含磷有机金属化合物的合成及其对聚乙烯的阻燃作用
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摘要
随着人们在阻燃有机高分子材料领域的绿色环保的追求及阻燃法规的日益苛刻,开发新型无卤阻燃剂及传统无卤阻燃剂的协同复配已成为大势所趋。本论文针对化学膨胀阻燃剂及金属离子在阻燃有机高分子材料中出现的优缺点,设计并合成了含磷和氮的化学膨胀阻燃剂,并将金属离子以配位键或共价键的形式结合上去,考察了不同的有机官能团及不同金属离子对有机高分子材料阻燃效果及阻燃机理的影响。
首先,采用邻苯二胺、水杨醛及亚磷酸二乙酯合成了含有磷氮元素的TEPAPM,并将Zn(Ⅱ)与此配体螯合得到了Zn-TEPAPM化合物。分别采用红外及核磁表征了其分子结构。在氮气中的热失重分析表明Zn-TEPAPM具有良好的自身催化成炭能力,热稳定性适于阻燃聚乙烯。随着Zn-TEPAPM的加入,不仅使聚乙烯的热稳定性和极限氧指数有一定程度的提高,还使聚乙烯的热释放速率、一氧化碳释放量和总放热量显著降低。当添加1wt%的Zn-TEPAPM于聚乙烯时,在锥形量热测试中热释放速率峰值比纯聚乙烯树脂的峰值降低了34%。
其次在合成TEPAPM基础上,采用乙二胺、苯甲醛(或3-甲醛吡啶)和亚磷酸二乙酯合成了两种膦酸酯EIBPE及EIPPE,并用浓盐酸将其水解分别得到EIBPA及EIPPA.利用有机膦酸与过渡金属离子反应活性高的特点将EIBPA及EIPPA与Zn(Ⅱ)反应得到EIBPA-Zn和EIPPA-Zn.热失重分析表明EIBPA-Zn及EIPPA-Zn的热稳定性要分别远高于EIBPA及EIPPA,且EIPPA-Zn的残炭量要大于EIBPA-Zn.在阻燃聚乙烯中发现的EIPPA-Zn易于催化树脂基体成炭,具有较好的阻燃效果。当添加量为25wt%时,热释放速率的峰值比纯树脂的峰值降低了70%,残炭量达到了59wt%。含这两个化合物的聚乙烯样品在氧指数测试中也取得了较好的阻燃效果。
第三,采用哌嗪、甲醛和亚磷酸合成了具有双膦酸官能团的有机膦酸化合物PPMPA,并将其与Zn(Ⅱ)在160℃下水热反应2d得到PPMPA-Zn.热失重测试中表明PPMPA-Zn具有较高的热稳定性,起始热分解温度达到了354℃。同时发现PPMPA-Zn在燃烧中具有体积膨胀效应。在阻燃聚乙烯中发现在仅添加5wt%的PPMPA-Zn时,样品在锥形量热测试中就已经形成良好的物理阻隔层,大幅度降低了热释放速率的峰值。当PPMPA-Zn的添加量达到25wt%时,已经形成完整且非常致密的物理阻隔层,热释放峰值比纯树脂的峰值降低了63%,炭层具有较高的强度。虽然在锥形量热测试中PPMPA-Zn可以达到很好的效果,但是由于PPMPA-Zn在热分解之后的产物的极性较强,与熔融的HDPE-MA树脂的极性相差较大,因此在氧指数测试中易产生炭层滑落的现象而导致氧指数不高。
第四,采用吗啡啉、甲醛和亚磷酸合成了具有单膦酸官能团的MMPA。 MMPA与过渡金属离子Zn(Ⅱ)和稀土金属离子Ce(Ⅲ)通过水热反应分别得到了层状的MMPA-Zn和纤维状的MMPA-Ce化合物。在锥形量热测试中,当MMPA-Zn的添加量增加至25wt%时,热释放峰值与纯树脂的峰值相比降低了47%,残炭量达到32.2wt%。由于残炭的表面形貌较粗糙,形成的物理阻隔层不够致密,所以热释放速率的峰值降低程度不如添加EIPPA-Zn和PPMPA-Zn的聚乙烯样品。纤维状的MMPA-Ce在阻燃聚乙烯时,发现添加为5wt%或25wt%于HDPE树脂中,热释放峰值相差较小,与纯树脂相比降低了约30%,这是因为MMPA-Ce在燃烧后剩下的磷酸铈化合物具有很高的熔点而导致炭层表面未形成较为完整致密的物理阻隔层。
最后,有机金属膦酸盐EIBPA-Zn、EIPPA-Zn、PPMPA-Zn、MMPA-Zn及MMPA-Ce对PE树脂的拉伸强度和杨氏模量均有不同程度的提高,主要归结于有机金属膦酸盐的晶体结构是由内层的P-O-M和外层的有机官能团构成。
The increased application of flammable polymeric materials in everyday life led to increased fire hazards and so flame retardants are very often incorporated into them to limit their flammability. Intumescent flame-retardant (IFR) additives containing phosphorus and nitrogen, which are halogen-free and more environmentally friendly, have been developed for imparting flame retardancy to polymeric materials. However, conventional IFRs also have some disadvantages, such as high loading fractions at the expense of the apparent decrease of the mechanical properties of the flame retardant polymers. So, the compounds containing transition metal element have been utilized for reducing the flammability of polymers due to these compounds can act both in the vapor phase, the condensed phase and at the gas/solid interface through a chemical and/or physical mechanism to reduce the flammability.
