工程科学学报.第42卷，第3期：365-371.2020年3月 Chinese Journal of Engineering,Vol.42,No.3:365-371,March 2020 https://doi.org/10.13374/j.issn2095-9389.2019.04.12.006;http://cje.ustb.edu.cn 宽温域高阻尼聚氨酯弹性体的制备 卢珣，徐敏)，李志鹏)，李翰模，庄文辉)区 1)华南理工大学材料科学与工程学院，广州5106402)广州华工机动车检测技术有限公司，广州510640 ☒通信作者，E-mail:whzhuang@scut.edu.cn 摘要为拓宽材料的阻尼温域，增大聚氨酯应用范围，基于聚氨酯的结构可设计性，引人含有甲苯-2,4-二异氰酸酯(TDI)和 聚乙二醇单甲醚(MPEG)的预聚体制备带长支链的聚氨酯.长支链一端固定一端活动的特点赋予其特有的运动与松弛.甲 苯2,4二异氰酸酯的存在不仅延长了支链长度，增大了支链与分子间的缠结程度，还使支链含有强极性的吸电子的异氰酸酯 基和氨基甲酸酯基，使得支链与主链间具有较强的氢键作用.因此.从氢键及微相分离角度来分别探究聚氨酯阻尼的影响因 素.结果表明，长支链占比增加，储能模量比值达到26828，聚氨酯的微相分离程度降低，氢键作用增强，在氢键作用和微相分 离程度降低的双重作用下聚氨酯的有效阻尼（阻尼因子大于0.3）温域超过150℃(-50~100℃)，极大改善了聚氨酯弹性体的 阻尼性能.此外，加入支链后聚氨酯具有一定的自修复性，对延长聚氨酯的使用寿命有较大意义. 关键词阻尼：长支链：聚氨酯：自修复性：氢键：微相分离 分类号TQ334.1 Preparation of polyurethanes with broad temperature range and high damping factor LU Xun,XU Min,LI Zhi-peng,LI Han-mo,ZHUANG Wen-hu 1)School of Materials Science and Engineering.South China University of Technology,Guangzhou 510640,China 2)Guangzhou Huagong Motor Vehicle Inspection Technology Co.,LTD,Guangzhou 510640,China Corresponding author,E-mail:whzhuang@scut.edu.cn ABSTRACT The continuous improvement of people's living standards and quality puts higher and higher demands on polymer materials,and damping materials such as polyurethane elastomer used for vibration and noise reduction have also received increasing attention.However,the application of polyurethanes is limited to some extent owing to the narrow effective damping temperature range of polyurethane.Therefore,polyurethane containing a branched chain has been prepared from the perspective of its structural designability,in which the prepolymer synthesized by the reaction of polyethylene glycol monomethyl ether(MPEG)with toluene 2,4- diisocyanate(TDI)is performed as a branched chain.Herein,the long branched chain with one end fixed at the end gives its unique movement and relaxation,contributing to the superior damping performance of polyurethane to some extent,and the presence of TDI not only prolongs the length of the branch and increases the entanglement degree between the branches and the molecules but also makes the branches contain a strong polar electron-withdrawing isocyanate group and a urethane group,impacting the branch and the main chain with strong hydrogen bonding effect.Herein,the influencing factors of polyurethane on damping property are explored separately from the perspective of hydrogen bonding and microphase separation.By means of Fourier transform infrared spectroscopy (FTIR),dynamic mechanical analysis(DMA),atomic force microscopy (AFM),and broadband dielectric relaxation spectroscopy,the results show that cis able to reach 268.28 with the increased proportion of branches,indicating the dropped degree of microphase separation of polyurethanes.Furthermore,the hydrogen bonding effect is enhanced by characterization with FTIR.The two aforementioned effects make the damping properties of polyurethanes more excellent;the effective damping(tan0.3)can even exceed 150C(-50-100C). 