CN108976462A - 一种二氧化硅改性聚氨酯复合材料及其制备方法 - Google Patents

一种二氧化硅改性聚氨酯复合材料及其制备方法 Download PDF

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CN108976462A
CN108976462A CN201810823740.3A CN201810823740A CN108976462A CN 108976462 A CN108976462 A CN 108976462A CN 201810823740 A CN201810823740 A CN 201810823740A CN 108976462 A CN108976462 A CN 108976462A
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张原僖
张伟
梁建强
赵燕平
赵建卿
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TIANYI TECHNOLOGY Co Ltd SHANXI NANOMATERIALS
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Abstract

本发明提供一种二氧化硅改性聚氨酯复合材料及其制备方法,解决了聚氨酯阻燃效果差,不能耐高温的问题,此保温材料由黑料、白料、二氧化硅及其他助剂组成,所述白料为聚醚多元醇或聚酯多元醇多羟基化合物,所述黑料为多苯基多亚甲基多异氰酸酯(PAPI),所述二氧化硅为合成的无定型纳米二氧化硅,所述助剂包括有机阻燃剂和无机阻燃剂、催化剂、发泡剂。本发明生产的聚氨酯保温板燃烧等级达到了A级,且导热系数极低,重量轻质、稳定性好、抗收缩性好。

