聚氨酯改性TDE-85/MeTHPA树脂的固化反应机理及动力学研究

 以聚醚二元醇、甲苯二异氰酸酯为原料,合成了聚醚型聚氨酯预聚体(PUP)。采用该预聚体、扩链剂1,4-丁二醇、交联剂三羟甲基丙烷对TDE-85/甲基四氢邻苯二甲酸酐（MeTHPA)环氧树脂体系进行改性,通过示差扫描量热法与红外光谱法分析,探讨了聚氨酯(PU)改性环氧树脂体系固化反应机理及固化反应动力学特征。固化反应机理研究表明,TDE-85与MeTHPA之间的固化反应形成环氧聚合物网络Ⅰ,1,4-丁二醇及三羟甲基丙烷同PUP进行了扩链、交联反应形成了PU聚合物Ⅱ。异氰酸酯基同环氧基反应,使得聚合物Ⅰ与聚合物Ⅱ形成了接枝化学键。固化反应动力学研究表明,PU的加入可明显降低环氧树脂固化反应的表观活化能,活化能由TDE-85/MeTHPA树脂体系时的83.14 kJ/mol降至PU改性后的67.91 kJ/mol。     

Flexible rGO/Fe_3O_4 NPs/polyurethane film with excellent electromagnetic properties

Large-area and flexible reduced graphene oxide(rGO)/Fe_3O_4 NPs/polyurethane(PU) composite films are fabricated by a facile solution-processable method. The monolayer assembly of Fe_3O_4 nanoparticles with a high particle-stacking density on the graphene oxide(GO) sheets is achieved by mixing two immiscible solutions of Fe_3O_4 nanoparticles in hexane and GO in dimethylformide(DMF) by a mild sonication. The x-ray diffraction and Raman spectrum confirm the reduced process of rGO by a simple thermal treatment. The permittivity value of the composite in a frequency range of 0.1 GHz–18 GHz increases with annealing temperature of GO increasing. For 5-wt% rGO/Fe_3O_4 NPs/PU, the maximum refection loss(RL) of over-35 dB appears at 4.5 GHz when the thickness of film increases to 5 mm. The rGO/Fe_3O_4 NPs/PU film, exhibiting good electromagnetic properties over GHz frequency range, could be a potential candidate as one of microwave absorption materials in flexible electronic devices.     

聚氨酯改性TDE-85/MeTHPA环氧树脂的力学性能研究

 采用自制的聚氨酯预聚体(PUP)制备聚氨酯(PU)改性TDE-85/ MeTHPA环氧树脂体系,探讨了聚醚二元醇(PPG)分子量的大小、PUP加入量等因素对PU改性TDE-85/ MeTHPA环氧树脂体系力学性能的影响。研究结果表明,PU改性TDE-85/ MeTHPA环氧树脂的拉伸强度和冲击强度随着合成的PUP加入量的增加先呈上升趋势,达到最大值后又开始下降。采用的PPG分子量不同,得到的改性材料的力学性能相差悬殊。当PPG分子量为1 000,PUP质量分数为15%时,改性材料的拉伸强度达到69.39 MPa,冲击强度达到23.56 kJ/m²,力学综合性能显著提高。     

颜料含量对复合涂层红外发射率的作用机制研究

以聚氨酯(PU)为粘合剂,某片状金属粉为颜料,采用刮涂法制备了PU/片状金属复合涂层。对不同颜料含量条件下涂层的红外发射率进行了测试,并采用扫描电镜对涂层的微结构进行了观察。发射率测试结果表明,涂层发射率随金属粉含量增加呈“∪”型变化。微结构观察结果表明,PU/片状金属复合涂层由PU和片状金属粉交错堆叠而成,具有类似一维光子结构特征。基于涂层的微结构特征,对具有转折变化特征的4个金属粉含量点状态下涂层中一维光子结构的反射光谱进行了模拟计算,结果表明：PU/片状金属复合涂层的发射率随金属粉含量变化呈“∪”型变化关系特征主要是由涂层中一维光子结构的主反射峰中心波长随颜料含量增加所产生的蓝移现象引起的。     

