磷腈的磷酸酯化研究
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摘要
本文基于大量国内外发表的文献的基础上,结合环状磷腈化合物在P原子上的反应活性以及磷-氮组合的协同效应等特殊性及其在阻燃性能上的特殊贡献,与另外一种常用阻燃剂磷酸酯类化合物,如亚磷酸三苯酯,本身具有优良阻燃性能,通过化学的方法将两者结合起来。期望可以克服这些磷酸酯类化合物自身存在的一些不足,如气化温度低,给加工过程带来不便,同时大多磷酸酯类化合物都属于小分子范畴,容易迁移等缺点。本文综合设计一类新型酯化磷腈化合物。
本论文的研究内容主要包含以下2个方面:用间接的方法研究合成磷酸酯化环三磷腈,将9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)磷酸酯通过上面的活泼H与醛基的加成反应引入到磷腈体系中来,制备磷酸酯化环三磷腈[N_3P_3 (OC_6H_4) CHOHPO (O) (C_6H_4)_2]_(6-n) [OC_6H_4 CHO]_n THBDO,分析其化学结构,并通过TGA测试其热稳定性。用直接的方法研究合成磷酸酯化环三磷腈,将磷酸二苯乙酯通过亲核取代反应引入到磷腈体系中来,制备性能优异的磷酸酯化环三磷腈[N_3P_3(OP(O_2Cl_2)H_8)_2)_2(O_2Cl_2H_8)_2] DPPPz。并通过各种分析测试方法如核磁、元素分析等鉴定产品的结构,对于直接法制备的DPPPz积累了一定的量,测试了其热稳定性以及阻燃性。测试结果表明,DPPPz是一个具有优良热稳定性的化学产物,初始分解温度也高达330°C并且在PC体系中展现优异的阻燃性能,在添加量为15%的时候通过UL-94的V -0级测试。同时在加工过程中发现由于它良好的热稳定性,没有像TPP那样出现大量的白烟,在阻燃测试过程中生成的烟气较TPP也有明显的改善。
Based on lots of published papers either domestic or overseas, novel phophorylated phosphazene compounds were synthesized successfully in indirect and direct ways respectively. The phosphate compound DOPO was induced by two steps. 4-hydroxybenzaldenhyde (4-HBA) reacted with hxacyclorotriphosphazene(HCCP)through nuclioatric substitution reaction first, and then continued to react with DOPO by additive reaction to give THBDO. The thermal stability of THBDO was evaluated accordingly.
Another way to induce phosphate compound into the phosphazene system directly by the reaction between hexacyclorotriphosphazene (HCCP) with 2 equiv of 2,2’-dihydroxybiphenyl produced one of the reagents [N_3P_3Cl_2(O_2Cl_2H_8)_2](DCCP),and Diphenyl chlorophosphate with ethanol gave the other reagent [C_2H_5OP(O_2Cl_2H_8)_2](DPEP). And then DCCP reacted with DPEP at 210℃under magnetic stirrer in nitrogen atmosphere to give a new type of phospazene compound [N_3P_3(OP(O_2Cl_2H_8)_2)_2(O_2Cl_2H_8)_2](DPPPZ). The product was characterized by 31P-NMR, 1H-NMR spectroscopy , elemental analysis. Its thermal degradation behavior was investigated with TGA with onset temperature 330.6℃. The combustion behaviors of these DPPPZ-PC samples were evaluated by the UL-94 test on a CZF-3 type instrument, and with the content of 12 wt%, the blends passed V-0 for UL-94 test.
本论文的研究内容主要包含以下2个方面:用间接的方法研究合成磷酸酯化环三磷腈,将9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)磷酸酯通过上面的活泼H与醛基的加成反应引入到磷腈体系中来,制备磷酸酯化环三磷腈[N_3P_3 (OC_6H_4) CHOHPO (O) (C_6H_4)_2]_(6-n) [OC_6H_4 CHO]_n THBDO,分析其化学结构,并通过TGA测试其热稳定性。用直接的方法研究合成磷酸酯化环三磷腈,将磷酸二苯乙酯通过亲核取代反应引入到磷腈体系中来,制备性能优异的磷酸酯化环三磷腈[N_3P_3(OP(O_2Cl_2)H_8)_2)_2(O_2Cl_2H_8)_2] DPPPz。并通过各种分析测试方法如核磁、元素分析等鉴定产品的结构,对于直接法制备的DPPPz积累了一定的量,测试了其热稳定性以及阻燃性。测试结果表明,DPPPz是一个具有优良热稳定性的化学产物,初始分解温度也高达330°C并且在PC体系中展现优异的阻燃性能,在添加量为15%的时候通过UL-94的V -0级测试。同时在加工过程中发现由于它良好的热稳定性,没有像TPP那样出现大量的白烟,在阻燃测试过程中生成的烟气较TPP也有明显的改善。
Based on lots of published papers either domestic or overseas, novel phophorylated phosphazene compounds were synthesized successfully in indirect and direct ways respectively. The phosphate compound DOPO was induced by two steps. 4-hydroxybenzaldenhyde (4-HBA) reacted with hxacyclorotriphosphazene(HCCP)through nuclioatric substitution reaction first, and then continued to react with DOPO by additive reaction to give THBDO. The thermal stability of THBDO was evaluated accordingly.
Another way to induce phosphate compound into the phosphazene system directly by the reaction between hexacyclorotriphosphazene (HCCP) with 2 equiv of 2,2’-dihydroxybiphenyl produced one of the reagents [N_3P_3Cl_2(O_2Cl_2H_8)_2](DCCP),and Diphenyl chlorophosphate with ethanol gave the other reagent [C_2H_5OP(O_2Cl_2H_8)_2](DPEP). And then DCCP reacted with DPEP at 210℃under magnetic stirrer in nitrogen atmosphere to give a new type of phospazene compound [N_3P_3(OP(O_2Cl_2H_8)_2)_2(O_2Cl_2H_8)_2](DPPPZ). The product was characterized by 31P-NMR, 1H-NMR spectroscopy , elemental analysis. Its thermal degradation behavior was investigated with TGA with onset temperature 330.6℃. The combustion behaviors of these DPPPZ-PC samples were evaluated by the UL-94 test on a CZF-3 type instrument, and with the content of 12 wt%, the blends passed V-0 for UL-94 test.
引文
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