Novel functionalized periodic mesoporous organosilicons (Salen-PMOs) were synthesized by co-condensation of 1,2-bis(triethoxysilyl)ethane (BTEE) and the modified Salen-type Schiff-base compound N,N′-bis(salicylidene)ethylenediamine (Salen-Si) in the presence of Pluronic P123 surfactant as a template. N,N′-bis(salicylidene)ethylenediamine (Salen) grafted on the coupling agent 3-(triethoxysilyl)-propy-lisocyanate (TEPIC) was used as the precursor for the preparation of periodic mesoporous materials. The two kinds of resulting materials(denoted as Ln(Salen-PMOs)2 and Ln(Salen-PMOs)2phen, respectively Ln = Eu, Tb) were characterized in detail by Fourier-transform infrared spectra, ultraviolet–visible absorption spectra, small-angle X-ray diffraction, nitrogen adsorption/desorption isotherms, photoluminescence spectroscopy and luminescence decay time measurements. The results reveal that luminescent periodic mesoporous materials have high surface area, uniformity in the mesoporous structure and good crystallinity. Furthermore, the efficient intramolecular energy transfer in mesoporos material Ln(Salen-PMOs)2phen mainly occurs between the modified ligand Salen-Si and the central Eu3+ ion. In addition, the luminescent mesoporous hybrid containing terbium ions, designated as Tb(Salen-PMOs)2 and Tb(Salen-PMOs)2phen were also prepared, and were found to emit green photoluminescence characteristic of terbium ions.

•It is critical for H-bond interaction to affect the microphase separation of FPU.•Experimental and computational approaches are combined to study the microphase separation of FPU.•The degree of microphase separation is decreased when F is introduced into PUs.The microstructures of fluorinated polyurethanes (FPUs) possess separated soft and hard phases related to their unique mechanical and physiochemical properties. We studied the microstructures of FPUs and H-bond interactions focusing on the influences of fluorine (F) content on the separation between the soft and hard phases by combining experimental and computational approaches. FPUs featuring F in side chains were synthesized using fluorinated polyether glycol as soft segments, MDI as hard segments, and 1,4-butanldiol (BDO) as chain extenders with various molar ratio of hard/soft segments. Fourier transform infrared spectroscopy (FTIR) and molecular dynamics (MD) studies both show that increasing F content of soft segments enhances H-bond interactions between soft and hard segments, thus reducing the extent of microphase separation. The direct visual inspection of microstructures by SEM reveals that the soft and hard segments separate more significantly as the fraction of the hard segments increases, consistent with the increasing density fluctuation of F and N elements found in the MD simulations. The glass transition temperatures (Tg) measured by DMA indicate that the optimal working temperature window of FPUs separating soft and hard glass transitions becomes narrow with increasing F and weakened phase separation. Tg predicted by MD are in quantitative agreement with the DMA experiments. This work demonstrates that how experiments and computations can be combined to study composition-structure-property relationships of polymers to optimize the separated microphase structures of FPU for overall good balance among materials performance, synthesis costs, and environmental impacts.This work focuses on the influences of F contents on the microphase separation of FPUs. We combine experimental and theoretical (MD) approaches to show that H-bond interaction is critical to affect the microphase separation and glass transition temperatures. And demonstrate that how experiments and computations can be combined to study composition-structure-property relationship of polymers.

Novel luminescent polymer-functionalized mesoporous SBA-16 type hybrid materials with encapsulated lanthanide (Eu3+ and Tb3+) complexes for luminescence have been synthesized in situ. The organic molecule acrylamide (AM) was first modified by a silane coupling agent 3-(triethoxysilyl)propylisocyanate (TEPIC) to form an alkene precursor, which was then covalently bonded to a mesoporous SBA-16 backbone through co-hydrolysis and co-condensation reactions. Then, the flexible polymer chain polyacrylamide (PAM) within the pores of SBA-16 could be formed by initiating the monomer. Through introducing the lanthanide ions and the typical ligand 1,10-phenanthroline (phen), the luminescent mesoporous hybrids (denoted as Ln(S16-PAM-Si)3 and Ln(S16-PAM-Si)3phen, respectively) with the organic polymer acting as a flexible linker between the mesoporous framework and the lanthanide complex were finally attained. The results reveal that these materials exhibit high surface area, uniform mesostructure and efficient intramolecular energy transfer. Moreover, the ternary hybrids present higher red/orange ratio, stronger luminescent intensity, longer lifetime and higher 5D0 luminescence quantum efficiency than the binary one, suggesting that the luminescent properties have been significantly improved with the introduction of the organic ligand phen.

•Fluorinated glycol has been synthesized by the living/controlled polymerization.•The polymerization mechanism of fluorinated glycol was proposed.•1,4-Dioxane was used as nucleophilic additive to attain living polymerization.•The BF3·CH3OH has been developed to prepare fluorinated polyether glycol.•The reactivity ratios of monomers were calculated according to Kelen–Tudos method.A novel fluorinated polyether glycol with fluorinated side chains is synthesized via “living/controlled” cationic ring-opening polymerization of tetrahydrofuran and fluorine-containing epoxy compounds (FO). The effects of polymerization conditions on monomer conversion, number-average molecular weight (Mn), molecular weight distribution (Mw/Mn) are measured. Our investigations have shown that the use of a mixed solvent (dichloromethane/1,4-dioxane) can prevent intra- and intermolecular transfer reactions, due to more nucleophilic oxygen atom in 1,4-dioxane. Using BF3·CH3OH/CH2OHCH2OH as initiation system, polymers with predictable number-average molecular weight, narrow molecular weight distribution (1.03 < Mw/Mn < 1.08) were produced. On the basis of the reactivity ratio of FO/THF and monomer conversion, a mechanism of living/controlled polymerization has been proposed.A novel fluorinated polyether glycol with fluorinated side chains was successfully synthesized via “living/controlled” cationic polymerization. The reaction rate of polymers increased linearly with the increase of monomer conversion. The obtained polymer has predictable molecular weight, narrow molecular weight distribution.