CN104479213A - 一种垂直自熄的低烟阻燃的陶瓷化高聚物组合物及其用途 - Google Patents

一种垂直自熄的低烟阻燃的陶瓷化高聚物组合物及其用途 Download PDF

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CN104479213A
CN104479213A CN201410806080.XA CN201410806080A CN104479213A CN 104479213 A CN104479213 A CN 104479213A CN 201410806080 A CN201410806080 A CN 201410806080A CN 104479213 A CN104479213 A CN 104479213A
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Abstract

本发明公开了一种垂直自熄的低烟阻燃的陶瓷化高聚物组合物及其用途,该组合物包含:矿物硅酸盐10-45%;磷酸盐8-15%;氰尿酸三聚氰盐10-20%;高分子聚合物或其合金15-50%;有机硅聚合物1-5%;软化剂3-8%;发泡剂0-18%;其中,高分子聚合物或其合金可选择热塑性高聚物、热固性高聚物、热塑性弹性体、交联的高聚物、交联的弹性体或橡胶的共聚物或混合物中至少一种;有机硅聚合物为高分子量硅酮阻燃添加剂。本发明提供的高聚物组合物在380℃以上的有氧或无氧以及有焰或无焰的情况下,可垂直自熄、能烧结成非常坚硬的绝缘、隔火、隔温、阻燃、防火、耐火微孔陶瓷壳体;其在烧蚀过程中低烟、无毒、无害;可以承载2100℃,180分钟以上的烧蚀,能够承受喷淋、震动,不延燃、不滴落。

