热可逆自修复聚氨酯弹性体的制备及表征

为探究本征型自修复聚氨酯材料结构与性能的关系,平衡其自修复效率与强度之间的矛盾,采用六亚乙基二异氰酸酯(HDI)三聚体作交联剂,4,4-二氨基二苯二硫醚(AFD)作扩链剂,将可逆双硫键引入聚酯型聚氨酯弹性体中。研究发现:制备的自修复聚氨酯弹性体拉伸强度可达7.7MPa,在60℃,修复时间为24h的条件下,基于拉伸强度的自修复效率高达97.4%;而普通不含有双硫键(只含氢键作用)的弹性体拉伸强度为9.3MPa,在同等条件下的自修复效率为58.0%,表明双硫键的存在使得弹性体自修复效率在原来的基础上提高了67.9%。制备的弹性体具有多次自修复能力,其二次自修复效率为62.3%。     

可自愈合的紫外光响应形状记忆聚氨酯的制备及性能

采用溶液聚合法合成了以聚四氢呋喃(PTMG)为软段、4,4’-偶氮苯二甲酸(Azoba)和六亚甲基二异氰酸酯(HDI)为硬段、双(2-羟基乙基)二硫醚(HEDS)为扩链剂的不同硬段比例的形状记忆聚氨酯(SMPU_s)。红外光谱表征了聚氨酯薄膜化学结构;分别通过热重分析、差示扫描量热分析、动态力学分析(DMA)探究了硬段对聚氨酯材料热稳定性、熔融温度及形状记忆性能的影响;记录了SMPU_2在紫外光照刺激下响应、发生形变的过程;用划痕修复测试和接触角法表征自愈合能力。结果表明,调控软硬段比例可得到具有差异形状记忆性能的SMPU_s。DMA测试中SMPU_s的平均固定率高于75%,回复率均高于95%,其中硬段含量为44%的SMPU_2形状记忆性能最佳,固定率达91%,回复率达99%。引入含双硫键的单体,SMPU_s具有一定自愈合性能。其中SMPU_5在40℃修复30 min,能修复表面划痕,力学测试表征的修复性能在60℃修复120 min修复率可达90%。     

兼具高强度、高韧性和自修复性能的环氧树脂改性热可逆聚氨酯

将E51环氧树脂引入基于Diels-Alder反应的热可逆聚氨酯，制备出环氧树脂改性热可逆自修复聚氨酯材料。引入环氧树脂，可提高改性热可逆聚氨酯的拉伸强度、杨氏模量、冲击韧性和邵氏硬度且保持较高的断裂伸长率。添加20%的环氧树脂制备的环氧树脂改性热可逆聚氨酯材料兼具优异的强度、韧性、硬度等力学性能和良好自修复性能。当环氧树脂改性热可逆聚氨酯出现裂纹裂缝等损伤后，在130℃处理20 min及60℃处理24 h便可修复损伤，并可实现同一部位多次损伤的重复自修复。力学性能提高的原因，是刚性环氧树脂相与聚氨酯弹性相相互缠结形成互穿聚合物网络结构产生的“强迫互溶”和“协同效应”；而多次重复自修复则归因于热可逆Diels-Alder反应和分子链热运动的协同作用。     

一种基于Diels-Alder可逆共价键自修复聚合物的合成及性能EI北大核心CSCD

以环氧氯丙烷和糠醇为原料,合成中间体糠基缩水甘油醚(FGE)。再以聚醚胺D2000与FGE反应,生成端呋喃基树脂FGE-D2000。最后加入交联剂4,4’-二苯甲烷双马来酰亚胺(BDM),利用酰亚胺环和呋喃环发生Diels-Alder(DA)反应,得到交联聚合物FGE-D2000-BDM。采用红外光谱、核磁共振、差示扫描量热分析、热重分析、光学显微镜、电子万能材料试验机等测试手段对实验结果进行表征。结果表明,FGE-D2000-BDM在50~150℃内为热稳定的可逆自修复系统,凝胶含量为87.49%,Tg为-54.50℃,r-DA反应的起始温度为69.59℃,最佳DA反应温度为70℃,80℃修复12h后自修复效率达到71.04%。     

一种基于Diels-Alder可逆共价键自修复聚合物的合成及性能

以环氧氯丙烷和糠醇为原料,合成中间体糠基缩水甘油醚(FGE)。再以聚醚胺D2000与FGE反应,生成端呋喃基树脂FGE-D2000。最后加入交联剂4,4’-二苯甲烷双马来酰亚胺(BDM),利用酰亚胺环和呋喃环发生Diels-Alder(DA)反应,得到交联聚合物FGE-D2000-BDM。采用红外光谱、核磁共振、差示扫描量热分析、热重分析、光学显微镜、电子万能材料试验机等测试手段对实验结果进行表征。结果表明,FGE-D2000-BDM在50~150℃内为热稳定的可逆自修复系统,凝胶含量为87.49%,Tg为-54.50℃,r-DA反应的起始温度为69.59℃,最佳DA反应温度为70℃,80℃修复12h后自修复效率达到71.04%。     

