A photopolymer or light-activated resin is a polymer that changes its properties when exposed to light, often in the ultraviolet or visible region of the electromagnetic spectrum. These changes are often manifested structurally, for example hardening of the material occurs as a result of cross-linking when exposed to light. An example is shown below depicting a mixture of monomers, oligomers, and photoinitiators that conform into a hardened polymeric material through a process called curing. A wide variety of technologically useful applications rely on photopolymers; for example, some enamels and varnishes depend on photopolymer formulation for proper hardening upon exposure to light. In some instances, an enamel can cure in a fraction of a second when exposed to light, as opposed to thermally cured enamels which can require half an hour or longer. Curable materials are widely used for medical, printing, and photoresist technologies. Changes in structural and chemical properties can be induced internally by chromophores that the polymer subunit already possesses, or externally by addition of photosensitive molecules. Typically a photopolymer consists of a mixture of multifunctional monomers and oligomers in order to achieve the desired physical properties, and therefore a wide variety of monomers and oligomers have been developed that can polymerize in the presence of light either through internal or external initiation. Photopolymers undergo a process called curing, where oligomers are cross-linked upon exposure to light, forming what is known as a network polymer. The result of photo-curing is the formation of a thermoset network of polymers. One of the advantages of photo-curing is that it can be done selectively using high energy light sources, for example lasers, however, most systems are not readily activated by light, and in this case a photoinitiator is required. Photoinitiators are compounds that upon radiation of light decompose into reactive species that activate polymerization of specific functional groups on the oligomers. An example of a mixture that undergoes cross-linking when exposed to light is shown below. The mixture consists of monomeric styrene and oligomeric acrylates.
Most commonly, photopolymerized systems are typically cured through UV radiation, since ultraviolet light is more energetic. However, the development of dye-based photoinitiator systems have allowed for the use of visible light, having the potential advantages of being simpler and safer to handle. UV curing in industrial processes has greatly expanded over the past several decades. Many traditional thermally cured and solvent-based technologies can be replaced by photopolymerization technologies. The advantages of photopolymerization over thermally cured polymerization include higher rates of polymerization and environmental benefits from elimination of volatile organic solvents. There are two general routes for photoinitiation: free radical and ionic. The general process involves doping a batch of neat polymer with small amounts of photoinitiator, followed by selective radiation of light, resulting in a highly cross-linked product. Many of these reactions do not require solvent which eliminates termination path via reaction of initiators with solvent and impurities, in addition to decreasing the overall cost.
Ionic mechanism In ionic curing processes, an ionic photoinitiator is used to activate the functional group of the oligomers that are going to participate in cross-linking. Typically photopolymerization is a very selective process and it is crucial that the polymerization takes place only where it is desired to do so. In order to satisfy this, liquid neat oligomer can be doped with either anionic or cationic photoinitiators that will initiate polymerization only when radiated with light. Monomers, or functional groups, employed in cationic photopolymerization include: styrenic compounds, vinyl ethers, N-vinyl carbazoles, lactones, lactams, cyclic ethers, cyclic acetals, and cyclic siloxanes. The majority of ionic photoinitiators fall under the cationic class; anionic photoinitiators are considerably less investigated. There are several classes of cationic initiators, including onium salts, organometallic compounds and pyridinium salts. As mentioned earlier, one of the drawbacks of the photoinitiators used for photopolymerization is that they tend to absorb in the short UV region. Photosensitizers, or chromophores, that absorb in a much longer wavelength region can be employed to excite the photoinitiators through an energy transfer. Other modifications to these types of systems are free radical assisted cationic polymerization. In this case, a free radical is formed from another species in solution that reacts with the photoinitiator in order to start polymerization. Although there are a diverse group of compounds activated by cationic photoinitiators, the compounds that find most industrial uses contain epoxides, oxetanes, and vinyl ethers. One of the advantages to using cationic photopolymerization is that once the polymerization has begun it is no longer sensitive to oxygen and does not require an inert atmosphere to perform well.
Photolysis
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