Fabrication of Pre-tilted Vertical Alignment Layers for High-Speed Liquid Crystal Display Using Bi-functional Photoreactive Monomers

Abstract

To enable recent 3D and moving picture applications, liquid crystal displays (LCD) must exhibit fast response and wide viewing angle characteristics. Pre-tilted vertical alignment layers for high-speed LCD were fabricated using bi-functional photoreactive monomers. The monomers can be confined to the polyimide layer and photo-polymerized by UV exposure under voltage. Response characteristics of photo-controlled alignment films according to the structure were investigated. Vertical alignment properties were evaluated using a polarizing optical microscope, and electro-optical characteristics were compared through the voltage-transmittance curve and response time measurement. Faster response speed could be obtained by using photoreactive monomers having a long alkyl chain.     

Palladium complexes bearing an N‐heterocyclic carbene–sulfonamide ligand for cooligomerization of ethylene and polar monomers

Herein, we report the synthesis of palladium complexes bearing an N‐heterocyclic carbene (NHC)‐sulfonamide bidentate ligand and their application in ethylene oligomerization and ethylene/polar monomer cooligomerization. These catalysts could smoothly catalyze ethylene oligomerization and ethylene/methyl acrylate cooligomerization albeit the performance was lower compared to that of a NHC–phenoxide catalyst. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 474–477     

Radical polymerization in the presence of peroxide and reducing agent monomer for branched polymers

In this article, we report the radical polymerization in the presence of peroxide and commercially available or designed reducing agent monomer (RAM) for the preparation of branched poly(methyl methacrylate)s (PMMAs). The reaction behavior of the RAM was studied by NMR. Triple‐detection SEC (TD‐SEC) analysis was used to confirm the branching structure of the prepared PMMAs and to investigate the influence of peroxide concentration and RAM concentration on molecular weight and branched structure. The obtained branched PMMAs exhibited high molecular weights and relatively narrow polydispersities at high conversion of MMA. Interestingly, a significant increase in molecular weight and degree of branching of the obtained polymers are observed in higher BPO concentration, these results are quite different from that reported in the literature. The unique radical polymerization mechanism in the RAM/BPO redox‐initiated radical polymerization system resulted in branched PMMAs with high molecular weights at relatively high RAM and BPO concentrations. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 833–840     

Monomer relative affinity in a copolymer

This paper analyzes data from experiments on simple polymer chains. It measures the extent to which a particular monomer prefers to link with another of the same type. To analyze the data, it derives the likelihood function for a two‐state Markov model in which only the number in each state, but not the order, is observed. This technology is applied to a data set on which experimenters mixed lactic‐glycolic monomers with a known proportion of a contaminant consisting of an extra lactic acid. The resulting copolymers were subjected to matrix‐assisted laser desorption ionization mass spectrometry. This records the number of copolymers at each atomic weight, which can be associated with a given length of copolymer and number of contaminant monomers. Analysis of the data shows that the proportion of contaminant monomers exceeded the proportion of experimentally induced contaminant. Maximum likelihood estimates using the data show that lactic‐glycolic monomers show a positive affinity for the contaminant. Copyright © 2015 John Wiley & Sons, Ltd.     

A halide‐free pyridinium‐substituted η3‐cycloheptatrienide–Pd complex

We report the synthesis and characterization of a novel 4‐(dimethylamino)pyridinium‐substituted η³‐cycloheptatrienide–Pd complex which is free of halide ligands. Diacetonitrile{η³‐[4‐(dimethylamino)pyridinium‐1‐yl]cycloheptatrienido}palladium(II) bis(tetrafluoroborate), [Pd(C₂H₃N)₂(C₁₄H₁₆N₂)](BF₄)₂, was prepared by the exchange of two bromide ligands for noncoordinating anions, which results in the empty coordination sites being occupied by acetonitrile ligands. As described previously, exchange of only one bromide leads to a dimeric complex, di‐μ‐bromido‐bis({η³‐[4‐(dimethylamino)pyridinium‐1‐yl]cycloheptatrienido}palladium(II)) bis(tetrafluoroborate) acetonitrile disolvate, [Pd₂Br₂(C₁₄H₁₆N₂)₂](BF₄)₂·2CH₃CN, with bridging bromide ligands, and the crystal structure of this compound is also reported here. The structures of the cycloheptatrienide ligands of both complexes are analogous to the dibromide derivative, showing the allyl bond in the β‐position with respect to the pyridinium substituent. This indicates that, unlike a previous interpretation, the main reason for the formation of the β‐isomer cannot be internal hydrogen bonding between the cationic substituents and bromide ligands.     

