聚苯乙烯/层状双金属氢氧化物纳米复合材料的制备与表征

由离子交换法制备4,4′-偶氮二(4-氰基戊酸)根(ACP)单独插层和ACP/对苯乙烯磺酸根(VBS)复合插层的层状双金属氢氧化物(LDH),再通过原位悬浮聚合制得聚苯乙烯(PS)/LDH纳米复合材料,对插层改性LDH和复合材料进行了结构和性能表征.X-射线衍射和元素分析表明ACP可以单独或与VBS一起插入到LDH层间.透射电镜和X-射线衍射分析表明采用ACP/VBS复合插层LDH与苯乙烯原位聚合得到的复合材料中LDH剥离程度高,熔融加工后LDH基本以纳米层板形式分散在PS基体中.LDH的引入可明显提高PS的热稳定性,而熔体流动性下降.     

偏氯乙烯共聚物/层状双金属氢氧化物纳米复合材料的制备与表征

通过硝酸根插层层状双金属氢氧化物(LDH)与可逆加成-断裂链转移(RAFT)试剂S,S’-对(α,α’-二甲基-α″-乙酸)三硫代碳酸酯(CTA)阴离子的离子交换制备CTA阴离子插层LDH,再通过原位RAFT活性自由基聚合制备偏氯乙烯-丙烯酸甲酯(VDC-MA)共聚物/LDH纳米复合材料.采用傅里叶变换红外光谱、元素分析和X-射线衍射、透射电子显微镜、凝胶渗透色谱仪和热失重仪表征了CTA阴离子插层LDH和纳米复合材料的结构和性能.结果表明,CTA阴离子可以置换硝酸根阴离子插入到LDH层间,LDH层间距由0.89 nm增大到1.50 nm;在原位RAFT聚合过程中,LDH逐渐剥离,LDH以纳米层板形式分散在VDC-MA共聚物基体中;VDC-MA共聚物数均分子量随加入的插层CTA阴离子含量增加而减小,聚合具有活性特征.此外,含量LDH的引入可明显提高VDC-MA共聚物的热稳定性.     

聚(2-甲氧基-5-丁氧基)对苯乙炔/Eu2O3纳米复合材料的合成及其光学效应

采用原位脱氯化氢缩合聚合法制备了聚(2-甲氧基-5-丁氧基)对苯乙炔/氧化铕(PMOBOPV/Eu2O3)纳米复合材料. 傅里叶变换红外(FT-IR)光谱证实了在Eu2O3表面的包覆层为PMOBOPV. 高分辨透射电子显微镜(HRTEM)观察发现, PMOBOPV/Eu2O3纳米复合材料具有核-壳结构, 直径为75-145 nm, 其中PMOBOPV包覆层厚度约为25 nm. 紫外-可见(UV-Vis)吸收光谱表明, 随着Eu2O3含量增加, PMOBOPV/Eu2O3的最大吸收峰发生红移且强度提高. 荧光光谱研究表明, 随着Eu2O3含量增加, PMOBOPV/Eu2O3的最大发射波长发生蓝移且强度提高, Eu2O3与PMOBOPV之间形成了光致电子转移体系, 使π电子离域程度增加, 并且导致荧光量子效率提高. 根据光学禁带宽度(Eg)与入射光子能量(hυ)的关系, 拟合了PMOBOPV/Eu2O3薄膜的光学禁带宽度, 发现随着Eu2O3含量增加, Eg逐步减小. 采用简并四波混频方法测试它们的三阶非线性极化率(χ(3)), 发现随着Eu2O3含量增加, PMOBOPV/Eu2O3纳米复合体的非线性光学响应逐渐增强, 这说明PMOBOPV与Eu2O3之间形成了分子间光致电子转移体系, 产生了复杂的分子间离域π电子非线性运动.     

