功能化医用聚氨酯弹性体制备及生物医用研究进展※

热塑性聚氨酯(TPU)弹性体因其良好的可加工性、机械性能和生物安全性而被广泛应用于生物医学领域. 绝大部分TPU都由大分子二元醇软段以及异氰酸酯和小分子扩链剂形成的硬段组成, 这两者分别提供基体的弹性与链网络的框架刚性. 小分子扩链剂二元醇/胺和二异氰酸酯的结构设计是构建功能化TPU的主要途径. 研究者根据特定临床应用场景和使用需求, 设计和制备相应的功能化单体, 并开发出相应的医用TPU. 本综述首先介绍了大分子二元醇、二异氰酸酯以及扩链剂的种类以及各自的特点, 对其特有的微相分离结构做了介绍, 并明晰了化学/物理结构与最终性能的关系. 随后, 综述了国内外TPU在生物医学领域的研究进展和应用, 重点阐述了医用TPU在抗菌、抗凝血、耐水解耐氧化、自愈性以及可降解等方面的发展情况. 最后, 通过总结和分析医用TPU及其器械评价的相关标准, 提出了产业化应用的关键问题, 并展望了医用TPU未来的发展方向.     

生物医用PLA改性研究进展北大核心CSCD

聚乳酸(polylactic acid)材料是一种用途广泛的可生物降解高分子材料,已经成为生物医用材料中最受重视的材料之一。但是聚乳酸也存在许多缺陷,限制了其在医药领域的广泛应用。本文综述了聚乳酸疏水性强、细胞亲和性差、力学性能不足,降解产物造成局部酸性积累而导致机体发生无菌性炎症反应,缺乏修复、降解、吸收速度与细胞的增殖、组织修复速度匹配的系列产品,成本高,均聚物成孔性能差等缺陷,总结了近些年国内外针对以上各个缺陷做出的改进方案,并对聚乳酸医用改性的研究发展方向进行了展望。     

生物可降解医用聚氨酯及其应用

生物可降解医用聚氨酯由于其优良的生物相容性、降解性、功能化修饰和力学性能可调控等优点,逐渐引起研究者的关注,尤其在药物传递和组织工程支架等方面可望具有广阔的应用前景。结合本课题组开展的工作,本文综述了生物可降解医用聚氨酯材料在结构、功能化设计及医学应用上的研究进展,并展望了其在医学材料中的发展前景。     

蓖麻油及其衍生物在聚氨酯中的应用研究进展

蓖麻油是一种重要的可再生生物资源,在许多精细化学品以及聚合物方面有广泛的应用,介绍了蓖麻油及其衍生物在聚氨酯,互穿网络聚合物,聚氨酯弹性体,以及功能聚合物等方面的应用研究进展.指出以蓖麻油为原料改性和制备的聚合物材料不仅可以解决日趋紧缺的石油资源,加快聚合物工业的发展,而且改善了传统聚氨酯的耐热性,耐化学品性和力学性能等,拓宽了聚合物的应用领域.     

壳聚糖基生物医用材料及其应用研究进展

壳聚糖是一种极具发展潜力的天然生物材料,其在生物医学领域的研究和应用越来越受到重视。阐述了壳聚糖及其衍生物作为生物医用材料的特性,介绍了壳聚糖基生物医用材料的应用现状和发展趋势。     

生物医用材料表面仿细胞膜结构改性

细胞膜因其固有的生物相容性,可以作为体内植入材料及器件表面生物相容化改性的范例。大量研究结果表明,用细胞外层膜的亲水官能团－磷酰胆碱基团修饰材料表面,可显著提高材料的生物相容性,具有广阔的应用前景。本文综述了用含磷酰胆碱基团小分子及聚合物进行仿细胞膜结构改性的各种方法及其代表性工作;讨论了不同方法得到的仿细胞膜结构表面的性能;总结了几种有影响的生物相容性机理;对仿细胞膜结构表面改性研究及应用的前景做了展望。     

