【作者】 陈斌；

【导师】 王植源； 白俊玲；

【作者基本信息】 大连理工大学 ， 化学工程， 2024， 硕士

【摘要】 聚脲是由异氰酸酯组分和氨基化合物组分反应生成的弹性体聚合物,具有不含挥发性有机物,兼具较好的热稳定性和优异的理化性能的特点,被广泛应用于耐磨、防水、防腐和防护等领域。传统的芳香族聚脲和脂肪族聚脲以伯胺化合物为扩链剂,存在固化速度快,凝胶时间短的问题,需要配备专业的喷涂设备施工。天冬聚脲弹性体是以天冬氨酸酯仲胺化合物为扩链剂的第三代聚脲弹性体,其固化速度慢,凝胶时间可以延长到几分钟至几十分钟,易于施工,表现出较大的应用潜力。本论文的目的是从分子结构出发,制备出一系列具有不同扩链剂结构、异氰酸酯结构及软段分子量的天冬聚脲弹性体,并研究其结构与性能之间的关系,为天冬聚脲弹性体的制备提供基础的理论研究。（1）以马来酸二乙酯（DEM）与反式-1,4-环己二胺（trans-CHDA）、1,3-环己二甲胺（1,3-BAC）、间苯二甲胺（MXDA）为原料通过迈克尔加成反应制备了3种天冬氨酸酯扩链剂PAE-A、PAE-B、PAE-C,并以PAE-A的制备为例,确定了合适的反应条件,产率大于90%。（2）以制备的3种扩链剂,与3种分子量为1000g/mol的聚四氢呋喃二元醇（PTEMG1000）异氰酸酯低游离预聚体-甲苯二异氰酸酯预聚体（TDI-PTMEG1000）、对苯二异氰酸酯型预聚体（PPDI-PTMEG1000）、间苯二甲基二异氰酸酯预聚体（XDI-PTMEG1000）为原料,制备了一系列天冬聚脲弹性体。研究表明,XDI、PPDI型样品失重5%的温度(T_d5%)均大于320℃,样品失重50%的温度(T_d50%)均大于400℃,具有较好的热稳定性。硬段结构对称和规整,有利于硬段间的聚集,提高微相分离的程度,进而提升材料性能;就扩链剂结构来说,以PAE-A制备的样品,其微相分离程度最高,硬段玻璃化转变温度(T_gh)最高,拉伸强度和硬度最高;就异氰酸酯结构来说,TDI型样品和PPDI型样品具有更高的微相分离程度和T_gh,更高的拉伸强度和硬度。（3）以制备的3种扩链剂,与2种分子量为2000g/mol的聚四氢呋喃二元醇（PTEMG2000）低游离预聚体-TDI-PTMEG2000、PPDI-PTMEG2000为原料,制备了一系列天冬聚脲弹性体。研究表明,TDI型和PPDI型样品T_d5%均大于310℃,T_d50%均大于400℃,具有较好的热稳定性。软段含量的提高,有利于体现软段增韧的效果,样品的软段玻璃化转变温度(T_gs)向低温方向移动,断裂伸长率提高,韧性增加,特别是PPDI型天冬聚脲弹性体,断裂伸长率为1655%～2025%。更多还原

【Abstract】 Polyurea is an elastomeric polymer generated by the reaction of isocyanate component and amino compound component.Due to without volatile organic compounds and have both good thermal stability and excellent physical and chemical properties,polyurea is widely used in wear-resistant,waterproofing,anticorrosion and protection and other fields.Traditional aromatic polyurea and aliphatic polyurea was prepared by using primary amine compounds as chain extender.This method has the problem of fast curing speed and short gel time,and needs to use professional spraying equipment for construction.Aspartic polyurea elastomer is the third generation of polyurea elastomer with aspartic ester secondary amine compounds as chain extender,which has a slow curing speed and gel time that can be extended to a few minutes to tens of minutes,is easy to construct,and exhibits a large potential for application.The purpose of this thesis is to prepare a series of aspartic polyurea elastomers with different chain extender structures,isocyanate structures and soft-segment molecular weights from the molecular structure,and to study the relationship between their structures and properties.The studies of this thesis can provide basic theoretical studies for the preparation of aspartic polyurea elastomers.Firstly,three aspartate chain extenders PAE-A,PAE-B and PAE-C were prepared by Michael addition reaction of diethyl maleate（DEM）with trans-1,4-cyclohexanediamine（trans-CHDA）,1,3-bicyclohexanedimethanamine（1,3-BAC）,and m-xylenedimethanamine（MXDA）as raw materials.The preparation of PAE-A was taken as an example to explore the suitable reaction conditions.All the reactions of synthesizing chain extenders can achieve a yield of above 90%.Then,a series of aspartic polyurea elastomers were prepared by the reaction of the three prepared chain extenders with three polytetrahydrofuran diol（PTEMG1000）low free prepolymers,TDI-PTMEG1000,PPDI-PTMEG1000 and XDI-PTMEG1000,respectively.It was shown that the temperatures of 5%weight loss(T_d5%)of XDI and PPDI type polyurea elastomers were greater than 320℃,and the temperatures of 50%weight loss(T_d50%)of samples were greater than 400℃,which indicated that all the elastomers have good thermal stability.The symmetry and regularity of the hard segment structure are favorable for the aggregation between hard segments,which improves the degree of microphase separation and thus enhances the material properties.The samples prepared with PAE-A have the highest degree of microphase separation,the highest glass transition temperature of hard segments(T_gh),and the highest tensile strength and hardness.TDI-type samples and PPDI-type samples have higher degree of microphase separation and higher tensile strength and hardness.Finally,a series of aspartic polyurea elastomers were prepared from the three prepared chain extenders,together with two polytetrahydrofuran diol（PTEMG2000）low free prepolymers-TDI-PTMEG2000 and PPDI-PTMEG2000.It was shown that both TDI-type and PPDI-type samples had better thermal stability with greater than 310℃and greater than400℃.The increase in the content of soft segments is conducive to reflecting the effect of soft segment toughening.The soft segment glass transition temperature(T_gs)of the samples moved to the direction of low temperature.The elongation at break increased,the toughness increased,especially PPDI-type asphaltene polyurea elastomers,the elongation at break was 1655%～2025%.更多还原