阻燃剂的疏水改性对水性膨胀型防火涂料性能的影响
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摘要
水性膨胀型防火涂料由于具有低挥发性有机化合物、低能耗等优点,成为膨胀型防火涂料发展的一个重要方向。但由于防火涂料中主要组分(聚磷酸铵、季戊四醇)耐水性差,从而导致水性膨胀型防火涂料的综合性能不佳。因此,非常有必要提高水溶性组分的耐水性。
本论文采用工艺简捷、后处理方便且成本较低的物理方法,选用疏水性改性剂对耐水性差的防火助剂进行疏水改性。首先,考察改性剂包覆改性聚磷酸铵(APP)对防火涂料的耐水性能、热性能、耐火性能以及耐酸碱性能的影响;其次,考察甲基硅油疏水改性PER及其与改性后的APP相互作用对防火涂料耐水性的影响;最后,采用热失重分析法考察防火涂料组分之间的相互作用,并在此基础上,进一步考察防火助剂表面改性对防火涂料组分之间的相互作用的影响。本论文主要研究成果有:
1、采用物理方法对APP进行疏水改性,有效地提高防火涂料的耐水性能。通过水溶性以及耐水性测试手段比较发现甲基硅油疏水效果较液态石蜡好,2 wt%甲基硅油改性后的APP制得的防火涂料经48 h耐水性实验后无起泡、脱层现象。甲基硅油改性APP提高了防火涂料高温残炭量,800℃时,残炭量提高5%。甲基硅油改性APP后,一定程度上降低了钢板背温,提高了防火涂料的耐火性能,但对耐酸碱性无明显的影响。随着甲基硅油含量的增加,炭化层发泡更均匀。
2、甲基硅油疏水改性后的PER与改性后的APP协同作用对防火涂料耐水性的改善明显优于单独改性的APP、PER对防火涂料耐水性的影响。热失重分析结果显示,防火助剂之间以及防火助剂与BP108之间均具有协同作用,这种协同作用提高了残留物的高温热稳定性。甲基硅油与防火涂料的组分具有明显的协同作用,提高了高温残留量。甲基硅油对APP热行为的影响较PER大,800℃时,改性后的APP残留量提高了14%。单独改性APP制得的防火涂料残留量最大,800℃时,其残留量较单独改性PER制得的防火涂料及改性后的APP与改性后的PER制得的防火涂料提高约4%。
Water-borne intumescent fire retardant coatings become an important development trend because of its low energy consumption and low volatile organic compound. But their comprehensive properties may be influenced because of poor water resistance of the flame retardant. Therefore, hydrophobic modification of the flame retardant is needed.
The surface of the flame retardant was treated by hydrophobic modifiers in physical methods which had the advantages of short-cut process, low cost and convenient post-processing in this dissertation. First, the water resistance, fire resistance, acid and alkali resistance of the fire retardant coatings have been investigated after ammonium polyphosphate (APP) modified by hydrophobic modifiers. Next, effect of interaction between modified PER and modified APP on the water resistance of the fire retardant coatings has been investigated. Finally, interaction among the components of the fire retardant coatings and effect of the surface modification of the flame retardant on this interaction has also been investigated by thermal gravimetric analysis. The key works and conclusions were listed as following:
The water resistance was effectively improved with modified APP in physical method. Methylsilicone oil showed better hydrophobicity by the water-soluble and water resistance testing. Fire retardant coatings after modification showed better water resistance without bubbles after 48 h water resistance testing. The residual weight of the fire retardant coatings increased after adding methylsilicone oil. The residual weight increased by 5% at 800℃. Modified APP with methylsilicone reduced the back temperature, improved the fire resistance. But modified APP with methylsilicone had less effect on the acid and alkali resistance of the fire retardant coatings. Carbon foam became more uniform with increase of content of methylsilicone oil.
The synergistic effect of modified APP and modified PER strongly improved the water resistance of the fire retardant coatings, which showed better water resistance than the fire retardant coatings with modified APP, as well as that with modified PER. Synergistic effect existed not only among the flame retardants, but also between the flame retardants and BP108. This synergy improved the high-temperature heat stability of the residues. The obvious synergy between silicone fluid and the components of fire retardant coatings improved the residual weight. The effect of methylsilicone oil on thermal behavior of APP was larger than PER. The residual weight of modified APP increased by 14% than unmodified APP at 800℃. The residual weight of the fire retardant coating with modified APP increased by 4% than that with modified PER, as well as that with modified APP and modified PER at 800℃.