生物医用结冷胶及其改性水凝胶材料

结冷胶是一种线型聚阴离子微生物多糖,具有独特的凝胶特性和溶液流变学性质,自发现起即被应用于食品和化妆品中。近年来,随着生物医学学科的发展,天然高分子结冷胶及其水凝胶,在药物传递系统和组织工程材料等领域展现出了广阔的应用前景。结冷胶无毒,具有生物相容性和可生物降解性,所形成的水凝胶透明且稳定性好,并在一定条件下凝胶的力学性质与人体普通组织相近。结冷胶的这些优势使其成为一种良好的生物医用材料的制备来源。但是这种基于结冷胶的水凝胶也有其自身的缺点,如作为组织工程材料缺乏一定的韧性和组织负载能力等。这些不足在很大程度上限制了其在生物医学领域的应用。为了解决上述问题,许多研究者对结冷胶进行了化学和物理的改性。改性后的结冷胶材料在生物医学领域展现出更有发展的应用前景。本文综述了结冷胶凝胶的形成机理以及结冷胶的改性方法,重点详述了结冷胶及其改性材料在生物医学领域中的应用,并指出了结冷胶基组织工程材料在应用上应解决的一些挑战性问题。     

蓖麻油交联改性对室温自愈合聚氨酯性能的影响

以蓖麻油(CTO)或三羟甲基丙烷(TMP)作为交联剂,合成了一系列自愈合聚氨酯弹性体(PU)。借助核磁共振仪和红外光谱仪分析了产物结构,通过电子拉力试验机研究了交联剂添加量对PU的力学性能以及自愈合性能的影响。结果表明:CTO和TMP均能提高PU的拉伸强度,但是断裂伸长率会降低。随着交联剂用量的增加,PU内部交联度提升,自愈合性能下降。当PPG与TMP的物质的量之比为6∶4时,自愈合能力消失。在交联剂用量相同的情况下,CTO交联PU的自愈合性能保留效果比TMP交联PU更好。随着CTO用量的增加,断裂后愈合PU的拉伸强度先增加后减小。当聚丙二醇(PPG)与CTO的物质的量之比为7∶3时,总体性能最佳,在提高样品拉伸强度的同时,其自愈合后的拉伸强度恢复率为80.95%。     

酚氧树脂／蓖麻油交联聚氨酯

使2.2-(4’-羟基苯基)丙烷(双酚A)与环氧氯丙烷反应制得了带端羟基的酚氧树脂(HBA),将其与蓖麻油共混,用2.4-甲苯二异氰酸酯(TDI)作固化剂,制得了一系列交联聚氨酯。DSC和DMA测试结果表明,这种聚氨酯只有一个T_g。改变NCO/OH摩尔比及HBA/(HBA 蓖麻油)比可制得具有较好阻尼性能的聚氨酯材料。     

蓖麻油聚氨酯／聚甲基丙烯酸甲酯交联共聚物的溶胀

蓖麻油聚氨酯／聚甲基丙烯酸甲酯交联共聚物的溶胀刘和文，蔡宇东，施文芳，周永龙（中国科学技术大学应用化学系合肥２３００２６）（广西分析测试研究中心南宁）关键词蓖麻油聚氨酯，聚甲基丙烯酸甲酯，交联共聚物，溶胀，相逆转互穿网络聚合物（ＩＰＮ）的平衡溶胀度及...     

Development of hydrophobic polyurethane film from structurally modified castor oil and its anticorrosive performance

Hydrophobic polyurethane (PU) films are widely used for various commercial and industrial applications due to their excellent water repelling and self-cleaning property. Nevertheless, achieving appreciable hydrophobicity in PU film is quite a challenge. Herein, we report on the development of a novel hydrophobic PU (fluorinated polyurethane [FCO-PU]) film and comprehensively evaluate its anticorrosive property. The FCO-PU was prepared by structural modification of castor oil (CO) through attachment of long fluorocarbon chains as pendant groups onto the backbone of CO. A model PU film (CO-PU) was also prepared from unmodified CO to compare the properties of FCO-PU film. All intermediate compounds, FCO-PU and CO-PU films were characterized by various spectroscopic techniques. Morphological, thermal and mechanical properties of the PU films were analyzed by field emission scanning electron microscopy (FESEM), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and dynamic mechanical thermal analysis (DMTA) studies. Successful introduction of long fluorocarbon chains into the FCO-PU film is reflected by its high hydrophobicity with a water contact angle of 119.1°, compared to the model CO-PU film with a water contact angle of 84.4°. Anticorrosive properties of the PU films were evaluated by polarization technique and electrochemical impedance spectroscopy under corrosive environment and the obtained results reveal a significant corrosion resistance (corrosion rate: 6.72 × 10⁻⁶ mm/year) behavior by the FCO-PU film. This work represents an effective strategy for the backbone modification of CO to develop novel functional PU materials.     

