Photopolymerization structure

The post-exposure treatment of photopolymerized structures in resin and resist is of critical importance for the final retrieval of 3D structures [77]. Since development of positive or negative resists and resins is a wet process, the damaging effect of capillary forces should be considered during the rinsing and drying of the samples. 

Lahav et al. applied the empirical rule of a topochemically photopolymeric structure (O to the unsymmetric diolefin crystals, thus succeeding in obtaining optically active dimers and oligomers through the crystallization of an achiral monomer into a chiral crystal, followed by the four-center type photopolymerization (12). 

V. Hoffmann, D. FrOhlich, U. Hcllstcm, S. Kohlhage, W. Nahm, K. NuBbaumer, D. Oelkrug, Spectroscopical examination of photopolymerization, structure and permeability of thin polymer films, J. Mol. Struct. 293 (1993) 253-256. 

Previously, the same author [52] reported that compounds containing the tricoordinated sulfur cation, such as the triphenylsulfonium salt, worked as effective initiators in the free radical polymerization of MMA and styrene [52]. Because of the structural similarity of sulfonium salt and ylide, diphenyloxosulfonium bis-(me-thoxycarbonyl) methylide (POSY) (Scheme 28), which contains a tetracoordinated sulfur cation, was used as a photoinitiator by Kondo et al. [63] for the polymerization of MMA and styrene. The photopolymerization was carried out with a high-pressure mercury lamp the orders of reaction with respect to [POSY] and [MMA] were 0.5 and 1.0, respectively, as expected for radical polymerization. 

While the products of 2-furaldehyde polymerization by heat are branched polycondensates with highly conjugated structures (see Section Il-C), the photopolymerization of this furan derivative gives a linear polyaddition product 24>7S). 

The gas-phase photolysis of 2-furaldehyde in the it -n and ir <-it transitions76 proceeds with fragmentation to CO, furan and C3-hydrocarbons, but a certain amount of resinification is also noted (about 5% quantum yield with excitation of the it - n transition). The latter observation prompted a study of the vacuum liquid-phase photolysis by sunlight or by light from a medium-pressure mercury arc at room temperature24 7S. The resin obtained was submitted to fractionation and structural analysis. On the basis of the results obtained and other mechanistic evidence, the following sequence of events was postulated for the photopolymerization ... 

The polymer = 8.19 dlg in hexafluoro-2-propanol, HFIP, solution) in Figs 1 and 2 is prepared on photoirradiation by a 500 W super-high-pressure Hg lamp for several hours and subjected to the measurements without purification. The nmr peaks in Fig. 1 (5 9.36, 8.66 and 8.63, pyrazyl 7.35 and 7.23, phenylene 5.00, 4.93, 4.83 and 4.42, cyclobutane 4.05 and 1.10, ester) correspond precisely to the polymer structure which is predicted from the crystal structure of the monomer. The outstanding sharpness of all the peaks in this spectrum indicates that the photoproduct has few defects in its chemical structure. The X-ray patterns of the monomer and polymer in Fig. 2 show that they are nearly comparable to each other in crystallinity. These results indicate a strictly crystal-lattice controlled process for the four-centre-type photopolymerization of the [l OEt] crystal. 

Recently, Kondo and coworkers reported on the polymerization of St with diphenyl diselenides (37) as the photoiniferters (Eq. 39) [ 162]. In the photopolymerization of St in the presence of 37a and 37b, the polymer yield and the molecular weight of the polymers increased with reaction time. The chain-end structure of the resulting polymer 38 was characterized. Polymer 38 underwent the reductive elimination of terminal seleno groups by reaction with tri-n-butyltin hydride in the presence of AIBN (Eq. 40). It also afforded the poly(St) with double bonds at both chain ends when it was treated with hydrogen peroxide (Eq. 41). They also reported the polymerization of St with diphenyl ditelluride to afford well-controlled molecular weight and its distribution [163]. 

A variety of photo-initiators and water-soluble diluents were used to study the photopolymerization of 2-hydroxyethyl methacrylate (HEMA). The rate of polymerization can be correlated to the structures as well as the concentration of initiators and diluents. It was found that, in terms of rate of polymerization,... 

