, 51.9, 49.1, 46.9, 26.6, 11.7; IR (neat film, cm -1 ): 2967, 2809, 1717, 1293; HRMS (EC-CI): [M+Na]+ calc'd for C 16 H 25 NO 4 Na: 318.16758.…”

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confidence: 99%

Computational and Experimental Studies of Phthaloyl Peroxide-Mediated Hydroxylation of Arenes Yield a More Reactive Derivative, 4,5-Dichlorophthaloyl Peroxide

Camelio

Liang²,

Eliasen

et al. 2015

J. Org. Chem.

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The oxidation of arenes by the reagent phthaloyl peroxide provides a new method for the synthesis of phenols. A new, more reactive arene oxidizing reagent, 4,5-dichlorophthaloyl peroxide, computationally predicted and experimentally determined to possess enhanced reactivity, has expanded the scope of the reaction while maintaining a high level of tolerance for diverse functional groups. The reaction proceeds through a novel "reverse-rebound" mechanism with diradical intermediates. Mechanistic insight was achieved through the isolation and characterization of minor byproducts, the determination of linear free energy correlations, and computational analysis of substituent effects of arenes, each of which provided additional support for the reaction proceeding through the diradical pathway.

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“…The AlC13-CuC12 combination gave best results. [3][4][5] Subsequently, in studies of the chemistry of I, various derivatives, e.g., halo and nitro, were synthe~ized.~J In most cases, these exhibited the gross insolubility characteristic of the parent polymer. One exception was the highly sulfonated which is soluble in polar solvents.…”

Section: Introductionmentioning

confidence: 99%

Polymerization of aromatic nuclei. XVII. Catalytic hydrogenation of poly(p‐phenylene)

Durham

Kovacic

1977

J. Polym. Sci. Polym. Chem. Ed.

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Hydrogenation of poly(p‐phenylene) (I) in cyclohexane at high temperature and pressure with rhodium catalyst gave, in low yield, oligomers of 1,4‐cyclohexylene(II) in the range of 2–16 cyclohexyl units per chain. Apparently only the low molecular weight fraction in I is reduced because of extreme insolubility. II, which appears to be a novel class, was characterized by molecular weight, 1H‐NMR, 13C‐NMR, and infrared spectra, gas chromatography, and microanalyses. Dicyclohexyl and perhydro‐p‐sexiphenyl served as model compounds for comparison in characterization of II.

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Synthesis and Properties of p-Polyphenyl Derivatives¹

Cited by 36 publications

References 5 publications

Polyacetylene and Polyphenylene as Anode Materials for Nonaqueous Secondary Batteries

Polyacetylene and Polyphenylene as Anode Materials for Nonaqueous Secondary Batteries

Computational and Experimental Studies of Phthaloyl Peroxide-Mediated Hydroxylation of Arenes Yield a More Reactive Derivative, 4,5-Dichlorophthaloyl Peroxide

Polymerization of aromatic nuclei. XVII. Catalytic hydrogenation of poly(p‐phenylene)

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Synthesis and Properties of p-Polyphenyl Derivatives1

Cited by 36 publications

References 5 publications

Polyacetylene and Polyphenylene as Anode Materials for Nonaqueous Secondary Batteries

Polyacetylene and Polyphenylene as Anode Materials for Nonaqueous Secondary Batteries

Computational and Experimental Studies of Phthaloyl Peroxide-Mediated Hydroxylation of Arenes Yield a More Reactive Derivative, 4,5-Dichlorophthaloyl Peroxide

Polymerization of aromatic nuclei. XVII. Catalytic hydrogenation of poly(p‐phenylene)

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Synthesis and Properties of p-Polyphenyl Derivatives¹