新型聚氨酯/含羟基填料有机/无机杂化材料的制备与性能
摘要
有机/无机杂化材料是一种在纳米水平分散均匀的多相材料,兼备有机聚合物和无机材料的性能优势。它可以是无机改性有机聚合物,也可以是有机改性无机材料。可以通过调节有机相与无机相的组成及比例,实现对材料功能的“剪裁”和“组装”。本论文利用NCO基团易与OH基团发生反应的原理,首先通过机械共混原位反应法制备了新型聚氨酯/含羟基无机填料有机/无机杂化材料。通过研究发现,聚氨酯/沉淀法白炭黑(PU/P-Silica)有机/无机杂化体系具有最优的综合性能。根据这一结论,对PU/P-Silica杂化体系进行系统深入的研究,其中包括杂化体系的杂化原理、最佳杂化工艺条件以及杂化材料的性能等。
通过机械共混法制备的聚氨酯/埃洛石纳米管有机/无机杂化材料(PU/HNTs)、聚氨酯/气相法白炭黑有机/无机杂化材料(PU/F-Silica)、聚氨酯/沉淀法白炭黑有机/无机杂化材料(PU/P-Silica)与纯聚氨酯(PU)相比,力学性能明显提高,通过XRD、DSC等测试发现无机填料的加入相应地改变了聚氨酯的硬段结构,提高了杂化材料中的硬段含量。热稳定性测试发现,杂化材料具有比纯PU要好的热稳定性。表面接触角测试表明,三种杂化材料具有不同的亲、疏水性等特性。
三种杂化材料中,PU/P-Silica体系具有最好的综合性能。对PU/P-Silica杂化体系进行深入研究发现,采用三辊研磨机进行二次共混的杂化体系中白炭黑的分散效果得到改善,杂化材料具有最佳的力学性能,其拉伸强度达到51MPa,撕裂强度也达到了近100KN/m。通过力学性能测试确定了预聚体中-NCO与-OH的比为2:1时,杂化材料具备最佳的力学性能。这是因为预聚体合成过程中,通过控制-NCO与-OH的比,可以使预聚体分子链两端带有-NCO基团,两端的-NCO与白炭黑表面的-OH在一定条件下直接发生化学键合反应,生成有机/无机交联网络结构的杂化材料。同时,通过橡胶硫化仪以及DSC测试确定了PU/P-Silica杂化材料的最佳固化时间、固化温度以及固化活化能等。研究发现,PU/P-Silica杂化材料与金属铝还具有一定的粘结强度,其拉伸剪切强度可达到9MPa。
Organic-inorganic hybrid materials are a kind of multiphase materials with uniform dispersion at nanometer level. They have excellent properties over organic polymers and inorganic materials. The hybrid materials can be ranged from organic polymers modified by inorganic substance to inorganic materials modified by organic substance, and the properties of the materials are able to be tailored and constructed by adjusting the composision and ratio of organic and inorganic phase. In this dissertation, according to rapid reaction principle of NCO group with OH group, a new type of organic-inorganic hybrid materials consisting of polyurethane (PU) and hydroxyl group-containing fillers were prepared through the mechanical blending and in situ reacting method. It is found that PU/precipitated silica (PU/P-Silica) organic-inorganic hybrid material have the best overall properties. In the basis of the results, PU/P-Silica hybrid materials were investigated systematically and thoroughly, including the hybrid mechanism, the best hybrid process conditions and the properties of hybrid materials, etc.
Comparing PU and three kinds of hybrid materials, PU/Halloysite Nanotubes(PU/HNTs), PU/Fumed Silica(PU/F-Silica) and PU/Precipitated Silica(PU/P-Silica), which were prepared by mechanical blending and in-situ reacting method, the mechanical properties of three hybrid materials has improved significantly. It is found by XRD and DSC testings that the increase of the contents of inorganic fillers in the hybrid systems alters the hard segment structure and increases the relative content of hard segment of hybrid materials in PU. The thermal stability results showed that the hybrid materials had the better thermal stability than PU. The surface contact angle tests show that three kinds of hybrid materials had different hydrophilic and hydrophobic property.
PU/P-Silica hybrid material has the best comprehensive properties in three kinds of hybrid materials. The deep investigation on PU/P-Silica hybrid materials shows that the second mixing of PU prepolymer with P-Silica by three-roll mixing machine can improve the dispersion effect of silica in PU prepolymer, and hence enhance the mechanical properties of PU/P-Silica hybrid materials. The tensile strength achieves to 51 MPa and the tear strength was improved to nearly 100 MPa. As the NCO and OH in the ratio of 2:1, the hybrid material is provided with the best mechanical properties. It is because that under certain conditions, the NCO groups at both ends of molecular chains can make direct chemical reaction with OH groups at the silica surface and form the hybrid materials with organic-inorganic hybrid crosslinked network structure. In addition, the right curing time and curing temperature of PU/Silica hybrid materials were determined by rubber vulcanization instrument and curing activation energy by DSC test. It is found that PU/P-Silica hybrid materials and metal aluminium also have certain bond strength and the tensile cutting strength arrived to 9 MPa.
