A general survey of fluorinated phosphazene polymers starting from their synthesis in 1965 to recent times is presented. Various types of fluorinated phosphazenes are described depending on the way fluorine atoms are connected to the polyphosphazene skeleton. The characterization, properties and practical utilization of these compounds in different domains are critically discussed. 相似文献
Poly[bis(-phenoxyethoxy)phosphazene] [PBPEP] had been shown in our previous paper to be a very useful polymer for investigating the crystallization mechanism of polymers, as the crystallization rate of PBPEP is extraordinarily small when isothermally crystallized from the melt. The crystallization of the low molecular weight oligomers of PBPEP was first studied in comparison to the high molecular weight polymers. The oligomer-rich fraction was obtained by fractionation of the as-polymerized sample, which had a broad molecular weight distribution. The fractions thus obtained were characterized by solution viscometry and size exclusion chromatography. The melting temperature and the growth rate of the spherulite from the melt were investigated by differential scanning calorimetry and optical microscopy. The growth rate was one or two orders of magnitude smaller in the oligomer-rich fraction than in the other high molecular weight fractions. A collapsed spherulite appeared in the oligomer-rich fraction at high crystallization temperatures. It is speculated that in the oligomer-rich fraction there is an excess free energy due to defects in the crystal phase. This defect is considerably larger in the oligomer-rich fraction than in the other fractions because a large quantity of short length chains is present. 相似文献
Summary: This paper introduces a new inorganic poly(phosphazene disulfide) material. With unique element composition and molecular structure, the polymer has noncombustible safety and preferable conductivity. When used as cathode material for rechargeable lithium batteries, the polymer's first discharge capacity is as high as 467.9 mAh · g?1, which can be retained at 409.9 mAh · g?1 after 60 repeated cycles. Therefore, it has a great application potential in the field of lithium batteries.
Replacement of the Cl atoms by S? S groups by refluxing Na2S2 and linear poly(dichloro‐phosphazene). 相似文献
Low‐temperature anionic ring‐opening homopolymerizations and copolymerizations of two glycidol derivatives (allyl glycidyl ether (AGE) and ethoxyethyl glycidyl ether (EEGE)) are studied using a metal‐free catalyst system, 3‐phenyl‐1‐propanol (PPA) (an initiator) and 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris‐(dimethylamino)phosphoranylidenamino]‐2Λ5,4Λ5‐catenadi(phosphazene) (t‐Bu‐P4) (a promoter) in order to obtain well‐defined functional linear polyethers and diblock copolymers. With the aid of the catalyst system, AGE is found to successfully undergo anionic ring‐opening polymerization (ROP) even at room temperature (low reaction temperature) without any side reactions, producing well‐defined linear AGE‐homopolymer in a unimodal narrow molecular weight distribution. Under the same conditions, EEGE also undergoes polymerization, producing a linear EEGE‐homopolymer in a unimodal narrow molecular‐weight distribution. In this case, however, a side reaction (i.e., chain‐transfer reaction) is found to occur at low levels during the early stages of polymerization. The chemical properties of the monomers in the context of the homopolymerization reactions are considered in the design of a protocol used to synthesize well‐defined linear diblock copolyethers with a variety of compositions. The approach, anionic polymerization via the sequential step feed of AGE and EEGE as the first and second monomers, is found to be free from side reactions at room temperature. Each block of the obtained linear diblock copolymers undergoes selective deprotection to permit further chemical modification for selective functionalization. In addition, thermal properties and structures of the polymers and their post‐modification products are examined. Overall, this study demonstrates that a low‐temperature metal‐free anionic ROP using the PPA/t‐Bu‐P4 catalyst system is suitable for the production of well‐defined linear AGE‐homopolymers and their diblock copolymers with the EEGE monomer, which are versatile and selectively functionalizable linear aliphatic polyether platforms for a variety of post‐modifications, nanostructures, and their applications. 相似文献
High-resolution 19F, 1H, 31P and 13C solid-state NMR methods were assessed to ascertain their suitability for studying the morphological behavior in the crystalline
domain of phosphazene polymers with partially fluorinated side-chains. Poly[bis(trifluoroethoxy)phosphazene] (PBFP) was used as a sample system. Fast magic angle spinning (MAS), along with simultaneous
19F and 1H decoupling using the xy-16 sequence, were employed, as this has proven to greatly improve resolution in 13C spectra of perfluorinated materials. Information obtained from Discrimination Induced by Variable Amplitude Minipulses (DIVAM)
nutation experiments and cross-polarization (CP) methods aided the deconvolution analysis used to identify all components
in the 1H, 19F and 13C signals. DIVAM nutation experiments were also used to discriminate between signals from the amorphous and crystalline domain.
The crystallinity in the solvent-cast PBFP was determined to be approximately 70%, which was seen to increase to approximately
80% in the heat-treated material, for all nuclei studied. A preliminary assignment was made for the crystalline signals in
the 1H and 13C spectra to the α-, β- and γ-phases. Therefore, high-resolution 13C and 1H methods are valuable tools for morphological investigations into this class of polymer. 相似文献