Terpolymerization of acrylonitrile, styrene, and 2,3‐dibromopropyl acrylate

Sarić, Karla; Janović, Zvonimir; Vogl, Otto

doi:10.1002/pol.1983.170210704

Cited by 17 publications

(7 citation statements)

References 14 publications

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“…Many researchers [2][3][4][5][6][7][8][9][10][11][12][13] have used binary reactivity ratios (obtained from copolymerization experiments) in models dealing with terpolymerizations. Although this approximation has been successfully used in some instances (see, for example, [6][7][8]13]), it is not always accurate [2][3][4]10]. Using binary reactivity ratios to describe ternary systems effectively ignores the presence of the third comonomer, which will inevitably change the reaction conditions (and may ultimately affect the polymerization kinetics).…”

Section: Introductionmentioning

confidence: 99%

Binary vs. ternary reactivity ratios: Appropriate estimation procedures with terpolymerization data

Scott

Penlidis

2018

European Polymer Journal

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There is a widely accepted analogy between copolymerization and terpolymerization mechanisms that has allowed researchers to use reactivity ratios obtained for binary pairs (from copolymerization experiments) in models dealing with terpolymerizations. However, binary reactivity ratios are not always applicable to terpolymerization systems; using the binary-ternary analogy (even as an approximation) requires making considerable assumptions about the system.When binary reactivity ratios are used to describe ternary systems, the consequences may include substantial differences in reactivity ratio estimates, poor composition prediction performance, and incorrect determination of product (terpolymer) characteristics. Experimental results and reactivity ratio estimation (via the error-in-variables-model) for the terpolymerization of 2-acrylamido-2methylpropane sulfonic acid (AMPS), acrylamide (AAm) and acrylic acid (AAc) (and associated copolymers) are compared, all other conditions being equal.

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Section: Introductionmentioning

confidence: 99%

Binary vs. ternary reactivity ratios: Appropriate estimation procedures with terpolymerization data

Scott

Penlidis

2018

European Polymer Journal

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“…Moreover, it has been shown previously that even a pseudo‐homopolymerization approximation may be efficient in describing the kinetics of similar systems 30, 31. To confirm this, we used the Alfrey–Goldfinger equation for the calculation of unitary ( x f = x F ) and binary ( x f / x f = x F / x F ) azeotropic curves 32–34. These curves are shown in the triangular diagram in Fig.…”

Section: Resultsmentioning

confidence: 67%

“…The curves exhibit a common intercept, termed the true ternary azeotropic point,32, 33, 35 at x (MMA) = 0.385 ± 0.005, x (DDMA) = 0.59 ± 0.01 and x (ODMA) = 0.025 ± 0.015. A wide pseudo‐azeotropic region32, 34, 35 of negligible compositional heterogeneity (<5 mol%) as well as experimental monomer mixture compositions are also indicated in Fig. 11.…”

Section: Resultsmentioning

confidence: 79%

Terpolymerization kinetics of methyl methacrylate or styrene/dodecyl methacrylate/octadecyl methacrylate systems

Jukić¹,

Rogošić²,

Vidović³

et al. 2006

Polymer International

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This study describes low-conversion terpolymerization kinetic investigations of methyl methacrylate/dodecyl methacrylate/octadecyl methacrylate (MMA/DDMA/ODMA) and styrene/dodecyl methacrylate/octadecyl methacrylate (ST/DDMA/ODMA) systems. Terpolymerizations were performed isothermally (70-105• C), in 1 mol dm −3 xylene solutions, using 0.01 mol dm −3 of bifunctional peroxide initiator 1,1-di(tertbutylperoxy)-3,3,5-trimethylcyclohexane or monofunctional tert-butylperoxy-2-ethylhexanoate. Synthesized terpolymers were characterized with respect to composition and molar mass distribution. Initial polymerization reaction rates as well as terpolymer average molar masses decreased with increasing MMA or ST content in the monomer mixture, for both initiators and all investigated temperatures. Overall reaction rates were found to be significantly larger for the MMA/DDMA/ODMA system. In the MMA/DDMA/ODMA system, experimental terpolymer compositions were found to be similar to the initial monomer feed compositions -all the experimental monomer feed mixtures were close to the azeotropic composition. The Alfrey-Goldfinger terpolymerization equation was successfully used for the description of MMA/DDMA/ODMA terpolymerization kinetics, where the existence of the true azeotropic ternary point was established. The same equation did not perform as well for the ST/DDMA/ODMA terpolymerization system.

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“…Third, there are many ternary azeotropic systems with styrene. Styrene is able to produce not only true azeotropic systems but also partial azeotropes with AN and pentabromephenylacrylate when F st = f st or with AN and esters of cyanocinnamic acid . Additionally, many systems with styrene are known where the chemical composition slightly changes upon polymerization, for example, for terpolymerization with AN and tribromephenylacrylate or with MAN and methylstyrene .…”

Section: General Concept Of Living Radical Nitroxide‐mediated Terpolymentioning

confidence: 99%

Living Nitroxide‐Mediated Radical Terpolymerization: General Concept and Synthetic Possibilities

Zaremski

Plutalova

Eremeev

2016

Macro Theory & Simulations

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The general concept for nitroxide‐mediated radical terpolymerization is advanced. This concept is based on activation‐deactivation equilibria for terminal polymer‐nitroxide adducts. Depending on monomer activity and the stability of terminal nitroxide adducts, terpolymerization can be equilibrium living, quasi‐equilibrium (gradient) living, decaying living, decaying gradient, or non‐living. Expressions for the effective activation‐deactivation equilibrium constant, Kef, and the rate of terpolymerization are derived from theoretical speculations on equilibrium living and decaying living terpolymerization. For quasi‐equilibrium living terpolymerization, various types of gradient terpolymers are predicted. When activity of the active monomer M1 is, at least, one order of magnitude different from that of the two other monomers, the effective constant Kef is shown to approach K1 of the most active monomer. Experimental kinetic and equilibrium constants agree with the advanced concept for the equilibrium living terpolymerization of styrene with methyl methacrylate, and acrylonitrile in the presence of nitroxide SG1, as well as for decaying living terpolymerization in the same system in the presence of nitroxide TEMPO.

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Terpolymerization of acrylonitrile, styrene, and 2,3‐dibromopropyl acrylate

Cited by 17 publications

References 14 publications

Binary vs. ternary reactivity ratios: Appropriate estimation procedures with terpolymerization data

Binary vs. ternary reactivity ratios: Appropriate estimation procedures with terpolymerization data

Terpolymerization kinetics of methyl methacrylate or styrene/dodecyl methacrylate/octadecyl methacrylate systems

Living Nitroxide‐Mediated Radical Terpolymerization: General Concept and Synthetic Possibilities

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