Controlling the kinetics and gelation of photopolymerization is a significant challenge in the fabrication of complex three-dimensional (3D) objects as is critical in numerous imaging, lithography, and additive manufacturing techniques. We propose a novel, visible light sensitive "photoinitibitor" which simultaneously generates two distinct radicals, each with their own unique purpose-one radical each for initiation and inhibition. The Janus-faced functions of this photoinitibitor delay gelation and dramatically amplify the gelation time difference between the constructive and destructive interference regions of the exposed holographic pattern. This approach enhances the photopolymerization induced phase separation of liquid crystal/acrylate resins and the formation of fine holographic polymer dispersed liquid crystal (HPDLC) gratings. Moreover, we construct colored 3D holographic images that are visually recognizable to the naked eye under white light.

We synthesize zinc sulfide (ZnS) nanoparticles with a diameter of ∼5 nm and formulate novel photopolymer/ZnS nanocomposites for holographic recording. By taking advantage of the photoinitibitor, composed of 3,3′-carbonylbis­(7-diethylaminocoumarin) (KCD) and N-phenylglycine (NPG), with a capability of spatiotemporally tailoring the grating formation process, we successfully achieve high performance holographic photopolymer/ZnS nanocomposites with as high as 93.6% of diffraction efficiency (η), 26.6 × 10–3 of refractive index modulation (n 1), 8.4 per 200 μm of dynamic range, and 9.8 cm/mJ of photosensitivity. In addition, for an aim of roughly describing the grating formation process, we establish a novel exponential correlation between the ZnS nanoparticles segregation degree (SD) and the ratio of photopolymerization gelation time (t gel) to holographic mixture viscosity (v). Finally, we reconstruct and display 3D images that are clearly identifiable to the naked eye through a master technique, opening a versatile class of potential applications in high capacity data storage, stereoadvertisements, and anticounterfeiting.

A one-step and metal-free route to triblock quaterpolymers from mixtures of vinyl monomers, epoxides, anhydrides, and racemic lactide (rac-LA) has been described, which bridges three polymerization cycles involving ring-opening copolymerization (ROCOP) of epoxides/anhydrides, ring-opening polymerization (ROP) of rac-LA, and RAFT polymerization of vinyl monomers. Taking advantage of the switchable polymerization between ROCOP and ROP, concurrent chain propagation of ROCOP/RAFT and ROP/RAFT sequentially occurs by using a trithiocarbonate compound with carboxylic group (TTC–COOH) as a versatile chain transfer agent. The multiple-chain transfer effect enables independent and precise control over the molecular weights of the three blocks and ensures narrow distribution of the resultant triblock quaterpolymers (Đ < 1.20). This work demonstrates the possibility to acquire block copolymers with high degree of structural complexities in a single efficient process by combining different block polymerization strategies.

Holographic photopolymer composites have garnered a great deal of interest in recent decades, not only because of their advantageous light sensitivity but also due to their attractive capabilities of realizing high capacity three-dimensional (3D) data storage that is long-term stable within two-dimensional (2D) thin films. For achieving high performance holographic photopolymer composites, it is of critical importance to implement precisely spatiotemporal control over the photopolymerization kinetics and gelation during holographic recording. Though a monochromatic blue light photoinitibitor has been demonstrated to be useful for improving the holographic performance, it is impractical to be employed for constructing holograms under green light due to the severe restriction of the First Law of Photochemistry, while holography under green light is highly desirable considering the relatively low cost of laser source and high tolerance to ambient vibration for image reconstruction. Herein, we disclose the concurrent photoinitiation and inhibition functions of the rose bengal (RB)/N-phenylglycine (NPG) system upon green light illumination, which result in significant enhancement of the diffraction efficiency of holographic polymer-dispersed liquid crystal (HPDLC) gratings from zero up to 87.6 ± 1.3%, with an augmentation of the RB concentration from 0.06 × 10 to 9.41 × 10 mol L. Interestingly, no detectable variation of the ϕk/k, which reflects the initiation efficiency and kinetic constants, is given when increasing the RB concentration. The radical inhibition by RBH is believed to account for the greatly improved phase separation and enhanced diffraction efficiency, through shortening the weight-average polymer chain length and subsequently delaying the photopolymerization gelation. The reconstructed colored 3D images that are easily identifiable to the naked eye under white light demonstrate great potential to be applied for advanced anticounterfeiting.

Liquid-crystalline (LC) physical gels with a high modulus and low driving voltage were prepared through the self-assembly of sorbitol derivatives as gelators in a nematic liquid crystal, 4-pentyl-4 0 -cyanobiphenyl (5CB). The structural difference among the used gelators, i.e. 1,3:2,4-di-O-benzylidene-D-sorbitol (DBS), 1,3:2,4-di-O-p-methylbenzylidene-D-sorbitol (MDBS) and 1,3:2,4-di-O-m,p-dimethylbenzylidene-D-sorbitol (DMDBS), is only the number of methyl groups on their phenyl rings. The phase transition temperature, mechanical and electro-optical properties of three LC gels were systematically investigated. Compared with DBS, MDBS and DMDBS with methyl groups on phenyl rings have higher gelation ability in 5CB.The three LC gels exhibit good self-supporting ability with storage moduli higher than 10 4 Pa when the gelator content is increased to 1.5 wt%. At 3.0 wt% and a gelator content less than 1.0 wt%, both moduli of MDBS and DMDBS gels are obviously higher than that of DBS gel due to the enhanced reinforcement of the more rigid, thicker nano-fibrils and the formed nano-fibrillar network texture in MDBS and DMDBS gels. Also, the driving voltages of LC gels decrease in the order of DBS, MDBS and DMDBS gels with increase of LC domain size and nano-fibril diameter. For DMDBS gel with 3.0 wt% gelators, the threshold voltage and saturation voltage are only 0.5 and 3.5 V mm À1 , showing its potential application in self-supporting light-scattering electro-optical displays.