Description

一种二氧化硅改性聚氨酯复合材料及其制备方法
技术领域
本发明属于保温材料制备技术,特别涉及一种用廉价硅源硅酸钠制备二氧化硅气凝胶复合材料的方法。
背景技术
聚氨酯是一种非常重要的合成树脂品种,目前在世界上具有非常广泛的应用。硬质泡沫聚氨酯导热系数低,一般要求为0.018-0.024w/(m.k),并且具有防潮、防水性能,不会因吸潮使导热系数增大,广泛应用于冰箱、冰柜、冷库板、管道保温、建筑节能灯保温领域。但日常所用的聚氨酯不能耐高温,阻燃效果差,易变形,尺寸稳定性差,特别在发生火灾时,会产生大量的致命的浓烟。
国内外对聚氨酯阻燃的传统方法是在聚氨酯中添加阻燃剂,其中应用最多的是卤系阻燃剂和磷系阻燃剂,及其他一些无机阻燃剂。但这些阻燃剂的加入会大大损耗聚氨酯的力学性能,而且在使用过程中,阻燃剂小分子会随着时间的延长逐渐迁移出来,聚氨酯的阻燃性能就会逐渐丧失。于是近年来,随着纳米技术的迅速发展,纳米技术在聚氨酯阻燃中的应用已受到业内人士的广泛关注。
纳米二氧化硅是一种超微细的无机新材料,因其粒径很小,具有比表面积大,表面吸附力强,表面能大,分散性好等特点。由于Si-O键的键能大,所以Si-O键在高温下具有良好的热稳定性和抗氧化性能。如果二氧化硅粒子能达到纳米级而且在聚合物基体中能实现很好的分散(纳米级分散),二氧化硅与聚合物就会有极大的接触表面积,从而可以改善聚合物的热稳定性能。
A级聚氨酯保温材料应用而生,它不仅保持了聚氨酯的优点,更改变了其不耐高温阻燃等级低的毛病,燃烧等级达到了A级,市场前景非常广阔。
发明内容
本发明提供的A级聚氨酯保温材料,解决了聚氨酯不能耐高温,燃烧等级低的毛病。
本发明的技术解决方案:A级聚氨酯保温材料由下述重量份的黑料、白料、二氧化硅和助剂组成:所述白料为90-110份的聚醚多元醇或聚酯多元醇,所述黑料为90-110份的多苯基多亚甲基多异氰酸酯(PAPI),所述二氧化硅为20-50份的合成纳米材料,所述助剂包括20-40份的阻燃剂,2-4重量份的催化剂,2-4重量份的发泡剂。
其中优选地,所述阻燃剂包括20-30份的有机蒙脱土,30-40份的氢氧化铝,10-20份的氢氧化镁,4-8份的石墨粉。
其中聚醚多元醇或聚酯多元醇、多苯基多亚甲基多异氰酸酯、催化剂、发泡剂均为制备聚氨酯的常规原料。
其中,优选地,所述二氧化硅为硅酸钠为硅源合成的疏水气凝胶,粒径为20-30纳米。所述二氧化硅的制备方法按照如下步骤:
1)原料准备,硅酸钠模数为3.3-3.4、铁含量<200PPm、浓度2-10%;硫酸浓度为10-20%;
2)步骤1)中的硅酸钠与硫酸同时打入管道混合器,得到pH值为7-8的混合液;
3)另用容器盛装去离子水,在100-300r/min的搅拌速度下,保持温度为55-60℃的温水;温水与混合液的质量比为3-5:1;
4)将步骤2)的混合液喷淋至步骤3)的温水中,同时保持pH值为6.5-7.5,至将混合液喷淋完,继续搅拌20-30min,用硫酸调pH值为3-4;
5)步骤4)产物经过滤、洗涤、干燥、粉碎分级得到成品。
其中优选地,所述A级聚氨酯保温材料的制备方法如下:
将阻燃剂,纳米二氧化硅及助剂全部加到白料中,高速分散,1500r/min分散30min;
将混有助剂的白料与黑料混合起发泡反应,得到产品。
本发明采用喷淋-温水沉淀法,喷淋的混合液在温水提供的环境中完成反应,并在搅拌状态下产生碰撞,融合成较大的结构疏松的二氧化硅粒子,并经过过滤等后处理,得到的20-30纳米具有疏松而不规则的孔隙结构和外形,在不需要用偶联剂对二氧化硅进行改性的情况下,将纳米二氧化硅在白料中进行分散,使二氧化硅纳米颗粒在反应制备的聚氨酯中均匀分散,从而得到纳米级分散的聚氨酯复合材料。同时,本发明采用复合的阻燃剂,利用二氧化硅微粒及阻燃剂颗粒的双重作用,使聚氨酯燃烧等级达到了A级。
A级聚氨酯保温材料具有以下特点:
本发明的A级聚氨酯保温材料,本身抗高温、高阻燃、不熔化,并且导热系数低,重量轻,稳定性好,突发火灾时,由于其中分散有二氧化硅微粒及阻燃剂颗粒,其燃烧等级达到了A级。
具体实施方式
下面将结合实施例方式作进一步详细描述,具体实施方式如下:
实施例1
将有机蒙脱土、氢氧化铝、氢氧化镁、石墨粉按质量比20:30:10:8混合,得到阻燃剂;
将阻燃剂20份、二氧化硅20份、催化剂3份、发泡剂3份,全部加入100份的聚醚多元醇中,1500r/min高速分散30min,将110份的黑料加到上述混合后的聚醚多元醇中,快速搅拌5min,倒入模具中发泡即得成品。
实施例2,与实施例1 不同的是纳米二氧化硅加入量为30份。
实施例3,与实施例1不同的是纳米二氧化硅加入量为40份。
实施例4,与实施例1不同的是纳米二氧化硅加入量为50份。
实施例5
将有机蒙脱土、氢氧化铝、氢氧化镁、石墨粉按质量比30:35:15:6混合,得到阻燃剂;
将阻燃剂40份、二氧化硅30份、催化剂2份、发泡剂2份,全部加入90份的聚醚多元醇中,1500r/min高速分散30min,将100份的黑料加到上述混合后的聚醚多元醇中,快速搅拌5min,倒入模具中发泡即得成品。
实施例6
将有机蒙脱土、氢氧化铝、氢氧化镁、石墨粉按质量比25:40:20:4混合,得到阻燃剂;
将阻燃剂40份、二氧化硅30份、催化剂2份、发泡剂3份,全部加入90份的聚醚多元醇中,1500r/min高速分散30min,将100份的黑料加到上述混合后的聚醚多元醇中,快速搅拌5min,倒入模具中发泡即得成品。
实施例7
将有机蒙脱土、氢氧化铝、氢氧化镁、石墨粉按质量比25:35:10:5混合,得到阻燃剂;
将阻燃剂40份、二氧化硅30份、催化剂4份、发泡剂4份,全部加入90份的聚醚多元醇中,1500r/min高速分散30min,将100份的黑料加到上述混合后的聚醚多元醇中,快速搅拌5min,倒入模具中发泡即得成品。
实施例8
将阻燃剂偏硼酸钡35份、二氧化硅30份、催化剂4份、发泡剂4份,全部加入90份的聚醚多元醇中,1500r/min高速分散30min,将100份的黑料加到上述混合后的聚醚多元醇中,快速搅拌5min,倒入模具中发泡即得成品。
实施例9
将阻燃剂溴代二苯醚35份、二氧化硅30份、催化剂4份、发泡剂4份,全部加入90份的聚醚多元醇中,1500r/min高速分散30min,将100份的黑料加到上述混合后的聚醚多元醇中,快速搅拌5min,倒入模具中发泡即得成品。
实施例10
将有机蒙脱土、氢氧化铝、氢氧化镁、石墨粉按质量比25:35:10:5混合,得到阻燃剂;
将阻燃剂35份、二氧化硅30份、催化剂2份、发泡剂2份,全部加入90份的聚醚多元醇中,1500r/min高速分散30min,将100份的黑料加到上述混合后的聚醚多元醇中,快速搅拌5min,倒入模具中发泡即得成品。
其中,实施例1-9中二氧化硅的制备方法为:
1)原料准备,硅酸钠模数为3.3-3.4、铁含量<200PPm、浓度8%;硫酸浓度为15%;
2)步骤1)中的硅酸钠与硫酸同时打入管道混合器,得到pH值为7-8的混合液;
3)另用容器盛装去离子水,在200r/min的搅拌速度下,保持温度为55-60℃的温水;温水与混合液的质量比为4:1;
4)将步骤2)的混合液喷淋至步骤3)的温水中,同时保持pH值为6.5-7.5,至将混合液喷淋完,继续搅拌30min,用硫酸调pH值为3-4;
5)步骤4)产物经过滤、洗涤、干燥、粉碎分级得到成品。
实施例10中二氧化硅的为硅烷偶联剂改性的粒径20-30纳米的二氧化硅。
实施例1-10的产品测试结果如下:
本领域技术人员应理解,以上实施例仅是示例性实施例,在不背离本发明的精神和范围的情况下,可以进行多种变化、替换以及改变。

