聚对苯二甲酸乙二醇酯/层状双氢氧化物纳米复合材料

聚对苯二甲酸乙二醇酯(PET)/层状双氢氧化物(LDHs)纳米复合材料是一种性能优异并具有广泛应用前景的新型聚合物基纳米复合材料.与纯PET相比, 其力学性能、热稳定性、阻燃性能与耐紫外线功能等均有明显提高或改善.本文对近年来PET/LDH纳米复合材料的研究进展进行了综述.首先, 对LDHs 的化学组成和结构特点进行了简要介绍, 并且对其制备方法和物理化学性质等进行了简单论述, 然后, 对PET/LDH纳米复合材料的制备、结构表征、结晶行为、机械力学性能以及耐热、阻燃和耐紫外线等功能性质的最新研究进展进行重点综述; 最后, 对其应用前景进行展望.     

聚对苯二甲酸乙二醇酯/蛭石纳米复合材料的制备

聚对苯二甲酸乙二醇酯/蛭石纳米复合材料的制备     

聚对苯二甲酸乙二醇酯/聚乙二醇醚插层嵌段共聚物的结晶性能

合成了不同用量、不同分子量的聚乙二醇醚(PEG)或聚丁二醇醚(PTMC)与聚对苯二甲酸乙二醇酯(PET)/蒙脱土(MMT)的嵌段共聚物。研究了MMT在共聚物中的分散状态及PEG或PTMG对PET/MMT插层聚合物结晶性能的影响。结果表明,MMT在共聚物中以纳米尺寸分散;加入PEG或PTMG增强了聚酯链段的柔顺性,使共聚物熔体降温过程的结晶温度提高,冷结晶温度降低,即插层嵌段共聚物的结晶速率提高;在合成的共聚物中,分子量为2000,用量为DMT的6%的PEG对插层共聚物结晶速率的促进作用最大     

聚对苯二甲酸丁二酯/水滑石纳米复合材料的制备与表征

聚对苯二甲酸丁二酯;水滑石;对苯二甲酸;纳米复合     

锂铝水滑石对水杨酸及其异构体的选择性插层研究

[LiAl_2(OH)_6]Cl·yH_2O was prepared by co-precipitation. The competitive intercalation of geometric isomers of hydroxybenzoic acid into the interlayer of layered double hydroxides (LDHs) was studied by the reaction of [LiAl_2(OH)_6]Cl·yH_2O with various mixtures of o-hydroxybenzoic acid, m-hydroxybenzoic acid and p-hydroxybenzoic acid. Powder X-ray diffraction (XRD) results confirmed the intercalation of the isomers, and high performance liquid chromatography (HPLC) was used for the quantitative study. The order of the preferential intercalation of the three isomers was found to be: o-hydroxybenzoic acid (1,2-C_7H_6O_3)》 p-hydroxybenzoic acid (1,4-C_7H_6O_3) > m-hydroxybenzoic acid (1,3-C_7H_6O_3).     

聚对苯二甲酸乙二醇酯和聚对苯二甲酸丁二醇酯化学扩链反应

综述了用于聚对苯二甲酸乙二醇酯（ＰＥＴ）、聚对苯二甲酸丁二醇酯（ＰＢＴ）化学扩链反应的羧基加成型和羟基加成型扩链剂，以及缩合型扩链反应、羧基加成型扩链反应和羟基加成型扩链反应、羧羟基同时加成型扩链反应。讨论了扩链反应、反应特性和扩链产物的性能，并简要介绍了国内研究概况。参考文献２０篇。     

聚对苯二甲酸乙二醇酯切片的固相聚合规律

简要介绍了制备高分子量聚对苯二甲酸乙二醇酯的三种方法,重点介绍了其固相聚合的基本原理及主要副反应规律,固相聚合的各种影响因素,如预聚体原料路线、端羟基和羟基平衡、切片形状和尺寸、催化剂、反应副产物等。最后介绍了聚对苯二甲酸乙二醇酯固相滞反应动力学,如温度、时间对固相聚合反应速度的影响,低温固相聚合反应动力学等。     

