Analysis of the mechanism of copolymerization of styrene and acrylonitrile

Hill, D. J. T.; O’Donnell, James H.; O'Sullivan, Paul W.

doi:10.1021/ma00232a004

Cited by 173 publications

(104 citation statements)

References 8 publications

(11 reference statements)

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“…4 on a wt.% basis, whereas for the nmr the standard error was estimated at -1 1.75 on the same basis. (Note that the standard error for the nmr measurements is in good agreement with previously reported values (19,26)). Clearly, the approach suggested here can yield reliable quantitative information on the styrene content for SMMA copolymers.…”

Section: Meas~tretnenfssupporting

confidence: 91%

Detailed copolymer characterization using ultraviolet spectroscopy

García‐Rubio¹,

Ro²

1985

Can. J. Chem.

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(1985).A method is demonstrated for the interpretation of the ultraviolet spectra of styrene-containing copolymers. This method is based on the use of model molecules to approximate the absorption behaviour of the known chromophores and on the statistical estimation of the average spectra of the unknown chromophores. ' The analysis yields directly the copolymer composition and an estimate of the background spectra which arise from the different arrangements of the styril units along the polymer chains. It is shown that reliable composition estimates are obtaincd for styrene -methyl methacrylate and styrene-acrylonitrile copolymers. ' The results from the interpretation of the spectra are discussed and compared with results obtained from the statistical copolymerization models.

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Section: Meas~tretnenfssupporting

confidence: 91%

Detailed copolymer characterization using ultraviolet spectroscopy

García‐Rubio¹,

Ro²

1985

Can. J. Chem.

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“…The compositions of the copolymers (Fs and FA) were determined (1) by duplicate percentage nitrogen analysis using a LECO FP-428 automatic elemental analyzer, (2) by calculation from the experimental triad fractions, and (3) by the relative intensities of the aromatic (S units) and methylene and methine (A + S) resonances in the 'H NMR spectra. These spectra were obtained by Fourier transform techniques using, a Bruker AM-400 (400.14 MHz) or a Varian UNITY-300 (299.95 MHz) spectrometer at 60 "C, in 5 All the systems display a significant penultimate unit effect, which is recognized from the reactivity ratios listed in Table 5. The reactivity ratios were determined according to a NLLS technique based on principals outlined by Britt and Luecke."…”

Section: Methodsmentioning

confidence: 99%

Effect of Solvent on the Copolymerization of Styrene and Acrylonitrile. Application of the Bootstrap Effect to the Penultimate Unit Model

Klumperman¹,

Kraeger²

1994

Macromolecules

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ABSTFUCT The copolymerization of styrene and acrylonitrile has been investigated in bulk and in the solvents toluene, butanone, and NJV-dimethylformamide. The comparison of the copolymers prepared in the bulk system with copolymers obtained from copolymerizations in the various solvents reveals a relatively small but noticeable solvent effect. All the systems display a significant penultimate unit effect. From this work it is concluded that the copolymerization of styrene and acrylonitrile in the employed solvents can be explained by the qualitative description of the bootstrap model. The comparison of the bulk with the toluene system seems to indicate that the quantification of the bootstrap model is not realized by the assumption that the distribution coefficient K is constant. A modification of the earlier proposed method for quantification of the bootstrap effect is suggested. The distribution coefficient is linearly dependent on copolymer composition. The new method provides a good fit with experimental results, whereas the used parameters have a distinct physical meaning.

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“…The method for independent calibration of detectorsll has an important advantage, since it eliminates the estimation of interdetector volume or detector offset. The intrinsic viscosities ([VI) of PSTY standards in THF with 5% acetic acid were also measured and arereportedin (1) For individual detectors, universal calibration curves in terms of hydrodynamic volume (M[v]) were established using eq 1 along with primary calibration curves. Then the calibration curve for STYiMAnh copolymers (SMA) was established with a new technique" using only the on-line viscometer and the universal calibration curve.…”

Section: Methodsmentioning

confidence: 99%

Pulsed Laser Copolymerization of Styrene and Maleic Anhydride

Sanayei¹,

O'Driscoll²,

Klumperman³

1994

Macromolecules

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Pulsed laser polymerization (PLP) has been done for the free radical copolymerization of styrene (monomer 1) and maleic anhydride (monomer 2) at 25,35, and 50 OC in butanone (methyl ethyl ketone (MEK) and acetonitrile (Acn) using AIBN as photoinitiator. The mean values for the propagation rate constant, (k,), were determined and found to be independent of solvent. Copolymer compositions were measured as a function of comonomer ratio in an isothermal continuous stirred reactor using MEK as solvent over a temperature range from 60 to 140 "C. The combination of these data and the data from PLP experiments were used in model discrimination by multivariate nonlinear regression. The best description of this copolymerization is obtained from the penultimate unit model. No convergence could be reached in a multivariate nonlinear regression of the combined data set to the complex participation model. The mean k , is well described by the Mayo-Lewis model, where copolymer composition shows some deviation from the model. Numerical inspection reveals that invoking complex participation leads to a good fit of the copolymer composition data but very bad agreement with the mean k , data. The comonomer pair showed several peculiarities compared to systems described in the literature so far. Extremely high molecular weight copolymer was formed during the PLP experiments, the amount being dependent, among others, on solvent. Furthermore, large amounts of oligomers, i.e., dimers and trimers, are formed under PLP conditions. Two possible explanations for the anomalies of this comonomer pair are discussed. First, diradical initiation could account for the observed phenomena. Laser pulses are thought to excite electron donor-acceptor complexes, resulting in diradicals, which may initiate copolymerization. Second, "dark" polymerization might give rise to formation of high molecular weight copolymer. Due to significant or even total light absorption, part of the monomer solution is unaffected by the laser pulses.

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Analysis of the mechanism of copolymerization of styrene and acrylonitrile

Cited by 173 publications

References 8 publications

Detailed copolymer characterization using ultraviolet spectroscopy

Detailed copolymer characterization using ultraviolet spectroscopy

Effect of Solvent on the Copolymerization of Styrene and Acrylonitrile. Application of the Bootstrap Effect to the Penultimate Unit Model

Pulsed Laser Copolymerization of Styrene and Maleic Anhydride

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