Glass Transition Temperature Calculations for Styrene Derivatives Using the Energy, Volume, and Mass Model

Camelio, Philippe; Lazzeri, Véronique; Waegell, B.; Cypcar, Christopher C.; Mathias, Lon J.

doi:10.1021/ma970983t

Cited by 31 publications

(37 citation statements)

References 19 publications

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“…The results of the copolymerization are summarized in Table I. The copolymers with a high molecular weight (M n ¼ 2{14 Â 10 4 ) were obtained in yields of 54-83% during the copolymerization at 30 C for 5 h. The copolymers isolated after reprecipitation were a colorless powder, except for poly(4-alt-IB) which was pale brown. The alternating repeating structure of the copolymers was confirmed by 1 H NMR spectroscopy (Figure 1), similar to the results for the copolymerization of N-alkyl-and N-(alkyl-substituted phenyl)maleimides with IB.…”

Section: Resultsmentioning

confidence: 99%

“…For example, higher T g values were reported for the vinyl polymers containing any substituent near the main chain, such as the 2-position of a phenyl or cycloalkyl group in the side chain. [28][29][30] Considering a steric factor, poly(2-alt-IB) was expected to show the highest T g value due to the steric hindrance, but actually this was not true. In a previous paper, 18 the T g values of poly(XPhMI-alt-IB) containing 2-methyl and 2,6-dimethyl substituents in the Nphenyl group were reported to be 207 and 237 C, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…Finally the ampoule was sealed. After polymerization at 30 C for 5 h, the polymerization mixture was poured into a large amount of methanol or diethyl ether to precipitate the resulting poly(1-alt-IB) and the other poly(XPhMI-alt-IB)s, respectively. The copolymer was filtered, washed, and then dried in vacuo.…”

Section: Polymerizationmentioning

confidence: 99%

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Thermal Properties of N-Phenylmaleimide-Isobutene Alternating Copolymers Containing Polar Groups to Form Intermolecular and Intramolecular Hydrogen Bonding

Omayu

Matsumoto

2008

Polym J

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We have demonstrated that the alternating copolymers obtained from N-phenylmaleimides having hydroxy and carboxy substituents and isobutene show excellent thermal stabilities; namely, onset temperatures of decomposition higher than 350 C and glass transition temperatures higher than 220 C, depending on the structure and position of the polar groups in the N-phenyl group. The obtained copolymers were soluble in organic solvents, such as dimethyl sulfoxide, dimethylformamide, tetrahydrofuran, and acetone, and transparent and brittle films were obtained by casting from their acetone solutions. The role of intermolecular hydrogen bonding for an increase in the glass transition temperature by the introduction of the polar groups was investigated by temperature-controlled IR spectroscopy. The formation of intramolecular hydrogen bonding for the N-2-hydroxyphenyl derivative was also revealed. The molecular conformations were discussed on the basis of the results of DFT calculations for the model compounds of the repeating unit in the copolymers. Recently, new thermo-resistant polymers with a high transparency attract a great interest as key materials for optoelectronic applications. The radical polymerization and copolymerization of N-phenylmaleimide (PhMI, 1) and the thermal properties of the resulting polymers have been extensively studied in order to obtain thermally stable vinyl polymers.1-3 At the same time, various kinds of PhMI derivatives have also been synthesized and polymerized. [4][5][6][7][8][9][10][11][12] When alkyl substituents were introduced in the N-phenyl group, the polymers were soluble in non-polar solvents and showed an excellent thermal decomposition property, while poly(1) was soluble in limited kinds of polar solvents. 13,14 On the other hand, the introduction of polar substituents resulted in the formation of polymers with poor solubility. For example, thermally stable polymers were synthesized by the polymerization of N-(hydroxyphenyl)-, N-(carboxyphenyl)-, and N-(trifluoromethylphenyl)maleimides, but they were insoluble or had a very limited solubility in solvents. 4,[15][16][17] In 1996, Doi and coworkers reported that the alternating copolymerization of N-alkylmaleimides (RMI) with isobutene (IB) [poly(RMI-alt-IB)] produces high molecular weight copolymers with excellent thermal properties, as well as excellent mechanical and optical properties.18-21 Poly(RMI-alt-IB)s are soluble in a larger number of organic solvents and had a moderate softening temperature. The processing of poly-(RMI-alt-IB)s can be easily carried out for the fabrication of polymer films, sheets, and molded products. Recently, we synthesized the alternating copolymers of RMIs containing a functional group, such as hydroxy and carboxy groups, combined with IB, and revealed the role of the intermolecular hydrogen bond of the functional groups in the thermal properties of the obtained copolymers. 22 We demonstrated that poly(RMI-alt-IB)s containing hydroxy and carboxy groups showed high glass transition temperature (T g )...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Thermal Properties of N-Phenylmaleimide-Isobutene Alternating Copolymers Containing Polar Groups to Form Intermolecular and Intramolecular Hydrogen Bonding

Omayu

Matsumoto

2008

Polym J

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“…For comparison, we also applied group contribution method to predict T g of PIs [13]. This method is based on the contribution of each functional group to thermodynamic properties of polymeric materials, and it has been widely used in alkyl polymers [23,24]. However, in this study, the T g values of two PIs are the same using this method for it can not resolve the position effect of the imide group.…”

Section: Glass Transition Temperaturementioning

confidence: 99%

Molecular dynamics simulation on glass transition temperature of isomeric polyimide

Li¹,

Liu²,

Qin³

et al. 2009

Express Polym. Lett.