通过机械共混法制备的聚氨酯/埃洛石纳米管有机/无机杂化材料(PU/HNTs)、聚氨酯/气相法白炭黑有机/无机杂化材料(PU/F-Silica)、聚氨酯/沉淀法白炭黑有机/无机杂化材料(PU/P-Silica)与纯聚氨酯(PU)相比,力学性能明显提高,通过XRD、DSC等测试发现无机填料的加入相应地改变了聚氨酯的硬段结构,提高了杂化材料中的硬段含量。热稳定性测试发现,杂化材料具有比纯PU要好的热稳定性。表面接触角测试表明,三种杂化材料具有不同的亲、疏水性等特性。
三种杂化材料中,PU/P-Silica体系具有最好的综合性能。对PU/P-Silica杂化体系进行深入研究发现,采用三辊研磨机进行二次共混的杂化体系中白炭黑的分散效果得到改善,杂化材料具有最佳的力学性能,其拉伸强度达到51MPa,撕裂强度也达到了近100KN/m。通过力学性能测试确定了预聚体中-NCO与-OH的比为2:1时,杂化材料具备最佳的力学性能。这是因为预聚体合成过程中,通过控制-NCO与-OH的比,可以使预聚体分子链两端带有-NCO基团,两端的-NCO与白炭黑表面的-OH在一定条件下直接发生化学键合反应,生成有机/无机交联网络结构的杂化材料。同时,通过橡胶硫化仪以及DSC测试确定了PU/P-Silica杂化材料的最佳固化时间、固化温度以及固化活化能等。研究发现,PU/P-Silica杂化材料与金属铝还具有一定的粘结强度,其拉伸剪切强度可达到9MPa。
Organic-inorganic hybrid materials are a kind of multiphase materials with uniform dispersion at nanometer level. They have excellent properties over organic polymers and inorganic materials. The hybrid materials can be ranged from organic polymers modified by inorganic substance to inorganic materials modified by organic substance, and the properties of the materials are able to be tailored and constructed by adjusting the composision and ratio of organic and inorganic phase. In this dissertation, according to rapid reaction principle of NCO group with OH group, a new type of organic-inorganic hybrid materials consisting of polyurethane (PU) and hydroxyl group-containing fillers were prepared through the mechanical blending and in situ reacting method. It is found that PU/precipitated silica (PU/P-Silica) organic-inorganic hybrid material have the best overall properties. In the basis of the results, PU/P-Silica hybrid materials were investigated systematically and thoroughly, including the hybrid mechanism, the best hybrid process conditions and the properties of hybrid materials, etc.
Comparing PU and three kinds of hybrid materials, PU/Halloysite Nanotubes(PU/HNTs), PU/Fumed Silica(PU/F-Silica) and PU/Precipitated Silica(PU/P-Silica), which were prepared by mechanical blending and in-situ reacting method, the mechanical properties of three hybrid materials has improved significantly. It is found by XRD and DSC testings that the increase of the contents of inorganic fillers in the hybrid systems alters the hard segment structure and increases the relative content of hard segment of hybrid materials in PU. The thermal stability results showed that the hybrid materials had the better thermal stability than PU. The surface contact angle tests show that three kinds of hybrid materials had different hydrophilic and hydrophobic property.
PU/P-Silica hybrid material has the best comprehensive properties in three kinds of hybrid materials. The deep investigation on PU/P-Silica hybrid materials shows that the second mixing of PU prepolymer with P-Silica by three-roll mixing machine can improve the dispersion effect of silica in PU prepolymer, and hence enhance the mechanical properties of PU/P-Silica hybrid materials. The tensile strength achieves to 51 MPa and the tear strength was improved to nearly 100 MPa. As the NCO and OH in the ratio of 2:1, the hybrid material is provided with the best mechanical properties. It is because that under certain conditions, the NCO groups at both ends of molecular chains can make direct chemical reaction with OH groups at the silica surface and form the hybrid materials with organic-inorganic hybrid crosslinked network structure. In addition, the right curing time and curing temperature of PU/Silica hybrid materials were determined by rubber vulcanization instrument and curing activation energy by DSC test. It is found that PU/P-Silica hybrid materials and metal aluminium also have certain bond strength and the tensile cutting strength arrived to 9 MPa.
引文
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