Firstly, we designed and synthesized a novel Zn (II) chelate, i.e. Zn tetraethyl (1,2-phenylenebis(azanediyl)) bis (2-hydroxylphenylmethylene) diphosphonate (Zn-TEPAPM), on the basis of zinc acetate,1,2-diamine benzene,2-hydroxybenzaldehyde and diethyl phosphonate. The chemical structure of Zn-TEPAPM was characterized by IR,1H-NMR,13C-NMR and31P-NMR. The results of thermal analysis showed that Zn-TEPAPM had excellent char-forming ability and the thermal stability match well the processing temperature of PE. Incorporation of1wt%Zn-TEPAPM leads to a reduction of32%for the peak heat release rate in the cone calorimeter test. Moreover, Zn-TEPAPM was demonstrated to be a very effective synergist of ammonium polyphosphate (APP).
Secondly, based on the above results, we used raw material of benzaldehyde or3-pyridinecarboxaldehyde, diethylamine and diethyl phosphonate to synthesized2,2'-(ethylenedi-imino) bis (benzylphosphonic-acid)(EIBPA) and2,2'-(ethylenedi-imino) bis (3-pirydylphosphonic-acid)(EIPPA). And then, the EIBPA-Zn and EIPPA-Zn were prepared as a microcrystalline powder by the reaction of Zn(OOCCH3)2·2H2O with EIBPA and EIPPA in the refluxed ethanol solution. The results of thermal analysis showed that EIBPA-Zn and EIPPA-Zn had excellent thermal stability and char-forming ability, especially for EIPPA-Zn which had higher char-forming ability than EIBPA-Zn. Incorporation of EIPPA-Zn in PE not only resulted in the improved LOI values, but markedly reduced the heat release rate (the PHRR value reduced by70%ompared with pure PE resin), total heat release and mass loss rate of PE and the char residue as much for59wt%.
Thirdly, we synthesized a zinc N,N-piperazinebis(methylenephosphonic acid)(PPMPA-Zn), on the basis of zinc acetate, piperazine, phosphorous acid, and formaldehyde. The chemical structure of PPMPA-Zn was characterized by IR and powdery X-Ray diffraction. The results of thermal analysis showed that PPMPA-Zn had excellent thermal stability, char-forming ability, and the initial thermal decomposition temperature reach to354℃. Incorporating5wt%PPMPA-Zn in PE resin, the PHRR value reduced to38%relative to pure PE resin and the char residue is much more intact. When loading25wt%PPMPA-Zn, the PHRR value reduced to63%relative to pure PE resin and the char residual mass reach to70.7wt%. Although adding PPMPA-Zn in PE resin can get a better result of flame retardancy in cone calorimeter test, it can not get good result in LOI test due to the residue of PPMPA-Zn has higher polarity than melt PE resin so result to the char residue move off from the burning surface.
Subsequently, we synthesized a zinc morpholinomethylphosphonic acid (MMPA-Zn) and MMPA-Ce, on the basis of zinc acetate, cerium nitrate, morpholine, phosphorous acid, and formaldehyde. And the chemical structure of MMPA-Zn and MMPA-Ce was characterized by IR and powdery X-Ray diffraction. Incorporating25wt%MMPA-Zn in PE resin, the PHRR value reduced to47%relative to pure PE resin and char residual mass reach to32.2wt%in the test of cone calorimeter. Because of the surface char residue was not compact enough, the PHRR value was not greatly reduced as incorporating EPPA-Zn and PPMPA-Zn compounds in PE resin. Incorporation of5wt%or25wt%fiber like MMPA-Zn in PE resin, there was not much difference in PHRR values and reduced about30%compared with pure PE resin. Due to the melt temperature of the residual MMPA-Ce was more higher than combusting temperature, so the char residue was composed by large amount of small gram.