Claims (4)

1.一种二氧化硅改性聚氨酯复合材料,其特征在于包括的原料为白料、黑料、二氧化硅、阻燃剂、催化剂和发泡剂;所述原料按质量份计,白料为90-100份的聚醚多元醇或聚酯多元醇,黑料为90-110份的多苯基多亚甲基多异氰酸酯,二氧化硅为20-50份,阻燃剂为20-40份,催化剂为2-4份,发泡剂为2-4份;所述二氧化硅为硅酸钠为硅源合成的疏水气凝胶,粒径为20-30纳米。
2.根据权利要求1所述的二氧化硅改性聚氨酯复合材料,其特征在于,所述阻燃剂由以下重量份配比的原料组成:有机蒙脱土20-30,氢氧化铝30-40份,氢氧化镁10-20份,聚磷酸铵4-8份和石墨粉4-8份。
3.根据权利要求1所述的二氧化硅改性聚氨酯复合材料,其特征在于,所述二氧化硅的制备方法按照如下步骤:
1)原料准备,硅酸钠模数为3.3-3.4、铁含量<200PPm、浓度2-10%;硫酸浓度为10-20%;
2)步骤1)中的硅酸钠与硫酸同时打入管道混合器,得到pH值为7-8的混合液;
3)另用容器盛装去离子水,在100-300r/min的搅拌速度下,保持温度为55-60℃的温水;温水与混合液的质量比为3-5:1;
4)将步骤2)的混合液喷淋至步骤3)的温水中,同时保持pH值为6.5-7.5,至将混合液喷淋完,继续搅拌20-30min,用硫酸调pH值为3-4;
5)步骤4)产物经过滤、洗涤、干燥、粉碎分级得到成品。
4.根据权利要求1-3任一所述的二氧化硅改性聚氨酯复合材料的制备方法,其特征在于按照以下步骤:
1)将阻燃剂、二氧化硅、催化剂和发泡剂全部加到白料中、高速分散,1500r/min分散25-40min;
2)步骤1)混合后的白料与黑料混合,起发泡反应,得到产品。
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Application publication date: 20181211