聚(2-甲氧基-5-辛氧基)对苯乙炔/单壁碳纳米管复合材料的光物理性能研究

采用原位脱氯化氢缩合聚合法制备了聚(2-甲氧基-5-辛氧基)对苯乙炔/单壁碳纳米管(PMOCOPV/SWNTs)复合材料. 红外光谱和拉曼光谱证实了在SWNTs表面的包覆层为PMOCOPV. 高分辨透射电子显微镜观察发现, PMOCOPV/SWNTs复合材料直径为4~7 nm, 其中PMOCOPV包覆层厚度约为2~5 nm. 紫外-可见吸收光谱表明, 随着SWNTs含量的增加, PMOCOPV/SWNTs的吸收发生蓝移且强度提高. 荧光光谱研究表明, 随着SWNTs含量的增加, PMOCOPV/SWNTs的最大发射波长发生蓝移且强度减小, SWNTs与PMOCOPV之间形成了光致电子转移体系, 使π电子离域程度增加, 导致荧光量子效率降低. 根据E_g与入射光子能量hν的关系, 拟合了PMOCOPV/SWNTs薄膜的光学禁带宽度, 发现随着SWNTs含量的增加, E_g逐渐减小. 采用简并四波混频方法测试其三阶非线性极化率χ⁽³⁾, 结果表明, 随着SWNTs含量的增加, PMOCOPV/SWNTs复合体的非线性光学响应逐渐增强, 说明PMOCOPV与SWNTs之间形成了分子间光致电子转移体系, 产生了复杂的分子间π-π电子非线性运动.     

碳纳米管聚(3′,4′-亚乙基二氧-2,2′:5′,2″-三噻吩)复合材料的制备及其电化学性能研究

通过Stille反应合成了3′,4′-亚乙基二氧-2,2′:5′,2″-三噻吩(TET),并以其作为单体,采用化学氧化原位聚合方法在碳纳米管(CNT)的表面包覆新型聚(3′,4′-亚乙基二氧-2,2′:5′,2″-三噻吩)(PTET),制备了PTET-CNT纳米复合材料.通过TEM、SEM和IR对其进行了表征,并利用循环伏安、交流阻抗、恒电流充放电等电化学测试方法,比较研究了复合材料以及碳纳米管在0.1 mol/L四乙基四氟硼酸铵(Et4NPF4)的乙腈溶液中的电化学行为.实验结果表明,在电流密度为3 mA/cm2时,PTET-CNT复合材料的比电容为86 F/g,比原碳纳米管比电容20 F/g提高了3.3倍.基于这种复合材料的电容器的能量密度达到2.02 Wh/kg.     

双马来酰亚胺树脂/SiO_2纳米复合材料的制备及性能

以表面含有胺基官能团的纳米SiO_2为填料,通过一步原位聚合法制备双马来酰亚胺树脂/SiO_2纳米复合材料(BMI/SiO_2).采用热重分析仪(TGA)、红外光谱分析仪(FTIR)、邵氏D硬度计(H)等仪器设备对BMI/SiO_2纳米复合材料进行测试分析,探讨纳米SiO_2对双马来酰亚胺聚酯树脂的热稳定性能、硬度和界面强度的影响.结果表明,所制备的BMI/SiO_2纳米复合材料的硬度随加入的纳米SiO_2含量的增加,呈现逐渐升高趋势.当纳米SiO_2含量为3%时,相对于双马来酰亚胺聚酯,复合材料的硬度提高了80%.通过热稳定性分析可知,纳米SiO_2的加入降低了双马来酰亚胺树脂基体材料的热分解温度,使其从458℃降低到451℃.通过对双马来酰亚胺/SiO_2纳米复合材料的界面分析发现,纳米SiO_2的表面接枝了双马来酰亚胺分子链,说明纳米SiO_2参与了双马来酰亚胺的聚合过程,有利于提高聚合物基体材料与填料间的界面强度,进而提高复合材料的机械性能.     

