Su Shuang, Wang Jintao, Yan Qi, Li Anqi, Liu Chuang, Wu Xianli, Meng Yuezhong
College of Chemistry, Zhengzhou University, Zhengzhou 450001, China.
School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, China.
Polymers (Basel). 2025 Jun 16;17(12):1665. doi: 10.3390/polym17121665.
A series of PPCDL-PEG-TPU were prepared by melting method using CO based biodegradable polycarbonate diol (PPCDL) and polyethylene glycol (PEG1000) as soft segments, and hexamethylene diisocyanate (HDI) and 1,4-butanediol (BDO) as hard segments. Their structure and properties were characterized to show that the products have nanoscale microphase separation, excellent wear-resistance and high resilience. PPCDL-PEG-TPUs have high tensile strength, high elongation at break, controllable hardness and excellent wear resistance when the content of hard segment is about 20%. Compared to PPCDL-TPU with only PPCDL as soft segment, the mechanical properties of TPU increase rather than decrease after the addition of PEG due to the crystallization behavior of PEG units in block copolymers. When the ratios of n:n are 10:1 and 4:1, the tensile strength of PPCDL-PEG-TPU reaches 27.5 MPa and 16.5 MPa (an increase of nearly 200% and 20% than PPCDL-TPU). The elongation at break reaches 1995% and 2485% (an increase of nearly 40% and 75% than PPCDL-TPU). Hardness of the prepared PPCDL-PEG-TPUs' Shore A can be controlled in range of 70~85 by regulating the addition of PEG and their glass transition temperature (Tg) decreases with the increase of the amount of PEG incorporated. All PPCDL-PEG-TPUs exhibit good wear resistance with the average Akron wear volume of 12 mm after 4000 cycles of experiments according to national standards. PPCDL-PEG-TPUs show a high resilience performance with a negligible change in the hysteresis loop area after six cycles of tensile stretching. Furthermore, all PPCDL-PEG-TPUs possess high thermal stability, strong hydrophobicity, and low water absorption. This material has excellent application prospects and competitiveness in footwear and shock-absorbing materials.
以CO基可生物降解聚碳酸酯二醇（PPCDL）和聚乙二醇（PEG1000）为软段，六亚甲基二异氰酸酯（HDI）和1,4-丁二醇（BDO）为硬段，采用熔融法制备了一系列PPCDL-PEG-TPU。对其结构和性能进行了表征，结果表明该产品具有纳米级微相分离、优异的耐磨性和高弹性。当硬段含量约为20%时，PPCDL-PEG-TPU具有高拉伸强度、高断裂伸长率、可控硬度和优异的耐磨性。与仅以PPCDL为软段的PPCDL-TPU相比，由于嵌段共聚物中PEG单元的结晶行为，添加PEG后TPU的力学性能提高而非降低。当n:n的比例为10:1和4:1时，PPCDL-PEG-TPU的拉伸强度分别达到27.5 MPa和16.5 MPa（比PPCDL-TPU分别提高了近200%和20%）。断裂伸长率分别达到1995%和2485%（比PPCDL-TPU分别提高了近40%和75%）。通过调节PEG的添加量，制备的PPCDL-PEG-TPU的邵氏A硬度可控制在70~85范围内，其玻璃化转变温度（Tg）随PEG掺入量的增加而降低。根据国家标准进行4000次实验循环后，所有PPCDL-PEG-TPU均表现出良好的耐磨性，平均阿克隆磨耗体积为12 mm。经过六次拉伸循环后，PPCDL-PEG-TPU的滞后回线面积变化可忽略不计，表现出高弹性性能。此外，所有PPCDL-PEG-TPU均具有高的热稳定性、强疏水性和低吸水性。该材料在鞋类和减震材料方面具有优异的应用前景和竞争力。
