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Department of Chemistry and Chemical Biology at Rensselaer Chemistry and Chemical Biology
James V. Crivello
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James V. Crivello

Professor, Department of Chemistry and Chemical Biology
Rensselaer Polytechnic Institute

Education:
Ph.D., Organic Chemistry, University of Notre Dame, 1966
B.S., Chemistry, Aquinas College, 1962

Career Highlights:
Crivello 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. In 2011, he was named an American Chemical Society Fellow for his outstanding achievements in and contributions to polymer chemistry.”

Research Areas:
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.

Selected Publications:

            (1)        Crivello, J. V. "Redox Initiated Cationic Polymerization: The Unique Behavior of Alkyl Glycidyl Ethers" J. Polym. Sci., Part A: Polym. Chem. 2011, 49, 2147-2154.

            (2)        Crivello, J. V.; McGrath, T. M. "Photoinitiated Alternating Copolymerization of Dialkyl Maleates and Fumarates with Vinyl Ethers" J. Polym. Sci., Part A: Polym. Chem. 2010, 48, 4726-4736.

            (3)        Crivello, J. V.; Lee, J. L. "Redox Initiated Cationic Polymerization: Silane-N-Aryl Heteroaromatic Onium Salt Redox Couples" J. Polym. Sci., Part A: Polym. Chem. 2010, 48, 4484-4495.

            (4)        Crivello, J. V. "Silane Reduction of Onium Salts" Appl. Organomet. Chem. 2010, 24, 169-178.

            (5)        Molleo, M.; Crivello, J. V. "Redox-Initiated Cationic Polymerization: Reduction of Dialkylphenacylsulfonium Salts by Silanes" Macromolecules 2009, 42, 3982-3991.

            (6)        Crivello, J. V. "Design of Photoacid Generating Systems" J. Photopolym. Sci. Technol. 2009, 22, 575-582.

            (7)        Crivello, J. V. "Radical-Promoted Visible Light Photoinitiated Cationic Polymerization of Epoxides" J. Macromol. Sci. Part A Pure Appl. Chem. 2009, 46, 474-483.

            (8)        Crivello, J. V. "Redox Initiated Cationic Polymerization" J. Polym. Sci., Part A: Polym. Chem. 2009, 47, 1825-1835.

            (9)        Crivello, J. V. "Redox Initiated Cationic Polymerization: Reduction of Diaryliodonium Salts by 9-Bbn" J. Polym. Sci., Part A: Polym. Chem. 2009, 47, 5639-5651.

            (10)       Crivello, J. V. "Design and Synthesis of Photoacid Generating Systems" J. Photopolym. Sci. Technol. 2008, 21, 493-497.

            (11)       Crivello, J. V. "Effect of Temperature on the Cationic Photopolymerization of Epoxides" J. Macromol. Sci. Part A Pure Appl. Chem. 2008, 45, 591-598.

            (12)       Crivello, J. V. "Benzophenothiazine and Benzophenoxazine Photosensitizers for Triarylsulfonium Salt Cationic Photoinitiators" J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 3820-3829.

            (13)       Yu, Y. F.; Gao, Z. Y.; Zhan, G. Z.; Li, L.; Li, S. J.; Gan, W. J.; Crivello, J. V. "Formation of Fibril Structures in Polymerizable, Rod-Coil-Oligomer-Modified Epoxy Networks" Chem. Eur. J. 2007, 13, 2920-2928.

            (14)       Crivello, J. V. "Applications for Photoacid Generation in Photoimaging and Nanotechnology" J. Photopolym. Sci. Technol. 2007, 20, 599-603.

            (15)       Crivello, J. V. "Synergistic Effects in Hybrid Free Radical/Cationic Photopolymerizations" J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 3759-3769.

            (16)       Crivello, J. V. "Hybrid Free Radical/Cationic Frontal Photopolymerizations" J. Polym. Sci., Part A: Polym. Chem. 2007, 45, 4331-4340.

            (17)       Shelnut, E.; Chakraborty, R.; Crivello, J. V. "Synthesis and Evaluation of S-Aryl-S,S-Cycloalkylsulfonium Salts as Cationic Photoinitiators" J. Macromol. Sci. Part A Pure Appl. Chem. 2006, 43, 1339-1353.

            (18)       Crivello, J. V.; Bulut, U. "Indian Turmeric and Its Use in Cationic Photopolymerizations" Macromol. Symp. 2006, 240, 1-11.

            (19)       Crivello, J. V.; Bulut, L. "Dual Photo- and Thermally Initiated Cationic Polymerization of Epoxy Monomers" J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 6750-6764.

            (20)       Crivello, J. V. "Cationic Photopolymerization of Alkyl Glycidyl Ethers" J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 3036-3052.

            (21)       Crivello, J. V. "Design and Synthesis of Multifunctional Glycidyl Ethers That Undergo Frontal Polymerization" J. Polym. Sci., Part A: Polym. Chem. 2006, 44, 6435-6448.

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