Description

一种垂直自熄的低烟阻燃的陶瓷化高聚物组合物及其用途
技术领域
本发明属于高分子聚合物材料,涉及一种改性的高分子聚合物材料,具体涉及一种垂直自熄的低烟阻燃防火耐火的陶瓷化高聚物组合物。
背景技术
目前高分子聚合物材料,通过改性都只具有阻燃性,而没有防火性和耐火性。大多数的阻燃高分子聚合物燃烧以后,都会变成粉末状的灰烬,特别是在火灾高温的情况下,一边燃烧一边滴落或脱落,不能承受喷淋、震动和高温燃烧;有些阻燃高分子聚合物还有延燃、滴落现象,会造成二次火灾;还有些阻燃高分子聚合物在燃烧的过程中会产生大量的有毒、有害气体和粉尘产生,对人体会造成严重的伤害以致死亡;国内外的建筑住宅、医院、商场、影剧院、娱乐场所、宾馆、石油、化工、煤矿、冶金、钢铁等火灾,汽车线着火等等,都与高分子聚合物材料的阻燃性、防火性、耐火性有着直接的关系。
因此,迫切需要一种,可垂直自熄、在380℃以上的有氧或无氧以及有焰或无焰的情况下,可垂直自熄、能烧结成非常坚硬的隔火、隔温、阻燃、防火、耐火陶瓷壳体的陶瓷化高聚物组合物,高聚物组合物在烧蚀过程中低烟、无毒、无害;并且能够承受喷淋震动,不延燃、不滴落。
发明内容
本发明的目的是提供一种在380℃以上的有氧或无氧以及有焰或无焰的情况下,可垂直自熄、能烧结成非常坚硬的绝缘、隔火、隔温、阻燃、防火、耐火陶瓷壳体的陶瓷化高聚物组合物。
为达到上述目的,本发明提供了一种垂直自熄的低烟阻燃的陶瓷化高聚物组合物,该组合物包含以下按质量百分数计的原料:
矿物硅酸盐   10-45%
磷酸盐        8-15%
氰尿酸三聚氰盐  10-20%
高分子聚合物或其合金   15-50%
有机硅聚合物       1-5%
软化剂            3-8%
发泡剂           0-18%;
所述的高分子聚合物或其合金可选择热塑性高聚物、热固性高聚物、热塑性弹性体、交联的高聚物、交联的弹性体或橡胶的共聚物或混合物中至少一种;所述的有机硅聚合物为高分子量硅酮阻燃添加剂。
上述的高聚物组合物,其中,所述的矿物硅酸盐包含陶土、蒙脱土、蒙脱石、长钾石、高岭土、锂辉石、云母石、透锂辉石、长石、滑石,使用上述矿物硅酸盐两种或两种以上至少一种矿物化合物的混合物。
上述的高聚物组合物,其中,所述的磷酸盐是指磷酸氢二铵、磷酸二氢铵、磷酸氢钙、磷酸钙、焦磷酸钙、磷酸二氢钾、磷酸氢二钾、酸式焦磷酸钠、磷酸二氢钠、磷酸氢二钠、聚磷酸铵、磷酸钠、焦磷酸钠中的一种或几种的混合物。
上述的高聚物组合物,其中,所述的氰尿酸三聚氰盐为氰尿酸三聚氰胺。
所述的高分子聚合物选择热塑型和交联型的聚烯烃类共聚物或其混合物中至少一种。
上述的高聚物组合物,其中,所述的高分子聚合物选择聚烯烃、聚硅氧烷、乙烯基聚合物、氯磺化聚乙烯、氯化聚乙烯、聚氨酯、聚酯、聚酰胺、聚乙烯、聚醋酸乙烯脂、三元乙丙橡胶、二元乙丙橡胶、氯化聚乙烯、天然橡胶、顺丁橡胶、丁苯橡胶、丁腈橡胶、氯丁橡胶、丁基橡胶、环氧树脂、酚醛树脂以及均聚物、共聚物、弹性体或树脂及其混合物中的至少一种。
上述的高聚物组合物,其中,所述的软化剂为低分子聚合物,该低分子聚合物选择矿物油、植物油脂、合成油脂中的任意一种或几种的混合物。
上述的高聚物组合物,其中,所述的发泡剂选择偶氮二异丁腈、偶氮二甲酰胺等中的一种或两种的混合物或其改性物。
上述的高聚物组合物,其中,该组合物烧结后的坚硬的陶瓷化残余物的弯曲强度达到0.3-9MPa;其燃烧后的坚硬的陶瓷化残余物质量保留量可达80-85%;尺寸变化率为1-7%。
本发明还提供了一种根据上述的垂直自熄的低烟阻燃的陶瓷化高聚物组合物的用途,该组合物能用于阻燃防火耐火高聚物发泡保温材料、阻燃防火耐火隔温隔热高聚物舰船发泡保温材料、阻燃防火耐火隔温隔热高聚物高速铁路列车发泡保温材料、阻燃防火耐火隔温隔热高聚物高铁保温材料、阻燃防火耐火隔温隔热高聚物汽车发泡保温材料、阻燃防火耐火隔温隔热高聚物飞机发泡保温材料、阻燃防火耐火隔温隔热高聚物建筑、汽车、舰船、飞机、家具、电气、家用电器用发泡材料、阻燃防火耐火隔温隔热高聚物外墙发泡保温建筑材料中。
本发明提供的高聚物组合物在380℃以上的有氧或无氧以及有焰或无焰的情况下,可垂直自熄、能烧结成非常坚硬的绝缘、隔火、隔温、阻燃、防火、耐火陶瓷壳体的陶瓷化高聚物组合物,高聚物组合物在烧蚀过程中低烟、无毒、无害,烧蚀时间越长,温度越高,陶瓷壳体越坚硬,可以承载2100℃,180分钟以上的烧蚀,能够承受喷淋震动,不延燃、不滴落。
具体实施方式
以下结合实施例对本发明的技术方案做进一步的说明。
实施1-6
在温度为150-170℃炼塑机上,将树脂加上,待熔融后再将其他料慢慢加入,混炼均匀后,打5个三角包,然后将辊距放至5mm下片;然后在温度为130℃的硫化机上进行试片的压片,然后对试片进行测试。实施例1-6的原料配方及所得高聚物组合物的性能测试数据如下表1所示。
表1:实施例1-6的原料配方及其产物的性能测试数据
                                                 
