Photochemical Reactions in Supramolecular Assemblies of Gels: Dimerizations and Polymerizations via Pericyclic Reactions

Gel state reactions offer new direction for the reactivity of the organic molecules or metal‐organic materials upon photoirradiation with shorter reaction times and high yields compared to solid and solution states. The restricted molecular movement among the molecules in the soft solids control the stereoselectivity of the photoproducts in the gel state reactions. To date, most of the strategies based on self‐assembly have been demonstrated in the solid state, in particular for [2+2] reactions of olefins and polymerization reactions of diacetylenes via 1,4 addition. The soft materials are of emerging materials in recent days given their many applicative day‐to‐day aspects. This review gives a glimpse of recent reports on pericyclic reactions in the gel state that are designed based on the self‐assembly concept. Also it highlights how such reactions accompany the physical changes in the structure of the gels and stereo controlled products with high yields.     

Synthesis,Properties, and Photopolymerization of Liquid‐Crystalline Oxetanes: Application in Transflective Liquid‐Crystal Displays

Mixtures of liquid‐crystalline di‐oxetanes and mono‐oxetanes are made for the purpose of making birefringent films by photopolymerization. The composition of a di‐oxetane mixture that forms spin‐coated films of planarly aligned nematic monomers is reported. These films are photopolymerized in air. The molecular order of the monomers can be changed on the microscale to form thin films with alternating birefringent and isotropic parts by using a combination of photopolymerization and heating. The interface observed between the birefringent and isotropic 10 μm × 10 μm domains is very sharp and the films show hardly any surface corrugation. In addition, the polymerized films are thermally stable, making them very suitable for use as patterned thin‐film retarders in high‐performance transflective liquid‐crystal displays (LCDs) which satisfy customer demand for displays that are brighter and thinner and that deliver better optical performance than conventional LCDs with an external non‐patterned retarder.     

Development of a comprehensive free radical photopolymerization model incorporating heat and mass transfer effects in thick films

A comprehensive kinetic model describing photopolymerization is developed which allows variation of temperature, species concentrations, and light intensity through the thickness of a photopolymerized film. Heat and mass transfer effects are included, as is the generation of heat by both reaction and light absorption. In addition to initiation, propagation, and termination mechanisms, both primary radical termination and inhibition are incorporated into the model. The possible presence and diffusion of an inert solvent are also accounted for. Thus, the model is useful for examining complex polymerization kinetics and behavior in industrially and commercially important thick film photopolymerizations, such as the curing of contact lenses, dental restorative materials, photolithographic resists, and optoelectronic coatings. The comprehensive model is used to predict polymerization rate, temperature, and conversion profiles in a variety of systems. The effects of heat generation and the thermal boundary conditions are explored, with the result that heat generation in thick samples leads to greatly increased conversions approaching 100 percent. Increased temperature in these samples also may lead to the appearance of two rate maxima, with the first due to the temperature increase and the second caused by the autoacceleration process. The magnitude of the temperature increase, along with the resultant effects, is more pronounced in insulated systems.     

Development of new dyeing photoinitiators based on 6H-indolo[2,3-b]quinoxaline skeleton

The series of new dyes, which structures are based on 6H-indolo[2,3-b]quinoxaline skeleton that possess characteristic electronic absorption band at a boundary of UV and visible light were tested as potential light absorbing chromophores for photoinitiated polymerization.The studied dyes can be classified into two different groups. The first is the group, so called ‘the branched dyes’, which structures possess the part of molecule that can rotate without restraints and are characterized by low photoinitiation ability. The second, planar and rigid group of molecules provides another chromophores, which possess quite different properties in comparison to that observed for the branched dyes. Their photoinitiation ability is comparable to that observed for many commercially available photoinitiating systems.The location of electronic absorption spectra at a boundary of UV and visible light makes the tested dyes the good candidates for the photoinitiating system applied in dental restorative materials. Their high molar absorption coefficient allows to decrease the dyes concentration in dental formulation in comparison to commonly used camphorquinone.     

