Sai Zhang,Khama Rani Ghosh,Zhe Yao,Lingling Li,Anran Qin,Wenqiang Qiao,Zhi Yuan Wang
We report an efficient and phosgene-free method for the synthesis of isocyanate group (NCO)-containing polymers via Lossen rearrangement. The key monomer of N -acetoxymethacrylamide ( AMAA ), possessing N -acetoxy amide (AA) group was synthesized from the reaction of N -hydroxymethacrylamide ( MHA ) with acetic anhydride. By adjusting the feed ratio of methyl methacrylate ( MMA ) and AMAA , a series of AA-containing polymers ( P1-P3 ) were prepared by free-radical polymerization. Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA) revealed that the AA groups in polymers P1-P3 can be readily converted to isocyanate groups by heating at 130 ℃ to afford the NCO-containing polymers P4-P6 with conversion percent of 60, 77 and 78, respectively. Furthermore, the AA-containing polymers can be used as a latent NCO-containing polymer for further chemical modification, such as in-situ grafting reaction with hydroxyl compounds. The spectroscopic analyses confirmed that the dye functional group of disperse red 1 (DR1) was successfully grafted on either NCO- or AA-containing polymers.
Wansheng Zong,Lixin Wang,Qing Guo,Juan Li,Wenbo Wu,Yingliang Liu,Shengang Xu,Shaokui Cao
A hyper-structured molecule (HSM) CRA-DR1 and a model molecule Ph-DR1 for photorefractive (PR) application under non-electric field were designed and synthesized via highly reactive “click” reaction between alkynyl derivatives of calix [4]resorcinarene (CRA) or resorcinol and an azide derivative of disperse red 1 (DR1) in satisfactory yields. XRD pattern and UV–Vis absorption spectra indicated that the CRA-DR1 with three-dimensional (3D) CRA core could effectively decrease the aggregation, packing and crystallization of the nonlinear optical (NLO) chromophores . AFM images showed a smooth and pinhole-free morphology of the CRA-DR1 film. Two-beam coupling (TBC) experiment was used to test the photorefractive performance in optically transparent films of Ph-DR1 and CRA-DR1 doped with [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) as a photosensitizer and N -ethyl-carbazole (ECz) as a plasticizer . Without poling and without external electric filed, the coupling gain coefficient obtained in the CRA-DR1-based composite is 147.4 cm −1 , which is higher than that of Ph-DR1-based composite (132.6 cm −1 ) owing to its asymmetrical 3D CRA core. Coupled with its convenient synthesis and commercial DR1, CRA-DR1 could serve as a good candidate for PR application.
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