Development of environmental friendly castor oil‐based waterborne polyurethane dispersions with polyaniline

This study describes the fabrication and characterization of castor oil‐based waterborne polyurethane/polyaniline (COWPU/PAni) conducting polymer blend films. The COWPU synthesized from isophorone diisocyanate was reacted with castor oil to form prepolymers, which were chain extended by reacting it with N‐methyldiethanolamine. Quaternization and self‐emulsification including deionized water followed in COWPU dispersions. Also, COWPU/PAni hybrid dispersions were synthesized with 2, 4, and 6 wt% of PAni–dodecyl benzene sulfonic acid to make different conductive composites. The outcome of COWPU/PAni was characterized by Fourier transform infrared spectrometer, differential scanning calorimeter, thermogravimetric analysis, dynamic mechanical and thermal analyzer, and scanning electron microscopy analysis. According to Fourier transform infrared spectrometer analysis, hydrogen bonding appears between –NH of PAni and C?O of COWPU. Meanwhile, incorporating PAni can improve the thermal stability of COWPU. The resulting COWPU/PAni conducting blend films can be used as antistatic and anticorrosive coating materials. Copyright © 2016 John Wiley & Sons, Ltd.     

Development of biobased polyurethane‐imides from maleinized cottonseed oil and castor oil

An eco‐friendly coating system, which is largely biobased, has been developed from castor and cottonseed oil. Cottonseed oil was functionalized with maleic anhydride by “ene” reaction to give maleinized cottonseed oil (MACSO); the anhydride groups were reacted with isocyanates to yield –NCO terminated polyurethane prepolymer. The prepolymer was further chain extended with hydroxyl groups of castor oil to give polyurethane‐imides (PUIs). The cross‐linked films thus obtained had good mechanical properties, and the imide groups in the backbone improved the corrosion resistance of PUIs as revealed by potentiodynamic polarization study. With increasing content of MACSO, thermal stability, glass transition temperatures (T_g), tensile strength, and corrosion resistance of resulting PUIs significantly increased.     

The influence of reactive organoclay on a biorenewable castor oil‐based polyurethane prepolymers toughened polylactide nanocomposites

Polylactide (PLA) is the most extensively reviewed and utilized biodegradable and renewable thermoplastic polyester, with potential to replace conventional petroleum‐based polymeric materials. To improve the toughness of PLA, castor oil‐based polyurethane prepolymer (COPUP) toughened PLA nanocomposites were prepared via the melt mixing process and investigated for its mechanical, thermal and morphological properties. X‐ray diffraction and transmission electron microscopy studies revealed the formation of polymer blend nanocomposites. Mechanical tests revealed optimum performance characteristics at PLA/COPUP ratio of 70:30. Further, loading of the organoclay showed higher tensile strength and modulus of the blend nanocomposites as compared to optimized blend. The morphological results indicated that the surface roughness increases as a function of the organoclay incorporation. Thermogravimetric measurements reveal that the thermal stability of the blend increases with the incorporation of organoclay. The improved mechanical properties along with its biodegradability might lead to new industrial and biomedical applications. Copyright © 2016 John Wiley & Sons, Ltd.     

蓖麻油与乳酸的共聚物合成与表征

用熔融聚合法合成了一种蓖麻油和乳酸的共聚物.以丁二酸酐作为共聚体系的引发剂和封端剂,制得端羧基共聚物P(LA-CO)-COOH.研究了反应条件对共聚物分子量的影响,通过核磁共振表征了共聚物的结构.DSC和TG研究表明,蓖麻油链段的引入破坏了聚乳酸的结晶性,提高了共聚物的热稳定性.     

Synthesis and properties of isocyanate curable millable polyurethane elastomers based on castor oil as a renewable resource polyol

Millable polyurethane elastomers based on difunctional castor oil and poly(propylene glycol), 2,4-toluene diisocyanate and 1,4-butane diol were prepared and cured using toluene diisocyanate dimer as crosslinking agent. All elastomers were characterized by conventional methods. Physical, thermal and mechanical properties of elastomers were studied. Investigation of these properties showed that the elastomers could be tailor made in order to fulfill industrial needs.     