聚苯胺/碳化钨导电复合材料的合成

以苯胺和过硫酸胺为原料,采用原位聚合方法合成了聚苯胺/碳化钨(PANI/WC)导电复合材料。研究了反应体系中碳化钨的含量对复合材料电导率的影响,确定了较佳的聚合条件,并且通过FT-IR、XRD、XPS和DSC-TGA等手段对复合材料的结构和性能进行了表征和分析。结果表明:碳化钨(WC)的加入提高了聚苯胺的电子导电性能,复合材料中聚苯胺组分为无定型,WC的晶型在反应前后并未发生变化,复合材料的热稳定性好并且质子化程度更高。     

甲基丙烯酸镁增强氢化丁腈橡胶的结构与形态和性能

用不同份量的甲基丙烯酸镁(MgMA)作增强剂,过氧化二异丙苯(DCP)作硫化剂,通过混炼和硫化过程的原位聚合制备了氢化丁腈橡胶/聚甲基丙烯酸镁(HNBR/PMgMA)纳米复合材料,用XRD、FTIR1、3C-NMR、SEM、TEM、DMA和交联密度分析等方法研究了其结构、形态和性能,并阐述了MgMA改性HNBR的相关机理.结果表明,MgMA在混炼过程中粒径明显变小,部分达到纳米级.硫化过程中发生原位自由基聚合,并部分接枝到HNBR分子链上,HNBR硫化胶和PMgMA有可能形成接枝互穿聚合物网络(接枝IPN).随着MgMA用量的增加,纳米复合材料硫化胶的定伸应力、拉伸强度、扯断伸长率、撕裂强度和热氧老化性能逐渐提高.当MgMA含量为30份时,体系的拉伸强度和扯断伸长率分别为38.5MPa和545%,并具有优异的热空气老化性能.MgMA能明显增加HNBR复合材料的储能模量,并降低其损耗因子.随着MgMA用量的增加,纳米复合材料硫化胶的总交联密度(Ve)和离子键交联密度(Ve2)增加,而共价键交联密度(Ve1)下降,表明离子键对HNBR/PMgMA纳米复合材料的力学性能起重要作用.     

纳米SiO_2/聚甲基丙烯酸甲酯复合材料的制备和力学性能

通过悬浮聚合的方法,用不同表面结构的纳米SiO2对聚甲基丙烯酸甲酯(PMMA)进行原位改性,得到纳米SiO2/聚甲基丙烯酸甲酯复合材料;利用红外光谱仪分析了复合材料的界面化学结构,利用热分析仪测定了其热稳定性,并采用冲击试验机测定了其力学性能.结果表明,不同表面结构的纳米SiO2均参与甲基丙烯酸甲酯的聚合反应,与PMMA基体之间形成化学键;而表面修饰有双键的纳米SiO2更易与甲基丙烯酸甲酯聚合,能更有效地提高PMMA的抗冲击性能.     

α-二亚胺镍(Ⅱ)配合物-TiCl4复合催化剂催化乙烯原位聚合制备支化聚乙烯

制备了α-二亚胺镍()配合物[C6H5—NC(CH3)—C(CH3)N—C6H5]NiBr2(NiL)-TiCl4负载在MgCl2-SiO2载体上的复合催化剂(NiL-TiCl4/MgCl2-SiO2),以AlR3为助催化剂(不用MAO)催化乙烯聚合.研究了NiL和TiCl4负载方法、NiL/TiCl4摩尔比、助催化剂种类及聚合反应温度等对催化剂性能的影响.用IR和13CNMR表征聚合产物支化度及支链结构;用GC-MS监测聚合反应.实验结果表明,NiL-TiCl4复合催化剂具有齐聚原位共聚特性,可催化乙烯原位聚合,合成支化聚乙烯.     

