|本期目录/Table of Contents|

[1]吴明丽,李永旭,曹 兰.“瓶刷状结构”绿色生物基超低温聚法尼烯纳米复合材料的制备及固化动力学[J].合成橡胶工业,2024,6:509.
　WU Ming-li,LI Yong-xu,CAO Lan?.Preparation and curing kinetics of “bottlebrush-like structure” green bio-based ultra-low-temperature polyfarnesene nanocomposites[J].China synthetic rubber industy,2024,6:509.
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“瓶刷状结构”绿色生物基超低温聚法尼烯纳米复合材料的制备及固化动力学(PDF)

《合成橡胶工业》[ISSN:1000-1255/CN:62-1036/TQ]

期数:
2024年6期
页码:
509
栏目:
出版日期:
1900-01-01

文章信息/Info

Title:
Preparation and curing kinetics of “bottlebrush-like structure” green bio-based ultra-low-temperature polyfarnesene nanocomposites
文章编号:
1000-1255（2024）06-0503-04
作者:
吴明丽; 李永旭; 曹 兰
青岛科技大学 高分子科学与工程学院，山东 青岛266042
Author(s):
WU Ming-li;  LI Yong-xu;  CAO Lan?鄢
College of Polymer Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China
关键词:
端羟基聚法尼烯; 改性氧化石墨烯; 复合材料; 耐低温性能; 流变性能; 固化反应动力学
Keywords:
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分类号:
-
DOI:
DOI:10.19908/j.cnki.ISSN1000-1255.2024.06.0509
文献标识码:
-
摘要:
采用自由基溶液聚合法合成了生物基端羟基聚法尼烯（HTPF），将其作为多元醇软段、异佛尔酮二异氰酸酯改性氧化石墨烯作为功能填料，采用一步法制备了增强型HTPF基PU纳米复合材料（HTPF-PU）；通过红外光谱的羰基峰分峰拟合计算HTPF-PU的氢键化程度，同时研究了其耐低温性能和流变性能，并基于Sestak-Berggren模型建立了固化动力学方程。结果表明，改性氧化石墨烯（iGO）的异氰酸酯基团与HTPF的羟基可形成共价键，由此可制得具有强界面结合作用的“瓶刷状结构”绿色生物基iGO/HTPF-PU纳米复合材料；HTPF-PU复合材料的氢键化程度增至87.2%，表明iGO在基体中分散性较好；随着iGO填充量的增加，iGO/HTPF-PU纳米复合材料的玻璃化转变温度逐渐降低，最低可至-82 ℃，表明添加iGO对其耐低温性能有较好的提升效果；随着固化反应的进行，复合材料的复数黏度和储能模量逐渐增大，iGO填充质量分数为0.1%时效果最佳；复合材料的固化动力学方程为：dα/dt=3.667×107 exp（-7.514×104/RT）α1.211（1-α）1.164。
Abstract:
Based on the requirements of dual-carbon strategy and the major needs of sustainable development, it was of great significance to develop green and environmentally-friendly bio-based rubbers. However, it was difficult for existing rubber materials to simultaneously meet the requirements of low-temperature resistance and excellent dynamic performance, which greatly limited its application in special fields at low temperature. To solve this problem, the bio-based acyclic sesquiterpene compound, trans-β-farnesene was autonomously synthesized by bio-fermentation in our laboratory. As a versatile monomer, trans-β-farnesene had a special structure of long side chain monosubstitution, which could be genetically edited from the source to form a “bottlebrush-like” polymer with a regular structure.　In this work, hydroxyl-terminated polyfarnesene (HTPF) was synthesized by free-radical solution polymerization, and enhanced HTPF-based polyurethane elastomers (HTPF-PU) was prepared using HTPF as soft segment and functionalized graphene oxide (GO) modified with isophorone diisocyanate (IPDI) as functional filler by one-step process for the first time, which allowed the isocyanate groups on modified graphene oxide (iGO) and the hydroxyl groups in HTPF to form covalent bonds to prepare nanocomposites with a strong interfacial bonding effect, as shown in Fig 1. The results showed that the layer spacing was enlarged from 1.006 nm to 1.075 nm after modification. In the range of 100-700 ℃, the mass loss fraction of GO was 48.22% and that of iGO was 58.49%. The grafting modification was successful and the thermal stability of iGO was improved. In addition, the result of the infrared spectroscopy carbonyl peak fitting for iGO/HTPF-PU nanocomposites showed increasing hydrogen bonding up to 87.2% compared to pure HTPF-PU, indicating better dispersion of iGO in the matrix. iGO/HTPF-PU nanocomposites had excellent thermal properties. With the increase in iGO fill amount, the glass transition temperature of the nanocomposites decreased gradually and reached as low as -82 ℃, which indica-ted that the nanocomposites had excellent low-temperature resistance.　Finally, the rheological properties and isothermal curing reaction kinetics of the nanocomposites were studied by rheological test. With the curing reaction, the complex viscosity and storage modulus of the nanocomposites increased gradually, and the effect was the best when the iGO fill mass fraction was 0.1%. Based on the Sestak-Berggren model of thermal analysis kinetics, the curing kinetic parameters were solved, including the reaction orders, pre-exponential factor and activation energy, and the curing kinetic equation of the composite, dα/dt=3.667×107exp(-7.514×104/RT)α1.211(1－α)1.164, where α was curing degree, t was curing time, R was molar gas constant and T was curing temperature, was established.

参考文献/References

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备注/Memo

备注/Memo:
Supported by National Natural Science Foundation of China (52403096).
更新日期/Last Update: 1900-01-01