Synthesis,characterization of phosphine oxide-containing polyimides and their use as selective membrane for dopamine

Tris-(p-aminophenoxy)phosphineoxide, t-APPO, was prepared from 4-nitrophenol and POCl₃, followed by hydrogenation. A series of polyimides prepared from t-APPO and the corresponding dianhydrides by two-stage polycondensation method was characterized by Fourier Transform Infrared Spectrometer (FTIR), GPC, thermal analysis and physical methods. Moreover, in order to check the permeation properties of the resulting polyimide film, the selectivity of the polyimide-coated electrode toward electroactive species (ascorbic acid and dopamine) was examined by means of cyclic voltammetry (CV), differential pulse voltammetry (DPV) and time-base amperometric measurement (TB) techniques. As a result, it has been found that polyimide electrode showed selective permeation for dopamine while blocking the permeation of ascorbic acid through film. Therefore, it has been claimed that phosphine oxide-containing polyimide electrode can be used as a dopamine-selective membrane in the presence of ascorbic acid.     

聚氨酯水凝胶的设计及在生物医学中的应用

介绍了聚氨酯水凝胶的配方设计和合成方法,综述了近年来聚氨酯水凝胶在医学工程方面的研究及发展情况,并对聚氨酯水凝胶在生物医学中应用的发展趋势和方向作了展望。     

超支化聚氨酯丙烯酸酯的合成及其固化膜性能

以合成的甲苯-2,4-二异氰酸酯.丙烯酸羟丙酯(TDI.HPA)单体对超支化聚酯(HBPE)进行端羟基改性,得到超支化聚氨酯丙烯酸酯(HBPUA)。研究了反应温度、时间对产物游离—NCO含量的影响,通过摆杆硬度、附着力、柔韧性、冲击强度等测试研究了活性单体的种类及用量对固化膜性能的影响,并采用FT-IR及TG对HBPE,HBPUA及其固化膜进行了表征和分析。结果表明,合成HBPUA的最佳条件为:n(2,4-TDI):n(HPA):n(HBPE)=6:6:1,反应温度70℃,反应时间3 h,催化剂二月桂酸丁基锡(DBTDL)用量为总质量的0.6%;TDI.HPA的合成反应温度35℃,反应时间2.5 h,DBTDL用量为总质量的0.4%。采用己二醇二丙烯酸酯为活性单体并控制其质量分数为20%时,超支化聚氨酯丙烯酸酯涂膜的力学性能、热稳定性较好。     

复合薄膜用聚氨酯复膜胶的研究现状和发展

综述了复合薄膜用聚氨酯(PU)复膜胶的特性和种类,概述了近年来PU复膜胶的研究和应用进展,重点介绍了几类主要的PU复膜胶及其发展动态,结合实际对PU复膜胶的发展方向作了展望。     

一种电子传感器封装用聚氨酯凝胶的研制

以端羟基聚丁二烯、邻苯二甲酸二辛酯、MDI、聚醚多元醇,N,N-二(2-羟基丙基)苯胺等为主要原料合成一种电子传感器封装用的双组分聚氨酯凝胶。本实验对影响聚氨酯凝胶的硬度,体积电阻率,操作性能的因素作了研究。     

复合薄膜用双组分水性聚氨酯胶黏剂的制备和性能

制备了复合薄膜用双组分水性聚氨酯胶黏剂,初步研究了两种外加型交联剂环氧树脂6360、三聚氰胺-甲醛树脂对胶黏剂性能的影响。红外谱图和差示扫描量热法分析的结果表明在双组分水性聚氨酯胶黏剂中水性聚氨酯和交联剂发生了交联反应。外加交联剂可增加水性聚氨酯胶黏剂的交联度和黏度,从而有效提高胶黏剂的T型剥离强度和耐溶剂性能。环氧树脂较佳加入量在5%左右而三聚氰胺-甲醛树脂约为10%。由双组分水性聚氨酯胶黏剂黏合的PET/PE薄膜在较高温度下适当处理一段时间,其黏合效果更佳。     

Effect of polymer architecture and hard/soft segment ratio on the surface morphology and mechanical properties of polyurethane films for potential orthodontic treatment

In this study, polyurethane (PU) films are prepared by using 1,4-butanediol and trimethylolpropane as chain extender and crosslinking agent, respectively. A series of prepolymers are synthesized by varying the feeding molar ratios of methylene diisocyanate to polytetramethylene ether glycol, which are hard and soft segments, respectively. The influence of polymer architecture, chemical composition, and artificial saliva treatment on the surface morphology and mechanical strength of PU films are studied. The crosslinking polymer architecture and higher content of hard segment correlates with enhanced tensile strength and less decrease of tensile strength in the condition of artificial saliva, but reduced elongation at break. The in vitro cytotoxicity study demonstrates that PU films have excellent cytocompatibility.     