微波法合成乙二醇插层镍铝层状双金属氢氧化物

乙二醇(EG)插层层状双金属氢氧化物(LDH)可作为层间催化反应器,用于原油中环烷酸与EG的酯化脱酸反应,但其合成过程需要较长时间。 以硝酸根型镍铝LDH为前体,在KOH促进下,采用微波辅助的离子交换法合成EG插层LDH,省时节能,提高效率。 考察了微波时间、微波温度和微波功率对EG插层LDH结构的影响。 并用XRD、FT-IR和TG-DSC等比较了微波法和常规方法合成的EG插层LDH的性质。 结果表明,微波辐射能提供高能量,促进待交换阴离子向层间的扩散,并减弱层板与层间原有阴离子间的作用力,在微波温度为120 ℃,微波时间为10 min和微波功率550 W的条件下,即可得到结晶度高的EG插层LDH。 微波法合成的EG插层LDH与常规方法合成的具有相似的性质和更高的结晶度,而合成时间可由12 h大幅缩短至10 min。     

纳米二氧化钛的制备、修饰及其在PET中的应用研究进展北大核心CSCD

纳米二氧化钛(TiO2)具有粒径小、比表面积大、紫外屏蔽能力强、催化活性高等特点,近年来,纳米TiO2在聚对苯二甲酸乙二醇酯(PET)中的应用成为研究热点。本文介绍了纳米TiO2的结构特点、不同形态纳米TiO2的制备方法和纳米TiO2的表面修饰技术,讨论了纳米TiO2的特性和含量对PET结晶和力学性能的影响,总结了PET/纳米TiO2复合材料的防紫外线和抗老化性能。同时,还综述了利用TiO2的光催化作用制备具有催化、杀菌、防臭和自清洁等功能的PET/纳米TiO2复合材料的研究进展,并对纳米TiO2在PET中的应用进行了展望。     

原位聚合法制备聚丙烯酸甲酯/ZnAl层状双氢氧化物插层纳米复合材料及其形貌特征

近 2 0年来 ,聚合物 /层状无机物纳米复合材料引起了广泛关注 ,与聚合物材料相比 ,该类纳米复合材料在力学、热稳定性、阻燃、气体阻隔等性能方面都有显著增强 .但所报道的绝大部分无机物均采用蒙脱土为代表的层状硅酸盐[1～ 3] ,而以层状双氢氧化物 (Layered double hydroxide,LDH)为基础制备的聚合物 /层状无机物纳米复合材料的报道极少 .LDH是由水镁石结构中的二价阳离子 (M2 + )被三价阳离子 (M3+ )取代而形成的 ,层上产生的剩余正电荷被吸附在层间的阴离子平衡 .与层状硅酸盐相比 ,L DH层间电荷密度高 ,层与层之间相互作用强 ,导…     

Preparation and thermal decomposition study of pyridinedicarboxylate intercalated layered double hydroxides

Supramolecular 2,3- and 2,5-pyridinedicarboxylate (PDC) intercalated ZnAl-layered double hydroxides (2,3- and 2,5-PDC–ZnAl–LDHs) have been prepared by ion exchange method. The structure and composition of the intercalated materials have been studied by X-ray diffraction (XRD) and inductively coupled plasma emission spectroscopy (ICP). The study indicates that the 2,3-PDC and 2,5-PDC anions are accommodated as interdigitated bilayer and monolayer arrangement respectively between the sheets of LDHs. Furthermore, their thermal decomposition processes were studied by the use of in situ high temperature X-ray diffraction (HT-XRD), and the combined technique of thermogravimetry-differential thermal analysis-mass spectrometry (TG-DTA-MS) under N2 atmosphere. Based on the comparison study on the temperatures of both decarboxylation and complete decomposition of interlayer PDC, it can be concluded that 2,5-PDC–ZnAl–LDHs has higher thermal stability than that of 2,3-PDC–ZnAl–LDHs.     

层状复合氢氧化物的药物控释动力学机制

以层状复合氢氧化物(LDH)为载体组装乙酰苯甲酸(ASP)的插层复合物LDH-ASP,以pH2.48~6.89的磷酸盐溶液为介质进行药物释放动力学实验,通过对不同时间药物释放度的测定及释放药物后载体结构变化分析研究了LDH对层间药物的控制释放机制。结果表明粉末状LDH-ASP能在较宽的pH范围表现明显缓控释作用,药物释放度积分方程与Higchi方程、Ritger-Peppas方程、Bhaskar方程及一级动力学方程等经验模型吻合。复合物与溶出介质的反应机制研究表明,药物释放速率及释放度大小取决于交换配比n(ASP)/n[HnPO4(3-n)-]所决定的LDH层间通道畅阻情况。     

