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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Thermally induced structural transformations of linear coordination polymers based on aluminum tris(diorganophosphates)
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Thermally induced structural transformations of linear coordination polymers based on aluminum tris(diorganophosphates)

机译：基于铝三（二有机磷酸盐）的线性配位聚合物的热诱导结构变换

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摘要

The thermal transitions of inorganic-organic hybrid polymers composed of linear aluminum tris(diorganophosphate) chains with a general formula of catena-Al[O2P(OR)(2)](3) (where R = C-1-C-8 alkyl group or phenyl moiety) have been studied by means of DSC, powder XRD, TGA and TG-QMS, as well as optical spectroscopy. DSC and XRD reveal that most of them undergo reversible structural transformations in the solid state between -100 and 200 degrees C caused by the changes in conformation of their organic substituents; however, a translational displacement of the rigid polymeric chains occurs only in the case of the derivative bearing long 2-ethylhexyl groups, which becomes liquid at about 140 degrees C. The thermal decomposition of the studied polymers begins between 200 and 265 degrees C depending on the type of organic substituent R decorating their aluminophospate core. TGA combined with mass spectrometry of the evolved gaseous products shows that the pyrolytic decomposition of Al[O2P(OR)(2)](3) proceeds either through -elimination of olefin (for compounds with C-2-C-8 aliphatic ligands), or a homolytic cleavage of the P-OR bond (for methyl and phenyl derivatives); both processes are accompanied by condensation of the newly formed POH groups and liberation of water. Powder XRD, FTIR and SEM analyses of the solid residues indicate that thermolysis of Al[O2P(OR)(2)](3) accompanied by olefin elimination leads to the formation of condensed aluminum phosphates, mainly aluminum cyclohexaphosphate, exhibiting porous morphology. On the other hand, thermal degradation of methyl or phenyl derivatives results in amorphous aluminophosphate residues, and the latter contains conducting carbonaceous phases.
机译：由线性铝三（二有机磷酸盐）链组成的无机 - 有机杂化聚合物的热转变，其具有Catena-Al [O2P（或）（2）（2）]（3）的通式（其中R = C-1-C-8烷基已经通过DSC，粉末XRD，TGA和TG-QM以及光学光谱研究了基团或苯基部分。 DSC和XRD揭示了大多数在其有机取代基的变化变化引起的-100和200摄氏度之间的固态中经过可逆的结构变换;然而，刚性聚合物链的平移位移仅在衍生轴承的长2-乙基己基的情况下发生，其在约140℃下变为液体。研究的聚合物的热分解取决于200和265摄氏度之间有机取代基r的类型装饰其铝化合物核心。 TGA与进化气态产物的质谱相结合，表明Al [O2P（或）（2）]（2）]（3）的热解分解通过烯烃的尿液进行（用于用C-2-C-8脂族配体的化合物） ，或对p-或键的均解裂解（对于甲基和苯基衍生物）;这两个过程都伴随着新形成的诗群和水的解放的凝结。固体残留物的粉末XRD，FTIR和SEM分析表明Al [O2P（或）（2）]（3）的热解伴有烯烃消除，导致形成浓缩铝磷酸铝，主要是铝环磷酸盐，表现出多孔形态。另一方面，甲基或苯基衍生物的热降解导致无定形的铝磷酸盐残基，后者含有导电碳质相。

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