Finally, incorporation of organic metal phosphonates of EIBPA-Zn, EIPPA-Zn, MMPA-Zn and MMPA-Ce in PE resin, the tensile stress and Young's modulus improve at a various degree due to the crystalline structure of organic metal phosphonates composed by inner inorganic group of P-O-M and outside organic group.
首先,采用邻苯二胺、水杨醛及亚磷酸二乙酯合成了含有磷氮元素的TEPAPM,并将Zn(Ⅱ)与此配体螯合得到了Zn-TEPAPM化合物。分别采用红外及核磁表征了其分子结构。在氮气中的热失重分析表明Zn-TEPAPM具有良好的自身催化成炭能力,热稳定性适于阻燃聚乙烯。随着Zn-TEPAPM的加入,不仅使聚乙烯的热稳定性和极限氧指数有一定程度的提高,还使聚乙烯的热释放速率、一氧化碳释放量和总放热量显著降低。当添加1wt%的Zn-TEPAPM于聚乙烯时,在锥形量热测试中热释放速率峰值比纯聚乙烯树脂的峰值降低了34%。
其次在合成TEPAPM基础上,采用乙二胺、苯甲醛(或3-甲醛吡啶)和亚磷酸二乙酯合成了两种膦酸酯EIBPE及EIPPE,并用浓盐酸将其水解分别得到EIBPA及EIPPA.利用有机膦酸与过渡金属离子反应活性高的特点将EIBPA及EIPPA与Zn(Ⅱ)反应得到EIBPA-Zn和EIPPA-Zn.热失重分析表明EIBPA-Zn及EIPPA-Zn的热稳定性要分别远高于EIBPA及EIPPA,且EIPPA-Zn的残炭量要大于EIBPA-Zn.在阻燃聚乙烯中发现的EIPPA-Zn易于催化树脂基体成炭,具有较好的阻燃效果。当添加量为25wt%时,热释放速率的峰值比纯树脂的峰值降低了70%,残炭量达到了59wt%。含这两个化合物的聚乙烯样品在氧指数测试中也取得了较好的阻燃效果。
第三,采用哌嗪、甲醛和亚磷酸合成了具有双膦酸官能团的有机膦酸化合物PPMPA,并将其与Zn(Ⅱ)在160℃下水热反应2d得到PPMPA-Zn.热失重测试中表明PPMPA-Zn具有较高的热稳定性,起始热分解温度达到了354℃。同时发现PPMPA-Zn在燃烧中具有体积膨胀效应。在阻燃聚乙烯中发现在仅添加5wt%的PPMPA-Zn时,样品在锥形量热测试中就已经形成良好的物理阻隔层,大幅度降低了热释放速率的峰值。当PPMPA-Zn的添加量达到25wt%时,已经形成完整且非常致密的物理阻隔层,热释放峰值比纯树脂的峰值降低了63%,炭层具有较高的强度。虽然在锥形量热测试中PPMPA-Zn可以达到很好的效果,但是由于PPMPA-Zn在热分解之后的产物的极性较强,与熔融的HDPE-MA树脂的极性相差较大,因此在氧指数测试中易产生炭层滑落的现象而导致氧指数不高。
第四,采用吗啡啉、甲醛和亚磷酸合成了具有单膦酸官能团的MMPA。 MMPA与过渡金属离子Zn(Ⅱ)和稀土金属离子Ce(Ⅲ)通过水热反应分别得到了层状的MMPA-Zn和纤维状的MMPA-Ce化合物。在锥形量热测试中,当MMPA-Zn的添加量增加至25wt%时,热释放峰值与纯树脂的峰值相比降低了47%,残炭量达到32.2wt%。由于残炭的表面形貌较粗糙,形成的物理阻隔层不够致密,所以热释放速率的峰值降低程度不如添加EIPPA-Zn和PPMPA-Zn的聚乙烯样品。纤维状的MMPA-Ce在阻燃聚乙烯时,发现添加为5wt%或25wt%于HDPE树脂中,热释放峰值相差较小,与纯树脂相比降低了约30%,这是因为MMPA-Ce在燃烧后剩下的磷酸铈化合物具有很高的熔点而导致炭层表面未形成较为完整致密的物理阻隔层。
最后,有机金属膦酸盐EIBPA-Zn、EIPPA-Zn、PPMPA-Zn、MMPA-Zn及MMPA-Ce对PE树脂的拉伸强度和杨氏模量均有不同程度的提高,主要归结于有机金属膦酸盐的晶体结构是由内层的P-O-M和外层的有机官能团构成。
The increased application of flammable polymeric materials in everyday life led to increased fire hazards and so flame retardants are very often incorporated into them to limit their flammability. Intumescent flame-retardant (IFR) additives containing phosphorus and nitrogen, which are halogen-free and more environmentally friendly, have been developed for imparting flame retardancy to polymeric materials. However, conventional IFRs also have some disadvantages, such as high loading fractions at the expense of the apparent decrease of the mechanical properties of the flame retardant polymers. So, the compounds containing transition metal element have been utilized for reducing the flammability of polymers due to these compounds can act both in the vapor phase, the condensed phase and at the gas/solid interface through a chemical and/or physical mechanism to reduce the flammability.
