James V. Crivello Professor Organic, Polymer Chemistry 3109 Empire State Hall 518.276.6825 crivej@rpi.edu

Dr. Crivello received his B.S. in Chemistry from Aquinas College in 1962, and his Ph.D. in Organic Chemistry from the University of Notre Dame in 1966. He worked for several years as a research project manager at the General Electric Corporate Research and Development Center. In 1980, he was elected a Coolidge Fellow and spent 1986-1987 as a visiting professor at the University of Mainz in the Federal Republic of Germany. He joined the faculty of Rensselaer in 1988.

New Polymer Forming Reaction

Using the hydrosilylation reaction, a number of novel interesting monomers and polymers have been prepared, which exhibit extraordinary reactivity in cationic polymerization. Crivello is seeking to explore other new areas of organic and synthetic polymer chemistry with a view towards making unusual polymeric materials of both practical and of theoretical interest. Having prepared new polymers, Crivello is undertaking a detailed investigation of their structures and properties.

Initiators

Diaryliodonium and triarylsulfonium salts are novel photo and thermal initiators of cationic polymerization. A wide number of structurally diverse compounds have been designed and prepared to absorb in specific regions of the UV spectrum. The use of these compounds in photo and thermally initiated polymerization with a variety of monomers is being conducted. Major uses in environmentally safe low-energy coatings and in microlithographic and other imaging applications are being explored.

Block Polymers

One challenge of modern synthetic polymer chemistry is the controlled design of new polymeric substances to achieve special tasks. In recent years, Crivello has been developing new approaches to the synthesis of block polymers. Using free radical chemistry, he is making a variety of copolymers, which incorporate one block which is derived by free radical chemistry and the other from condensation techniques. Silicone-vinyl block copolymers prepared by these techniques have very interesting and unusual mechanical properties and are being investigated as membranes for gas separations.

Metal-Catalyzed Ring-Opening Polymerizations

A new series of metal-catalyzed ring-opening and vinyl polymerizations have been discovered in one of Crivello’s laboratories. Using the platinum group metals in combination with hydrogen functional silanes, it is possible to carry out the polymerization of a wide variety of different heterocyclic and vinyl monomers. Investigations now center on exploring various metals and in determining the mechanism of the reaction.

J.V. Crivello, F. Jiang and J. Ma, “Photoinitiated Cationic Polymerization Using 5-Arylthianthrenium Salts” Polym. Preprints, 44(1), 13 (2003).
 
J.V. Crivello and Myoungsouk Jang, "The Development of Anthracene Photosensitizers for Photoinitiated Cationic Polymerizations." Polym. Preprints, 44(1), 845 (2003).
 
J.V. Crivello, B. Falk and S.M Vallinas, “Monitoring Photopolymerizations Using Optical Pyrometry” Polym. Mater. Sci. and Eng. Preprints, 88, 209 (2003).
 
J.V. Crivello, “Photosensitization of Onium Salt Initiated Cationic Polymerizations by Carbazole Monomers, Polymers and Oligomers” Photoinitiated Polymerization, ACS Symposium Series 847, K.D. Belfield and J.V. Crivello, Editors, ACS, Washington, D.C. 2003, p.219.
 
Y. Hua and J.V. Crivello, “Synergistic Free Radical Effects in Photoinitiated Cationic Polymerization” Photoinitiated Polymerization, ACS Symposium Series 847, K.D. Belfield and J.V. Crivello, Editors, ACS, Washington, D.C. 2003, p.178.
 
Z. Gomurashvili and J.V. Crivello, “Phenothiazine Photosenstizers for Onium Salt Photoinitiated Cationic Polymerization” Photoinitiated Polymerization, ACS Symposium Series 847, K.D. Belfield and J.V. Crivello, Editors, ACS, Washington, D.C. 2003, p.231.
 
Ky-Yong Song, R. Ghoshal and J.V. Crivello, “Synthesis and Photoinitiated Cationic Polymerization of Organic-Inorganic Hybrid Resins” Photoinitiated Polymerization, ACS Symposium Series 847, K. D. Belfield and J.V. Crivello, Editors, ACS, Washington, D.C. 2003, p.253.
 
M. Sangermano, S.N. Falling and J.V. Crivello, “The Photoinitiated Cationic Polymerization of 3,4-Epoxy-1-butene” Photoinitiated Polymerization, ACS Symposium Series 847, K.D. Belfield and J.V. Crivello, Editors, ACS, Washington, D.C. 2003, p.266.
 
M. Sangermano and J.V. Crivello, “Visible and Long-Wavelength Cationic Polymerization” Photoinitiated Polymerization, ACS Symposium Series 847, K.D. Belfield and J.V. Crivello, Editors, ACS, Washington, D.C. 2003, p.242.
 
J.V. Crivello and M. Jang, “Anthracene Electron-Transfer Photosensitizers for Onium Salt Induced Cationc Photopolymerizations” Journal of Photochemistry and Photobiology, 159(2), 173-188 (2003).
 
J.V. Crivello and J. Ahn, “Synthesis and Characterization of Second Generation S,S-Dialkyl-S-(hydroxyphenyl)sulfonium Salt Photoinitiators” J. Poly. Sci. Polym. Chem. Ed., 41(16), 2556-2569 (2003).
 
J.V. Crivello and J. Ahn, “Photo- and Thermally Induced Cationic Polymerizations Using S,S-dialkyl-S-(Dimethylhydroxyphenyl)sulfonium Salt Photoinitiators” J. Poly. Sci. Polym. Chem. Ed., 41(16), 2570-2587 (2003).
 
M. Jang and J.V. Crivello “Synthesis and Cationic Photopolymerization of Epoxy-Functional Siloxane Monomers and Oligomers” J. Polym. Sci. Polym. Chem. Ed., 41(19), 3056-3073 (2003).
 
J.V. Crivello “Diaryliodonium Salt Photoinitiators for Cationic Polymerization” The Tech. Assoc. Photopol. Japan, No. 23, July, 2003.
 
B. Falk, S.M Vallinas and J.V. Crivello “Optical Pyrometry: A Novel Method for Monitoring Photopolymerizations” Polym. Materials Sci and Eng. Prepr., 89, 279 (2003).