Development of antimicrobial‐loaded polyurethane films for drug‐eluting catheters

To prepare antibacterial, polymeric catheters for preventing catheter‐induced infections, sulfathiazole was loaded into polyurethane by solubilizing with solvents and the resultant films were cast. Fourier transform infrared spectroscopy confirmed the presence of sulfathiazole in the drug‐loaded polyurethane films. The thermal and mechanical properties of the films were assessed using differential scanning calorimetry and dynamic mechanical analysis. The drug‐loaded films were immersed in constantly stirred, deionized water at 37 °C for in vitro drug release study. The experimental data obtained from the in vitro drug release study were fit into mathematical models. Antibacterial efficiency of released sulfathiazole was evaluated by Escherichia coli growth inhibition test. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46467.     

Preparation,characterization, and release properties of hydrogels based on hyaluronan for pharmaceutical and biomedical use

Hyaluronic acid (HA) is a natural polysaccharide that is widely distributed in the human body. Its physicochemical properties and high biocompatibility make it a good candidate for biomedical and pharmaceutical uses. In the present work, we report HA‐based hydrogels that could be applied as drug delivery systems or as implants for the treatment of joint diseases. We use butanediol diglycidyl ether as a chemical crosslinker to obtain HA hydrogels. Using a new dissolution tester and ketoprofen (KP) as a model drug, we study the release properties of the hydrogels. We obtain homogeneous and transparent hydrogels with high strength and elasticity. The swelling ratio (SR) depends on the crosslinker concentration and pH of the medium. We also reveal differences between the release profile of KP from swollen and unswollen hydrogels. The characteristics and differences in KP release profiles depending on the SR suggest the possibility of obtaining controlled release from HA‐based hydrogels. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1377‐1382, 2013     

Preparation and properties of UV-curable polyurethane acrylate ionomers

Ultraviolet (UV)-curable polyurethane acrylate ionomer (PUAI) prepolymers were synthesized from isophorone diisocyanate (IPDI), poly(methylene ether) glycol (PTMG), 2,2-bis(hydroxymethyl) propionic acid (DMPA), triethylamine (TEA), 2-hydroxy ethyl acrylate (HEA), and dibutyl tin dilaurate (DBT) as a catalyst. UV-curable polyurethane acrylate ionomer aqueous dispersion was formulated from the prepolymers, water (30 wt %), and 1-hydroxycyclohexylhenyl ketone (Irgacure 184) as a photoinitiator. The films of UV-cured polyurethane acrylate ionomer were formed by curing the dispersion using a medium-pressure mercury lamp (80 W/cm; λ max = 365 nm). Gel content decreased with increasing water content in the aqueous dispersion. Effects of DMPA content and molecular weight of PTMG and the degree of neutralization on the physical properties were investigated. It was found that the storage modulus increased with increasing DMPA content. Tensile modulus and strength decreased with increasing the molecular weight of PTMG from 650 to 2000. The glass transition temperature shifted to a higher temperature as the content of DMPA increased. As the degree of neutralization increased, the tensile strength and modulus decreased. However, the elongation at break increased. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:2153–2162, 1998     

多重改性水性聚氨酯胶粘剂对聚烯烃薄膜的粘接机理

以自制的多重改性水性聚氨酯(WPU)复合乳液为基料,配合适量的消泡剂、润湿剂和偶联剂等,制备出软包装覆膜用多重改性WPU胶粘剂。考察了消泡剂、润湿剂和偶联剂用量对胶粘剂性能的影响,分析了胶粘剂对聚烯烃薄膜的粘接机理。结果表明:该胶粘剂对经过电晕处理的聚烯烃薄膜表面润湿性好、润湿速率快,并且和基材表面存在着广泛的氢键,因此其与聚烯烃薄膜表面有较强的吸附作用;通过外加偶联剂己二酰肼(ADH),强化了胶粘剂对聚烯烃表面的粘接效果;当w(消泡剂)=0.3%、w(润湿剂)=0.5%和w(ADH)=0.5%时,BOPP(双向拉伸聚丙烯)膜和CPP(流延聚丙烯)膜之间的最终粘接强度为264 N/m,可以满足软包装覆膜用胶粘剂的使用要求。     