氯化镧与聚氨酯相互作用的FTIR研究

将LaCl3 掺入PU制得LaCl3 /PU复合体系。DSC的结果显示LaCl3 的加入使得PU体系的相转变行为发生了变化 ,位于 11 5 8℃的吸热峰消失。通过FTIR研究表明 :La3 与PU体系内的羰基发生了络合配位作用 ,使得PU的氢键结构体系发生了变化 ,峰位分别由 16 33和 3311cm-1蓝移至 16 4 7和 335 5cm-1。远红外光谱的中 2 0 0cm-1峰的出现也进一步证明了La—O键的形成。这为PU与氯化镧的络合作用的存在提供了直接的证据。     

新型3,4-二烷基取代聚噻吩的合成、光学及电化学性能

通过Heck偶联法制备了一种新型聚噻吩衍生物——2,5-二乙烯基-3,4-二辛基噻吩-共-2,5-二苯基-1,3,4-(口恶)二唑(PO2TV-OXD),用核磁共振氢谱(1H NMR)及凝胶色谱(GPC)对其结构进行分析和表征.用紫外-可见光谱(UV-Vis)、荧光光谱(PL)及电化学分析研究其光学和电化学性能,并与3,4-二辛基噻吩均聚物(PO2T)进行了对比研究.研究表明:主链上引入吸电子能力较强的1,3,4-(口恶)二唑基团,明显增加了聚合物的能隙,提高了聚合物的荧光量子效率.     

苯乙烯与苯酚反应的前线轨道理论分析

采用密度泛函理论的M062X方法和6-311G(d,p)基组,对苯乙烯与苯酚的反应进行了分子轨道理论计算.通过讨论反应过程中各分子的最高占据轨道(HOMO)和最低空轨道(LUMO),预测了化学反应的方向和相应的反应产物.经过前线轨道理论分析,得出苯乙烯与苯酚反应的关键步骤是形成苯乙烯基碳正离子,反应中H+起到催化作用;反应产物主要有4-(1-苯基乙基)苯酚、2-(1-苯基乙基)苯酚、2,4-双-(1-苯基乙基)苯酚、2,4,6-三-(1-苯基乙基)苯酚(SP-3)、1,3-二苯基丁烯和4-(1,2-二苯丙基)苯酚.     

N-(2-吡咯亚甲基)芳胺的一锅法合成

以芳胺、2-吡咯甲醛和硼氢化钠为原料,采用一锅法合成了3种N-(2-吡咯亚甲基)芳胺.相对于分步法,一锅法合成N-(2-吡咯亚甲基)芳胺具有操作简单、反应时间短、反应产率高(68％-75％)、对环境友好等优点,是一种较为理想的N-(2-吡咯亚甲基)芳胺合成方法.     

铝(Ⅲ)-盐酸洛美沙星荧光体系的研究及应用

在HCl介质中,溶液中的铝(Ⅲ)能与盐酸洛美沙星反应生成一稳定的络合物.使盐酸洛美沙星的内源性荧光显著增强,据引建立了铝(Ⅲ)-盐酸洛美沙星体系测定铝(Ⅲ)的荧光分析新方法.该体系的最大激发波长λex=365nm,最大发射波长λem=420nm,铝(Ⅲ)浓度在8.0×10-10-3.2×10-8g/mL范围内.与荧光增强程度成正比.方法用于水样微量铝(Ⅲ)的测定,结果令人满意.     

高偏压金属─绝缘体─金属结的光发射

我们制作了一种可在6-11V偏压范围内均匀发射可见光的新型金属-绝缘体-金属结型发光器件,其内层结构是Al-Al₂O₃-MgF₂-An(Cu),其承受偏压、单位面积发光功率及相应的外量子效应高过迄今已知的M-O-M遂道结型发光器件.本文首次报导并论证了这一由Schottky热电子所激发的光发射及其物理图象:Schottky热电子在AO(Cu)-真空界面激发表面等离极化激元(SPP);Au(Cu)-真空界面的SPP通过表面粗糙度与外光子耦合.这一图象与该器件的电流-电压(I-V)、电流-温度(I-T)关系及其发射光谱的主要特征一致.     

