新型含磷阻燃型桐油基聚氨酯硬泡的制备及性能表征

Preparation and characterization of novel phosphorus-containing flame retardant tung oil-based rigid polyurethane foam

桐油与甘油在甲醇钠为催化剂的条件下发生醇解反应得到桐油醇解产物(GTO),GTO经环氧化得到环氧化桐油醇解产物(EGTO),EGTO与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)发生开环反应生成新型含磷阻燃型桐油基多元醇(PTOP)。PTOP部分取代聚醚多元醇(PPG4110)与异氰酸酯及助剂反应,通过一步法制备聚氨酯硬泡(RPUF)。采用万能试验机、热导率测定仪、热重分析仪和锥形量热仪分别考察RPUF的力学性能、热稳定性和燃烧行为。结果表明:随着PTOP替代石油基多元醇的比率增大,RPUF的压缩强度、密度、热导率先增大后减小,热稳定性提高,极限氧指数(LOI)由18.1%提高至26.0%,而总放热量先减小后增大,这主要是由于PTOP结构中的DOPO基团具有阻燃作用而PTOP结构中含有的桐油基脂肪链易于燃烧且热释放量较大。以上结果表明PTOP部分取代PPG4110制备的RPUF具有良好的阻燃性能和热稳定性。

The monoglyceride of tung oil (GTO) was prepared by using tung oil as raw material,sodium methoxide as catalyst,through alcoholysis reaction with glycerol,and epoxidized monoglyceride of tung oil (EGTO) synthesized by epoxidation.The novel flame retardant tung oil-based polyol (PTOP) was prepared through the ring opening reaction of EGTO with 9,10-dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide (DOPO).Rigid polyurethane foam (RPUF) was formed by one step via the reaction of PTOP,polyether polyol (PPG4110) with PAPI and chemical agents.The mechanical behavior,thermal stability and fire behavior of RPUFs were determined by an universal mechanical tester,thermal analyzer and cone calorimetry,respectively.The results showed that with the increase of the substitution of PPG4110 by PTOP,the compressive strength,density and thermal conductivity of RPUFs were increased then decreased,the thermal stability was elevated,the limiting oxygen index (LOI) of RPUF was raised from 18.1% to 26.0% and the total heat released was decreased and then increased,which was due to the flame retardancy of DOPO in PTOP while the fat chain of monoglyceride of tung oil in PTOP was easy to burn and the heat released was higher.RPUF was prepared by PTOP at different levels with good flame retardancy and excellent thermal stability.