Preparation of body-temperature-triggered shape-memory polyurethane with biocompatibility using isosorbide and castor oil

Shape memory polyurethanes (SMPUs) have attracted much attention in the biomedical field because they can easily control the transition temperature (T_trans) to shape memory and are biocompatible. In this study, a shape memory polyurethane with both biocompatibility and a T_trans close to the body temperature was synthesized by using natural derivatives of isosorbide and castor oil in place of petroleum-based materials. Isosorbide and castor oil were used to form net points, and polycaprolactone diol (PCL diol) acted as the switching segment. The synthesized four polyurethane (PCL diol/isosorbide/castor oil, PICU-1, 2, 3, 4) with different isosorbide contents exhibited desired thermal and mechanical properties. In the thermo-cyclic shape memory testing experiment, the PICU series demonstrated good shape memory property, with more than 95% shape recovery ratio (R_r) and more than 90% shape fixity ratio (R_f), and PICU-3 recovered its shape within 20 s in a 37 °C water bath. In addition, the PICU series proved to be safe materials with excellent biocompatibility, as indicated by the observed C2C12 cells viability and proliferation. The stent made with the PICU-3 film showed near complete magnetization at 37 °C within 18 s and proved to be a suitable self-expanding stent.     

Optimization of alkaline transesterification of soybean oil and castor oil for biodiesel production

This article reports experimental data on the production of fatty acid ethyl esters from refined and degummed soybean oil and castor oil using NaOH as catalyst. The variables investigated were temperature (30–70°C), reaction time (1–3 h), catalyst concentration (0.5–1.5 w/wt%), and oil-to-ethanol molar ratio (1:3–1:9). The effects of process variables on the reaction conversion as well as the optimum experimental conditions are presented. The results show that conversions >95% were achieved for all systems investigated. In general, an increase in reaction temperature, reaction time, and in oil-to-ethanol molar ratio led to an enhancement in reaction conversion, whereas an opposite trend was verified with respect to catalyst concentration.     

Surface patterning and modification of polyurethane biomaterials using silsesquioxane-gelatin additives for improved endothelial affinity

Polyurethanes (PUs) are well-known for their biocompatibility but their intrinsic inert property hampers cell-matrix interactions. Surface modifications are thus necessary to widen their use for biomedical applications. In this work, surface modifications of PU were achieved first by incorporating polyhedral oligomeric silsesquioxane (POSS), followed by alteration of the surface topography via the breath figures method. Subsequently, surface chemistry was also modified by immobilization of gelatin molecules through grafting, for the enhancement of the surface cytocompatibility. Scanning electron microscopy (SEM) was used to verify the formation of highly ordered microstructures while static contact angle, FTIR and XPS confirmed the successful grafting of gelatin molecules onto the surfaces. In vitro culture of human umbilical vein endothelial cells (HUVECs) revealed that endothelial cell adhesion and proliferation were significantly enhanced on the gelatin-modified surfaces, as shown by live/dead staining and WST-1 proliferation assay. The results indicated that the combination of the strategies yielded an interface that improves cell attachment and subsequent growth. This enhancement is important for the development of higher quality biomedical implants such as vascular grafts.     

Surface modification of pyrophyllite for optimizing properties of castor oil-based polyurethane composite and its application in controlled-release fertilizer

The high cost and difficulty in sustainability have hindered the wide application of the general synthetic resins in the controlled-release fertilizers (CRF). Here, the degradable castor oil-based polyurethane (PU) was filled by the natural pyrophyllite (PY) powders, which were pre-modified with few amount (≤0.5 %) of NDZ-201 coupling agent though a simple and economic mechanochemical method. Furthermore, the composite materials of PU and the modified PY (MPY/PU) with enhanced comprehensive properties were prepared and applied in CRF. Moreover, the release behaviors of the coated fertilizers were investigated while tuning the addition amount of modifier or the filling amount of MPY, and it was confirmed that the release performance was highly depended on the hydrophobic and mechanical properties of the composite coating. As a result, the best optimized MPY/PU coating exhibited significantly superior performance to the pure PU materials, and the duration of 80 % nitrogen release was more than 40 days. This confirms that the MPY/PU composite is a promising coating material for the CRF granules.