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It is an abnormal phenomenon that glass transition temperature (Tg) of isomeric polyimide (PI) is higher than its corresponding symmetrical PI. To illustrate this phenomenon at the molecular scale, we applied molecular dynamics method to predict the Tg of PI, which were prepared based on 4,4’-oxydianiline (ODA) and 3,3’,4,4’-biphenyltetracarboxylic dianhydride (3,3’,4,4’-BPDA), and its isomeric system (2,2’,3,3’-BPDA-ODA). Simulation result is consistent with experimental value. Non-bond energy plays an important role in glass transition process, for it has an abrupt change near Tg. The higher free volume fraction of isomeric PI can provide the polymer with more space to obtain segmental motion. However, from the torsion angle distribution calculations, it is shown that the torsion angle of its biphenyl group is constrained. Furthermore, from mean square displacement and vector autocorrelation functions calculations, this group is observed to rotate against other groups in the glassy state, and increases the chain rigidity to a great extent. So the isomeric PI needs much more relaxation time for the segment motion. Therefore, the higher Tg of isomeric PI is mainly attributed to the chain rigidity for the time scale, not the free volume for the space scale

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“…La Jusqu'à présent, les coefficients A, B et C du modèle avaient été estimés par régression linéaire multiple (MLR) pour une famille de polymères donnée (polyacrylates [6,7] ou polystyrènes [7][8][9]). Connaissant, pour cette famille de composés qui constitue notre matrice d'expériences (ξ N ), les réponses expérimentales (Y), nous pouvons déterminer, à partir de la matrice du modèle (X), les estimateurs des coefficients du modèle (B) (Fig.…”

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Experimental research methodology for a model of glass transition temperature for acrylates and methacrylates

Camelio¹,

Campisi²,

Carro-Diaz³

et al. 1998

Analusis

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Depuis de nombreuses années, le laboratoire de Stéréochimie travaille au développement de monomères acryliques originaux [1-2] afin d'améliorer les propriétés de matériaux déjà existants en utilisant ces monomères comme comonomères ou bien en développant de nouveaux matériaux sur la base de ces monomères. Un des problèmes majeurs dans ce type de recherche est que l'on ne connaît pas à l'avance les propriétés macroscopiques des matériaux que l'on obtient à partir des monomères. Pour obtenir un polymère, il faut dans un premier temps synthé-tiser le monomère, puis le polymériser et enfin, on caracté-rise les matériaux obtenus. Si les propriétés recherchées sont obtenues, on peut passer à une phase de développement, sinon, il faut recommencer en modifiant la structure du monomère. Cette approche est lente car elle repose sur un processus itératif d'essais-erreurs. De plus, elle dépend essentiellement de l'expérience de l'homme de l'art et de son imagination. Pour rationaliser ce travail, l'utilisation d'un modèle pour une ou plusieurs propriétés basées sur la structure du monomère est d'une grande importance car on peut estimer la (les) propriété(s) rapidement d'un grand nombre de molécules en s'affranchissant dans un premier temps des problèmes liés à l'expérience. L'homme de l'art consacrera alors ses efforts sur les molécules qui présentent un intérêt potentiel au regard des résultats du modèle. C'est une démarche appliquée depuis un certain nombre d'années en chimie pharmaceutique ou en agrochimie (pesticides, fongicides, …) et qui tend à se développer en chimie des polymères.C'est dans ce but que nous avons développé un modèle de prédiction de la température de transition vitreuse, T g , pour les polymères acryliques et méthacryliques : le modèle EVM (pour Énergie, Volume et Masse) [3][4][5][6][7]. La Jusqu'à présent, les coefficients A, B et C du modèle avaient été estimés par régression linéaire multiple (MLR) pour une famille de polymères donnée (polyacrylates [6,7] ou polystyrènes [7][8][9]). Connaissant, pour cette famille de composés qui constitue notre matrice d'expériences (ξ N ), les réponses expérimentales (Y), nous pouvons déterminer, à partir de la matrice du modèle (X), les estimateurs des coefficients du modèle (B) (Fig. 1).Une série de tests statistiques permet ensuite de voir quels sont les niveaux de signification des résultats obtenus par l'Analyse de la Variance et avec le test de Student t sur les coefficients). C'est la démarche a posteriori. Ce modèle donnait pleinement satisfaction, au regard des informations D-optimal design has been used for constructing a experimental database required to set up a high quality model. We show that using a priori statistics criteria (i.e., before making the experiences) it is possible to select the minimum number of molecules required to set up the database. Using the same tools, and the previous results, it is possible to evaluate the quality of the predicted value for a set of new candidates and decide whether or not they have to be taken into account...

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Glass Transition Temperature Calculations for Styrene Derivatives Using the Energy, Volume, and Mass Model

Cited by 31 publications

References 19 publications

Thermal Properties of N-Phenylmaleimide-Isobutene Alternating Copolymers Containing Polar Groups to Form Intermolecular and Intramolecular Hydrogen Bonding

Thermal Properties of N-Phenylmaleimide-Isobutene Alternating Copolymers Containing Polar Groups to Form Intermolecular and Intramolecular Hydrogen Bonding

Molecular dynamics simulation on glass transition temperature of isomeric polyimide

Experimental research methodology for a model of glass transition temperature for acrylates and methacrylates

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