Jin Peng, Yao Qiang, Cao Weihong, Sun Jinhao, Zhao Yueying
School of Chemistry and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, China.
Key Laboratory of Bio-Based Polymeric Materials Technology and Application of Zhejiang Province, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China.
Polymers (Basel). 2025 May 5;17(9):1254. doi: 10.3390/polym17091254.
To understand the effect of the hydroxyl group and processing temperatures on dielectric losses of flame retardants and flame-retardant polymers, the performance difference between 6-methyldibenzo[c,e][1,2]oxaphosphinine 6-oxide (DOPO-Me) and 6-(hydroxymethyl)dibenzo[c,e][1,2]oxaphosphinine 6-oxide (DOPO-HM) has been investigated, respectively, in non-polar and polar polymers at 7-20 GHz. DOPO-HM and DOPO-Me differ by only one OH group. The former demonstrates a lower dissipation factor (Df) than the latter, owing to hydrogen bonds. In polystyrene and crosslinked polyphenylene oxide, both flame retardants increase a dielectric loss of flame-retardant polymers, with DOPO-HM being less detrimental because of its higher crystallizability and lower plasticization. In polar poly(methyl methacrylate) (PMMA), conformational changes in PMMA main chains caused by flame retardants and high processing temperatures lead to an early Df drop of PMMA at low loadings of the flame retardants. At high loadings, a change in the physical form of flame retardants from a primitive crystalline state to an amorphous state increases a dielectric loss of flame retardant PMMA, with DOPO-HM resulting in a slightly higher dielectric loss than DOPO-Me. These results prove that the effect of a hydroxyl group in organophosphorus structures on the dielectric loss of flame-retardant polymers is crucially dependent on its interaction with the polymer matrix.
为了解羟基和加工温度对阻燃剂及阻燃聚合物介电损耗的影响,分别研究了6-甲基二苯并[c,e][1,2]氧杂磷杂环庚烷6-氧化物(DOPO-Me)和6-(羟甲基)二苯并[c,e][1,2]氧杂磷杂环庚烷6-氧化物(DOPO-HM)在7-20 GHz频率下于非极性和极性聚合物中的性能差异。DOPO-HM与DOPO-Me仅相差一个羟基。由于氢键作用,前者的损耗因子(Df)低于后者。在聚苯乙烯和交联聚苯醚中,两种阻燃剂均会增加阻燃聚合物的介电损耗,而DOPO-HM因其较高的结晶性和较低的增塑作用,影响较小。在极性聚甲基丙烯酸甲酯(PMMA)中,阻燃剂和高加工温度引起的PMMA主链构象变化导致在低阻燃剂负载量时PMMA的Df提前下降。在高负载量时,阻燃剂物理形态从原始结晶态转变为非晶态会增加阻燃PMMA的介电损耗,其中DOPO-HM导致的介电损耗略高于DOPO-Me。这些结果证明,有机磷结构中的羟基对阻燃聚合物介电损耗的影响关键取决于其与聚合物基体的相互作用。