343 nm飞秒激光制备微孔阵列以增强聚氨酯合成革透湿性

为了提高聚氨酯(PU)合成革透湿性,分别使用343 nm飞秒激光和作为对比的1030 nm飞秒激光及1064 nm纳秒激光制备微孔阵列。采用扫描电镜(SEM)和3D激光扫描显微镜对比研究了微孔形貌。结果表明,343 nm飞秒激光可以制备出效果最佳的微孔。此外,分析了3种激光与PU涂层的作用机理,揭示了343 nm飞秒激光合成革微钻孔过程仅表现为光化学烧蚀,光化学和光热烧蚀同时发生于1030 nm飞秒激光钻孔过程,而1064 nm纳秒激光只显示了光热烧蚀。激光合成革表面钻孔后,测量其透湿性和抗张力。结果显示: 微孔密度越大,皮革透湿性(WVP)越大而抗张力越低,脉冲重叠的增加会导致WVP的增加和抗张力的下降;同时,随着脉冲重叠从91.7%降到50%,微孔直径从45 μm降低到30 μm,而微孔锥度从0.7°增加到12.1°;当脉冲重叠率为91.7%,微孔密度为2550/cm²时,最大的WVP增长率为306%。     

Gel permeation chromatographic analysis of polyurethane prepolymer synthesis kinetics II. The effects of stoichiometry and type of diisocyanate

The kinetics of formation of polyurethane prepolymers is studied by an analytical technique which involves reactive quenching of the isocyanate, separation of the oligomeric species by GPC, and measurement by UV absorbance of the quenched moieties. The precision of the kinetic parameters and the ratios of the oligomers are determined. The effect of changes in reactant stoichiometry on the ratio of oligomers is measured and compared to the value predicted by an equation from Flory. Toluene diisocyanate is shown to give fewer high oligomers than predicted, while methylene diphenylene diisocyanate gives nearly the predicted values. Tetramethylxylene diisocyanate gives more high oligomers than predicted, an unexpected but possibly important result. Catalyst is shown to increase the reaction rate of the last by more than 200 times. © 1994 John Wiley & Sons, Inc.     

Novel Ibuprofen‐based Polyurethane: A New Approach for Drug Delivery

Facile synthesis of novel ibuprofen bearing polyurethane 1 has been achieved for the first time and found to display the release pattern of ibuprofen based on the easy cleavage of ester linkages. Thorough characterizations (FT‐IR, UV‐Vis, NMR, and elemental analysis) were performed to ascertain the structure of polyurethane 1.     

交联聚氨酯水分散体的合成

将硅氧烷封端的含亲水基团的线性聚氨酯预聚体分散于水中 ,获得稳定的聚氨酯分散体 .由于硅氧基团水解、缩合 ,在分散体粒子内产生扩链交联反应 ,生成了交联水基聚氨酯分散体 .透射电子显微镜研究表明分散体粒径小、分布宽 .扫描电子显微镜研究了成膜结构及成膜性能与粒径的关系 .溶胀实验计算获得的两交联点之间的平均分子量与理论平均分子量相符 .研究还发现此分散体膜在干燥过程中可进一步交联 .膜的水溶胀及机械性能表明 ,此分散体具有极大的工业应用价值 .     

正电子湮没谱研究聚烯烃聚氨酯的自由体积、微观结构和溶剂的扩散行为

用正电子湮没技术(PAS)结合示差扫描量热法(DSC)研究了聚烯烃聚氨酯的自由体积特征和微相分离结构的关系.结果表明,硬段含量增加,自由体积孔洞平均半径和自由体积分数减小;丁腈聚氨酯相分离程度小,相应自由体积孔洞平均半径和自由体积分数小,而丁羟聚氨酯的情况正好相反.石英弹簧法对苯和乙醇蒸气的溶解和扩散行为的研究表明,聚烯烃聚氨酯的自由体积孔洞平均半径和自由体积分数与苯和乙醇溶剂蒸气的无限稀释扩散系数呈正相关,但它们的无限稀释扩散系数和自由体积分数关系无法用Fujita的自由体积模型描述,可能归因于它们对聚烯烃聚氨酯复杂的溶胀行为.     