实施例7-12
在温度为小于70℃炼胶机上,将橡胶加上,待橡胶包辊后,再将其他料慢慢加入,混炼均匀后,打6个三角包,然后将辊距放至2mm下片;然后在温度为175℃的硫化机上进行试片的压片,然后对试片进行测试。实施例7-12的原料配方及所得高聚物组合物的性能测试数据如下表2所示。
表2:实施例7-12的原料配方及其产物的性能测试数据
 
通过以上实施例均可以获得在380℃以上的有氧或无氧以及有焰或无焰的情况下,可垂直自熄、能烧结成非常坚硬的绝缘、隔火、隔温、阻燃、防火、耐火陶瓷壳体的陶瓷化高聚物组合物,高聚物组合物在烧蚀过程中低烟、无毒、无害,烧蚀时间越长,温度越高,陶瓷壳体越坚硬,可以承载2100℃,180分钟以上的烧蚀,能够承受喷淋震动,不延燃、不滴落。
本发明的高聚物组合物在火灾的情况下,可以烧结成非常坚硬的微孔陶瓷结构,能起到很好的挡火、隔温、隔热、绝缘的作用。
本发明的高聚物组合物包含钡、锶、铯、锆、铁、镁、铅、钴、铝、锰、钙、锌、钾、钠、铵、镍、铷的矿物硅酸盐和磷酸盐,与其他无机填料在烧蚀过程中形成陶瓷;由于硅酸盐和磷酸盐在高温下的分解和高聚物的分解,在陶瓷体内形成细小的微孔,这些微孔占据了分解的高聚物和硅酸盐、磷酸盐所占的位置,使得高温分解和转化后重新形成无机的陶瓷壳体物质,体积的转化,使得其变化率不会超过5-7%;分解的部分物质变成了无害的水和二氧化碳脱离陶瓷壳体,覆盖住在陶瓷壳体的周围,还有在烧蚀过程中有5-10%的液相和升华的物质吸附在陶瓷壳体的表面,形成一种粉状隔离层,将空气中的氧气隔绝开,进一步增加了一层挡火、隔温、隔热、绝缘的无机物质阻隔层。上述在高温下形成的非常坚硬的微孔陶瓷壳体,可以在2100℃以上的温度下,180分钟以上的时间下,保持很好的绝缘性,以及挡火、隔温、隔热,承受喷淋和震动的特性,且不会熔融、滴落。
上述实施例的组合物经高温烧蚀后,形成非常坚硬的陶瓷壳体,其燃烧后的坚硬的陶瓷化残余物达到83%;经检测其强度至少可以达到0.5MPa。
本发明的陶瓷化组合物还包括矿物硅酸盐,矿物硅酸盐包括:陶土、蒙脱土、蒙脱石、长钾石、高岭土、锂辉石、云母石、透锂辉石、水合硅石、滑石,使用上述矿物硅酸盐两种或两种以上至少一种矿物化合物的混合物。
一些较优的实施例中,本发明的高聚物组合物可以采用挤出、注塑、模压、压延各种加工方式,加工成片材、型材和各种复杂的形状,在火灾情况下形成的非常坚硬的陶瓷壳体,不但绝缘,还可挡火、隔温、隔热,承受喷淋和震动的,且不会熔融、滴落。
尽管本发明的内容已经通过上述优选实施例作了详细介绍,但应当认识到上述的描述不应被认为是对本发明的限制。在本领域技术人员阅读了上述内容后,对于本发明的多种修改和替代都将是显而易见的。因此,本发明的保护范围应由所附的权利要求来限定。

Claims (10)

