含磷型聚合甘油脂肪酸酯阻燃增塑剂的制备与应用

Preparation and Application of a P-containing Polyglycerol Ester Fire-retardant Plasticizer

为了提高油脂增塑剂的阻燃性,开发以生物柴油副产粗甘油为直接原料的高附加值产品,以粗甘油、油酸和9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物（DOPO）为主原料,经聚合、酯化、环氧化和开环反应,合成含磷型大分子阻燃增塑剂DOPO-环氧乙酰化聚合甘油脂肪酸酯（DOPO-EAPFAE）,并通过红外谱图（FT-IR）和核磁共振（~1H NMR）确认了其结构。研究了DOPO-EAPFAE用量对聚氯乙烯（PVC）体系力学性能的影响;通过对PVC样条的热重分析（TG）、极限氧指数（LOI）测定和垂直燃烧测试等,分析了PVC制品的热稳定性和阻燃性能。结果表明：当DOPOEAPFAE代替邻苯二甲酸二辛酯（DOP）用量为60%时,PVC样条仍具有良好的力学性能;而LOI从21.3上升到了28.7,阻燃级别达到V0级;说明该阻燃增塑剂可有效地改善PVC增塑体系的阻燃性。与小分子阻燃剂磷酸三（2-氯丙基）酯（TCPP）相比,DOPO-EAPFAE阻燃性不仅优于TCPP,而且具有更好的热稳定性能。

In order to improve the flame retardancy of oil plasticizer and develop high value-added products using crude glycerin from by-product of diesel oil as starting materials,a novel P-containing soybean-oil-based fire-retardant plasticizer（ DOPOEAPFAE） was synthesized using crude glycerin,oleic acid and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide（ DOPO）as raw material through polymerization,esterification,epoxidation and ring opening reaction. The structure was verified by Fourier transform infrared（ FT-IR） spectrometry and nuclear magnetic resonance spectroscopy. Thermo-gravimetric behavior and flame retardant properties were evaluated by thermal gravimetric analysis,oxygen index test and vertical burning test. When the amount60% of phthalic acid dioctyl ester（ DOP） was replaced by DOPO-EAPFAE in PVC blends,PVC blends still has good mechanical properties. The limiting oxygen index（ LOI） of the blends increased from 21. 3 to 28. 7,and flame retardant level reached V0 grade. This indicated that the product can effectively improve the flame retardancy of PVC blends. The plasticity and flammability of DOPO-EAPFAE was better than tris（ chlorisopropyl） phosphate（ TCPP）. Comparing to small molecular flame retardant tris（ 1-chloro-2-propyl） phosphate（ TCPP）,flame retardant of DOPO-EAPFAE was not only superior to TCPP,but also exhibited better thermal stability.