Applicability of samarium(III) complexes for the role of luminescent molecular sensors for monitoring progress of photopolymerization processes and control of the thickness of polymer coatings.

Applicability of 15 trivalent samarium complexes as novel luminescent probes for monitoring progress of photopolymerization processes or thickness of polymer coatings by the Fluorescence Probe Technique (FPT) was studied. Three groups of samarium(III) complexes were evaluated in cationic photopolymerization of triethylene glycol divinyl ether monomer (TEGDVE) and free-radical photopolymerization of trimethylolpropane triacrylate (TMPTA). The complexes were the derivatives of tris(4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionate)samarium(III), tris(4,4,4-trifluoro-1-phenyl-1,3-butanedionate)samarium(III) and tris(4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedionate)samarium(III), which were further coordinated with auxiliary ligands, such as 1,10-phenanthroline, triphenylphosphine oxide, tributylphosphine oxide and trioctylphosphine oxide. It has been found that most of the complexes studied are sensitive enough to be used as luminescent probes for monitoring progress of cationic photopolymerization of vinyl ether monomers over entire range of monomer conversions. In the case of free-radical polymerization processes, the samarium(III) complexes are not sensitive enough to changes of microviscosity and/or micropolarity of the medium, so they cannot be used to monitor progress of the polymerization. However, high stability of luminescence intensity of some of these complexes under free-radical polymerization conditions makes them good candidates for application as thickness sensors for polymer coatings prepared by free-radical photopolymerization. A quantitative relationship between a coating thickness and the luminescence intensity of the samarium(III) probes has been derived and verified experimentally within a broad range of the thicknesses.

[1]  Joanna Ortyl,et al.  Performance of amidocoumarins as probes for monitoring of cationic photopolymerization of monomers by fluorescence probe technology , 2010 .

[2]  X. Allonas,et al.  Photoinitiating systems for cationic photopolymerization: Ongoing push toward long wavelengths and low light intensities , 2017 .

[3]  M. Soucek,et al.  Cure-on-command technology: A review of the current state of the art , 2016 .

[4]  J. Crivello.  The discovery and development of onium salt cationic photoinitiators , 1999 .

[5]  F. Chang,et al.  Characterization of negative-type photoresists containing polyhedral oligomeric silsesquioxane methacrylate , 2008 .

[6]  Marco Sangermano,et al.  Visible Light Curable Restorative Composites for Dental Applications Based on Epoxy Monomer , 2014, Materials.

[7]  Mariusz Galek,et al.  Aminophthalimide probes for monitoring of cationic photopolymerization by fluorescence probe technology and their effect on the polymerization kinetics , 2012 .

[8]  Joanna Ortyl,et al.  The performance of 7‐hydroxycoumarin‐3‐carbonitrile and 7‐hydroxycoumarin‐3‐carboxylic acid as fluorescent probes for monitoring of cationic photopolymerization processes by FPT , 2012 .

[9]  Dong-Woo Cho,et al.  A study on microreplication of real 3D-shape structures using elastomeric mold: from pure epoxy to composite based on epoxy , 2004 .

[10]  R. Mülhaupt,et al.  Polymers for 3D Printing and Customized Additive Manufacturing , 2017, Chemical reviews.

[11]  Jeremiah A. Johnson,et al.  Light-Controlled Radical Polymerization: Mechanisms, Methods, and Applications. , 2016, Chemical reviews.

[12]  Reinhold Schwalm,et al.  UV Coatings: Basics, Recent Developments and New Applications , 2007 .

[13]  A. Lees,et al.  Organometallic complexes as luminescence probes in monitoring thermal and photochemical polymerizations , 1998 .

[14]  Jerzy Paczkowski.  Sondy fluorescencyjne jako narzędzie badawcze w chemii polimerÓw , 2005 .

[15]  S. Chatani,et al.  The power of light in polymer science: photochemical processes to manipulate polymer formation, structure, and properties , 2014 .

[16]  Chunhua Lu,et al.  An investigation of the effect of ligands on thermal stability of luminescent samarium complexes , 2014 .

[17]  J. Fisher,et al.  Photoinitiated Polymerization of Biomaterials , 2001 .

[18]  C. Vallo,et al.  Monitoring of visible light photopolymerization of an epoxy/ dimethacrylate hybrid system by Raman and near-infrared spectroscopies , 2013 .

[19]  J. Ortyl,et al.  New photoinitiators for cationic polymerization , 2012 .

[20]  Damian Nowak,et al.  Photopolymerization of hybrid monomers: Part I: Comparison of the performance of selected photoinitiators in cationic and free-radical polymerization of hybrid monomers , 2017 .

[21]  Mariusz Galek,et al.  Relative sensitization efficiency of fluorescent probes/sensitizers for monitoring and acceleration of cationic photopolymerization of monomers , 2015 .

[22]  D. Morse,et al.  Nature of the lowest excited state in tricarbonylchloro-1,10-phenanthrolinerhenium(I) and related complexes , 1974 .

[23]  Dariusz Bogdał,et al.  Application of a carbazole derivative as a spectroscopic fluorescent probe for real time monitoring of cationic photopolymerization , 2014 .

[24]  W. Schnabel.  Polymers and Light: Fundamentals and Technical Applications , 2007 .

[25]  A. Lees,et al.  Organometallic compounds as luminescent probes in the curing of epoxy resins , 1991 .

[26]  R. Liska,et al.  Toughening of photo-curable polymer networks: a review , 2016 .

[27]  Chun-hui Huang,et al.  Rare Earth Coordination Chemistry: Fundamentals and Applications , 2010 .

[28]  Joanna Ortyl,et al.  Mechanism of interaction of coumarin-based fluorescent molecular probes with polymerizing medium during free radical polymerization of a monomer , 2016 .

[29]  Joanna Ortyl,et al.  Applicability of quinolizino-coumarins for monitoring free radical photopolymerization by fluorescence spectroscopy , 2015 .

[30]  Carmen Peinado,et al.  Fluorescent probes for sensing processes in polymers. , 2005, Chemistry.