Mechanical and flame‐retardant properties and thermal decomposition of vinyl ester resin modified by different phenyl silsesquioxanes

The mechanical properties and fire resistance of vinyl ester resin (VER) composites containing cage‐shaped octaphenyl silsesquioxane (OPS), incompletely cage‐shaped phenyl silsesquioxane (PhT₇POSS), and ladder‐shaped phenyl silsesquioxane (PPSQ) were investigated. The POSS structure and dispersion have a great influence on the mechanical properties, thermal stability, and decomposition process of VER composites. The bending strength at break and modulus of the VER‐POSS composites were enhanced obviously, especially for VER‐PPSQ composite and VER‐OPS composite, respectively. In addition, PhT₇POSS‐based VER composites revealed the lower values of the peak heat release rate, total heat release, and total smoke release in cone calorimetry tests due to the formation of dense carbon/silica protective layers that acted as a barrier to heat and mass transfer. Moreover, the flame‐retardant mechanisms of condensed phase and gas phase were also investigated in detail. These results illustrate VERs modified by OPS, PhT₇POSS, and PPSQ are providing an applicable method to fabricate the composites with excellent flame‐retardant and mechanical properties.     

Comparative study between core-shell and interpenetrating network structure polyurethane/polyacrylate composite emulsions

Anionic aqueous polyurethane dispersion was prepared by using carboxyl acid group to make the polyurethane dispersible, and then nanograde core-shell and crosslinked IPN structure polyurethane/polyacrylate composite latex (PUA) were synthesized by soap-free emulsion polymerization method with polyurethane dispersion as seed. FTIR, DSC, dynamic light scattering, TEM, ESCA, TGA, electronic tensile machine were employed to investigate the structures and properties of the composite latex and their polymers. Meanwhile the core-shell composite PUA emulsion and the crosslinked IPN composite PUA emulsion were compared. The results showed that the particle morphology of PUA composite emulsion is inverted core-shell structure with polyacrylate as the core and with polyurethane as the shell. The morphology of the crosslinked PUA emulsion was multi-core structure. The surface in core-shell PUA contains rich PU phase. The phase structure of the crosslinked PUA is more uniform. Three transition temperatures are observed for the core-shell composite PUA, two transitions are observed for the film from the crosslinked PUA. The TGA curves of core-shell PUA and crosslinked PUA exhibit two stages, the first stage corresponds to the thermal decomposition of hard segments in seed polyurethane; the second stage corresponds to the decomposition of soft segments in PUA and decomposition of polyacrylate. With the increase of glycidyl methacrylate (GMA) amounts in PUA composite emulsions, the tensile strength of the PUA films as well as the average diameter of the PUA composite emulsion particles increase, the elongation at break of the PUA films decreases.     

A simple route to interpenetrating network hydrogel with high mechanical strength

A simple two-step method was introduced to improve the hydrogel mechanical strength by forming an interpenetrating network (IPN). For this purpose, we synthesized polyacrylate/polyacrylate (PAC/PAC), polyacrylate/polyacrylamide (PAC/PAM), polyacrylamide/polyacrylamide (PAM/PAM) and polyacrylamide/poly(vinyl alcohol) (PAM/PVA) IPN hydrogels. The PAC/PAC IPN and PAC/PAM IPN hydrogels showed compressive strength of 70 and 160 kPa, respectively. For the PAM/PAM IPN and PAM/PVA IPN hydrogels, they exhibited excellent tensile strength of 1.2 and 2.8 MPa, and elongations at break of 1750% and 3300%, respectively. A strain relaxation was also observed in the case of PAM series IPN hydrogels. From FTIR, TGA and SEM measurements, we confirmed that physical entanglement, hydrogen bonds and chemical crosslinking played major roles in improving hydrogel strength and toughening. The two-step technique contributes to the understanding of ideal networks, provides a universal strategy for designing high mechanical strength hydrogels, and opening up the biomedical application of hydrogels.     

pH and ionic sensitive chitosan/carboxymethyl chitosan IPN complex films for the controlled release of coenzyme A

pH and ionic sensitive interpenetrating polymer network (IPN) complex films based on chitosan (CS) and carboxymethyl chitosan (CM-CS) were prepared by using glutaraldehyde as crosslinking agent. Its structure was characterized by FT-IR, which indicated that the IPN was formed. The films were studied by swelling, weight loss with time, and release of coenzyme A (CoA). It was found that the IPN films were sensitive to pH and ionic strength of the medium. The cumulative release rate of CoA decreased with CoA loading content, ionic strength or crosslinking agent increasing. The composition of the IPN films and pH of release medium also had significant effect on the release of CoA. The differences in the rates and amounts of released CoA may be attributed to the swelling behavior, the degradation of films, and interaction between drug molecule and polymer matrix. These results suggested CS/CM-CS IPN films could be used as drug delivery carrier.     

