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摘要: 為拓寬材料的阻尼溫域，增大聚氨酯應用范圍，基于聚氨酯的結構可設計性，引入含有甲苯-2,4-二異氰酸酯（TDI）和聚乙二醇單甲醚（MPEG）的預聚體制備帶長支鏈的聚氨酯。長支鏈一端固定一端活動的特點賦予其特有的運動與松弛。甲苯-2,4-二異氰酸酯的存在不僅延長了支鏈長度，增大了支鏈與分子間的纏結程度，還使支鏈含有強極性的吸電子的異氰酸酯基和氨基甲酸酯基，使得支鏈與主鏈間具有較強的氫鍵作用。因此，從氫鍵及微相分離角度來分別探究聚氨酯阻尼的影響因素。結果表明，長支鏈占比增加，儲能模量比值達到268.28，聚氨酯的微相分離程度降低，氫鍵作用增強，在氫鍵作用和微相分離程度降低的雙重作用下聚氨酯的有效阻尼（阻尼因子大于0.3）溫域超過150 ℃（?50～100 ℃），極大改善了聚氨酯彈性體的阻尼性能。此外，加入支鏈后聚氨酯具有一定的自修復性，對延長聚氨酯的使用壽命有較大意義。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). Simultaneously, the polyurethane has a certain self-healing property after the introduction of branches, which is of great significance to extend the service life of polyurethanes
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Key words:
- damping /
- long branched chain /
- polyurethane /
- self-healing /
- hydrogen bonding /
- microphase separation
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圖 2 不同支鏈占比的聚氨酯的阻尼?溫度曲線
Figure 2. Curves of damping temperature of polyurethanes with different proportion of branched chains
圖 3 不同支鏈占比的聚氨酯的阻尼?頻率曲線
Figure 3. Curves of damping frequency of polyurethanes with different proportion of branched chains
圖 4 不同支鏈占比聚氨酯體系的FTIR曲線. （a）亞氨基；（b）羰基
Figure 4. FTIR curve of polyurethanes with different proportion of branched chains: (a) N-H; (b) C=O
圖 5 聚氨酯的原子力顯微圖. （a）無支鏈；（b）支鏈占比33%
Figure 5. AFM image of polyurethanes: (a) no branched chains; (b) 33% branched chain
圖 6 聚氨酯原子力顯微鏡三維高度圖. （a）無支鏈；（b）支鏈占比33%
Figure 6. AFM three-dimensional height map of polyurethanes: (a) no branched chains; (b) 33% branched chain
圖 7 不同支鏈占比聚氨酯的自修復率變化曲線
Figure 7. Curve of self-repair rate of polyurethanes with different proportion of branched chains
表 1 亞氨基氫鍵化與非氫鍵化分峰數值
Table 1. Peak values of free N-H bond and ordered N-H bond
Wb/% H-bond peak integral Non H-bond
peak integralPeak ratio of H-bond and
non-H-bond33 1.5584 1.7620 0.8844 50 2.4290 2.7284 0.8903 60 3.5887 3.4588 1.0376 
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中文字幕在线观看表 2 甲苯-2,4-二異氰酸酯型聚氨酯的儲能模量
Table 2. Store modulus of polyurethanes based on TDI
Wb/% E'?30 °C/MPa E'70 °C/MPa E'?30 °C/E'70 °C 0 265.68 3.08 86.26 33 97.77 1.09 89.70 50 52.98 0.55 96.33 60 67.07 0.25 268.28
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參考文獻
[1] Xiao Y L, Wang J B, Yang Z P, et al. Finite element simulation and optimization design of the parameters of vibration reduction for damped wheels. Noise Vib Control, 2018, 38(3): 83 doi: 10.3969/j.issn.1006-1355.2018.03.015肖玉蘭, 王俊彪, 楊志鵬, 等. 阻尼車輪減振參量的有限元仿真與優化設計. 噪聲與振動控制, 2018, 38(3):83 doi: 10.3969/j.issn.1006-1355.2018.03.015 [2] Li B, Yang L B, Zhang B S, et al. Preparation of damping materials and its engineer applications on bridge bearing. World Rubber Ind, 2017, 44(3): 40 doi: 10.3969/j.issn.1671-8232.2017.03.015李斌, 楊麗博, 張保生, 等. 高分子阻尼材料的制備及其在橋梁支座上的應用. 世界橡膠工業, 2017, 44(3):40 doi: 10.3969/j.issn.1671-8232.2017.03.015 [3] Sun Y F, Gong J, Liu Y, et al. Viscous, damping, and mechanical properties of epoxy asphalt adhesives containing different penetration-grade asphalts. J Appl Polym Sci, 2019, 136(5): 47027 doi: 10.1002/app.47027 [4] Niu W, Tang D M. Study on damping characteristics and microscopic mechanism of polymer modified mortar repair material. Constr Technol, 2017, 46(15): 85牛文, 唐德密. 聚合物改性砂漿修補材料阻尼特性及微觀機理研究. 施工技術, 2017, 46(15):85 [5] Shi M X, Zheng J L, Huang Z X, et al. Synthesis of polyurethane pre-polymers and damping property of polyurethane/epoxy composites. Adv Sci Lett, 2011, 4(3): 740 doi: 10.1166/asl.2011.1597 [6] Kumar D, Kumar N, Jindal P. Effect of MWCNTs on damping behavior of polyurethane based nanocomposites. Mater Today Proc, 2018, 5(2): 5636 doi: 10.1016/j.matpr.2017.12.156 [7] Li H M, Yang Y L, Li Z P, et al. Preparation of high damping polyurethane with wide temperature range based on network structure designing. Polym Mater Sci Eng, 2017, 33(6): 146李翰模, 楊一林, 李志鵬, 等. 