Bulk polymerization of styrene catalyzed by bi- and trifunctional cyclic initiators

Cerna, J. R.; Morales, G.; Eyler, Gladys N.; Cañizo, Adriana I.

doi:10.1002/app.2225.abs

Cited by 27 publications

(55 citation statements)

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“…cyclic diperoxide derived from 3, 3-dimethyl-2-butanone (pinacolone) decomposes in different solvents at higher rates than ACDP. 2,8,11 The presence of deuterium in dACDP and the kinetic behavior shown allow postulating a KIE. The relation between kinetic constants that are greater than 1 (k H /k D > 1) is referred to as normal KIE, while those that are less than one is referred to as inverse KIE (k H /k D <1).…”

Section: Kinetic Analysismentioning

confidence: 99%

“…In aromatic or aliphatic solvents with low polarity (toluene, benzene and n-octane), the rate constant values are smaller 2,8,9 . The trend demonstrates that an increase in the solvent polarity is accompanied by an increase in the reaction rate as a consequence of a reaction mechanism involving a more dipolar-activated complex than the diperoxide initial molecule, which could be stabilized by polar solvents.…”

Section: Kinetic Analysismentioning

confidence: 99%

“…On the other hand, substituent effects on the rate constant and on the activation parameters of cyclic organic peroxides have been analyzed and discussed in previous works. 2,10 The corresponding rate constant values of ACDP thermal decomposition reaction are shown in Table 4, where some data obtained in a previous work were included. The alcohols in Table 4 may be classified as primary and secondary, and in that sense the results have shown that the reaction is accelerated in the secondary ones, probably because 2-propanol interacts more with the ACDP molecule favoring the biradical formation.…”

Section: Kinetic Analysismentioning

confidence: 99%

“…Additionally, different results related with new synthetic methods or alternative techniques that involve greater yields of peroxide compound in a shorter preparation time were reported. [1][2][3][4][5] Peroxides are shock sensitive and their overall decompositions are exothermic so that special handling precautions must be taken. Depending on the molecular group linked on the peroxide ring, their decomposition may be explosive in different degrees.…”

Section: Introductionmentioning

confidence: 99%

“…This behavior allows to obtain polymers with high molecular weights, in a lower polymerization time and with improved mechanical properties than those obtained with mono-or bifunctional classic initiators. 2,7 In previous works, it was demonstrated that an important substituent effect is operative on kinetic and activation parameters of the thermal decomposition reaction of substituted tetraoxacyclohexanes derived from acetone, pinacolone, 4-heptanone, benzophenone, dibenzylketone, cyclohexanone or acetophenone in different organic solvents. 3,[8][9][10][11] It has been widely published that the rate-determining step of the thermal decomposition reaction of the cyclic peroxides is the biradical intermediate formation (Eq.…”

Section: Introductionmentioning

confidence: 99%

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Thermal decomposition reaction in ethanol solution of deuterated acetone cyclic diperoxide and acetone diperoxide. Secondary inverse isotopic effect

Nesprías¹,

Eyler²,

Cañizo³

et al. 2017

Quim. Nova

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The characterization by mass spectrometry and the kinetic study of the thermal decomposition reaction of deuterated acetone diperoxide (dACDP) was studied in ethanol in the 140-165 °C temperature range. The comparison with the non deuterated species (ACDP) was also made. The kinetic behavior observed for both compounds follows a pseudo first order kinetic law up to at least 86 % peroxide conversions. It could be observed that under the established experimental conditions, the dACDP decomposes ca. 1.2 times faster than the ACDP. The activation parameters were calculated for both peroxides and allowed to postulate a single process initial step, the unimolecular thermal decomposition through the O-O bond cleavage to form an intermediate biradical. The products of the acetone derived peroxides thermal decomposition support a radical-based decomposition mechanism. The changes in kinetic parameters between dACDP and ACDP were justified attending to differences in ring substituents sizes. A secondary inverse kinetic isotope effect is observed (k H /k D <1).

