离子液体改性聚氨酯的制备及性能研究
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摘要
本文的主要研究工作和试验结果如下:
1.室温离子液体(RTILs)是一种应用广泛的化合物,RTILs独特的物理和化学特性都是与“离子”特性有关,其离子化程度和自电离度可以通过离子液体的电导性质来反映。本文选用了咪唑与氯乙醇合成了1,3-二羟乙基咪唑氯盐(1,3- diethoxylimidazoles chloride)[D_2mim][Cl],用红外光谱IR和1HNMR进行了结构表征,此离子液体的合成成功对新型离子液体的合成具有一定的指导作用。聚氨酯材料具有原料易得,价格低廉,弹性优良,是常规的电绝缘性材料,其表面电阻率一般为1×10~(12)～1×10~(15)Ω,因此其在导电材料方面的应用就受到了很大的限制。而前人对导电聚氨酯也作了大量的研究,导电聚氨酯复合材料有良好的导电性,但是其的溶解性很差,导致其涂覆性及成膜性很差;聚氨酯聚合物的溶解性较好,但是其导电性能很差,不能满足人们对其的需求。所以本文就考虑用离子液体[D2mim][Cl]与二异氰酸酯(TDI及HDI)聚合合成离子型聚氨酯,并对其导电性,溶解性进行了详细的研究。
结果表明:该新型离子型聚氨酯具有优良的导电性能,并且在极性溶剂中具有良好的溶解性能;当单体为HDI时合成的离子型聚氨酯(PUR-H)的导电性能远远优于单体为TDI时合成的离子型聚氨酯(PUR-T)。在最优条件下PUR-H的表面电阻可达1.0×10~4Ω,而PUR-T表面电阻为1.0×10~6Ω。
2.为了拓展离子液体的应用,合成了一种新型的离子液体1-羟乙基-3-正丁烷基咪唑氯盐离子液体。以所制备的离子液体为反应型抗静电填充剂,制备了丙烯酸抗静电涂料。
对所制备的抗静电涂料进行抗静电性能进行了测试。结果表明:1-羟乙基-3-正丁烷基咪唑氯盐离子液体是很好的导电添加剂,当添加量为0时,丙烯酸树脂的表面电阻﹥10~(12）Ω,即为绝缘体;当离子液体的添加量为总量的5%(丙烯酸树脂+N-75+离子液体)时,丙烯酸树脂涂料的表面电阻为10~(10)Ω;当离子液体的添加量为总量的10%时,丙烯酸树脂涂料的表面电阻为10~6Ω,满足用户需求。
The major researches and conclusions of this thesis are as follows:
1. Room temperature ionic liquids (RTILs) are regarded as a novel class of green materials, which have great promise in practical industrial application. The unique Chemical and Physical properties of RTILs are mostly depended on their ionization and autoionization degree. In this paper, a new ionic liquid 1,3-diethoxylimidazoles chloride [D2mim][Cl] was synthesized from imidazoles and chlorohydrin, and characterized by IR and 1HNMR. The ionic liquid was successfully synthesized,which is beneficial for the synthesis of other novel ionic liquids.
Polyurethane possesses a lot of excellent properties, such as cheaper, good flexibility, but application of Polyurethane is limited in electroconductive area because of its electric insulativity. In recent years, some researchers have studyed on the electroconductivity of Polyurethane. The results indicated that the electro conductive composites of Polyurethane have good electricity conductivity, but the properties of coating and film forming are great poor because of their poor dissolubility. The Polyurethane polymer possesses excellent properties of dissolubility, coating and film forming, but the electroconductivity is very poor. Therefore, in this article, two novel electroconductive Polyurethanes with the backbone of ionic liquid were synthesized from [D2mim][Cl] and diisocyanate(TDI and HDI) by Chemical Polymerization. Their propeties of electrical conductivity and dissolubility were discussed. The results indicated that the novel ionic Polyurethanes possess good electrical conductivity and good solubility in polar solvent. The electrical conductivity of PUR-H(PUR-H: synthesized with isocyanate HDI; PUR-T: synthesized with isocyanate TDI;) is great better than that of PUR-T. The PUR-H, which exhibited an electrical conductivity of 1.0×10~4Ωsurface resistance, while the surface resistance of PUR-T is 1.0×10~6Ω.
2. Antistatic acrylic resin coating was prepared with 1- ethoxy-3-butyl alkyl imidazoles Chloride ionic liquid as filler. The effect of additive amount on the electricity conductivity of the coating was investigated. The results showed that the ionic liquid prepared was excellent antistatic filler. The surface resistance of acrylic resin coating was greater than 1012 ?, when the additive amount was 0, that is to say, the coating was electrical insulating coating. That of the coating was 10~(10)Ωwhen the additive amount was 5% ( acrylic resin + N-75 + ionic liquid), while the surface resistance was 10~6Ωwhen the amount of ionic liquid was 10%.
The results showed that 1- ethoxy-3-butyl alkyl imidazoles Chloride ionic liquid prepared was excellent antistatic filler, which satisfied necessary of customer.