1.一种垂直自熄的低烟阻燃的陶瓷化高聚物组合物,其特征在于,该组合物包含以下按质量百分数计的原料:
矿物硅酸盐   10-45%
磷酸盐        8-15%
氰尿酸三聚氰盐  10-20%
高分子聚合物或其合金   15-50%
有机硅聚合物       1-5%
软化剂            3-8%
发泡剂           0-18%;
所述的高分子聚合物或其合金可选择热塑性高聚物、热固性高聚物、热塑性弹性体、交联的高聚物、交联的弹性体或橡胶的共聚物或混合物中至少一种;所述的有机硅聚合物为高分子量硅酮阻燃添加剂。
2.如权利要求1所述的高聚物组合物,其特征在于,所述的矿物硅酸盐包含陶土、蒙脱土、蒙脱石、长钾石、高岭土、锂辉石、云母石、透锂辉石、长石、滑石,使用上述矿物硅酸盐两种或两种以上至少一种矿物化合物的混合物。
3.如权利要求1所述的高聚物组合物,其特征在于,所述的磷酸盐是指磷酸氢二铵、磷酸二氢铵、磷酸氢钙、磷酸钙、焦磷酸钙、磷酸二氢钾、磷酸氢二钾、酸式焦磷酸钠、磷酸二氢钠、磷酸氢二钠、聚磷酸铵、磷酸钠、焦磷酸钠中的一种或几种的混合物。
4.如权利要求1所述的高聚物组合物,其特征在于,所述的氰尿酸三聚氰盐为氰尿酸三聚氰胺。
5.如权利要求1所述的高聚物组合物,其特征在于,所述的高分子聚合物选择热塑型和交联型的聚烯烃类共聚物或其混合物中至少一种。
6.如权利要求1所述的高聚物组合物,其特征在于,所述的高分子聚合物选择聚烯烃、聚硅氧烷、乙烯基聚合物、氯磺化聚乙烯、氯化聚乙烯、聚氨酯、聚酯、聚酰胺、聚乙烯、聚醋酸乙烯脂、三元乙丙橡胶、二元乙丙橡胶、氯化聚乙烯、天然橡胶、顺丁橡胶、丁苯橡胶、丁腈橡胶、氯丁橡胶、丁基橡胶、环氧树脂、酚醛树脂以及均聚物、共聚物、弹性体或树脂及其混合物中的至少一种。
7.如权利要求1所述的高聚物组合物,其特征在于,所述的软化剂为低分子聚合物,该低分子聚合物选择矿物油、植物油脂、合成油脂中的任意一种或几种的混合物。
8.如权利要求1所述的高聚物组合物,其特征在于,在未添加发泡剂情况下获得密实的高分子阻燃耐火材料;在添加发泡剂的情况下,获得发泡型高分子阻燃耐火材料,所述的发泡剂选择偶氮二异丁腈、偶氮二甲酰胺等中的一种或两种的混合物或其改性物。
9.如权利要求1所述的高聚物组合物,其特征在于,该组合物烧结后的坚硬的陶瓷化残余物的弯曲强度达到0.3-9MPa;其燃烧后的坚硬的陶瓷化残余物质量保留量可达80-85%;尺寸变化率为1-7%。
10.一种根据权利要求1所述的垂直自熄的低烟阻燃的陶瓷化高聚物组合物的用途,其特征在于,该组合物能用于阻燃防火耐火高聚物发泡保温材料、阻燃防火耐火隔温隔热高聚物舰船发泡保温材料、阻燃防火耐火隔温隔热高聚物高速铁路列车发泡保温材料、阻燃防火耐火隔温隔热高聚物高铁保温材料、阻燃防火耐火隔温隔热高聚物汽车发泡保温材料、阻燃防火耐火隔温隔热高聚物飞机发泡保温材料、阻燃防火耐火隔温隔热高聚物建筑、汽车、舰船、飞机、家具、电气、家用电器用发泡材料、阻燃防火耐火隔温隔热高聚物外墙发泡保温建筑材料中。
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CN106397896A (zh) * 2015-08-02 2017-02-15 广东南缆电缆有限公司 一种耐高温高分子改性组合物
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CN105733050A (zh) * 2016-02-18 2016-07-06 合肥市再德高分子材料有限公司 一种耐热耐油阻燃改性丁腈橡胶复合材料
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