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Section: Kinetic Analysismentioning

confidence: 99%

Section: Kinetic Analysismentioning

confidence: 99%

Section: Kinetic Analysismentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Thermal decomposition reaction in ethanol solution of deuterated acetone cyclic diperoxide and acetone diperoxide. Secondary inverse isotopic effect

Nesprías¹,

Eyler²,

Cañizo³

et al. 2017

Quim. Nova

View full text Add to dashboard Cite

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Synthetic, Crystallographic, and Computational Studies of Extensively Hydrogen Bonded Bilayers in Thermally Stable Adamantane Hydroperoxides

et al. 2016

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The use of moleculari odine as ah eterogeneous catalyst for the peroxidation of adamantan-2-one with 30 % H 2 O 2 resulted in an unexpected hydroperoxydiadamantyl peroxide and oxahomoadamantan-5-one,i na ddition to the expected adamantanylb ishydroperoxide. The crystal structures of both the hydroperoxides are reported for the first time. Crystallographic studies revealed that thesep eroxides are stabilized by extensive intra-and intermolecular hydrogen bonds, which are combined in hydrogen-bonded double layers. These bilayers envelop the hydrophilic interiors consisting of sensitivep eroxy groups with the outer surface covered by hydrophobic adamantane groups. The bilay-ers are held together by weak van der Waals interactions at the layer boundary,w hichf urther enhances the thermal stability.T hermal studies demonstrate the remarkable stability of crystalline hydroperoxides at room temperature. Ac omputational study rationalizes the stability of these peroxides. NCI (non-covalent interactions) plots help to decipher the nature of the interaction between the adamantane units as stabilizing dispersion contacts. QTAIM (quantum theory of atoms in molecules) topological analysisa lso indicates the presence of strong intermolecular hydrogen bonds along with anumber of weak dihydrogenc ontacts. Results and DiscussionAdamant-2-one was chosen as an appropriate precursor for the presenti nvestigation because the higher molecular weight[a] C.

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Analysis of the influence of glycidyl methacrylate on molecular weight and refractive index in styrene‐methylmethacrylate‐glycidyl methacrylate copolymers through mixture design of experiments

Cerna

Alejandro

Matla

2009

J of Applied Polymer Sci

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To analyze the influence of the percentage of glycidyl methacrylate (GMA) coupled with polymeric chains to determine their effect on molecular weight (M w ) and refractive index (n D ), a Mixture Design of Experiments (MDOE) has been used. A ''d'' optimal mixture design for four components was used for planning the runs and analyzing the information using statistical tools. The prototypes generated were synthesized using styrene (St) 73-89.98%, methylmethacrylate (MMA) 8-22%, and glydicyl methacrylate (GMA) 2-10% at different ratios according to the experiment design. In this sense, the prototypes are terpolymers (St-MMA-GMA). According to the desired properties of the prototypes reviewed in literature and market studies, this is expressed in materials with a preferred n D (ca. 1.5750-1.5894) and molecular weight (ca. 300,000 g/mol) the ratios were established. In a radical polymerization process using a commercial initiator (Trigonox 22E-50) and a temperature program (120-200 C) simulating an industrial process, the polymerization reactions were conducted. The detailed information derived from DOE here is presented.

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Bulk polymerization of styrene catalyzed by bi- and trifunctional cyclic initiators

Cited by 27 publications

References 0 publications

Thermal decomposition reaction in ethanol solution of deuterated acetone cyclic diperoxide and acetone diperoxide. Secondary inverse isotopic effect

Thermal decomposition reaction in ethanol solution of deuterated acetone cyclic diperoxide and acetone diperoxide. Secondary inverse isotopic effect

Synthetic, Crystallographic, and Computational Studies of Extensively Hydrogen Bonded Bilayers in Thermally Stable Adamantane Hydroperoxides

Analysis of the influence of glycidyl methacrylate on molecular weight and refractive index in styrene‐methylmethacrylate‐glycidyl methacrylate copolymers through mixture design of experiments

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