Frontal Polymerization: Self-Propagating High-Temperature Synthesis of Polymeric Materials

Fortenberry, Dionne I.; Hussain, Akhtar; Ilyashenko, Victor M.

doi:10.1021/bk-1998-0681.ch019

Cited by 7 publications

(7 citation statements)

References 20 publications

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“…The extensive work from Russia was reviewed by Davtyan et al 2 Pojman and coworkers [3][4][5][6][7] investi-gated the macrokinetics and dynamics of frontal polymerization, and applications for materials synthesis were also considered. 8,9 Frontal polymerization has been used to prepare a variety of materials including thermochromic composites, 8 epoxies, 10 interpenetrating polymer networks, 6,11 functionally gradient materials, [12][13][14] and hydrogels. 15 Ring-opening metathesis chemistry has been accomplished frontally.…”

Section: Introductionmentioning

confidence: 99%

Effect of orientation on thermoset frontal polymerization

Bazile

Nichols

Volpert

2002

J. Polym. Sci. A Polym. Chem.

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We observed that the velocities of descending thermoset polymerization fronts were strongly affected by the orientation of the tube. The front remained approximately perpendicular to the gravitational vector but propagated almost 1.8 times as fast at 75° along the axis of the tube. We performed a study of the velocity and front‐shape dependence on orientation with propagating fronts of triethylene glycol dimethacrylate with peroxide initiator and acrylamide/bisacrylamide polymerization in dimethyl sulfoxide with persulfate initiator. The percentage increase of velocity was independent of the initiator concentration but strongly dependent on the viscosity. Convection under the front flowed away from the tube wall nearest the vertical axis and was stronger as the angle increased. The front shape also changed, becoming significantly distorted near the wall from which the convection originated. We applied a simple geometric argument to explain the angular dependence for small angles on the basis of the assumption that convection did not affect the velocity of propagation normal to the front. The increase in velocity along the tube axis could be explained by a projection of the normal velocity onto the tube axis, following a 1/cosθ dependence. For higher angles, the convection was not sufficiently strong to maintain a level front. When the difference from a 180° orientation was considered, the velocity dependence exactly followed the geometric relationship. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3504–3508, 2002

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Section: Introductionmentioning

confidence: 99%

Effect of orientation on thermoset frontal polymerization

Bazile

Nichols

Volpert

2002

J. Polym. Sci. A Polym. Chem.

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“…The maximum temperature, T f , reached by the front was 167 • C. In all cases, the temperature versus time plots and the reported V f values are an average of at least three runs. For comparison, the reported V f values for frontal free-radical polymerizations are typically of the order of 1 cm/min [41]. It is well known that the rates of cationic polymerization are markedly affected by temperature whereas free-radical polymerizations are less influenced by this factor [42,43].…”

Section: Use Of Optical Pyrometry To Monitor the Frontal Polymerizatimentioning

confidence: 99%

Photoactivated cationic ring-opening frontal polymerizations of oxetanes

Crivello¹,

Bulut²

2005

Designed Monomers and Polymers

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The photoinitiated cationic ring-opening polymerizations of 3,3-disubstituted oxetanes display a characteristic induction period followed by very rapid thermally accelerated polymerization. When a thin-film sample of such a monomer is irradiated for a time within the induction period and then allowed to stand at room temperature, no appreciable further conversion of monomer to polymer takes place. However, when heat is applied to a small portion of the films rapid polymerization takes place as a front, which propagates rapidly throughout the entire reaction mass. To characterize these frontal polymerizations, a new monitoring technique, employing optical pyrometry has been instituted. This method provides a simple, rapid means of following these polymerizations and quantitatively determining their frontal velocities.

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“…[7][8][9][10] Frontal polymerization was originally discovered by Chechilo and Enikolopyan in the 1970s [11][12][13][14] and then independently rediscovered by Pojman in the early 1990s. [15][16][17][18][19][20][21] Since its discovery, FP research has been extended to other areas such as deep eutectic solvents, [22][23][24][25] hydrogels, 26 ROMP, 27,28 gradient materials 29 and cationicinitiated polymerization. [30][31][32][33][34][35] Charge transfer complexes (CTCs) are a potential replacement for peroxide-based initiators and have been shown to act as dual thermal and photoinitiators.…”

Section: Introductionmentioning

confidence: 99%