聚叠氮缩水甘油醚/聚乙二醇双软段含能聚氨酯弹性体的性能

为改善聚叠氮缩水甘油醚(GAP)的性能,以三羟甲基丙烷(TMP)为交联剂,异佛尔酮二异氰酸酯(IPDI)为固化剂,选用聚乙二醇(PEG)制备出GAP/PEG/TMP/IPDI双软段含能聚氨酯弹性体,采用红外光谱(FT-IR)、差示扫描量热(DSC)等手段进行了表征。实验结果表明,弹性体中引入聚乙二醇(PEG),拉伸强度提高168%,延伸率提高77%,所选PEG软段分子量较小,弹性体中只出现了GAP软段的Tg。随交联剂含量的增大,GAP软段的Tg由-36.85℃上升到-34.81℃,继而又下降到-40.31℃,弹性体的热分解分两段进行,初始分解温度为183℃。     

原位聚合法制备石墨烯/聚酰亚胺复合材料及其性能

以石墨烯(GNS)为改性填料,采用原位聚合法制备了GNS/聚酰亚胺(GNS/PI)复合材料,对有关产物的形貌和结构进行了表征。研究了GNS添加量对复合材料力学、电学和热学性能的影响。结果表明:GNS为较薄的片层状,表面较光滑,褶皱较少,有含氧基团残留;当GNS质量分数为1.5%时,复合材料力学性能达到最佳,其拉伸强度达126.7MPa,断裂伸长率达3.4%,邵氏硬度达89.7,摩擦系数和磨损率分别比纯PI降低了50.0%和70.6%;当GNS质量分数为1.0%时,复合材料电导率比纯PI提高了6个数量级;当GNS质量分数为2.0%时,复合材料热起始分解温度达559.2℃,比纯PI提高11.4℃。     

具有自修复性能的纤维素纳米晶/聚氨酯复合材料的制备EI北大核心CSCD

在两步法制备聚氨酯弹性体的基础上,利用溶液共混的方法将纤维素纳米晶添加到热塑性聚氨酯弹性体中制备得到纤维素纳米晶/聚氨酯复合材料,并对复合材料的组成与结构、热力学及力学性能和自修复性能进行了表征。结果表明,与单纯的聚氨酯弹性体相比,纤维素纳米晶/聚氨酯复合材料表现出良好的力学性能,在纤维素纳米晶的质量分数为1%时,拉伸断裂强度和伸长率能够同时提高140%以上。同时,纤维素纳米晶/聚氨酯复合材料中存在的大量动态氢键赋予了材料优异的自修复性能,在50℃修复36h的样品断裂强度和伸长率分别可以达到5.4 MPa和1113%。     

具有自修复性能的纤维素纳米晶/聚氨酯复合材料的制备

在两步法制备聚氨酯弹性体的基础上,利用溶液共混的方法将纤维素纳米晶添加到热塑性聚氨酯弹性体中制备得到纤维素纳米晶/聚氨酯复合材料,并对复合材料的组成与结构、热力学及力学性能和自修复性能进行了表征。结果表明,与单纯的聚氨酯弹性体相比,纤维素纳米晶/聚氨酯复合材料表现出良好的力学性能,在纤维素纳米晶的质量分数为1%时,拉伸断裂强度和伸长率能够同时提高140%以上。同时,纤维素纳米晶/聚氨酯复合材料中存在的大量动态氢键赋予了材料优异的自修复性能,在50℃修复36h的样品断裂强度和伸长率分别可以达到5.4 MPa和1113%。     

基于可逆硼氧六元环交联的自修复聚氨酯

自修复聚氨酯一直是近年来的研究热点。文中以聚四氢呋喃二醇(PTMEG)、异佛尔酮二异氰酸酯(IPDI)和4-羟基苯硼酸(HPBA)为原材料，制备了基于硼氧六元环的高强度自修复聚氨酯(PU)。利用傅里叶变换红外光谱仪对其进行结构表征；利用热重分析和差示扫描量热法考察其热性能；研究了PU的力学性能、自修复性能和形状记忆性能。结果表明，硼氧六元环结构的引入使PU具有高强度和优异的自修复性能。当HPBA含量从0 mmol增加到0.75mmol时，PU的拉伸强度从(23.8±1.8) MPa提高到(51.3±4.2) MPa；在80℃修复36 h后，PU/P-0.7的修复效率达到80.9%±4.2%。此外，PU还具有热响应的形状记忆性能，75℃时，其形状回复率达到96.1%±1.7%。利用凝胶渗透色谱法测试了PU的相对分子质量，其数均分子量为3.28×10⁴。     

