Photoinitiation acrylate

Complexes (181)-(183) may also be used to polymerize acrylates449 and methacrylonitrile450 in a living manner, although (181) again requires photoinitiation. Acrylates such as BuA polymerize faster than methacrylates. The rate of propagation of methacrylonitrile is much slower than methacrylates, although in the presence of (185), 100 equivalents are consumed within 3 hours. 

Probably the most important observation of this research was that in practical terms, the polymerization was not inhibited by ambient oxygen (12) and thus was differentiated from photoinitiated acrylic or methacrylic polymerizations. Structural limitations on the reactivity of the olefinic component were noted (13) and the observation that internal olefins exhibited lower reactivity, in general, agreed with earlier studies that showed that cyclic olefins such as cyclohexene or cyclopentene had low relative reaction rates (14) with thiols when compared with terminal olefins. The present study has determined that certain cyclic olefins, such... 

An imaging system based on photopolymerizable microcapsules has recently been developed (8-101. The microcapsules (Figure 1) contain photoinitiators, acrylic monomers, and a colorless dye precursor. 

Compositionally, photoinitiated acrylics are much like the formulations already reported in this chapter, but it should be noted that these use special photoinitiators in place of redox or other forms of generating free radicals. The only significant difference is found in the use of acrylate, rather than methacrylate, as the carrier monomer. The acrylates are much more prone to UV initiation and propagation than the methacrylates and are consequently the better choice for the formulators. 

Functionalized rubbers. Butyl rubber (isobutylene with about 2% iso-prene) has been functionalized through the residual double bonds via the bro-mobutyl intermediate to produce a material with 2% conjugated diene (see Fig. 19). This resin shows high reactivity towards e-beam or UV (free radical or cationic [53]). The bromo butyl intermediate has also been used to attach acrylate or photoinitiator groups to the butyl backbone [54]. 

Polyalkylene oxides (PAO) are prone to chain transfer. This tendency was used by Union Carbide to graft acrylate side chains via UV exposure of a PAO/acrylic monomer(carbamyloxy alkyl acrylate)/photoinitiator blend [58]. The final product was a water-sensitive PSA. 

Strohmeier and Hartmann [14] first reported in 1964 the photoinitiation of polymerization of ethyl acrylate by several transition metal carbonyls in the presence of CCI4. Vinyl chloride has also been polymerized in a similar manner [15,16] No detailed photoinitiation mechanisms were discussed, but it seems most likely that photoinitiation proceeds by the route shown in reaction Scheme (9). 

Triphenylsulfonium tetrafluoroborate [(C6Hs)3 S" BF4 ] is used instead of diphenyl iodonium chloride to give phenyl radical as the initiating species. Potassium [tris(oxalato) cobaltate) (III)] with diphenyl iodonium chloride also has been used as the photoinitiator of acryl-... 

Iwai and coworkers [56] have introduced a novel type of multicomponent photoinitiating system for water-soluble monomer (acrylamide, acrylic acid, acrylonitrile, etc). 

This reaction is utilized by Burrows et al. [70] to photoinitiate grafting of acrylamide, acrylic acid, methacrylamide, and acrylonitrile on cellulose triacetate in acidic aqueous solution. 

Polymers in Schemes 12 and 13 were the first examples of the preparation of pyridinium and iminopyridinium ylide polymers. One of the more recent contributions of Kondo and his colleagues [16] deals with the sensitization effect of l-ethoxycarbonyliminopyridinium ylide (IPYY) (Scheme 14) on the photopolymerization of vinyl monomers. Only acrylic monomers such as MMA and methyl acrylate (MA) were photoinitiated by IPYY, while vinylacetate (VA), acrylonitrile (AN), and styrene were unaffected by the initiator used. A free radical mechanism was confirmed by a kinetic study. The complex of IPYY and MMA was defined as an exciplex that served as a precursor of the initiating radical. This ylide is unique in being stabilized by the participation of a... 

The free radicals then initiate curing by attacking residual double bonds in acrylic oligomers and monomers, or in styrene and unsaturated polyester resins. Since most pigments absorb u.v. radiation and can prevent it reaching sufficient photoinitiator molecules, this technique is best suited to transparent coatings or thin pigmented layers (e.g. inks). 

Polyvinyl chloride has been modified by photochemical reactions in order to either produce a conductive polymer or to improve its light-stability. In the first case, the PVC plate was extensively photochlorinated and then degraded by UV exposure in N2. Total dehydrochlorination was achieved by a short Ar+ laser irradiation at 488 nm that leads to a purely carbon polymer which was shown to exhibit an electrical conductivity. In the second case, an epoxy-acrylate resin was coated onto a transparent PVC sheet and crosslinked by UV irradiation in the presence of both a photoinitiator and a UV absorber. This superficial treatment was found to greatly improve the photostability of PVC as well as its surface properties. 

The crosslinking of such types of silicones can be described by means of a polymerization reaction. The reaction rate (rP) of this process is a function of the light intensity, the exposure time, the acrylate content, the molecular weight of the uncrosslinked silicone, the photoinitiator and also of the oxygen content of the system. A typical reaction rate/time profile is shown in the Fig. 1. 

Difunctional vinvl ether/difunctional N-maleimide. Up until this point, our results have centered on the reactivity of monofunctional maleimide divinyl ether mixtures. From Kloosterboer s26 work for acrylate polymerization, it is known that the rate of polymerization of a free-radical process is increased dramatically as the functionality of the acrylate is increased. In order to enhance the polymerization rates of maleimide divinyl ether systems, it was decided to synthesize difimctional maleimides for copolymerization with difunctional vinyl ethers. The results in Table V indicate that the photoinitiated TTDBM [bismaleimide made from maleic anhydride and 4,7,10-... 

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