Firstly, we designed and synthesized a novel Zn (II) chelate, i.e. Zn tetraethyl (1,2-phenylenebis(azanediyl)) bis (2-hydroxylphenylmethylene) diphosphonate (Zn-TEPAPM), on the basis of zinc acetate,1,2-diamine benzene,2-hydroxybenzaldehyde and diethyl phosphonate. The chemical structure of Zn-TEPAPM was characterized by IR,1H-NMR,13C-NMR and31P-NMR. The results of thermal analysis showed that Zn-TEPAPM had excellent char-forming ability and the thermal stability match well the processing temperature of PE. Incorporation of1wt%Zn-TEPAPM leads to a reduction of32%for the peak heat release rate in the cone calorimeter test. Moreover, Zn-TEPAPM was demonstrated to be a very effective synergist of ammonium polyphosphate (APP).
Secondly, based on the above results, we used raw material of benzaldehyde or3-pyridinecarboxaldehyde, diethylamine and diethyl phosphonate to synthesized2,2'-(ethylenedi-imino) bis (benzylphosphonic-acid)(EIBPA) and2,2'-(ethylenedi-imino) bis (3-pirydylphosphonic-acid)(EIPPA). And then, the EIBPA-Zn and EIPPA-Zn were prepared as a microcrystalline powder by the reaction of Zn(OOCCH3)2·2H2O with EIBPA and EIPPA in the refluxed ethanol solution. The results of thermal analysis showed that EIBPA-Zn and EIPPA-Zn had excellent thermal stability and char-forming ability, especially for EIPPA-Zn which had higher char-forming ability than EIBPA-Zn. Incorporation of EIPPA-Zn in PE not only resulted in the improved LOI values, but markedly reduced the heat release rate (the PHRR value reduced by70%ompared with pure PE resin), total heat release and mass loss rate of PE and the char residue as much for59wt%.
Thirdly, we synthesized a zinc N,N-piperazinebis(methylenephosphonic acid)(PPMPA-Zn), on the basis of zinc acetate, piperazine, phosphorous acid, and formaldehyde. The chemical structure of PPMPA-Zn was characterized by IR and powdery X-Ray diffraction. The results of thermal analysis showed that PPMPA-Zn had excellent thermal stability, char-forming ability, and the initial thermal decomposition temperature reach to354℃. Incorporating5wt%PPMPA-Zn in PE resin, the PHRR value reduced to38%relative to pure PE resin and the char residue is much more intact. When loading25wt%PPMPA-Zn, the PHRR value reduced to63%relative to pure PE resin and the char residual mass reach to70.7wt%. Although adding PPMPA-Zn in PE resin can get a better result of flame retardancy in cone calorimeter test, it can not get good result in LOI test due to the residue of PPMPA-Zn has higher polarity than melt PE resin so result to the char residue move off from the burning surface.
Subsequently, we synthesized a zinc morpholinomethylphosphonic acid (MMPA-Zn) and MMPA-Ce, on the basis of zinc acetate, cerium nitrate, morpholine, phosphorous acid, and formaldehyde. And the chemical structure of MMPA-Zn and MMPA-Ce was characterized by IR and powdery X-Ray diffraction. Incorporating25wt%MMPA-Zn in PE resin, the PHRR value reduced to47%relative to pure PE resin and char residual mass reach to32.2wt%in the test of cone calorimeter. Because of the surface char residue was not compact enough, the PHRR value was not greatly reduced as incorporating EPPA-Zn and PPMPA-Zn compounds in PE resin. Incorporation of5wt%or25wt%fiber like MMPA-Zn in PE resin, there was not much difference in PHRR values and reduced about30%compared with pure PE resin. Due to the melt temperature of the residual MMPA-Ce was more higher than combusting temperature, so the char residue was composed by large amount of small gram.
Finally, incorporation of organic metal phosphonates of EIBPA-Zn, EIPPA-Zn, MMPA-Zn and MMPA-Ce in PE resin, the tensile stress and Young's modulus improve at a various degree due to the crystalline structure of organic metal phosphonates composed by inner inorganic group of P-O-M and outside organic group.
引文
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