Fluorinated Polyphosphazenes: A Survey

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.     

Oligomer-Rich Fraction from Polydisperse Sample of Poly(bis(β-phenoxyethoxy)phosphazene)

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.     

锂离子电池用磷腈类聚合物电解质的制备与性能

采用六氯环三磷腈高温开环聚合方法制备了聚二氯磷腈,然后采用醇钠法,取代聚二氯磷腈的氯,制备了聚二（二乙二醇单甲醚）磷腈（MEEP）,探索出了较佳的合成工艺,采用FT-IR、31P-NMR、13C-NMR、质谱对其进行了结构表征和分析。结果表明,所制备的磷腈聚合物确实为MEEP。采用自制的MEEP,与三氟甲基磺酸锂（LiCF3SO3）盐进行复配,制备了锂离子电池用聚合物固体电解质,对其热稳定性、导电性进行了测试,其开始分解温度在200℃以上,室温电导率达到了1.187×10-4S/cm（25℃）,具有较佳的导电性和热稳定性,可用于锂离子电池的电解质。     

A Novel Inorganic Polymer as Cathode Material for Secondary Lithium Batteries

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).     

含磷腈环氧树脂阻燃和热解动力学

采用热重(TG)和微商热重(DTG)实验分析技术,分别对自制的六-对氨基苯氧基环三磷腈(PNH)和4,4’-二氨基二苯甲烷(DMA)为E51型环氧树脂的固化剂,研究了在氮气和空气氛围中2种环氧树脂的阻燃特性和热解动力学;运用Achar法和Coats-Redfern法建立了二者的热裂解动力学模型,得到了2种体系的动力学表观活化能和指前因子。研究表明,与不含磷环氧树脂相比,磷腈固化的环氧树脂更易发生热裂解,而在高温阶段却明显具有阻燃特性;磷腈固化的环氧树脂裂解后期残炭量较高,其活化能与其阻燃机理有关:即表观活化能越大阻燃性越强。     

聚双正丁氧基磷腈的合成与表征

通过六氯环三磷腈的热开环聚合合成了线性聚二氯磷腈(PDCP)中间体,探讨了聚合时间、聚合温度单体纯度及空气湿度等对PDCP合成的影响,采用FT-IR、TGA对PDCP进行了表征。TGA结果表明,PDCP呈现明显的二段降解性;通过正丁醇对PDCP进行亲核取代合成了聚双正丁氧基磷腈,采用FT-IR、TGA、SEM对聚双正丁氧基磷腈进行了表征,TGA结果表明,聚双正丁氧基磷腈具有优良的热稳定性和较高的残留率,SEM结果表明,材料形貌呈现无定形态分布,而且其表面比较光滑无明显缺陷。     

Well‐Defined Functional Linear Aliphatic Diblock Copolyethers: A Versatile Linear Aliphatic Polyether Platform for Selective Functionalizations and Various Nanostructures

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.     

Synthesis and properties of cyclotriphosphazene and perfluoropolyether‐based lubricant with polar functional groups

A novel hard disk lubricant IDL2 was synthesised by reacting sodium 4‐((2,2‐dimethyl‐1,3‐dioxolan‐4‐yl)methoxy)phenoate with hexachlorocyclotriphosphazene, followed by treatment with 1H,1H‐perfluoro‐3,6,9‐trioxatridecan‐1‐ol in the presence of sodium hydride and subsequent hydrolysis using sulfuric acid. The chemical structure of IDL2 was confirmed by proton nuclear magnetic resonance (¹H NMR), phosphorus‐31 (³¹P) NMR spectroscopy and mass spectrometer. The thermal property of IDL2 was analysed using thermal gravimetric analysis (TGA) and it shows better thermal stability than two commercial lubricants Z‐DOL and Z‐Tetraol with two and four terminal hydroxy groups, respectively. IDL2 was found to have comparable hydrophobicity to commercial lubricants Z‐DOL, A20H and Z‐Tetraol with water contact angles in the range of 78 – 85°, revealing that IDL2 has analogous surface energy to these commercial lubricants. IDL2 exhibits comparable friction coefficient to A20H and Z‐Tetraol, but much lower than Z‐DOL. More interestingly, it has a much high bonding ratio when compared with commonly used commercial lubricants under the same testing conditions due to the presence of two polar hydroxy groups, which enhance the interaction between lubricant and substrate. These promising properties of IDL2 show that it would be very potential for real application as a hard disk drive lubricant. Copyright © 2016 John Wiley & Sons, Ltd.     

A Morphological Study of Poly[bis(trifluoroethoxy)phosphazene] Using High Resolution Solid-State 1H, 19F, 31P and 13C NMR Spectroscopy

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.     

一种磷腈化合物的合成及其在PS无卤阻燃体系中的应用

阐述了以新的方法合成无卤素的低相对分子质量磷腈化合物二(苯氧基)磷酰基三(苯氧基)磷腈，对其结构和其他性能进行了表征。将其与聚苯乙烯按比例共混后测试了其氧指数和力学性能等指标，发现当该化合物含量提高时，其氧指数升高，力学性能呈现先升后降的趋势。以电镜和红外表征，发现两相相容性能良好。说明二(苯氧基)磷酰基三(苯氧基)磷腈是一种新型的无卤阻燃剂，可以改善聚苯乙烯的阻燃性能，在一定含量范围中，对力学性能影响不大。可以预测，在选择合适的协调体系下，此化合物可以极大地改善聚苯乙烯的阻燃性能和力学性能。