本论文采用工艺简捷、后处理方便且成本较低的物理方法,选用疏水性改性剂对耐水性差的防火助剂进行疏水改性。首先,考察改性剂包覆改性聚磷酸铵(APP)对防火涂料的耐水性能、热性能、耐火性能以及耐酸碱性能的影响;其次,考察甲基硅油疏水改性PER及其与改性后的APP相互作用对防火涂料耐水性的影响;最后,采用热失重分析法考察防火涂料组分之间的相互作用,并在此基础上,进一步考察防火助剂表面改性对防火涂料组分之间的相互作用的影响。本论文主要研究成果有:
1、采用物理方法对APP进行疏水改性,有效地提高防火涂料的耐水性能。通过水溶性以及耐水性测试手段比较发现甲基硅油疏水效果较液态石蜡好,2 wt%甲基硅油改性后的APP制得的防火涂料经48 h耐水性实验后无起泡、脱层现象。甲基硅油改性APP提高了防火涂料高温残炭量,800℃时,残炭量提高5%。甲基硅油改性APP后,一定程度上降低了钢板背温,提高了防火涂料的耐火性能,但对耐酸碱性无明显的影响。随着甲基硅油含量的增加,炭化层发泡更均匀。
2、甲基硅油疏水改性后的PER与改性后的APP协同作用对防火涂料耐水性的改善明显优于单独改性的APP、PER对防火涂料耐水性的影响。热失重分析结果显示,防火助剂之间以及防火助剂与BP108之间均具有协同作用,这种协同作用提高了残留物的高温热稳定性。甲基硅油与防火涂料的组分具有明显的协同作用,提高了高温残留量。甲基硅油对APP热行为的影响较PER大,800℃时,改性后的APP残留量提高了14%。单独改性APP制得的防火涂料残留量最大,800℃时,其残留量较单独改性PER制得的防火涂料及改性后的APP与改性后的PER制得的防火涂料提高约4%。
Water-borne intumescent fire retardant coatings become an important development trend because of its low energy consumption and low volatile organic compound. But their comprehensive properties may be influenced because of poor water resistance of the flame retardant. Therefore, hydrophobic modification of the flame retardant is needed.
The surface of the flame retardant was treated by hydrophobic modifiers in physical methods which had the advantages of short-cut process, low cost and convenient post-processing in this dissertation. First, the water resistance, fire resistance, acid and alkali resistance of the fire retardant coatings have been investigated after ammonium polyphosphate (APP) modified by hydrophobic modifiers. Next, effect of interaction between modified PER and modified APP on the water resistance of the fire retardant coatings has been investigated. Finally, interaction among the components of the fire retardant coatings and effect of the surface modification of the flame retardant on this interaction has also been investigated by thermal gravimetric analysis. The key works and conclusions were listed as following:
The water resistance was effectively improved with modified APP in physical method. Methylsilicone oil showed better hydrophobicity by the water-soluble and water resistance testing. Fire retardant coatings after modification showed better water resistance without bubbles after 48 h water resistance testing. The residual weight of the fire retardant coatings increased after adding methylsilicone oil. The residual weight increased by 5% at 800℃. Modified APP with methylsilicone reduced the back temperature, improved the fire resistance. But modified APP with methylsilicone had less effect on the acid and alkali resistance of the fire retardant coatings. Carbon foam became more uniform with increase of content of methylsilicone oil.
The synergistic effect of modified APP and modified PER strongly improved the water resistance of the fire retardant coatings, which showed better water resistance than the fire retardant coatings with modified APP, as well as that with modified PER. Synergistic effect existed not only among the flame retardants, but also between the flame retardants and BP108. This synergy improved the high-temperature heat stability of the residues. The obvious synergy between silicone fluid and the components of fire retardant coatings improved the residual weight. The effect of methylsilicone oil on thermal behavior of APP was larger than PER. The residual weight of modified APP increased by 14% than unmodified APP at 800℃. The residual weight of the fire retardant coating with modified APP increased by 4% than that with modified PER, as well as that with modified APP and modified PER at 800℃.
引文
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[2]加万里.水性超薄型钢结构防火涂料耐火性能的研究[D].西安;西北大学, 2010.
[3]王华进,王坚明,管朝祥.薄型钢结构防火涂料[J].涂料工业, 2001, 3(2): 16-18.
[4]张赟.膨胀型水性防火涂料的研究[J].现代涂料与涂装, 2000, (5): 12-13.
[5]舒凯征.水性硅丙树脂超薄膨胀型钢结构防火涂料的研制[D].南京;南京工业大学, 2006.
[6]王锦成.膨胀型阻燃剂的研制及其在聚氨酯涂料中的应用[D].上海;东华大学2003.
[7] Li G, Liang G, He T, Et Al. Effects of EG and MoSi2 on thermal degradation of intumescent coating[J]. Polymer Degradation and Stability 2007, 92:569-579.
[8] Wang Z, Han E, Ke W. Influence of nano-LDHs on char formation and fire-resistant properties of flame-retardant coating[J]. Progress in Organic Coatings, 2005, 53(1): 29-37.
[9] Wang Z, Han E, Ke W. Fire-resistant effect of nanoclay on intumescent nanocomposite coatings[J]. Journal of Applied Polymer Science, 2007, 103(3): 1681-1689.
[10] Wang Z, Han E, Ke W. Influence of expandable graphite on fire resistance and water resistance of flame-retardant coatings[J]. Corrosion Science, 2007, 49(5): 2237-2253.
[11]杨卫疆,诸秋萍,陆亨荣.膨胀型防火涂料炭化层形成过程的探讨[J].化学建材, 2001, (6): 20-23.
[12]欧育湘,李建军.阻燃剂—性能、制造及应用[M].北京:化学工业出版社,2005.
[13]杜建科,卢艳萍,陈建.差示扫描量热法分析防火涂料的膨胀体系[J].材料保护, 2002, 35(8): 5-7.
[14] Camino G, Costa L, Cortemiglia Mpld. Overview of Fire Retardant Mechanisms [J]. Polymer Degradation and Stability, 1991, 33:131-154.
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