Mechanical,Thermal and Morphological Behaviors of Castor Oil Based PU/PS Interpenetrating Polymer Network-Metakaolin Composites

The meta kaolin (MK) clay particulate filler with different weight ratios viz., 0, 5, 10, 20 and 30 wt% were incorporated into castable polyurethane (PU)/polystyrene (PS) (90/10) interpenetrating polymer network (IPN). The effects of MK particulate filler loading on the mechanical and thermal properties of PU/PS (90/10) IPN composites have been studied. From the tensile behavior, it was noticed that a significant improvement in tensile strength and tensile modulus as an increase in MK filler content. Thermogravimetric analysis (TGA) data reveals the marginal improvement in thermal stability after incorporation of MK filler. TGA studies of the IPN composites have been performed in order to establish the thermal stability and their mode of thermal degradation. It was found that degradation of all composites takes place in two steps. Degradation kinetic parameters were obtained for the composites using three mathematical models. Tensile fractured composite specimens were used to analyze the morphology of the composites by scanning electron microscopic (SEM) technique.     

Effects of polystyrene‐b‐poly(ethylene/propylene)‐b‐polystyrene compatibilizer on the recycled polypropylene and recycled high‐impact polystyrene blends

The recycled polypropylene/recycled high‐impact polystyrene (R‐PP/R‐HIPS) blends were melt extruded by twin‐screw extruder and produced by injection molding machine. The effects of polystyrene‐b‐poly(ethylene/propylene)‐b‐polystyrene copolymer (SEPS) used as compatibilizer on the mechanical properties, morphology, melt flow index, equilibrium torque, and glass transition temperature (T_g) of the blends were investigated. It was found that the notch impact strength and the elongation at break of the R‐PP/R‐HIPS blends with the addition of 10 wt% SEPS were 6.46 kJ/m² and 31.96%, which were significantly improved by 162.46% and 57.06%, respectively, than that of the uncompatibilized blends. Moreover, the addition of SEPS had a negligible effect on the tensile strength of the R‐PP/R‐HIPS blends. Additionally, the morphology of the blends demonstrated improved distribution and decreased size of the dispersed R‐HIPS phase with increasing the SEPS content. The increase of the melt flow index and the equilibrium torque indicated that the viscosity of the blends increased when the SEPS was incorporated into the R‐PP/R‐HIPS blends. The dynamic mechanical properties test showed that when the content of SEPS was 10 wt%, the difference of T_g decreased from 91.72°C to 81.51°C. The results obtained by differential scanning calorimetry were similar to those measured by dynamic mechanical properties, indicating an improved compatibility of the blends with the addition of SEPS.     

Mechanical and acoustical properties of particleboards made with date palm branches and vermiculite