自修复聚氨酯弹性体的制备及性能研究

目的对自修复聚氨酯弹性体的制备工艺及性能进行综述,为制备高修复效率的聚合物提供指导,并指出其未来的发展趋势。方法从聚氨酯弹性体的修复机理出发,收集并分析自修复聚氨酯弹性体的最新研究进展,总结典型自修复聚氨酯弹性体的制备工艺和性能指标;根据修复机理进行分类,对近年来本征型(Diels-Alder反应、Disulfide键、氢键等)和外援型(微胶囊化)自修复聚氨酯弹性体的制备和性能进行综述,并讨论自修复聚氨酯弹性体的修复效率。结论虽然基于不同动态键的自修复聚氨酯弹性体取得了一定的发展,但开发高修复效率的材料仍然是一个巨大的挑战。总结了提高自修复聚氨酯弹性体力学性能的途径,为实现修复性能与力学性能的平衡提供了指导。     

Preparation and properties of adjacency crosslinked polyurethane---urea elastomers

Adjacency crosslinked polyurethane--urea (PUU) elastomers with different crosslinking density were prepared by using hydroxyl-terminated liquid butadiene-nitrile (HTBN), toluene diisocyanate (TDI) and chain extender 3,5-dimethyl thio-toluene diamine (DMTDA) as raw materials, dicumyl peroxide (DCP) as initiator, and N,N'-m-phenylene dimaleimide (HVA-2) as the crosslinking agent. The influences of the crosslinking density and temperature on the structure and properties of such elastomers were investigated. The crosslinking density of PUU elastomer was tested by the NMR method. It is found that when the content of HVA-2 is 1.5%, the mechanical properties of polyurethane elastomer achieve optimal performance. By testing thermal performance of PUU, compared with linear PUU, the thermal stability of the elastomers has a marked improvement. With the addition of HVA-2, the loss factor tanδ decreases. FT-IR spectral studies of PUU elastomer at various temperatures were performed. From this study, heat-resistance polyurethane could be prepared, and the properties of PUU at high temperature could be improved obviously.     

Anti-corrosive,weatherproof and self-healing polyurethane developed from hydrogenated hydroxyl-terminated polybutadiene toward surface-protective applications

Self-healing polyurethane (PU) faces aging deterioration due to active dynamic bonds, which remain a challenging predicament for practical use. In this work, a novel strategy is developed to address this predicament by leveraging the hydrophobicity and gas barrier of hydrogenated hydroxyl-terminated polybutadiene (HHPB). The dynamic oxime-carbamate bonds derived from 2, 4-pentanedione dioxime (PDO) enable the elastomer to exhibit surface self-repairability upon applied mild heat and achieve ~99.5% mechanical self-healing efficiency. The mechanical properties remained nearly intact after 30-d exposure to thermal oxidation, xenon lamp, acids, bases, and salts. Gas permeability, positron annihilation lifetime spectroscopy (PALS), and contact angle measurements reveal the pivotal role of gas barrier, free volume, and hydrophobicity in blocking undesirable molecules and ions which effectively protects the elastomer from deterioration. HHPB-PU also exhibits excellent adhesion to steel substrate. The shear strength achieves (3.02 ± 0.42) MPa after heating at 80 °C for 4 h, and (3.06 ± 0.2) MPa after heating at 130 °C for 0.5 h. Regarding its outstanding anti-corrosive and weatherproof performances, this self-healable elastomer is a promising candidate in surface-protective applications.     

TiO_2填充聚氨酯弹性体复合材料的性能

以聚己二酸乙二醇酯二醇(PEA)、甲苯二异氰酸酯(TDI)、3,3-二氯-4-4-二苯基甲烷二胺(MOCA)为原料,采用预聚法合成聚氨酯弹性体,并选用微米级的TiO2对聚氨酯弹性体进一步增强,考察了TiO2加入量及交联剂MOCA用量对聚氨酯弹性体复合材料力学性能的影响。结果表明,微米级的TiO2对聚氨酯弹性体的力学性能有一定的提高,并且在TiO2加入量为4%(相对于PEA而言),MOCA用量为理论用量的82%~87%时,复合材料综合力学性能最好。SEM对其表面和断口形貌分析表明,TiO2在复合材料中分布较均匀,其断裂为韧性断裂。     

Colorless,Transparent, Robust,and Fast Scratch‐Self‐Healing Elastomers via a Phase‐Locked Dynamic Bonds Design

Robust self‐healing thermoplastic elastomers are expected to have repeated healing capability, remarkable mechanical properties, transparency, and superior toughness. The phase‐locked design in this work provides excellent tensile mechanical properties and efficient healability at a moderate temperature due to the dynamic disulfide bonds embedded in the hard segments and mainly being locked in the viscoelastic hard microphase region. The self‐healing elastomers exhibit a maximum tensile stress of 25 MPa and a fracture strain of over 1600%, which are quite prominent compared to previous reports. The nanoscale domains of the elastomer are smaller than the wavelength of visible light by microphase separation control resulting in colorless, nearly 100% transparency, and are as good as quartz glasses. The high dynamics of the phase‐locked disulfide bonds renders a high healing efficiency of scratches on the surface within 60 s at 70 °C. The rapid scratch healing and complete transparency recovery of the elastomers provide new avenues in the highly transparent surface or protective films which finds potential applications for precision optical lenses, flexible display screens, and automobile or aircraft lighting finishes.     

