Temperature dependence of stereospecificity in the radical polymerization of di-n-butyl itaconate in bulk

Hirano, Tomohiro; Tateiwa, Sachiko; Seno, Makiko; Sato, Tsuneyuki

doi:10.1002/1099-0518(20000701)38:13<2487::aid-pola200>3.0.co;2-l

Cited by 20 publications

(14 citation statements)

References 14 publications

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“…However, it also should also be noted that there has been a detailed study of DBI free radical polymerization with regard to possible backbiting and transfer to polymer reactions in these systems. 40 Within this study it has been shown that the stereochemistry of the generated pDBI depends on the polymerization temperature. Polymers with a wide range of tacticities, from syndiotactic to isotactic-rich, can be obtained, which has been demonstrated by 13 C NMR spectroscopy.…”

Section: Effect Of Depropagation On the Resulting Molecular Weight DImentioning

confidence: 99%

Depropagation Kinetics of Sterically Demanding Monomers: A Pulsed Laser Size Exclusion Chromatography Study

et al. 2005

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Conventional pulsed laser polymerization coupled with size exclusion chromatography (PLP-SEC) as well as multipulse pulsed laser polymerization has been employed to study the depropagation kinetics of the sterically demanding 1,1-disubstituted monomers dicyclohexyl itaconate (DCHI), dibutyl itaconate (DBI), and dimethyl itaconate (DMI). The effective rate coefficient of propagation, k p eff , was determined in bulk and solution of cyclohexanone (DCHI) and N-methylformamide (DMI) for monomer concentrations between 1.5 < c M 0 < 7.1 mol L -1 in the temperature range 0 < T < 90°C. The resulting Arrhenius plots (i.e., ln kp eff vs 1/RT) displayed a significant curvature in the higher temperature regimes and were analyzed in their respective linear parts to yield the activation parameters of the forward reaction. In the temperature region where no depropagation was observed, the following set of Arrhenius parameters for k p were obtained for the bulk systems: DCHI (Ep ) 26.5 kJ mol -1 , ln Ap/L mol -1 s -1 ) 11.5), DBI (Ep ) 21.3 kJ mol -1 , ln Ap/L mol -1 s -1 ) 10.4), DMI (Ep ) 27.8 kJ mol -1 , ln Ap/L mol -1 s -1 ) 13.5). In addition, the kp eff data were analyzed in the depropagation regime for DCHI, resulting in estimates for the associated enthalpy and entropy (∆H ) -53.5 kJ mol -1 and ∆S ) -142.3 J mol -1 K -1 ) of polymerization. The value for the heat of polymerization was independently measured via on-line differential scanning calorimetry (DSC) as well (∆H ) -55.0 kJ mol -1 ). ∆H of DBI and DMI were also determined via DSC or are available in the literature (∆H ) -42.0 and -60.5 kJ mol -1 ). These numbers were used to determine the respective entropies of polymerization for both monomers (∆S ) -110 and -156 J mol -1 K -1 ) by a fitting procedure of the kp eff data. DBI polymerization displays significantly different activation parameters as well as thermodynamic properties in comparison with the corresponding DCHI and DMI polymerizations. With decreasing monomer concentration, it is increasingly more difficult to obtain well-structured molecular weight distributions. The DCHI system displayed a significant reduction in k p eff with increasing cyclohexanone concentration.

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Section: Effect Of Depropagation On the Resulting Molecular Weight DImentioning

confidence: 99%

Depropagation Kinetics of Sterically Demanding Monomers: A Pulsed Laser Size Exclusion Chromatography Study

et al. 2005

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“…271 Generally, 1,2-disubstituted olefins exhibit little or no tendency to undergo homopolymerizations due to their steric inhibition. However, fumaric acid diesters (BM-55) with bulky alkyl substituents were radically homopolymerized to form poly(methylene) derivatives.…”

Section: Polymerization Of Bulky Monomersmentioning

confidence: 99%

Stereospecific Living Radical Polymerization: Dual Control of Chain Length and Tacticity for Precision Polymer Synthesis

2009

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“…[ 369 ] Sato and co‐workers then extended these investigations to dibutyl itaconate (DBI), and studied the influence of the temperature of radical polymerization on stereospecificity. [ 370 ] Isotactic‐enriched polymers were obtained at elevated temperatures (60% of mm triads at 120 °C) while a syndiotactic character was observed at low temperatures (80% of rr triads at −78 °C), as is observed for MMA. It is important to point out here that no successful anionic polymerization of itaconates has been performed so far, owing to the acidity of the methylene protons (the same protons that increase the transfer to the monomer in radical polymerization).…”

Section: Polymerization Of (Meth)acrylic Monomers and Analogsmentioning

confidence: 68%

Production and Polymerization of Biobased Acrylates and Analogs

Fouilloux

Thomas

2021

Macromol. Rapid Commun.

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To prepare biobased polymers, particular attention must be paid to the obtention of the monomers from which they are derived. (Meth)acrylates and their analogs constitute such a class of monomers that have been extensively studied due to the wide range of polymers accessible from them. This review therefore aims to highlight the progresses made in the production and polymerization of (meth)acrylates and their analogs. Acrylic acid production from biomass is close to commercialization, as three different high‐potential intermediates are identified: glycerol, lactic acid, and 3‐hydroxypropionic acid. Biobased methacrylic acid is less common, but several promising options are available, such as the decarboxylation of itaconic acid or the dehydration of 2‐hydroxyisobutyric acid. Itaconic acid is also a vinylic monomer of great interest, and polymers derived from it have already found commercial applications. Methylene butyrolactones are promising monomers, obtained from bioresources via three different intermediates: levulinic, succinic, or itaconic acid. Although expensive, methylene butyrolactones have a strong potential for the production of high‐performance polymers. Finally, β‐substituted acrylic monomers, such as cinnamic, fumaric, muconic, or crotonic acid, are also examined, as they provide an original access to biobased materials from various renewable raw materials, such as protein waste, lignin, or wastewater.

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Temperature dependence of stereospecificity in the radical polymerization of di-n-butyl itaconate in bulk

Cited by 20 publications

References 14 publications

Depropagation Kinetics of Sterically Demanding Monomers: A Pulsed Laser Size Exclusion Chromatography Study

Depropagation Kinetics of Sterically Demanding Monomers: A Pulsed Laser Size Exclusion Chromatography Study

Stereospecific Living Radical Polymerization: Dual Control of Chain Length and Tacticity for Precision Polymer Synthesis

Production and Polymerization of Biobased Acrylates and Analogs

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