Kinetics of 2-Pentadecylaniline Polymerizations in Monolayers: Relationships between Experimental Data and a New Theoretical Model

Bodalia, Raj; Manzanares, José A.; Reiss, Howard; Duran, Randolph S.

doi:10.1021/ma00086a004

Cited by 16 publications

(6 citation statements)

References 22 publications

(41 reference statements)

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“…While showing the effect of surface pressure on reaction rate, these studies did not address the autoacceleration rate effect on the complex polymerization kinetics. Furthermore, the polymerization was assumed first order in terms of the monomer concentration during the course of the reaction, potentially oversimplifying the kinetics compared to what is observed in the polymerization of aniline by chemical and electrochemical oxidation. − Bodalia et al furthered this work by addressing autoacceleration and assigning a second rate constant to the overall rate of the polymerization . However, this method was accurate only when the initial polymerization rate was orders of magnitude slower than the maximum rate, which is not always the case for aniline surfactant polymerizations…”

Section: Introductionmentioning

confidence: 99%

Polymerization and Surface Behavior of Alkyl-Substituted Aniline Surfactants at the Air−Aqueous Interface: A Kinetic Study

Kloeppner

Duran

1998

Langmuir

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The surface behavior of 2-, 3-, and 4-pentadecylaniline (3a, 3b, and 3c, respectively) was studied at the air−aqueous interface of an acidic subphase. Surface dipole moments (μn) were calculated from the surface potentials (ΔV) of 3a−c and were related to the orientation of the anilinium ion at the interface. Further, 3a and 3b were polymerized in a Langmuir film, and analysis of the absorption spectra showed that the resulting polymers were in different oxidative states upon completion of the polymerization. A method that monitors the change in the mean molecular area (A) of the surfactant at a constant applied surface pressure and predicts the concentrations of monomer and polymer and/or oligomer at the interface in order to determine the formation rate (R p) of poly(alkylaniline) is presented. The R p values of 3a and 3b are expressed in terms of the concentrations of the monomer and polymer at the interface. It was determined that the R p of 3a was dependent on the applied surface pressure while 3b showed little dependence on surface pressure. Differences in R p can be explained by the conformation of the anilinium group and the steric hindrance of the alkyl group at the interface. A characteristic “autoacceleration effect” was observed for both 3a and 3b but was more significant in the case of 3a.

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Section: Introductionmentioning

confidence: 99%

Polymerization and Surface Behavior of Alkyl-Substituted Aniline Surfactants at the Air−Aqueous Interface: A Kinetic Study

Kloeppner

Duran

1998

Langmuir

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“…Wei et al [21] have studied the chemical polymerization of aniline by open circuit potential measurements. Bodalia et al [22] have explored the kinetics of polymerization of 2-pentadecylaniline at the air/water interface and proposed a kinetic scheme based on the one suggested by Tzou and Gregory [23] for the conventional polymerization of aniline. Gill et al [24] have studied the kinetics of polymerization of aniline using 1 H NMR spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

Course of poly(4-aminodiphenylamine)/Ag nanocomposite formation through UV–vis spectroscopy

Thanjam

Philips

Komathi

et al. 2011

Spectrochimica Acta Part A: Molecular and Biomolecular Spectros

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“…Similar investigations aimed at forming monolayer films of conducting polymers from a variety of tethered monomers have been reported. [16][17][18][19][20][21][22][23][24] Although ultrathin films of poly(aniline) have been created using Langmuir-Blodgett films 15,25,26 and anilinium ions coordinated to sulfonic acid terminated thiol monolayers, 24 the use of aniline-terminated alkanethiol monolayers in the study of polymerization reactions on surfaces would allow more facile evaluation of the effects of experimental variables on the resulting polymer properties.…”

Section: Introductionmentioning

confidence: 99%

Surface-Confined Monomers on Electrode Surfaces. 10. Electrochemical and Infrared Spectroscopic Characteristics of Aniline-Terminated Alkanethiol Monolayers on Au Electrochemically Treated in Aqueous Solution

Schomburg

McCarley

2001

Langmuir

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We have synthesized and conducted studies on two self-assembled monolayers which have an oxyaniline tail group that is tethered to a gold surface via an alkanethiol chain. Reflection-absorption infrared spectroscopy (RAIRS), electrochemical, and contact angle measurements were performed on pristine 2-(6mercaptohexan-1-oxy)aniline (AnC6SH) and 2-(7-mercaptoheptan-1-oxy)aniline (AnC7SH) monolayers on planar Au surfaces. The pristine monolayers were electrochemically oxidized in 1 M H2SO4, and the resulting voltammetry was compared to that of dimeric model compounds and electrochemically deposited poly(o-phenetidine) films on Au electrodes. RAIRS and electrochemical data reveal that electrochemical oxidation of AnC6SH and AnC7SH monolayers on Au results in the formation of surface-confined poly-(aniline) as well as aniline dimers and hydrolyzed aniline dimers.

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Kinetics of 2-Pentadecylaniline Polymerizations in Monolayers: Relationships between Experimental Data and a New Theoretical Model

Cited by 16 publications

References 22 publications

Polymerization and Surface Behavior of Alkyl-Substituted Aniline Surfactants at the Air−Aqueous Interface: A Kinetic Study

Polymerization and Surface Behavior of Alkyl-Substituted Aniline Surfactants at the Air−Aqueous Interface: A Kinetic Study

Course of poly(4-aminodiphenylamine)/Ag nanocomposite formation through UV–vis spectroscopy

Surface-Confined Monomers on Electrode Surfaces. 10. Electrochemical and Infrared Spectroscopic Characteristics of Aniline-Terminated Alkanethiol Monolayers on Au Electrochemically Treated in Aqueous Solution

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