混合异氰酸酯型聚氨酯的制备与耐黄变性能

以脂肪族异氟尔酮二异氰酸酯(IPDI)和芳香族二苯基甲烷二异氰酸酯(MDI)为原料,将其与聚四氢呋喃醚二醇2000(PTMG-2000)进行反应,合成了聚氨酯预聚体,将预聚体用1,4-丁二醇(BDO)扩链,制得一系列n(IPDI)/n(MDI)不同的混合异氰酸酯型聚氨酯(IMP-1~11),进一步制得聚氨酯膜IMPU-1~11,对聚氨酯膜的力学性能及紫外老化前后的色差值、黄变等级和紫外透过率进行了测定。采用FTIR、XRD、TG对聚氨酯膜的结构与性能进行了测定。结果表明:随着n(IPDI)/n(MDI)的减小,聚氨酯膜耐黄变性能逐渐降低,其断裂强度由IMPU-6的18.73 N增加到IMPU-11的42.85 N,而断裂伸长率则由IMPU-1的763.44%减小到IMPU-11的463.85%。紫外老化前后的色差值由IMPU-1的0.72增加到IMPU-11的22.92,黄变等级由IMPU-1的5级降低到IMPU-11的1级;同时,波长为400 nm时的紫外透过率由IMPU-1的89.74%降低到IMPU-11的35.04%,结晶度由IMPU-1的2.02%增加到IMPU-11的11.27%,450℃时残炭率由IMPU-1的1.07%增加到IMPU-11的18.11%,温度为285℃时的残炭率由IMPU-1的97.01%降低到IMPU-11的91.84%。     

三官能度含磷聚氨酯丙烯酸酯的合成及性能研究

采用异佛尔酮二异氰酸酯、羟基封端的聚丙二醇或聚己二酸丁二醇酯、丙烯酸羟乙酯合成含异氰酸基的聚氨酯丙烯酸酯与三氯氧磷和乙二醇合成的磷酸三乙二醇酯反应,制备了三官能度的含磷聚氨酯丙烯酸酯聚合物,并用红外光谱对其进行了表征。以该类聚合物和三缩丙二醇双丙烯酸酯为基料配制光固化涂料,并对其固化膜性能进行了研究。结果表明:不同聚合物所配制的涂料性能有一定差异,但都具有较好的光固化性能,固化涂膜各种物理性能优良,热稳定性能好,480℃下残重7.8%以上。     

Preparation and properties of microencapsulated octadecane with waterborne polyurethane

A series of microencapsulated blends of waterborne polyurethane (WBPU) as a matrix polymer and phase change material octadecane as a domain material were prepared in the presence of emulsifier. Nylon fabrics were coated with the coating materials formulated from microencapsulated blends, thickener, and hardener. The morphology and thermal behaviors of microencapsulated octadecane and WBPU/octadecane‐coated nylon fabrics were investigated using SEM, DSC, and KES‐F7. The size of octadecane microspheres increased with increasing octadecane contents. However, the size of microcsphere (1–6 μm) decreased with increasing emulsifier contents. ΔH_fusion, ΔH_{crystallization}, and their filling efficiencies of octadecane in film samples were found to increase with increasing microencapsulated blends, thickener, and hardener contents. Especially, thickener and hardener could function in trapping microencapsulated octadecane. Thermal characteristic Q_max (J/cm² s) values of WBPU/octadecane‐coated nylon fabrics are much higher than those of the control nylon fabric and WBPU‐coated nylon fabrics, indicating that the nylon fabrics coated with WBPU/octadecane blends have cooler touch sensation compared with nylon fabrics and WBPU‐coated nylon fabrics. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1596–1604, 2005     

功能聚氨酯材料在生物医学工程中的研究进展及应用

讨论了提高聚氨酯材料生物相客性和生物稳定性的改性方法,如表面活性端基改性、表面接枝聚合、表面形成互穿网络、使用表面活性剂、与纳米无机材料共混,介绍了功能性聚氨酯材料在生物医学工程中的应用及研究进展,表明聚氨酯材料的功能化改性仍然是今后的发展方向。     

锂离子电池用水性聚氨酯粘结剂的制备与性能研究

以异佛尔酮二异氰酸酯(IPDI)、聚氧化丙烯二醇(N220)、聚己二酸新戊二醇酯(PNA)、聚己二酸-1,4-丁二醇酯(PBA)为主要原料,制备了3种水性聚氨酯(WPU)粘结剂。采用IR、DSC和TG对3种水性聚氨酯膜进行了结构表征并测试了它们的力学和溶胀性能。通过循环、倍率等测试考察了以这3种水性聚氨酯为粘结剂的锂电池的电化学性能,并与以聚偏二氟乙烯(PVDF)为粘结剂的电池进行了比较。结果表明:以N220为软段的水性聚氨酯胶膜的拉伸强度为11 MPa,玻璃化转变温度为?52℃,初始分解温度为273.6℃,符合电池粘结剂的要求。并且以其作为粘结剂的电池在200次循环后,容量保持率可达到97.7%,明显高于以PBA型(87.9%)、PNA型(84.1%)水性聚氨酯和PVDF(90.5%)为粘结剂的电池。     

