Calorimetric investigation of polymerization reactions. I. Diffusion‐controlled polymerization of methyl methacrylate and styrene

Horie, Kazuyuki; Mita, Itaru; Kambe, Hirotaro

doi:10.1002/pol.1968.150060921

Cited by 175 publications

(66 citation statements)

References 30 publications

(2 reference statements)

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“…In this communication the model is applied to the bulk polymerization of styrene by the free radical mechanism. From free volume theory (4,5,6), the glass transition temperature,…”

mentioning

confidence: 99%

Transformation of liquid to amorphous solid: The time to vitrify for styrene polymerization

Aronhime

Gillham

1984

J of Applied Polymer Sci

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A model is presented for the calculation of the time to vitrify vs. temperature for isothermal polymerization by the chain growth mechanism. The model is based on the glass transition temperature (Tg) rising from its initial value to the reaction temperature. The relationships between Tg and the volume fraction of polymer and monomer, the volume fraction of polymer and the extent of reaction, and the extent of reaction and time are also required. In a plot of temperature vs. time the vitrification curve is generally S‐shaped; the time passes through a maximum just above the glass transition temperature. The model applies to linear polymerization in which monomer and high molecular weight polymer are the dominant species, i.e., to chain reactions. In this communication the model is applied to the bulk polymerization of styrene by the free radical mechanism.

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“…In this communication the model is applied to the bulk polymerization of styrene by the free radical mechanism. From free volume theory (4,5,6), the glass transition temperature,…”

mentioning

confidence: 99%

Transformation of liquid to amorphous solid: The time to vitrify for styrene polymerization

Aronhime

Gillham

1984

J of Applied Polymer Sci

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“…Horie et a/. 17 stated that the propagation rate constant is independent of conversion when x<0.4, but decreases with further promotive polymerization, since the rate becomes diffusioncontrolled. This is consistent with the present case.…”

Section: Discussionmentioning

confidence: 99%

“…17 On making more detailed consideration, k/kP 2 at x> 0.5 must be obtained by extending the Brooks experiment, 11 and then the most probable relationship between kP and vr can be discussed. This will be carried out in the following paper.…”

Section: Discussionmentioning

confidence: 99%

Evaluation of Termination Rate by the Free Volume Thoery in Radical Polymerization

Ito

1981

Polym J

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ABSTRACT:Kinetic data on the radical polymerization of methyl methacrylate are treated in terms of termination rate equations based on Stokes law and the reptation model. The values of klk/ obtained are of initiation rate, where k corresponds to the rate constant of the diffusion-controlled reaction between segment radicals and kP is the propagation rate constant. When x (conversion) is less than 0.5, an equation as klk" 2 oc exp ( -l.liVr) (Vr, free volume) is obtained. When x>0.5, klk/ deviates from such an equation. This deviation may show that the propagation rate decreases with increasing in x, since this rate becomes diffusion-controlled.

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“…The reaction still proceeds below the T g but becomes slow and eventually stops. 14,16 In the present work, a phenomenological expression for the reaction rate is proposed. The experimental kinetic results measured in dynamic or isothermal DSC runs, with cure temperatures higher than the glass transition temperature of the reactive system, were fitted with the empirical Kamal kinetic model.…”

Section: Introductionmentioning

confidence: 99%

Curing kinetics of divinyl ester resins with styrene

Auad

Aranguren

Eliçabe

et al. 1999

J. Appl. Polym. Sci.

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ABSTRACT:The curing reaction of a divinyl ester resin with different proportions of styrene-4, 20, and 40% by weight-was investigated by differential scanning calorimetry (DSC) using isothermal and dynamic modes. The different constraints on the reaction rate was globally considered, taken the reaction as divided in two regimens: below the vitrification regimen and during the vitrification regimen. Below the vitrification regimen, the autocatalytic model developed by Kamal was used to perform the analysis of the curing kinetics of divinyl ester resin with styrene. Experimental data from dynamic and isothermic runs, at a fixed composition, were simultaneously considered, while the actual temperature records (measured during the DSC runs) were also taken into account. The adjusted kinetic parameters took into account the gel effect on the radicals' termination rate and the structure constraints on the reactivity of pendant vinyls groups, present during this stage. During the vitrification stage, the diffusion control due to the low mobility of the reactive groups and molecules was incorporated into the overall rate constant according to the Rabinowitch model, which considers the two regimen contributions to the overall reaction rate kinetic. The Vogel-Fulcher relationship was adopted to express the temperature dependence of the rate constant during the vitrification stage. The method presented here has been satisfactorily applied to dynamic and isothermal curing reactions, allowing a simple and general kinetic expression useful in the design, optimization, and control of the processing of composites based on these thermoset polymers to be obtained.

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Calorimetric investigation of polymerization reactions. I. Diffusion‐controlled polymerization of methyl methacrylate and styrene

Cited by 175 publications

References 30 publications

Transformation of liquid to amorphous solid: The time to vitrify for styrene polymerization

Transformation of liquid to amorphous solid: The time to vitrify for styrene polymerization

Evaluation of Termination Rate by the Free Volume Thoery in Radical Polymerization

Curing kinetics of divinyl ester resins with styrene

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