Recent Advances in Polyurethane/POSS Hybrids for Biomedical Applications

Advanced organic-inorganic materials-composites, nanocomposites, and hybrids with various compositions offer unique properties required for biomedical applications. One of the most promising inorganic (nano)additives are polyhedral oligomeric silsesquioxanes (POSS); their biocompatibility, non-toxicity, and phase separation ability that modifies the material porosity are fundamental properties required in modern biomedical applications. When incorporated, chemically or physically, into polyurethane matrices, they substantially change polymer properties, including mechanical properties, surface characteristics, and bioactivity. Hence, this review is dedicated to POSS-PU composites that have recently been developed for applications in the biomedical field. First, different modes of POSS incorporation into PU structure have been presented, then recent developments of PU/POSS hybrids as bio-active composites for scaffolds, cardiovascular stents, valves, and membranes, as well as in bio-imaging and cancer treatment, have been described. Finally, characterization and methods of modification routes of polyurethane-based materials with silsesquioxanes were presented.     

Structure analysis of polyether-based thermoplastic polyurethane elastomers by FTIR, 1H NMR and 13C NMR

One kind of unknown structure sequence and composition ratio of thermoplastic polyurethane elastomers were characterized by nuclear magnetic resonance spectroscopy, Fourier transformed infrared spectroscopy, and gel permeation chromatography (GPC). The results showed that the polyurethane (PU) was obtained from poly(tetramethylene glycol) (PTMG) as soft segment, 1,4-butanediol (BDO) as chain extender, and 4,4′-methylenediphenyl diisocyanate (MDI) as hard segment. Furthermore, the composition ratio of MDI:PTMG:BDO was 2.07:1.22:1.00. At last, the molecular weight of PU was determined by GPC, and the number average molecular weight (M_n) and weight average molecular weight (M_w) are 63,300 and 133,800?g?mol^?1, respectively.     

Self‐Healing Polyester Urethane Supramolecular Elastomers Reinforced with Cellulose Nanocrystals for Biomedical Applications

Stretchable self‐healing urethane‐based biomaterials have always been crucial for biomedical applications; however, the strength is the main constraint of utilization of these healable materials. Here, a series of novel, healable, elastomeric, supramolecular polyester urethane nanocomposites of poly(1,8‐octanediol citrate) and hexamethylene diisocyanate reinforced with cellulose nanocrystals (CNCs) are introduced. Nanocomposites with various amounts of CNCs from 10 to 50 wt% are prepared using solvent casting technique followed by the evaluation of their microstructural features, mechanical properties, healability, and biocompatibility. The synthesized nanocomposites indicate significantly higher tensile modulus (approximately 36–500‐fold) in comparison to the supramolecular polymer alone. Upon exposure to heat, the materials can reheal, but nevertheless when the amount of CNC is greater than 10 wt%, the self‐healing ability of nanocomposites is deteriorated. These materials are capable of rebonding ruptured parts and fully restoring their mechanical properties. In vitro cytotoxicity test of the nanocomposites using human dermal fibroblasts confirms their good cytocompatibility. The optimized structure, self‐healing attributes, and noncytotoxicity make these nanocomposites highly promising for tissue engineering and other biomedical applications.     

Short Twaron aramid fiber reinforced thermoplastic polyurethane

Mechanical, dynamic mechanical, and rheological behaviors of a short p‐aramid fiber reinforced thermoplastic polyurethane (TPU) have been studied in the range of 0–30 wt% of fibers. The tensile strength of the composite is improved slightly at higher fiber content with a minimum at around 10 wt% of fibers. The addition of fibers markedly reduces elongation at break and entails a steady increase in the elastic modulus, but decreases the wear resistance of the matrix. Storage modulus (E′) is increased and the shapes of loss tangent (tan δ) peaks point to a possible fiber–matrix interaction. Rheological studies show a power law behavior for all composites and increased viscosity with fiber loading. Study of the tensile and cryogenic fracture surfaces by scanning electron microscopy (SEM) indicates good correlation between the modes of failure and strength of the composites. The micrographs reveal good interfacial adhesion and extensive peeling and fibrillation of the fibers in the compounded and fractured composites. Theoretical models have been used to fit the experimental modulus data. Copyright © 2008 John Wiley & Sons, Ltd.