基于網絡結構設計制備寬溫域高阻尼聚氨酯彈性體. 高分子材料科學與工程, 2017, 33(6):146 [8] Yan X Q, Yin Z H, Luo S, et al. Research progress of polyurethane damping materials. China Adhes, 2018, 27(4): 46閆曉琦, 尹朝輝, 羅順, 等. 聚氨酯阻尼材料的研究進展. 中國膠粘劑, 2018, 27(4):46 [9] Lee K S, Choi J I, Kim S K, et al. Damping and mechanical properties of composite composed of polyurethane matrix and preplaced aggregates. Constr Build Mater, 2017, 145: 68 doi: 10.1016/j.conbuildmat.2017.03.233 [10] Kim J M, Kim D H, Kim J, et al. Effect of graphene on the sound damping properties of flexible polyurethane foams. Macromol Res, 2017, 25(2): 190 doi: 10.1007/s13233-017-5017-9 [11] Yu W W, Du M, Ye W J, et al. Relaxation behavior of layered double hydroxides filled dangling chain-based polyurethane/polymethyl methacrylate nanocomposites. Polymer, 2014, 55(10): 2455 doi: 10.1016/j.polymer.2014.03.039 [12] Zhou R, Gao W Q, Xia L C, et al. The study of damping property and mechanism of thermoplastic polyurethane/phenolic resin through a combined experiment and molecular dynamics simulation. J Mater Sci, 2018, 53(12): 9350 doi: 10.1007/s10853-018-2218-3 [13] Kausar A. Interpenetrating polymer network and nanocomposite IPN of polyurethane/ epoxy: a review on fundamentals and advancements. Polym-Plast Technol Mater, 2019, 58(7): 691 doi: 10.1080/25740881.2018.1563114 [14] Yu W W, Zhang D Z, Du M, et al. Role of graded length side chains up to 18 carbons in length on the damping behavior of polyurethane/epoxy interpenetrating polymer networks. Eur Polym J, 2013, 49(6): 1731 doi: 10.1016/j.eurpolymj.2013.03.024 [15] Zhu Y D, He G W, Li H F, et al. Modification and damping performance of the polyurethane elastomers. J Funct Mater, 2014, 45(21): 21006 doi: 10.3969/j.issn.1001-9731.2014.21.002朱耀東, 賀國文, 李衡峰, 等. 聚氨酯彈性體的改性及阻尼性能. 功能材料, 2014, 45(21):21006 doi: 10.3969/j.issn.1001-9731.2014.21.002 [16] Yu W W, Du M, Zhang D Z, et al. Influence of dangling chains on molecular dynamics of polyurethanes. Macromolecules, 2013, 46(18): 7341 doi: 10.1021/ma401260d [17] Lee H S, Wang Y K, Hsu S L. Spectroscopic analysis of phase separation behavior of model polyurethanes. Macromolecules, 1987, 20(9): 2089 doi: 10.1021/ma00175a008 [18] Xu K M, Zhang F S, Zhang X L, et al. Molecular insights into hydrogen bonds in polyurethane/ hindered phenol hybrids: evolution and relationship with damping properties. J Mater Chem A, 2014, 2(22): 8545 doi: 10.1039/C4TA00476K [19] Zhou J H, Li H M, Lu X. Damping elastomer with broad temperature range based on irregular networks containing hyperbranched polyester and dangling chains. Polym Adv Technol, 2018, 29(8): 2308 doi: 10.1002/pat.4342 [20] Ren L F, Chen T, Qiang T T, et al. Study on the preparation and properties of HBPU/PU blend films. J Shaanxi Univ Sci Technol Nat Sci Ed, 2016, 34(1): 11任龍芳, 陳婷, 強濤濤, 等. 超支化聚氨酯/聚氨酯共混膜的制備及其性能研究. 陜西科技大學學報:自然科學版, 2016, 34(1):11 [21] Castagna A M, Wang W Q, Winey K I, et al. Structure and dynamics of zinc-neutralized sulfonated polystyrene ionomers. Macromolecules, 2011, 44(8): 2791 doi: 10.1021/ma2001614 [22] Yao K J. Study on surface performance of modified montmorillonite/polyurethane composites. Polyurethane Ind, 2018, 33(3): 10 doi: 10.3969/j.issn.1005-1902.2018.03.003姚克儉. 改性蒙脫土/聚氨酯復合材料表面性能研究. 聚氨酯工業, 2018, 33(3):10 doi: 10.3969/j.issn.1005-1902.2018.03.003 [23] Castagna A M, Pangon A, Choi T, et al. The role of soft segment molecular weight on microphase separation and dynamics of bulk polymerized polyureas. Macromolecules, 2012, 45(20): 8438 doi: 10.1021/ma3016568 [24] Tian D D, Lv Z P, Wu Y K, et al. Preparation and properties of polyurethane/glycine-barium chloride semiorganic crystal composites. Polym Mater Sci Eng, 2016, 32(7): 136田丹丹, 呂志平, 吳怡康, 等. 聚氨酯/甘氨酸-氯化鋇半有機晶體復合材料的制備與性能. 高分子材料科學與工程, 2016, 32(7):136 -
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