改性聚氨酯复合材料的制备与性能研究

论文总字数：28847字

摘 要

热塑性聚氨酯(TPU)是一类以多异氰酸酯与二元或多元醇反应制得的具有独特加工性能的高聚物。热塑性聚氨酯材料由于强度不高，耐热性差，易燃、抗静电性能差，并且当温度较高时，聚氨酯材料容易发生软化和分解，导致材料的机械性下降显著，这些性能上的局限性大大限制了聚氨酯材料的应用范围。无机材料一般都具有高硬度、高熔点、耐腐蚀、耐磨损以及良好的抗氧化性等特点。另外，无机纳米粒子还具有与宏观颗粒所不同的特殊的体积效应、表面界面效应和宏观量子隧道效应等,因而表现出独特的光、电、磁和化学特性,这为制备高性能、多功能复合材料指明了一个全新的方向。

本论文以碳纳米管为基础，通过水解反应在碳纳米管表面包覆纳米SiO₂和纳米TiO₂颗粒制得O-MWCNTs@SiO₂和O-MWCNTs@SiO₂-TiO₂无机复合材料。通过溶液共混法制备了两种TPU/无机粒子功能复合材料。并采用傅里叶红外变换光谱（FTIR）、透射电子显微镜（TEM）、X射线衍射（XRD）、热重分析（TGA）、拉伸强度测试对复合材料进行了表征。从FTIR、TEM、XRD的表征结果可以判断，SiO₂和TiO₂都均匀的包覆在碳纳米管表面。从TGA结果可以看出，与TPU材料相比，TPU/O-MWCNTs@ SiO₂复合材料在O-MWCNTs@SiO₂的质量分数为2%时热分解温度提高了20℃左右，TPU/O-MWCNTs@ SiO₂-TiO₂无机复合材料也得到相近的温度提升。从拉伸强度的表征结果可以看出，随着无机填料质量分数的升高，复合材料的拉伸强度也有所提高，在质量分数为2%时，拉伸结果的提高最为明显。

通过实验结果可以判断，以O-MWCNTs@SiO₂和O-MWCNTs@ SiO₂-TiO₂无机复合材料作为改性剂制备的两种改性聚氨酯材料在耐热性与机械强度方面都有了较大的提升。

关键词：热塑性聚氨酯、碳纳米管、制备、改性、耐热性、拉伸强度、

A STUDY ON THE PREPARATION OF MODIFIED TPU COMPOSITE MATERIALS

Abstract

TPU is a kind of polymer that made from the reaction of more isocyanate and glycol. Thermoplastic polyurethane has excellent performance, it has both the properties of elastomers and plastics. As a commonly used polymer materials, Thermoplastic polyurethane material with a low strength, heat resistance is poor, flammable, antistatic performance is poor, and when the temperature is high, polyurethane materials prone to soften and break down, Thanks to inorganic materials exhibit excellent properties of complementary, inorganic materials are high hardness, high melting point, corrosion resistance, wear resistance and good oxidation resistance, etc. In addition, the inorganic nanoparticles have the different special volume effect and macro particles, surface interface effect and macroscopic quantum tunneling effect, etc. Thus showing the unique optical, electrical, magnetic and chemical properties, for the preparation of High performance, multi-function pointed out a new direction of composite materials.

This thesis is based on carbon nanotubes, through hydrolysis reaction on the surface of carbon nanotubes coated SiO₂ and nano TiO₂ particles made O-MWCNTs@SiO₂ and O- MWCNTs@SiO₂ –TiO₂ inorganic composite materials. By solution blending of the two kinds of function of TPU/inorganic particles prepared by the composite materials. And use the Fourier infrared spectrum (FTIR), transmission electron microscope (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), tensile strength test of composite materials have been characterized. From the FTIR, TEM, XRD characterization results can be judged, SiO₂ and TiO₂ are evenly coated on the surface of carbon nanotubes. Can be seen from the results of TGA, compared with the TPU material, TPU/O-MWCNTs@SiO₂ composite materials in when the mass fraction of 2% of the O-MWCNTs@SiO₂ improves the thermal decomposition temperature 20℃ or so, TPU/O-MWCNTs@SiO₂-TiO₂ inorganic composite materials have been close to the temperature rise. As can be seen from the characterization results of the tensile strength, with the increase of mass fraction of inorganic filler, it also improved the tensile strength of the composite material, when the mass fraction of 2%, the tensile results increase was most pronounced.

Can be judged by the results of the experiment, with O-MWCNTs@SiO₂ and O- MWCNTs@SiO₂–TiO₂ inorganic composite materials as a modifier of the preparation of two kinds of modified polyurethane materials in heat resistance and mechanical strength has a larger increase.

Key words: Thermoplastic polyurethane、MWCNTs、Preparation、Modify、Heat resistance、The tensile strength.

目 录

摘要 ………………………………………………………………………………………… Ⅰ

Abstract …………………………………………………………………………………… Ⅱ

第一章：绪论………………………………………………………………………………… 3

1.1 引言………………………………………………………………………………… 3

1.2 聚氨酯树脂简介

1.2.1 聚氨酯树脂发展史……………………………………………………… 3

1.2.1 热塑性聚氨酯简介……………………………………………………… 4

1.3 TPU/无机粒子复合材料的制备方法

1.3.1 共混法…………………………………………………………………… 4

1.3.2 原位聚合法……………………………………………………………… 5

1.3.3 溶胶-凝胶法……………………………………………………………… 5

1.3.4 插层聚合法……………………………………………………………… 5

1.4 TPU/无机粒子复合材料的功能化及其应用

1.5.1 纳米二氧化硅改性TPU复合材料……………………………………… 6

1.5.2 纳米二氧化钛改性TPU复合材料……………………………………… 6

1.5.3 纳米炭材料改性TPU复合材料………………………………………… 6

1.6 本章小结…………………………………………………………………………… 7

第二章：TPU/O-MWCNTs@SiO₂复合材料的制备及性能研究

2.1 引言………………………………………………………………………………… 8

2.2 实验部分

2.2.1 实验试剂…………………………………………………………………… 8

2.2.2 实验仪器设备……………………………………………………………… 8

2.2.3 实验操作

2.2.3.1 碳纳米管酸化…………………………………………………… 9

2.2.3.2 O-MWCNTs@ SiO₂的制备……………………………………… 9

2.2.3.3 O-MWCNTs@ SiO₂的改性……………………………………… 9

2.2.3.4 TPU/ O-MWCNTs@ SiO₂的制备……………………………… 10

2.2.4 表征及测试方法……………………………………………………………10

2.3 结果与讨论

2.3.1 TEM图分析………………………………………………………………… 10

2.3.2 XRD图分析………………………………………………………………… 12

2.3.3 FTIR谱图分析……………………………………………………………… 13

2.3.4 TGA曲线分析……………………………………………………………… 14

2.3.5 拉伸性能分析……………………………………………………………… 16

2.4 本章小结…………………………………………………………………………… 16

第三章：TPU/O-MWCNTs@ SiO₂-TiO₂复合材料的制备及性能研究

3.1 引言……………………………………………………………………………… 18

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