Hybrid free radical/cationic frontal photopolymerizations

The irradiation of hybrid photopolymer systems consisting of a free radically polymerizable multifunctional acrylate monomer and a cationically polymerizable epoxide or oxetane monomer was conducted under conditions where only the free radical polymerization takes place. This results in the formation of a free‐standing polyacrylate network film containing quiescent oxonium ions along with the unreacted cyclic ether monomer. The subsequent application of a point source of heat to the film ignites a cationic ring‐opening frontal polymerization that emanates from that site and propagates to all portions of the irradiated sample. This article examines the impact of various molecular structural and experimental parameters on these novel hybrid frontal polymerizations that produce interpenetrating network polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4331–4340, 2007     

Curcumin: A naturally occurring long‐wavelength photosensitizer for diaryliodonium salts

Curcumin, a naturally occurring, intensely yellow dye extracted from the spice turmeric, is an efficient photosensitizer for diaryliodonium salt photoinitiators at wavelengths ranging from 340 to 535 nm. With curcumin as a photosensitizer, it is possible to carry out the cationic photopolymerization of a wide variety of epoxide, oxetane, and vinyl monomers with long‐wavelength UV and visible light. An example of the photopolymerization of an epoxide monomer with ambient solar irradiation is provided. Several other curcumin analogues were synthesized, and their use as photosensitizers is examined. With such photosensitizers, the range of spectral sensitivity can be extended well into the visible region of the electromagnetic spectrum. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5217–5231, 2005     

Monitoring photopolymerization reactions with optical pyrometry

This article describes the development of optical pyrometry (OP) as a new analytical technique for the continuous monitoring of the progress of both free‐radical and cationic photopolymerizations. The method is rapid, reproducible, and very easy to implement. A temperature profile of a photopolymerization can be obtained. Preliminary studies have shown that the temperatures of some polymerizing monomers can easily reach temperatures in excess of 250 °C. The effects of the mass and reactivity of the monomer, light intensity, structures, and concentrations of the photoinitiators and monomers as well as the presence or absence of oxygen on various free‐radical and cationic photopolymerizations were examined with this method. Coupling of real‐time infrared spectroscopy with OP provides a convenient method for simultaneously monitoring both the chemical conversion and the temperature of a photopolymerization. This combined technique affords new insights into the effects of temperature‐induced autoacceleration on the course of photopolymerizations. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 579–596, 2003     

Novel platinum-containing initiators for ring-opening polymerizations

A novel class of platinum-based initiating systems for the ring-opening polymerization of a wide variety of heterocyclic compounds including epoxides, oxetanes, and 1,3,5-trioxane have been discovered. In addition to a platinum complex as a catalyst, a cocatalyst, consisting of a compound or polymer containing silicon-hydrogen bonds must also be present. This article reports on a preliminary survey of the scope and limitations of these new initiator systems. Particular emphasis in this article has been placed on the ring-opening polymerization of epoxides which have been studied in some detail and which proceed rapidly and exothermically at room temperature. A number of mechanistic studies have been conducted and the best current evidence suggests that polymerization proceeds by a cationic mechanism. Evidence is also presented which suggests that platinum metal colloids may function as the active initiating species.     

The synthesis and cationic polymerization of multifunctional silicon-containing epoxy monomers and oligomers

Several series of multifunctional silicon-containing epoxide monomers and oligomers have been prepared using rhodium catalyzed hydrosilation reactions. Dialkyl and diarylsilanes can be condensed with vinyl epoxides to give high yields of the desired diepoxides while the hydrosilation of alkyl and aryl silanes yields a mixture of di and tri epoxy substituted products. The condensation of αω,? Si? H difunctional compounds with vinyl epoxides can be carried out regioselectively to give α-hydrogen-ω-epoxy intermediates, which can be further reacted with di and tri olefins bearing terminal double bonds to give a series of well characterized epoxy functional oligomers. An investigation of the photoinitiated cationic polymerization of the monomers and oligomers, which were prepared during the course of these studies, was carried out. © 1994 John Wiley & Sons, Inc.     

Regioselective hydrosilations. III. The synthesis and polymerization of ambifunctional silicon-containing epoxy monomers

Silicon-containing epoxide compounds bearing Si ? H groups can be readily prepared in high yields by the regioselective rhodium-catalyzed monohydrosilation of α,ω-dihydrogen functional siloxanes and silanes with vinyl epoxides. The remaining Si ? H groups in these compounds can be further selectively hydrosilated with unsaturated epoxides to give a series of unique ambifunctional monomers containing two different epoxide groups in the same molecule. The photopolymerization of these monomers has been studied using analytical techniques including real time infrared spectroscopy and differential scanning photocalorimetry. On photopolymerization, the new monomers yield interesting networks. © 1993 John Wiley & Sons, Inc.     

Synthesis and photopolymerization of monomers bearing isopropenylphenoxy groups

The synthesis of a series of monomers containing isopropenylphenoxy groups was carried out. On irradiation with UV light in the presence of onium salt photoacid generators, these monomers undergo a chain extension reaction consisting of a dimerization followed by a Friedel-Crafts ring closure which results in the formation of polymers with indane groups in the backbone. Aryl imide-containing monomers bearing isopropenylphenoxy groups were also shown to undergo facile photoinduced cationic polymerization. The resulting polymers displayed excellent thermal stability. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of photosensitive polyimides

All aromatic polyimides bearing diarylsulfide linkages in the main chain were prepared either by condensation of a sulfur containing dianhydride with an aromatic diamine or the condensation of a sulfur containing aromatic diamine with a dianhydride. Phenylation with diphenyl iodonium salts was then used to convert the diarylsulfide groups to triarylsulfonium salts. The resulting photosensitive polyimides were shown to undergo main chain cleavage during photolysis using UV irradiation. These new polyimides are candidates for positive working, high temperature photoresist materials.     

Catalysis of ring-opening and vinyl polymerizations by dicobaltoctacarbonyl

In the presence of Si? H containing cocatalysts, dicobaltoctacarbonyl has been found to very efficiently catalyze the ring-opening polymerization of cyclic ethers, especially epoxides, as well as certain vinyl monomers. The reaction conditions employed are very similar to those used in Co₂(CO)₈ catalyzed hydrogenation and hydrosilylation reactions. Detailed investigations have been carried out to elucidate the nature of the active species for this catalytic system. A cationic mechanism is proposed based on the experimental results of those investigations.     

Photoinitiated cationic polymerization with triarylsulfonium salts

Triarylsulfonium salts Ar₃S⁺MX with complex metal halide anions such as BF, AsF, PF, and SbF are a new class of highly efficient photoinitiators for cationic polymerization. In this article we describe several synthetic routes to the preparation of these compounds along with their physical and spectroscopic properties. Mechanistic studies have shown that when these compounds are irradiated at wavelengths of 190–365 nm carbon–sulfur bond cleavage occurs to form radical fragments. At the same time the strong Br??nsted acid HMX_n, which is the active initiator of cationic polymerization that takes place in subsequent “dark” steps, is also produced. A study of the parameters that affect the photolysis of triarylsulfonium salts is reported with a measurement of the absolute quantum yields. The cationic polymerizations of four typical monomers—styrene oxide, cyclohexene oxide, tetrahydrofuran, and 2-chloroethyl vinyl ether—with triarylsulfonium salt photoinitiators are described.