Fluorescence Probe Techniques (FPT) for Measuring the Relative Efficiencies of Free-Radical Photoinitiators

Hu, Shengkui; Popielarz, Roman; Neckers, Douglas C.

doi:10.1021/ma971390l

Cited by 43 publications

(39 citation statements)

References 14 publications

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“…14 Fluorescence probe techniques (FPT) have been recently introduced to measure and compare photoinitiator efficiencies. 12,13,15,16 FPT allow one to measure the polymerization kinetics from relative conversion data collected during the polymerization of systems that are similar. These methods are particularly useful for the evaluation of initiators that are similar in structure and for optimizing their performance.…”

Section: Introductionmentioning

confidence: 99%

Relative Activity of Possible Initiating Species Produced from Photolysis of Tetraphenyl and Triphenylbutyl Borates As Measured by Fluorescence Probe Techniques

et al. 1998

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Fluorescence probe techniques (FPT) have been used to obtain curing profiles for the polymerization of a model monomer, triethylene glycol diacrylate (TEGDA). A number of new chromophore ammonium salt triphenylbutyl and tetraphenylborates differing only in the structure of the ammonium salt moiety have been used as photoinitiators. The borates were chosen for study so that a comparison of their initiation efficiency would reveal information about the relative activity of possible initiating species produced upon borate photodecomposition. The results support our previous postulate that an R-aminoalkyl radical formed immediately after unimolecular decomposition from the tetraphenylborates is the most effective initiating species and that R-aminoalkyl radicals significantly increase the photoinitiator efficiency of triphenylbutylborates as well. The importance of other radicals to the initiation step is also discussed. IntroductionThe photochemistry of tetrasubstituted borate salts has attracted substantial recent research interest. [2][3][4][5][6][7][8] Triphenylbutylborates have been studied most extensively, and the butyl radical formed when they are oxidized has been found to be the dominant initiating species for radical polymerization. 3,7-10 Interestingly, tetraphenylborates paired with a similar cationic partner have been observed to have similar initiating efficiencies. 11-13 Tetraphenylborates, when oxidized, are often prone to back electron transfer. Since phenyl radicals are produced from tetraphenylborates upon oxidation inefficiently, if at all, we have surmised that other initiating species must account for the efficiency of tetraarylborate salts. In our most recent work R-aminoalkyl, phenyl, and p-benzoylbenzyl radicals were trapped by methyl methacrylate when benzophenonemethylenetributylammonium triphenylbutylborate was photolyzed in its presence in solution. 14 Fluorescence probe techniques (FPT) have been recently introduced to measure and compare photoinitiator efficiencies. 12,13,15,16 FPT allow one to measure the polymerization kinetics from relative conversion data collected during the polymerization of systems that are similar. These methods are particularly useful for the evaluation of initiators that are similar in structure and for optimizing their performance. The possibility of collecting data over short time intervals (<1 s) makes the analysis simple and accurate. Several borates differing in the ammonium salt but possessing benzophenone and acetonaphthone chromophores have been chosen for the current work.

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Section: Introductionmentioning

confidence: 99%

Relative Activity of Possible Initiating Species Produced from Photolysis of Tetraphenyl and Triphenylbutyl Borates As Measured by Fluorescence Probe Techniques

et al. 1998

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“…Paczkowski and Neckers354 and Hu et al355 were among the first to show that the fluorescent probe technique was a successful tool to monitor polymerization processes in real‐time. They followed the kinetics of polymerization and post‐irradiation of multifunctional acrylates in real‐time and determined relative initiation efficiencies of photoinitiators.…”

Section: On‐line Sensors For Polymer Property Trajectory Monitoringmentioning

confidence: 99%

A Critical Overview of Sensors for Monitoring Polymerizations

Fonseca

Dubé

Penlidis

2009

Macro Reaction Engineering

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The available on‐line and in‐line sensor technologies developed for polymerization reactors from 1990 until today are discussed and critically reviewed. About 600 references are included, which evidence the growth in sensor technology in the last two decades. Sensors for operational parameters in polymer reactors (i.e. temperature, pressure, level and flow) as well as sensors for polymer property monitoring (i.e. calorimetry, chromatography and spectroscopy, among others) are included. Complementary topics such as state estimation, multivariate statistical methods, fault diagnosis techniques and optimal sensor selection and location are briefly covered.

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“…Among the methods adaptable for monitoring progress of fast chemical processes, fluorescence spectroscopy meets the requirements of speed and robustness. In particular, the method based on fluorescent molecular probes, called Fluorescence Probe Technique, or just "FPT" has been developed and implemented [13,14]. In the FPT method, single molecules are used as sensors of changes occurring in their environment, while photons are used to transfer the information from the molecules to an appropriate detector.…”

Section: Introductionmentioning

confidence: 99%

Applicability of quinolizino-coumarins for monitoring free radical photopolymerization by fluorescence spectroscopy

2015

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Fluorescence Probe Techniques (FPT) for Measuring the Relative Efficiencies of Free-Radical Photoinitiators

Cited by 43 publications

References 14 publications

Relative Activity of Possible Initiating Species Produced from Photolysis of Tetraphenyl and Triphenylbutyl Borates As Measured by Fluorescence Probe Techniques

Relative Activity of Possible Initiating Species Produced from Photolysis of Tetraphenyl and Triphenylbutyl Borates As Measured by Fluorescence Probe Techniques

A Critical Overview of Sensors for Monitoring Polymerizations

Applicability of quinolizino-coumarins for monitoring free radical photopolymerization by fluorescence spectroscopy

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