Table 2 summarizes the peak times for the photopolymerization of HEMA. Among initiators with structures known, the ranking of more active initiators, in terms of decreasing polymerization rate was ... 

A number of photopolymer printing plates are already known. Their basic structures are to combine one of the general purpose resins such as cellulose (1), polyamide (2J, polyester, poly urethane (3j, polyvinyl alcohol (4), synthetic rubber (5) and the like with photopolymerizing vinyl monomer, photopolymerization initiator and so on. Any one of the plates of such structures can be used as a press plate, but they can not be used as an original plate for duplicate plate owing to their insufficient hardness, toughness and the similar negative properties. 

Therefore, metal plates have been conventionally used. We have performed the research and development of a photopolymer printing plate for a master plate with a new basic structure by combining an oligomer of urea structure having a polyvinyl base with polyvinyl alcohol, photopolymerization initiator and other ingredients. The result shows that the newly developed plate (6) is so good that it has replaced metal plates and has been stably used at leading newspaper companies in Japan where several millions of newspapers are daily issued. 

This reliable control of the curing process allows for stopping the polymerization after gelation, when the system has a fixed three-dimensional structure but is still mbbery and contourable. One potential application for employing the temporal control of the photopolymerization process would be in designing contourable fraction fixation plates. Figure 3(b) are the... 

The general approach of graded radiation exposure can also be used to examine light driven processes such as photopolymerization [19]. For example, Lin-Gibson and coworkers used this library technique to examine structure-property relationships in photopolymerized dimethacrylate networks [38] and to screen the mechanical and biocompatibility performance of photopolymerized dental resins [39]. In another set of recent studies, Johnson and coworkers combined graded light exposure with temperature and composition gradients to map and model the photopolymerization kinetics of acrylates, thiolenes and a series of co-monomer systems [40 2]. 

Lin-Gibson S, Landis FA, Drzal PL (2006) Combinatorial investigation of the structure-properties characterization of photopolymerized dimethacrylate networks. Biomaterials 27 1711-1717... 

The synthesis of cis-1,4 polymers was also tried by e use of monomers with an s-cis conformation. The solid-state photopolymerization of pyridone derivatives, which is a six-membered cyclic diene amide and is a tautomer of 2-hydroxypyridine, was attempted [100]. Pyridones make hydrogen-bonded cocrystals with a carboxylic acid in the crystalline state. Because the cyclic structure fixes its s-cis conformation, if the polymerization proceeds, a cis-2,5 polymer would be obtained. Actually, however, the photopolymerization did not occur, contrary to our expectation, but [4-1-4] photodimerization proceeded when the carbon-to-carbon distance for the dimerization was small (less than 4 A) [101]. A closer stacking distance of the 2-pyridone moieties might be required for the topochemical polymerization of cychc diene monomers. 

The DnPont photopolymeric system consists of polymeric binder resins, e.g. PVA, PMMA, cellnlose acetates and styrene-acrylates, reactive acrylic monomers, e.g. aryloxy or alkoxy acrylates, a dye sensitiser and a radical or charge transfer photoinitiator, e.g. DEAW and HABI respectively (see Chapter 4, section 4.5.2), and plasticisers. The process for producing the refractive index structures is as follows ... 

Fang G, Javier M-R, Zhigang P, Colan EH, Kenneth DMH (2008) Direct structural understanding of a topochemical solid state photopolymerization reaction. J Phys Chem C 112 19793-19796... 

Structure Determination of the Product Phase from a Solid-State Photopolymerization Reaction... 

An example is the photopolymerization of 2,5-distyrylpyrazine (DSP) (Fig. 17), with polymerization occurring via intermolecular [2-1-2] photocyclization reactions at each end of the monomer molecule. Although this reaction is regarded as a classic solid-state reaction, having been studied extensively around 40 years ago [121,122], structure determination of the polymeric product phase was only carried... 

Fig. 17 The solid-state photopolymerization reaction of DSP (shown at top), (a) Crystal structure of the polymeric product phase obtained directly from the solid-state photopolymerization reaction of DSP, viewed along the i)-axis (for clarity, only half the unit cell is shown along the direction of view), and (b) overlay of the monomer (green) and polymer (orange) in their crystal structures...

---