Vinyl Monomer Based Polyperoxides as Potential Initiators for Radical Polymerization: An Exploratory Investigation with Poly(.alpha.-methylstyrene peroxide)

Murthy, K. S. R.; Kishore, K.; Mohan, Vivek

doi:10.1021/ma00102a017

Cited by 49 publications

(36 citation statements)

References 8 publications

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“…In fact, the initiation of radical polymerizations by polymeric peroxides was investigated for poly(amethylstyrene peroxide) by Kishore and Mohan [5] before.…”

Section: Introductionmentioning

confidence: 99%

Thermal Initiation of MMA in High Temperature Radical Polymerizations

Nising

Meyer

Carloff³

et al. 2005

Macro Materials & Eng

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Summary: Several researches have dealt with the thermal initiation of methyl methacrylate (MMA) in the past. Some of them already discussed the presence of peroxide containing species that are formed from dissolved oxygen and the monomer itself as main reason for this initiation. However, a more detailed investigation as well as a kinetic description of this phenomenon is still due in literature. In this paper, the formation and decomposition of methyl methacrylate peroxides are described. MMA that has been in contact with air forms macromolecular peroxides at temperatures below 100 °C from physically dissolved oxygen. These peroxides have molecular weights of approximately 3 000–5 000 g · mol−1, depending on the temperature during formation. Above this temperature, these peroxides decompose quickly and initiate the radical polymerization. Depending on the reaction conditions, monomer conversions from 15 to 30% are obtained. In combination with additional initiators, the MMA peroxides provoke an acceleration of the reaction rate and can also lead to bimodal molecular weight distributions. An analytical method based on UV‐spectrophotometry was developed for the quantification of the peroxide content in the monomer. The kinetic rate constants for the formation were determined in batch experiments with purified, air‐saturated monomer to be kf,0 = 6.28 · 107 l2 · mol−2 · s and EA = 7.75 · 104 J · mol−1. The decomposition rate constants were determined from batch dead‐end polymerizations and found to be kd,0 = 4.73 · 107 l · mol−1 · s−1 and EA = 8.56 · 104 J · mol−1. magnified image

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“…In fact, the initiation of radical polymerizations by polymeric peroxides was investigated for poly(amethylstyrene peroxide) by Kishore and Mohan [5] before.…”

Section: Introductionmentioning

confidence: 99%

Thermal Initiation of MMA in High Temperature Radical Polymerizations

Nising

Meyer

Carloff³

et al. 2005

Macro Materials & Eng

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“…The intensity of the peak at d EXPERIMENTAL Å 037.93 ppm, however, reaches a maximum and then diminishes, whereas the intensity of the The polyperoxides (PSP, PMMAP, and PMSP) peak at d Å 23.03 ppm increases steadily with were prepared, purified, and characterized as previously reported. [5][6][7] The TPP obtained from Ferak Berlin, Germany, was used as such. Solvents like, petroleum ether, ethyl acetate, n-ethanol, etc., were purified according to the usual procedures.…”

Section: Introductionmentioning

confidence: 99%

Reaction of polyperoxides with triphenylphosphine

Jayanthi

Kishore

1997

J. Polym. Sci. A Polym. Chem.

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“…Formation of poly(styrene peroxide) (PSP) was confirmed from 1 H NMR spectroscopy in CDCl 3 , which showed resonance signals at 4.0, 5.3, and 7.2 ppm due to methylene, methine, and aromatic protons, respectively [22]. For poly(a-methylstyrene peroxide) (PAMSP), the signals were at 1.46, 4.16, and 7.2 ppm for methyl, methylene, and aromatic protons, respectively [23]. For poly(a-phenylstyrene peroxide) (PAPSP), the signals were at 4.44 and 6.87-7.25 ppm for methylene and aromatic protons, respectively [24].…”

Section: Resultsmentioning

confidence: 90%

Kinetic and thermochemical study of the oxidative polymerization of α-substituted styrenes

Pal

Ghorai

2012

Polym. Bull.

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This article reports a systematic kinetic study on the oxidative polymerization of a-substituted styrene monomers such as styrene (St), a-methylstyrene (AMS), 4-chloro a-methylstyrene (CAMS), and a-phenylstyrene (APS) in the presence of 2,2 0 -azobisisobutyronitrile as a free radical initiator at 100 psi oxygen pressure and 40-50°C in toluene. The rate of oxidative polymerization follows the order:Theoretical calculations have been performed using density functional theory to support the order of oxidative polymerization rates. In addition, the synthesis and characterization of poly(4-chloro a-methylstyrene peroxide) (PCAMSP) is reported here for the first time. Elemental analysis and nuclear magnetic resonance spectroscopy confirm the alternating copolymer structure of PCAMSP with -O-O-bonds in the main chain. Thermal degradation studies using differential scanning calorimeter and thermogravimetric analysis reveal that PCAMSP degrades highly exothermically and the average enthalpy of degradation at various heating rates is found to be 48.7 ± 0.6 kcal/mol, which is of the same order reported for other vinyl polyperoxides.

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Vinyl Monomer Based Polyperoxides as Potential Initiators for Radical Polymerization: An Exploratory Investigation with Poly(.alpha.-methylstyrene peroxide)

Cited by 49 publications

References 8 publications

Thermal Initiation of MMA in High Temperature Radical Polymerizations

Thermal Initiation of MMA in High Temperature Radical Polymerizations

Reaction of polyperoxides with triphenylphosphine

Kinetic and thermochemical study of the oxidative polymerization of α-substituted styrenes

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