The study of the copolymerization of styrene and acrylonitrile to high conversion. application of low conversion reactivity ratios

Hill, David J. T.; Lang, A.P.; O’Donnell, James H.

doi:10.1016/0014-3057(91)90005-9

Cited by 18 publications

(4 citation statements)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…1. Comonomer (/g) and Copolymer (Fg) Compositions Expressed as the Mole Fraction of Styrene with Conversions and Experimental Triad Fractions for the Copolymerization of Styrene and Acrylonitrile at 60 °C in eight percent of total monomer feed 6. Arithmetic average from % N elemental analysis, -NMR spectra, and from the triad fractions; estimated error Fs ±1.0%.…”

mentioning

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

View full text Add to dashboard Cite

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.

show abstract

mentioning

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

View full text Add to dashboard Cite

show abstract

“…Monomer feed compositions were planned according to the approximate design scheme proposed by McFarlane et al 26 This method is based on Tidwell and Mortimer, who gave a simplification of the D‐optimal criterion for copolymer composition determination 27, 28. The use of this criterion will result in the smallest possible confidence interval for the monomer reactivity ratios with a given number of experiments.…”

Section: Resultsmentioning

confidence: 99%

Monomer reactivity ratios for lauryl methacrylate–isobutyl methacrylate in bulk free radical copolymerization

Habibi

Vasheghani‐Farahani

Semsarzadeh

et al. 2003

Polymer International

View full text Add to dashboard Cite

Statistical copolymers of isobutyl methacrylate and lauryl methacrylate were prepared by free radical bulk copolymerization at 70 • C using 2,2 -azobisisobutyronitrile as initiator. The synthesis of these copolymers was investigated over a wide composition range at low conversion levels. Copolymer compositions were determined from the C, H and O contents obtained by elemental analysis. The monomer reactivity ratios and the 95% individual confidence intervals and 95% joint confidence intervals were calculated by the Fineman-Ross, Ezrielev-Brokhina-Roskin, Kelen and Tüdös, Extended Kelen and Tüdös methods and a linear iterative method proposed by Mao and Huglin. The estimation process was performed by applying non-linear techniques based on Marquardt optimization, ordinary least-squares (OLS) and generalized least-squares approaches and the results were compared. Monomer reactivity ratios and monomer partition coefficients were also analysed on the basis of the bootstrap models by applying the non-linear least-squares approach. Good agreement between experimental and calculated copolymer compositions was obtained. The results show that this copolymerization system is strictly describable by the simple bootstrap terminal model (SBTM) and accurate monomer reactivity ratios can be obtained. The monomer sequence distributions were also calculated using the monomer reactivity ratios obtained from SBTM.

show abstract

“…An interesting aspect of high conversion free radical copolymerization is the extent to which the copolymer composition can be predicted as a function of conversion using the terminal model monomer reactivity ratios ( r 1 and r 2 ) as estimated at low conversion. Good agreement has been reported for several copolymerization systems over various conversion ranges based on the cumulative copolymer composition (e.g., by use of the integrated copolymerization equation). ,− Without disputing these important findings, this type of analysis should not be treated as a strict test of the validity of the low conversion terminal model at high conversion with regards to copolymer composition due to the relative insensitivity of the cumulative copolymer composition to possible changes in the instantaneous copolymer composition over a relatively narrow high conversion range. It is therefore instructive to examine the instantaneous copolymer composition in reactions taken to high conversion even though this quantity can be difficult to access directly by any experimental method.…”

Section: Introductionmentioning

confidence: 99%

Instantaneous Copolymer Composition in High Conversion Copolymerization of Acrylonitrile and Methyl Acrylate Assessed by in Situ ¹³C NMR Measurements of Individual Monomer Reaction Rates

2005

View full text Add to dashboard Cite

The copolymerization of acrylonitrile with methyl acrylate initiated by azobis(isobutyronitrile) in dimethyl sulfoxide at 60 °C has been investigated to high conversion using in situ 13 C NMR spectroscopy. The focus has been on the relative rates of individual monomer consumption as a function of time up to as high a conversion as experimentally feasible. It has been found that the relative rates of monomer consumption, i.e., the instantaneous copolymer composition, cannot be described by the low conversion values of the monomer reactivity ratios r 1 and r2. These findings are discussed within the framework of possible effects of monomer diffusion rates and explicit penultimate unit effects in connection with monomer composition drift.

show abstract

The study of the copolymerization of styrene and acrylonitrile to high conversion. application of low conversion reactivity ratios

Cited by 18 publications

References 20 publications

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

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

Monomer reactivity ratios for lauryl methacrylate–isobutyl methacrylate in bulk free radical copolymerization

Instantaneous Copolymer Composition in High Conversion Copolymerization of Acrylonitrile and Methyl Acrylate Assessed by in Situ ¹³C NMR Measurements of Individual Monomer Reaction Rates

Contact Info

Product

Resources

About

The study of the copolymerization of styrene and acrylonitrile to high conversion. application of low conversion reactivity ratios

Cited by 18 publications

References 20 publications

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

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

Monomer reactivity ratios for lauryl methacrylate–isobutyl methacrylate in bulk free radical copolymerization

Instantaneous Copolymer Composition in High Conversion Copolymerization of Acrylonitrile and Methyl Acrylate Assessed by in Situ 13C NMR Measurements of Individual Monomer Reaction Rates

Contact Info

Product

Resources

About

Instantaneous Copolymer Composition in High Conversion Copolymerization of Acrylonitrile and Methyl Acrylate Assessed by in Situ ¹³C NMR Measurements of Individual Monomer Reaction Rates