1.室温离子液体(RTILs)是一种应用广泛的化合物,RTILs独特的物理和化学特性都是与“离子”特性有关,其离子化程度和自电离度可以通过离子液体的电导性质来反映。本文选用了咪唑与氯乙醇合成了1,3-二羟乙基咪唑氯盐(1,3- diethoxylimidazoles chloride)[D_2mim][Cl],用红外光谱IR和1HNMR进行了结构表征,此离子液体的合成成功对新型离子液体的合成具有一定的指导作用。聚氨酯材料具有原料易得,价格低廉,弹性优良,是常规的电绝缘性材料,其表面电阻率一般为1×10~(12)～1×10~(15)Ω,因此其在导电材料方面的应用就受到了很大的限制。而前人对导电聚氨酯也作了大量的研究,导电聚氨酯复合材料有良好的导电性,但是其的溶解性很差,导致其涂覆性及成膜性很差;聚氨酯聚合物的溶解性较好,但是其导电性能很差,不能满足人们对其的需求。所以本文就考虑用离子液体[D2mim][Cl]与二异氰酸酯(TDI及HDI)聚合合成离子型聚氨酯,并对其导电性,溶解性进行了详细的研究。
结果表明:该新型离子型聚氨酯具有优良的导电性能,并且在极性溶剂中具有良好的溶解性能;当单体为HDI时合成的离子型聚氨酯(PUR-H)的导电性能远远优于单体为TDI时合成的离子型聚氨酯(PUR-T)。在最优条件下PUR-H的表面电阻可达1.0×10~4Ω,而PUR-T表面电阻为1.0×10~6Ω。
2.为了拓展离子液体的应用,合成了一种新型的离子液体1-羟乙基-3-正丁烷基咪唑氯盐离子液体。以所制备的离子液体为反应型抗静电填充剂,制备了丙烯酸抗静电涂料。
对所制备的抗静电涂料进行抗静电性能进行了测试。结果表明:1-羟乙基-3-正丁烷基咪唑氯盐离子液体是很好的导电添加剂,当添加量为0时,丙烯酸树脂的表面电阻﹥10~(12）Ω,即为绝缘体;当离子液体的添加量为总量的5%(丙烯酸树脂+N-75+离子液体)时,丙烯酸树脂涂料的表面电阻为10~(10)Ω;当离子液体的添加量为总量的10%时,丙烯酸树脂涂料的表面电阻为10~6Ω,满足用户需求。
The major researches and conclusions of this thesis are as follows:
1. Room temperature ionic liquids (RTILs) are regarded as a novel class of green materials, which have great promise in practical industrial application. The unique Chemical and Physical properties of RTILs are mostly depended on their ionization and autoionization degree. In this paper, a new ionic liquid 1,3-diethoxylimidazoles chloride [D2mim][Cl] was synthesized from imidazoles and chlorohydrin, and characterized by IR and 1HNMR. The ionic liquid was successfully synthesized,which is beneficial for the synthesis of other novel ionic liquids.
Polyurethane possesses a lot of excellent properties, such as cheaper, good flexibility, but application of Polyurethane is limited in electroconductive area because of its electric insulativity. In recent years, some researchers have studyed on the electroconductivity of Polyurethane. The results indicated that the electro conductive composites of Polyurethane have good electricity conductivity, but the properties of coating and film forming are great poor because of their poor dissolubility. The Polyurethane polymer possesses excellent properties of dissolubility, coating and film forming, but the electroconductivity is very poor. Therefore, in this article, two novel electroconductive Polyurethanes with the backbone of ionic liquid were synthesized from [D2mim][Cl] and diisocyanate(TDI and HDI) by Chemical Polymerization. Their propeties of electrical conductivity and dissolubility were discussed. The results indicated that the novel ionic Polyurethanes possess good electrical conductivity and good solubility in polar solvent. The electrical conductivity of PUR-H(PUR-H: synthesized with isocyanate HDI; PUR-T: synthesized with isocyanate TDI;) is great better than that of PUR-T. The PUR-H, which exhibited an electrical conductivity of 1.0×10~4Ωsurface resistance, while the surface resistance of PUR-T is 1.0×10~6Ω.
2. Antistatic acrylic resin coating was prepared with 1- ethoxy-3-butyl alkyl imidazoles Chloride ionic liquid as filler. The effect of additive amount on the electricity conductivity of the coating was investigated. The results showed that the ionic liquid prepared was excellent antistatic filler. The surface resistance of acrylic resin coating was greater than 1012 ?, when the additive amount was 0, that is to say, the coating was electrical insulating coating. That of the coating was 10~(10)Ωwhen the additive amount was 5% ( acrylic resin + N-75 + ionic liquid), while the surface resistance was 10~6Ωwhen the amount of ionic liquid was 10%.
The results showed that 1- ethoxy-3-butyl alkyl imidazoles Chloride ionic liquid prepared was excellent antistatic filler, which satisfied necessary of customer.
引文
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