寬溫域高阻尼聚氨酯彈性體的制備

盧珣; 徐敏; 李志鵬; 李翰模; 莊文輝

doi:10.13374/j.issn2095-9389.2019.04.12.006

寬溫域高阻尼聚氨酯彈性體的制備

doi: 10.13374/j.issn2095-9389.2019.04.12.006

1.
華南理工大學材料科學與工程學院，廣州 510640
2.
廣州華工機動車檢測技術有限公司，廣州 510640

基金項目: 國家自然科學基金資助項目（51873065）；廣東省自然科學基金資助項目（2017A030313277）

詳細信息

通訊作者:
E-mail：whzhuang@scut.edu.cn

中圖分類號: TQ334.1
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出版歷程
- 收稿日期: 2019-04-12
- 刊出日期: 2020-03-01

Preparation of polyurethanes with broad temperature range and high damping factor

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

More Information

Corresponding author: E-mail: whzhuang@scut.edu.cn

摘要

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。
- 阻尼 /
- 長支鏈 /
- 聚氨酯 /
- 自修復性 /
- 氫鍵 /
- 微相分離
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
- damping /
- long branched chain /
- polyurethane /
- self-healing /
- hydrogen bonding /
- microphase separation

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圖 1 長支鏈聚氨酯合成流程

Figure 1. Procedure of polyurethanes with long branched chains

下載: 全尺寸圖片幻燈片

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

下載: 全尺寸圖片幻燈片

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

下載: 全尺寸圖片幻燈片

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

下載: 全尺寸圖片幻燈片

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

下載: 全尺寸圖片幻燈片

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

下載: 全尺寸圖片幻燈片

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

下載: 全尺寸圖片幻燈片

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

W_b/% H-bond peak integral Non H-bond
peak integral Peak ratio of H-bond and
non-H-bond

33 1.5584 1.7620 0.8844
50 2.4290 2.7284 0.8903
60 3.5887 3.4588 1.0376

下載: 導出CSV

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

W_b/% 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

下載: 導出CSV

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