The main goal of this study was to determine the performance of particleboards made from date palm branches (DPB, Phoenix dactylifera), as a low-value raw material and expanded vermiculite (VER), as a natural inorganic filler. DPB is underutilized abundant byproduct in southern parts of Iran. For the purpose of evaluation, compositions of DPB and VER at different mixture rates were compared for some properties. Variable parameters were: number of particleboard layers (single- and three-layer), VER size (micro and nano meter), and VER content (0, 10 and 20 wt%). Other parameters such as resin content (10%), hardener content (2%), pressing time (6 min), board density (0.75 g/cm³), press pressure (35 kg/m²) and press temperature (175 °C) were held constant. Physical properties (thickness swelling (TS), water absorption (WA), and sound absorption coefficient (SAC)), and mechanical properties (modulus of rupture (MOR), modulus of elasticity (MOE), and internal bond strength (IB)) of the boards were determined. Based on the findings of this study, all mechanical properties of the boards slightly decreased when the VER content was increased from 0 to 20 wt%. Analysis of data revealed that the mechanical properties were significantly different among the board types. In general, WA and TS increased with the increase of WER content. The presence of nano VER in the particleboards resulted in higher WA and TS. The SACs of composite boards filled with VER increased as the frequency increased. Nano VER and single-layer boards showed higher SACs in frequency range of 800–1250 Hz. Finally, it can be stated that DPB has potential as replacement fibrous material for particleboard manufacturing and indoor applications.     

Preparation and properties of PP/PC/POE blends

In order to develop PP (polypropylene)‐based blends with balanced toughness and rigidity, the poly‐blends of PP/PC (polycarbonate)/POE (ethylene–octene copolymer) were prepared by applying styrene–ethylene–propylene–styrene (SEPS) as the macromolecular compatibilizer. The compatibilizing effect was studied in terms of the mechanical, morphologies and thermal properties, and the compatibilized PP‐based blends presented remarkable improvement in impact toughness and balanced tensile strength due to the formed special morphology structure. Additionally, by preparing the pre‐blend of PC/SEPS, the melt viscosity of the PP matrix can match that of the dispersed phase PC and POE, which led to a further improvement in the mechanical property of the blends. Copyright © 2009 John Wiley & Sons, Ltd.     

Mechanism of adhesion of polyurethane/polymethacrylate simultaneous interpenetrating networks adhesives to polymer substrates

Polyether-based polyurethane/poly (methyl methacrylate-co-ethyleneglycol dimethacrylate) interpenetrating polymer networks [PU/P (MMA–co–EGDMA)-IPNs] were synthesized and used as adhesives to adhere vulcanized natural rubber (NR) and soft polyvinyl chloride (PVC). The structure and morphology of the IPN adhesives in bulk and near the adhesive/substrate interfaces were investigated. A new mechanism of adhesion called conjugate interpenetration of networks across interfaces, which is suitable for IPN adhesives and polymer substrates, was put forward. According to this mechanism, while forming simultaneous interpenetrating networks in the adhesive, the monomers in the IPN adhesive can permeate polymer substrates and polymerize in situ to form gradient IPNs, thereby producing conjugate three-component IPNs near the adhesive/substrate interfaces. It is the conjugate interpenetration of the networks across the interfaces that strengthens interfacial combination remarkably and results in high bond strength of IPN adhesives. © 1994 John Wiley & Sons, Inc.     

Natural and acid-treated attapulgite reinforced soybean oil-based polyurethane/epoxy resin interpenetrating polymer networks

Soybean oil-based polyurethane (PU)/epoxy (EP) interpenetrating polymer network (IPN) nanocomposites were prepared with natural attapulgite (N-ATT) and acid-treated attapulgite (A-ATT). The structure, glass transition, damping properties, thermal stability, mechanical properties and morphology of PU/EP IPN/ATT nanocomposites were characterized by X-ray diffraction (XRD), dynamic mechanical analysis (DMA), thermogravimetric analyzer, universal test machine and scanning electronic microscope (SEM). XRD showed that interaction with PU did not change the crystal structures of ATT. DMA results revealed the addition of ATT improved the glass transition temperature of the soybean oil-based PU/EP IPN, especially for A-ATT. However, the incorporation of ATT slightly decreased the damping properties of the soybean oil-based PU/EP IPN. Tensile tests confirmed that A-ATT had a significant reinforcement effect on the soybean oil-based PU/EP IPN. The tensile strength of the soybean oil-based PU/EP IPN increased by 56% with the addition of 4 mass% A-ATT. SEM demonstrated the relatively uniform dispersion of both N-ATT and A-ATT in the soybean oil-based PU/EP IPN matrix.