Preparation of Robust,Room-Temperature Self-Healable and Recyclable Polysiloxanes Based on Hierarchical Hard Domains

The contradiction between high mechanical strength and mild healing conditions has long existed in self-healing materials, which limits the application of self-healing materials. The preparation of robust materials with excellent healing performance under mild conditions can effectively reduce resource waste and environmental pollution. Herein, self-healing polysiloxane elastomer materials, APDMS-MDI-IPDI-Bs, based on microphase separation strategy are reported. Through the synergistic effect of the designed urea hydrogen bond and the nitrogen-coordinated boroxine structure, the materials can maintain high mechanical properties (maximum tensile strength up to 3.35 MPa, elongation at break up to 316%), while maintaining excellent self-healing and recyclable ability (24 h healing efficiency at room temperature can reach 94.77 ± 3.23%), and the performance can be repeated many times without decay. APDMS-MDI-IPDI-Bs also exhibit unique hydrophobicity, expanding the application scenarios of materials containing boroxine structure.     

低分子量HTPB聚氨酯弹性体的制备及其性能

为改善高固含量高聚物黏结炸药(PBX)和丁羟推进剂的工艺性能,以低分子量的端羟基聚丁二烯(HTPB)、异佛尔酮二异氰酸酯(IPDI)为主要原料,选用一缩二乙二醇(DEG)为扩链剂,采用二步法制备了聚氨酯弹性体。研究了催化剂用量对浆料黏度的影响,固化参数R及扩链剂用量对HTPB聚氨酯弹性体力学性能的影响。试验结果表明,当催化剂质量分数为0.004%时,适用期可达5 h;R值为1.1,DEG羟基含量占反应总羟基量的60%时,聚氨酯弹性体力学性能较好,拉伸强度达7.60 MPa,断裂伸长率达540.21%。动态力学分析(DMA)测试结果显示,低分子量HTPB聚氨酯弹性体有两个明显的玻璃化转变温度,说明样品存在明显的微相分离结构。     

MDI-50型聚氨酯弹性体材料合成及性能研究

利用MDI-50、聚醚多元醇和3,3′-二氯-4,4′-二氨基-二苯基甲烷(MOCA)扩链剂制备了MDI-50型聚氨酯弹性体,研究了游离异氰酸酯基质量含量、聚醚多元醇相对分子质量对MDI-50聚氨酯弹性体力学性能的影响,采用示差扫描量热分析(DSC)、热重分析(TG)、红外光谱(FTIR)及力学性能等测试方法对MDI-50型聚氨酯弹性体的结构及性能进行了表征和分析,并与TDI-80型聚氨酯弹性体相比较。结果表明:MDI-50型聚氨酯弹性体的综合性能明显优于TDI-80型。MDI-50型弹性体的硬度、撕裂强度和抗拉强度都随预聚体游离-NCO质量含量的提高而增大,随聚醚多元醇软链段相对分子质量增大而减小,而断裂伸长率相反。     

Einfluss einer praxisüblichen Härtetoleranz auf die thermo-mechanischen und schwingungsisolierenden Eigenschaften eines Acrylnitril-Butadien-Elastomers

The Shore hardness is still used as a characteristic property for elastomers. Rubber compounds with a hardness of 60 Shore A are often used for vibration insulation elements. The hardness of pneumatic seals lies in the range of 80 Shore A, and for hydraulics it is around 95 Shore A. The hardness of a rubber compound is fine-tuned by the filler content. With increasing filler content, usually carbon black, the hardness and thus the stiffness of the rubber compound increases. Industrial rubber manufacturers often accept a tolerance within ±3 Shore A. This value practically seems low and is therefore often accepted by the end-users. The effect of this tolerance on the application properties is investigated on the example of an acrylonitrile-butadiene rubber compound with a Shore hardness of 60 Shore A and samples with hardness of plus and minus 3 Shore A. Results of tensile tests and dynamic mechanical thermal analysis show that even such small deviation from the nominal value has a significant influence on material stiffness and damping performance over the entire application temperature range. Vibration tests by means of a shaker up to 700 Hz also prove a large variation in vibration transmission behaviour of a vibration de-coupler due to the rubber compound tolerance.