支化与交联型聚氨酯弹性体的合成与性能分析

为提高聚氨酯弹性体力学性能和耐热性,本文以聚己二酸二乙二醇酯二醇、二苯基甲烷二异氰酸酯和 1,4-丁二醇为原料,以聚氧化丙烯三醇（PPG-3）或丙三醇为支化单体,并通过调控其添加量（1%、3%和5%,相对于PDGA-2000的摩尔分数）,采用本体预聚物法合成支化或交联型聚氨酯弹性体。与线型聚氨酯相比,支化聚氨酯具有较高机械强度和耐热性。添加3% PPG-3所制备支化聚氨酯的拉伸强度提高170%（33.9MPa）,撕裂强度提高36%（90.7MPa）,维卡软化点温度为95.1℃;然而,5%的丙三醇引发交联结构的形成,交联型聚氨酯的拉伸强度提高154%（31.8MPa）,撕裂强度提高26%（84.4MPa）,维卡软化点温度为150.6℃。此外,PPG-3和丙三醇发挥聚氨酯软段和硬段相容剂的作用,抑制微相分离,使聚氨酯弹性体的橡胶平台增大。动态流变行为测试结果表明,支化和交联型聚氨酯弹性体具有更高的弹性模量和复数黏度。     

蓖麻油改性聚醚型水性聚氨酯乳液的性能

以聚醚、甲苯二异氰酸酯(TDI)、一缩二乙二醇、蓖麻油为主要原料,二羟甲基丙酸(DMPA)为亲水扩链剂,三乙胺为中和剂制备了稳定的阴离子水性聚氨酯乳液(WPU),研究了NCO/OH摩尔比、DMPA及蓖麻油的加入量对WPU的耐水性、稳定性和力学性能的影响,结果表明:改性后的乳液具有较好的稳定性,适量的蓖麻油可提高胶膜的拉伸强度及耐水性。当聚醚与蓖麻油质量比为7︰3、DMPA为5%、NCO与OH摩尔比为1.3时,WPU综合性能最好。     

聚氨酯/水滑石复合材料的制备及性能研究

以水滑石(LDH)和聚氨酯(PU)为原料,采用溶液流延法成膜,制备了一系列不同LDH含量的复合材料;借助广角X射线衍射和扫描电镜对PU/LDH复合材料的结构和形貌进行了表征,并对其热稳定性能和力学性能进行了测试。结果表明:LDH在PU基体中以插层结构为主,PU大分子链部分插入LDH层间;适量的LDH粒子能够均匀分散在PU基体中;LDH对PU材料的热分解无阻隔作用;适量的LDH粒子能有效提高PU材料的拉伸强度和断裂伸长率,当PU/LDH复合材料中LDH的质量分数为5%时,复合材料的拉伸强度和断裂伸长率达到最大,分别为15.9 MPa和443.8%。     

Shape memory thin films of polyurethane: Synthesis,characterization, and recovery behavior

Polyurethane thin films with inherent two phase segregated characters are exceptional candidates for the development of shape memory materials. However, controlling the phase behavior of such complex structures for decoding their recovery behavior still experiences its early stage of development. In this work, polyurethane thin films were synthesized based on two polyols, ester-based polyols (ESP), and ether-based polyols (ETP) together with diphenyl diisocyanate (MDI). The effects of ingredient ratio of PETP (ether-based prepolymer)/PESP (ester-based prepolymer) on the chemical structure and final properties of polyurethanes were studied by the Fourier-transformed infrared spectroscopy (FTIR), the differential scanning calorimetry (DSC), the scanning electron microscopy (SEM), the dynamic mechanical thermal analysis (DMTA), a tensiometer, and the atomic force microscopy (AFM). The shape memory behaviors were explored by the thermomechanical cycles applied by a DMTA device in the controlled force mode. The PU films showed various properties compared with the bulk PU since they formed spherulitic textures with different structures. All the PU films except PU-0 showed high shape recovery ca. 90% in the first cycle with a large glassy storage modulus in the range of 2,800–4,040MPa, and a recovery ratio enhanced by increasing the number of cycle to a maximum of 95%.