Photopolymer kinetics using light intensity gradients in high-throughput conversion analysis

Light intensity gradients and light exposure time gradients were combined to produce contours of constant dose on a sample substrate. These polymerized samples were subsequently analyzed using high-throughput Fourier transform infrared spectroscopy to measure conversion as a function of both gradients. Three (meth)acrylate monomers were analyzed over light doses ranging from 0 mJ/cm² to 920 mJ/cm², demonstrating that in thin films, higher light intensities at a constant light dose produce higher conversion due to a decreased oxygen inhibition time and larger thermal excursions. At a light dose of 75 mJ/cm², the conversion of 2-ethylhexyl acrylate increases from 40 ± 2% at a light intensity of 0.9 mW/cm² to 59 ± 3% at 7.2 mW/cm². The two acrylate monomers exhibited rapid photopolymerization up to a specific conversion, after which additional radiation dose produced only marginal increases in overall conversion. For hexanediol diacrylate, a light dose of 300 mJ/cm² was the minimum amount required to reach the maximum conversion over the entire range analyzed. For the dimethacrylate system, a similar effect was seen, with a reduced oxygen inhibition time and conversion above 70% showing a similar conversion at a constant light dose of 500 mJ/cm². In all three systems, dose contours were used to determine a range of light intensities at which a statistically similar conversion would occur for a specified light dose.     

Using a cross-flow microfluidic chip for monodisperse UV-photopolymerized microparticles

In this paper, we report a microfluidic chip containing a cross-junction channel for the manipulation of UV-photopolymerized microparticles. Hydrodynamic-focusing is used to form a series of using 365 nm UV light to solidify the hydrogel droplets. We were able to control the size of the hydrogel droplets from 75 to 300 μm in diameter by altering the sample and by changing the flow rate ratio of the mineral oil in the center inlet channel to that of the side inlet channels. We found that the size of the emulsions increases with an increase in average velocity of the dispersed phase flow (polymer solution flow). The size of the emulsions decreases with an average velocity increase of the continuous phase flow (mineral oil flow). Experimental data show that the emulsions are very uniform. The developed microfluidic chip has the advantages of ease of fabrication, low cost, and high throughput. The emulsions generated are very uniform and have good regularity.     

聚合物网络稳定液晶光栅的制备与特性研究

将光敏预聚物单体与向列相液晶按一定比例混合,注入液晶盒;采用光掩模法,在紫外灯照射下,使混合物产生定域光聚合反应,形成聚合物网络稳定液晶光栅。利用光学显微镜和He-Ne激光器进行测试,实验检测结果表明,该光栅具有周期性的栅结构,且衍射效率具有先增大后减小电场调制特性,并利用折射率调制机理对该现象进行分析。     

Photocurable ceramic/monomer feedstocks containing terpene crystals as sublimable porogen for UV curing-assisted 3D plotting

This study presents a novel strategy to construct ceramic structures comprised of microporous filaments using photocurable ceramic/monomer feedstocks containing terpene crystals as sublimable porogens for UV curing-assisted 3D plotting technique. The biphasic calcium phosphate (BCP) feedstock, composed of frozen terpene crystals surrounded by BCP/UDMA walls, could be favorably extruded through a fine nozzle and then effectively photopolymerized by UV light. Thus, green filaments with high shape retention could be obtained. In addition, a number of pores could be created in BCP filaments after removing terpene crystals via freeze-drying and the porosity could be tailored by adjusting terpene content in BCP feedstocks. This approach allowed for the construction of dual-scale porous structures comprising microporous filaments in a periodic pattern, with tailored overall porosities and compressive strengths. Several types of self-supporting structures were also successfully constructed using our approach.     

Photoinitiator system and water effects on C=C conversion and solubility of experimental etch-and-rinse dental adhesives

The purpose of this study was to determine the influence of the photoinitiator system and moisture condition on the degree of C=C conversion (DC), the water sorption (W_sp), and the solubility (W_sl) of experimental two-step etch-and-rinse dental adhesives. Different photoinitiator systems were added at 0.5 mol% to an experimental adhesive blend (55:45 wt% Bis-GMA:HEMA), defining the experimental groups: camphorquinone (CQ)+ethyl-4-dimethylaminobenzoate (EDMAB), 9,10-phenanthrenequinone (PQ), PQ+EDMAB, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (BAPO). The adhesives were tested in two moisture conditions: neat and wet (with the addition of 10 wt% D₂O). The DC (n=6) was evaluated by Fourier-transformed infrared spectroscopy (FTIR). W_sp and W_sl were determined (n=10) after successive weighting procedures. Data were submitted to two-way ANOVA and Tukey׳s post hoc test (α=0.05). Pearson׳s correlation tests were used to analyze the correlation between DC and W_sp or W_sl. TPO and BAPO presented the highest DC in the neat condition while CQ+EDMAB presented the highest in the wet condition. W_sp and W_sl were both dependent on the photoinitiator system and moisture condition. PQ–based materials presented the highest W_sp and W_sl in both neat and wet conditions. Pearson׳s tests were not able to detect any significant correlation between DC and W_sp or DC and W_sl. Within the limitations of the present study, it can be concluded that the photoinitiator system and moisture condition influenced the DC, W_sp, and W_sl of experimental two-step etch-and-rinse adhesives.