Damping,Thermal, and Mechanical Properties of Polycaprolactone-Based PU/EP Graft IPNs: Effects of Composition and Isocyanate Index

A series of polycaprolactone (PCL)-based polyurethane (PU)/epoxy resin (EP) graft interpenetrating polymer networks (IPNs) were prepared and their damping propertiesand thermal stability, as well as mechanical properties, were systematically studied in terms of composition and the values of the PU isocyanate index (R). The morphologies of the PU/EP IPNs were observed by scanning electron microscope (SEM) and atomic force microscope (AFM) characterization and the relationship between the morphologies and the properties is also discussed. The damping properties and thermal stability measurements revealed that the formation of PU/EP IPNs could significantly improve not only the damping properties but also the thermal stability. Meanwhile, the mechanical tests showed that the tensile strengths of the IPNs decreased, while their impact strengths increased with increasing PU content. The value of the PU isocyanate index also had significant impacts on the properties of the IPNs when the PU to EP ratio was fixed, which could be an effective means for manipulating the fabrication of PU/EP IPNs. From the results obtained, the PCL-based PU/EP IPNs hold promise for use in structural damping materials.     

Damping,thermal, and mechanical properties of polyurethane based on poly(tetramethylene glycol)/epoxy interpenetrating polymer networks: effects of composition and isocyanate index

A series of polyurethane (PU) samples based on poly(tetramethylene glycol)/epoxy resin (EP) graft interpenetrating polymer networks (IPNs) were prepared and their damping, thermal, and mechanical properties were systematically studied in terms of composition and the value of the PU isocyanate index (R). The damping properties and thermal stability measurements revealed that the formation of PU/EP IPN could improve not only the damping capacity but also the thermal stability. Meanwhile, mechanical tests showed that the tensile strengths of the IPNs decreased while their impact strengths increased with increasing PU content. The value of R also had significant impacts on the properties of the IPNs when the PU and EP ratio was fixed, which could be an effective means for manipulating the fabrication of PU/EP IPNs. The morphologies of the PU/EP IPNs were observed by SEM and AFM characterization and the relationship between the morphologies and properties is discussed. With the results in hand, the PU/EP IPNs hold promise for use in structural damping materials.     

Structure Development and Interfacial Interactions in Flexible Polyurethane Foam-Layered Silicate Nanocomposites

Unmodified Na-montmorillonite (MMT) was swollen in a polyol/water mixture using an ultrasound technique. Polyurethane (PU) foam nanocomposites were formed via reaction of these polyol/water/Na-MMT mixtures with toluene diisocyanate (TDI). Forced-adiabatic attenuated total reflectance FTIR spectroscopy was used to determine the kinetics of both the PU copolymerisation and of the microphase separation between poly(ether-urethane) soft segments and polyurea hard segments. Consumption of TDI during the initial stages of the copolymerisation was accelerated significantly by the addition of ≤10 wt% Na-MMT. The initial rate of formation of urea groups also increased significantly upon addition of Na-MMT, but at reaction times >100 s a significant retardation occurred in the development of hydrogen bonding within the urea groups of the hard-segment phase that was recovered only after 1000 s. The reasons for this extensive disruption in structure development were investigated using flow microcalorimetry (FMC), diffuse reflectance Fourier-transform infrared spectroscopy (DRIFTS), and wide angle X-ray scattering (WAXS) to monitor the adsorption process and any chemical reaction between hydrated Na-MMT and a model monoisocyanate; 4-ethylphenyl isocyanate (4-EPI). DRIFTS spectra of 4-EPI adsorbed on Na-MMT revealed urea groups, indicating formation of N,N′-bis(4-ethylphenyl) urea. FMC indicated that a significant quantity of this urea formed at the surface and then desorbed. In addition, DRIFTS spectra indicated that the 4-EPI reacted with hydroxyl groups present at the edges of the silicate platelets to form urethane linkages. Thus, in a PU-foam reaction mixture, the water will tend to associate with the Na-MMT, either within the galleries or on the surfaces of silicate lamellae. Upon reaction with isocyanate, the presence of the Na-MMT both promotes the formation of urea and generates urethane linkages between silicate lamellae and the polyurethane.     

