Primary radical termination and unimolecular termination in the heterogeneous polymerization of acrylamide initiated by a fluorinated azo-derivative initiator: A kinetic study

Lebreton, Pierre; Boutevin, Bernard

doi:10.1002/(sici)1099-0518(20000515)38:10<1834::aid-pola690>3.0.co;2-j

Cited by 10 publications

(11 citation statements)

References 35 publications

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“…It is noteworthy that the k prt / k i k p values of the acrylamide/ACVA38 and FATRIFE/TBCPC systems are very close. Thus, it can be supposed on the one hand that the k p value of acrylamide39 is higher than that of α‐fluoroacrylic monomers7 by a factor of ten or more in the temperature range 70–80 °C.…”

Section: Resultsmentioning

confidence: 86%

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Evaluation of the termination mode in the radical polymerization of 2,2,2‐trifluoroethyl α‐fluoroacrylate

Alric

David

Boutevin

et al. 2002

Polymer International

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The mode of termination of 2,2,2-tri¯uoroethyl a-¯uoroacrylate (FATRIFE) in radical polymerization was studied, and only termination by recombination occurred, which led to telechelic macromolecular structures. The radical polymerization in acetonitrile was carried out to synthesize oligomers with a low number average degree of polymerization (DP n ) cum (about 20), using tertbutylcyclohexyl peroxydicarbonate (TBCPC) as initiator at 75°C. The initial [TBCPC] 0 /[FATRIFE] 0 molar ratio was monitored to evaluate its in¯uence on the (DP n ) cum of a-¯uoroacrylic oligomers. The 1 H NMR analysis of the polymers showed that the (DP n ) cum values obtained were higher than 40, in spite of a high C 0 value. To explain these results, the mode of termination was evaluated using the following kinetic law: R pi % I 2 0:27 0 M 1:24 0 . The development of kinetic relationships allowed us to calculate the ratio k prt /k i . k p as about 17±30 mol s l À1 , and to con®rm that primary radical termination (PRT) was in competition with bimolecular macromolecular termination (BMT).

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Section: Resultsmentioning

confidence: 86%

“…Nevertheless, Lebreton and Boutevin38 demonstrated that the rate of polymerization was $\def\ex{\hbox{ }} R_{\rm pi}\approx [\hbox{ACVA}]_{0}^{0.29}[\hbox{acrylamide}]_{0}^{1.95}$ . These results have been interpreted in light of the contribution of PRT, and a very high amount of telechelic polyacrylamide (88% for C 0 = 0.1) was also obtained.…”

Section: Resultsmentioning

confidence: 99%

Evaluation of the termination mode in the radical polymerization of 2,2,2‐trifluoroethyl α‐fluoroacrylate

Alric

David

Boutevin

et al. 2002

Polymer International

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“…Polymerization reactions of monomers such as MMA and acrylamide end by termination by a disproportionation mechanism, and the consequent materials are mainly composed of diblock structures, rather than triblocks. However, the utilization of high initiator concentrations can direct reactions toward termination by a combination mechanism 26–30. Boutevin et al29 successfully showed that the utilization of high initiator concentrations leads to termination by combination even for polymerizations of monomers that do terminate by a disproportionation mechanism under ordinary conditions.…”

Section: Resultsmentioning

confidence: 99%

Synthesis of fluorinated oligomers for supercritical carbon dioxide applications

Bilgin

Baysal

Menceloǵlu

2005

J. Polym. Sci. A Polym. Chem.

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Syntheses of various fluorine-based surfactants, namely fluorinated-segment-containing block co-oligomers, were achieved by the radical polymerization of mainly acrylate-based monomers. These types of surfactants serve as stabilizers for supercritical carbon dioxide (scCO 2 ) media based applications, for which the effective solubilization of materials in the supercritical phase is generally not possible because of solubility problems faced when CO 2 is involved. Initially, a difunctional fluorinated initiator was synthesized in two steps. First, 4,4 0 -azobis-4-cyanovaleric acid was chlorinated with SOCl 2 , and then the product, 4,4 0 -azobis-4-cyanovaleryl chloride, was reacted with a fluorinated alcohol to obtain the initiator for the polymerization reactions. The synthesized triblock co-oligomers consisted of fluorinated side blocks and a hydrocarbon intermediate block. Efficient solubilization of the materials in scCO 2 was observed. It was experimentally shown that the solubility efficiency was affected by specific interactions between CO 2 and the oligomers, and these were determined by the nature and size of the inner block and by the chain length of the fluorinated side blocks in comparison with the inner block. V V C 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5312-5322, 2005

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“…Some researchers10–14 have characterized the dependence of the initial initiator concentration on the polymerization rate and PRT. Then the rate constant of PRT ( k PRT ) and especially the determination of the k PRT / k i · k p ratio were subjected to several studies 15–18…”

Section: Introductionmentioning

confidence: 99%

Determination of the cumulative degree of polymerization for the dead‐end polymerization of styrene

David

Boutevin

Robin

2002

J. Polym. Sci. A Polym. Chem.

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This article explores the use of a new relation correcting theoretical (DPn) with experimental values obtained in the dead-end polymerization of styrene with azocompound. The syntheses were realized for several starting initiator-to-monomer ratios (C 0 's); values comprised between 10 and 0.1%, and the experimental (DPn) were obtained by size exclusion chromatography. Concerning the theoretical (DPn), a new relation is proposed considering the loss of initiating radicals [I ⅐ ] used in primary termination and both stationary states of I ⅐ and M ⅐ (macromolecular radicals) introduced as Bamford. Finally, (DPn) cum , previously defined by us, is introduced to consider the monomer conversion during oligomerization. Our relation fit very well in a large range of C 0 's, contrary to the application of the usual Mayo rule, and a discussion of validity is proposed. Our model also allows the prediction of (DPn) cum in a large range of telechelic oligomers from 10 to 150.

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Primary radical termination and unimolecular termination in the heterogeneous polymerization of acrylamide initiated by a fluorinated azo-derivative initiator: A kinetic study

Cited by 10 publications

References 35 publications

Evaluation of the termination mode in the radical polymerization of 2,2,2‐trifluoroethyl α‐fluoroacrylate

Evaluation of the termination mode in the radical polymerization of 2,2,2‐trifluoroethyl α‐fluoroacrylate

Synthesis of fluorinated oligomers for supercritical carbon dioxide applications

Determination of the cumulative degree of polymerization for the dead‐end polymerization of styrene

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