Controllably Growing Topologies in One-shot RAFT Polymerization via Macro-latent Monomer Strategy

The controlled and efficient synthesis of polymers with tailored topologies is challenging but important for exploring structure/property research. Herein, we proposed a concept of macro-latent monomer to achieve the controlled growth of polymer topologies.The macro-latent monomer was installed by a dynamic furan/maleimide covalent bond at the chain terminal. One-shot reversible additionfragmentation chain transfer(RAFT) polymerization of styrene and the macro-latent monomer created controlled growth of polymer topologies.Low temperature such as 40 ℃ could not activate the macro-latent monomer and thus the polymerization created the homo-polystyrene. By contrast, high temperature of ～110 ℃ activated the macro-latent monomer, and a maleimide-terminated macro-monomer was released via the retro-Diels Alder reaction. This macro-monomer immediately joined the cross polymerization with styrene and thus produced the side chains. By delicately manipulating the polymerization temperature, the predetermined placement of the macro-latent monomer-derived polymeric sidechains created controllably growing topologies, including star-, π-shaped, and density-variable grafting copolymers. This work paved a new way for creating on-demand topologies and would greatly enrich the topology synthesis.     

Polymerization of a Photocleavable Monomer Using Visible Light

The polymerization of the photocleavable monomer, o‐nitrobenzyl methacrylate (NBMA), is investigated using photoinduced electron/energy transfer reversible addition‐fragmentation chain transfer polymerization. The polymerizations under visible red (λ _max = 635 nm, 0.7 mW cm⁻²) and yellow (λ _max = 560 nm, 9.7 mW cm⁻²) light are performed and demonstrate rational evidence of a controlled/living radical polymerization process. Well‐defined poly(o‐nitrobenzyl methacrylate) (PNBMA) homopolymers with good control over the molecular weight and polymer dispersity are successfully synthesized by varying the irradiation time and/or targeted degree of polymerization. Chain extension of a poly(oligo(ethylene glycol) methyl ether methacrylate) macro‐chain transfer agent with NBMA is carried out to fabricate photocleavable amphiphilic block copolymers (BCP). Finally, these self‐assembled BCP rapidly dissemble under UV light suggesting the photoresponsive character of NBMA is not altered during the polymerization under yellow or red light. Such photoresponsive polymers can be potentially used for the remote‐controlled delivery of therapeutic compounds.

     

基于单体的Q和e值绘制二元共聚双曲线*

采用Matlab中的Plot函数,首次以单体的Q、e值为中间变量,绘制出二元共聚双曲线。将二元共聚物组成曲线F1-f1和F2-f2同时呈现在一个图上,使隐含的第二单体的共聚行为可视化,有助于加深学习者对二元共聚的理解。     

Rational design of methacrylate monomers containing oxadiazole moieties for single‐layer organic light emitting devices

Methacrylate derived monomers functionalized with pendant oxadiazole moieties were synthesized and copolymerized with carbazole containing monomers to form polymers with electron and hole transporting fragments in the same molecule. Substituents on the oxidazole moiety were varied with the purpose of bandgap tuning and performance optimization when employed in single‐layer organic light emitting devices (OLED). Quantum mechanical calculations of the HOMO‐LUMO levels of the oxidazole derivatives were used to down‐select promising candidates for chemical synthesis and testing in single‐layer OLEDs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1663–1673