芳羧酸功能化的聚苯乙烯与Tb(Ⅲ)离子形成的 高分子-稀土配合物的荧光发射性能

通过大分子反应将苯甲酸(BA)键合在聚苯乙烯(PS)侧链, 制得芳羧酸功能化的聚苯乙烯PSBA。以PSBA为大分子配基, 以邻菲啰啉(Phen)为小分子配体, 与Tb(Ⅲ)离子配位, 分别制备了二元配合物PS-(BA)₃-Tb(Ⅲ)与三元配合物PS-(BA)₁-Tb(Ⅲ)-(Phen)₂及PS-(BA)₁-Tb(Ⅲ)-(Phen)₃,采用红外光谱(FTIR)和紫外吸收光谱(UV) 对配合物进行了表征, 深入研究了配合物(溶液与薄膜)的荧光发射性能。 研究结果表明, 大分子配基PSBA与Tb(Ⅲ)离子所形成的二元或三元高分子-稀土配合物均能发射出很强的Tb(Ⅲ)离子特征荧光, 即键合在PSBA侧链的配基BA能有效地敏化Tb(Ⅲ)离子的荧光发射。与二元配合物相比较, 以小分子Phen为第二配体所形成的两种三元配合物具有强度更高的荧光发射。     

Preparation and Properties of 2, 4-2-Isocyanic Acid Methyl Ester/Poly(ϵ-caprolactone)/Diethylene Glycol Hydrogels

The hydrophilic polyurethane (PU) hydrogels have become attractive in the biomedical field for drug delivery. In this work 2, 4-2-isocyanic acid methyl ester (TDI), poly(?-caprolactone) (PCL), and poly(ethylene glycol) (PEG) were used to prepare a prepolymer and then diethylene glycol (DEG) was used as a chain extender to prepare a novel hydrophilic polyurethane, TDI/PCL-PEG/DEG. The obtained PU hydrogels were characterized by Fourier transform infrared (FT-IR) spectroscopy and scanning electronic microscopy (SEM). By varying the ratio of PCL to PEG in the copolymer, modulations of hydrophilicity and drug release behavior were observed. FT-IR analysis confirmed the successful synthesis of the TDI/PCL-PEG/DEG hydrogels. The introduction of PEG into the PU hydrogels led to a porous structure. The water contact angle and swelling ratio results confirmed that the hydrophilicity increased with increasing amounts of the PEG segments. The introduction of PEG also increased the release rate of chloramphenicol, used as model drug, from the PU hydrogels.     

萘甲酸功能化的聚苯乙烯与Eu(Ⅲ)离子所形成的高分子-稀土配合物的荧光发射特性

通过大分子反应将萘甲酸(NA)键合在聚苯乙烯(PS)侧链, 制得萘甲酸功能化的聚苯乙烯PSNA。 以PSNA为大分子配基, 以邻菲罗啉(Phen)为小分子配体, 与Eu(Ⅲ)离子配位, 分别制备了高分子-稀土二元发光配合物PS-(NA)₃-Eu(Ⅲ)与高分子-稀土三元发光配合物PS-(NA)₃-Eu(Ⅲ)-Phen。 采用红外光谱(FTIR)和紫外吸收光(UV)谱对配合物进行了表征, 深入研究了配合物的化学结构与发光性能的关系, 并应用Antenna效应理论, 从微观机理上进行了深入分析。 制备了配合物的固体薄膜, 考察了固体薄膜的荧光发射性能。 研究结果表明, 大分子配基PSNA与Eu(Ⅲ)离子所形成的二元或三元高分子-稀土配合物, 均能发射出很强的Eu(Ⅲ)离子的特征荧光, 即键合在PSNA侧链的配基NA能有效地敏化Eu(Ⅲ)离子的荧光发射。 大分子侧链的萘甲酸配基比苯甲酸配基对Eu(Ⅲ)离子荧光发射具有更强的敏化作用。 第二配体的协同配位效应导致三元配合物的荧光发射强度高于二元配合物。     