收稿日期：2019-04-12 基金项目：国家自然科学基金资助项目(51873065)：广东省自然科学基金资助项目(2017A030313277)宽温域高阻尼聚氨酯弹性体的制备 卢    珣1)，徐    敏1)，李志鹏1)，李翰模1)，庄文辉2) 苣 1) 华南理工大学材料科学与工程学院，广州 510640    2) 广州华工机动车检测技术有限公司，广州 510640 苣通信作者，E-mail：whzhuang@scut.edu.cn 摘    要    为拓宽材料的阻尼温域，增大聚氨酯应用范围，基于聚氨酯的结构可设计性，引入含有甲苯-2,4-二异氰酸酯（TDI）和 聚乙二醇单甲醚（MPEG）的预聚体制备带长支链的聚氨酯. 长支链一端固定一端活动的特点赋予其特有的运动与松弛. 甲 苯-2,4-二异氰酸酯的存在不仅延长了支链长度，增大了支链与分子间的缠结程度，还使支链含有强极性的吸电子的异氰酸酯 基和氨基甲酸酯基，使得支链与主链间具有较强的氢键作用. 因此，从氢键及微相分离角度来分别探究聚氨酯阻尼的影响因 素. 结果表明，长支链占比增加，储能模量比值达到 268.28，聚氨酯的微相分离程度降低，氢键作用增强，在氢键作用和微相分 离程度降低的双重作用下聚氨酯的有效阻尼（阻尼因子大于 0.3）温域超过 150 ℃（−50～100 ℃），极大改善了聚氨酯弹性体的 阻尼性能. 此外，加入支链后聚氨酯具有一定的自修复性，对延长聚氨酯的使用寿命有较大意义. 关键词    阻尼；长支链；聚氨酯；自修复性；氢键；微相分离 分类号    TQ334.1 Preparation of polyurethanes with broad temperature range and high damping factor LU Xun1) ，XU Min1) ，LI Zhi-peng1) ，LI Han-mo1) ，ZHUANG Wen-hui2) 苣 1) School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China 2) Guangzhou Huagong Motor Vehicle Inspection Technology Co., LTD, Guangzhou 510640, China 苣 Corresponding author, E-mail: whzhuang@scut.edu.cn ABSTRACT    The  continuous  improvement  of  people ’s  living  standards  and  quality  puts  higher  and  higher  demands  on  polymer materials, and damping materials such as polyurethane elastomer used for vibration and noise reduction have also received increasing attention. However, the application of polyurethanes is limited to some extent owing to the narrow effective damping temperature range of  polyurethane.  Therefore,  polyurethane  containing  a  branched  chain  has  been  prepared  from  the  perspective  of  its  structural designability, in which the prepolymer synthesized by the reaction of polyethylene glycol monomethyl ether (MPEG) with toluene 2,4- diisocyanate (TDI) is performed as a branched chain. Herein, the long branched chain with one end fixed at the end gives its unique movement and relaxation, contributing to the superior damping performance of polyurethane to some extent, and the presence of TDI not only prolongs the length of the branch and increases the entanglement degree between the branches and the molecules but also makes the branches contain a strong polar electron-withdrawing isocyanate group and a urethane group, impacting the branch and the main chain with strong hydrogen bonding effect. Herein, the influencing factors of polyurethane on damping property are explored separately from the perspective of hydrogen bonding and microphase separation. By means of Fourier transform infrared spectroscopy (FTIR), dynamic mechanical analysis (DMA), atomic force microscopy (AFM), and broadband dielectric relaxation spectroscopy, the results show that E'30 °C/E'70 °C is able to reach 268.28 with the increased proportion of branches, indicating the dropped degree of microphase separation of polyurethanes. Furthermore, the hydrogen bonding effect is enhanced by characterization with FTIR. The two aforementioned effects make the damping properties of polyurethanes more excellent; the effective damping (tan δ ≥ 0.3) can even exceed 150 °C (−50−100 °C). 收稿日期: 2019−04−12 基金项目: 国家自然科学基金资助项目（51873065）；广东省自然科学基金资助项目（2017A030313277） 工程科学学报，第 42 卷，第 3 期：365−371，2020 年 3 月 Chinese Journal of Engineering, Vol. 42, No. 3: 365−371, March 2020 https://doi.org/10.13374/j.issn2095-9389.2019.04.12.006; http://cje.ustb.edu.cn