Schif f碱配合物荧光粉的合成及光谱性能研究

有机电致发光材料具有主动发光、视角广、对比度高等显著特点。稀土有机配合物电致发光材料目前备受广大研究者的关注。以水杨醛和苯甲酸衍生物为原料,经酯化、肼化及希夫碱缩合合成了水杨醛对甲氧基苯甲酰腙(1-H₂L)、水杨醛对甲基苯甲酰腙(2-H₂L)、水杨醛对溴基苯甲酰腙(3-H₂L) 3种配体,以Pr(NO₃)₃为原料,合成了水杨醛酰腙系列镨稀土配合物,经红外光谱、紫外光谱等分析手段对该类配合物的结构进行表征,配体在3 136～3 141 cm-1出现羟基ν(OH)伸缩振动峰,在配合物的红外光谱中消失,配合物在3 330～3 368 cm-1之间的吸收峰归属为结晶的H₂O的ν(O-H)羟基弯曲振动吸收峰,配合物在与配体对应的3 140 cm-1均不出现羟基吸收峰,三种配体及配合物的吸收波形相似,反映出配体及配合物的结构基本一致,但配体与配合物的吸收波峰相差较大,据此可推测配体已经配位。采用荧光分光光度计测定了该类配合物的荧光光谱,并讨论了配体取代基的变化对荧光强度的影响。配体分别在352,369,365和417 nm波长监测下,于517 nm处出现发射峰。其中3-H₂L的荧光强度最高。配合物均在470 nm的蓝光激发下,分别于608和617 nm出现镨的电偶极跃迁特征发射峰,归属于3P₀→3F₂跃迁。配合物均可被470 nm蓝光激发,在608～617 nm处有较好的红光发射,该类荧光粉有望应用于OLED上进行应用。     

新型三元配合物Tb(DPAB)_3IP的制备与发光性能

合成了邻菲罗啉的衍生物咪唑并[5,6-f]邻菲罗啉(IP),并以其为第二配体,二苯胺羰基邻苯甲酸(HDPAB)为第一配体,制备出新型稀土铽三元有机配合物Tb(DPAB)3IP。采用元素分析、红外光谱和紫外光谱对合成的配体及配合物进行了表征。通过荧光光谱研究了配合物的荧光性质,结果表明第二配体IP有较大的共轭体系,在紫外光激发下,配合物中的配体可将吸收的能量传递给稀土Tb3+离子,表现出较强的Tb3+离子的特征发射,且配体Tb(DPAB)3IP的荧光强度明显大于Tb(DPAB)3phen的荧光强度。这说明适宜的第二配体对配合物有很好的敏化发光作用,合成的Tb(DPAB)3IP是一种良好的绿光材料。     

Synthesis and Characterization of a Novel Self-colored Fluorescent Polycarbonate Urethane based on the 1,8-Naphthalimide Group

Abstract

The synthesis of a novel self-colored polyurethane (PU) is described using 4-amino-N-propanoic acid-1,8-naphthalimide dye. To synthesize the self- colored PU, the dye was added to the PU prepolymer at the chain extension step. PU and self-colored PU were characterized by using Fourier transform infrared spectroscopy (FTIR), UV-visible spectroscopy and Fluorometry. The thermal behavior of the PU and self-colored PU were investigated by differential scanning calorimetry (DSC). The spectra indicated that the addition of dye to the polymer chain did not affect the glass transition temperature (T_g?=?-39?°C). Tensile strengths and Young’s modulus of the samples were assessed using a tensile strength test; they revealed that addition of the dye to the polymer structure enhanced the Young’s modulus and increased the mechanical strength of the PU. X-ray diffraction (XRD) was used for evaluation of the crystal phase of the polymer; it revealed that both components were amorphous.