Investigation of layered double hydroxides intercalated by oxomolybdenum catecholate complexes

Oxomolybdenum(VI) complexes of 3,4-dihydroxybenzoic acid (3,4-H 2dhb) have been incorporated into layered double hydroxides (LDHs) by treatment of the LDH-nitrate (Zn-Al, Mg-Al) or LDH-chloride (Li-Al) precursors with aqueous or water/ethanol solutions of the complex (NMe 4) 2[MoO 2(3,4-dhb) 2].2H 2O at 50 or 100 degrees C. The texture and chemical composition of the products were investigated by elemental analysis and scanning electron microscopy (SEM) with coupled energy dispersive spectroscopy (EDS). Microanalysis for N and EDS analysis for Cl showed that at least 90% of nitrate or chloride ions were replaced during the ion exchange reactions. The final Mo content in the materials varied between 6.5 and 11.6 wt %. Mo K-edge EXAFS analysis, supported by IR, Raman, UV-vis, and (13)C{ (1)H} CP/MAS NMR spectroscopic studies, showed the presence of cointercalated [MoO 2(3,4-dhb) 2] ( m- ) and [Mo 2O 5(3,4-dhb) 2] ( m- ) complexes in proportions that depend on the type of LDH support and the reaction conditions. The binuclear bis(catecholate) complex, with a Mo...Mo separation of 3.16 A, was the major species intercalated in the Zn-Al and Li-Al products prepared using only water as solvent. The X-ray powder diffraction (XRPD) patterns of all the Mo-containing LDHs showed the formation of an expanded phase with a basal spacing around 15.4 A. High-resolution synchrotron XRPD patterns were indexed with hexagonal unit cells with a c-axis of either 30.7 (for Li-Al-Mo LDHs) or 45.9 A (for a Zn-Al-Mo LDH). Fourier maps ( F obs) calculated from the integrated intensities extracted from Le Bail profile decompositions indicated that the binuclear guest species are positioned such that the Mo --> Mo vector is parallel to the host layers, and the overall orientation of the complex is perpendicular to the same layers. The thermal behavior of selected materials was studied by variable-temperature XRPD, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC).     

Sulfate intercalated layered double hydroxides prepared by the reformation effect

The removal of the sulfate anion from water using synthetic hydrotalcite (Mg/Al LDH) was investigated using powder X-ray diffraction (XRD) and thermogravimetric analysis (TG). Synthetic hydrotalcite Mg₆Al₂(OH)₁₆(CO₃)·4H₂O was prepared by the co-precipitation method from aluminum and magnesium chloride salts. The synthetic hydrotalcite was thermally activated to a maximum temperature of 380 °C. Samples of thermally activated hydrotalcite where then treated with aliquots of 1000 ppm sulfate solution. The resulting products where dried and characterized by XRD and TG. Powder XRD revealed that hydrotalcite had been successfully prepared and that the product obtained after treatment with sulfate solution also conformed well to the reference pattern of hydrotalcite. The d₍₀₀₃₎ spacing of all samples was found to be within the acceptable region for a LDH structure. TG revealed all products underwent a similar decomposition to that of hydrotalcite. It was possible to propose a reasonable mechanism for the thermal decomposition of a sulfate containing Mg/Al LDH. The similarities in the results may indicate that the reformed hydrotalcite may contain carbonate anion as well as sulfate. Further investigation is required to confirm this.     

Enhanced luminescence of europium-doped layered double hydroxides intercalated by sensitiser anions

Four sensitising anions naphthalene-1,5-disulfonate (15-NDS), naphthalene-2,6-dicarboxylate (26-NDC), benzoate (BA) and terephthalate (TA) were intercalated into a Eu(3+)-doped Zn/Al layered double hydroxide. The carboxylate anions enhanced the red luminescence of Eu(3+) much more strongly than the sulfonate, in the descending order TA > 26-NDC > BA > 15-NDS.     

New basic catalysts obtained from layered double hydroxides nanocomposites

A new route for the preparation of basic mixed oxides using nanocomposite precursors obtained from layered double hydroxides (LDH) was investigated. These nanocomposites have been prepared by intercalation of negatively charged guest entities containing Ca²⁺, Sr²⁺, Ba²⁺ or La³⁺ cations in the interlayer space of host Mg/Al LDH by anionic exchange. The guest entities have been previously prepared by complexation of the required cations in the presence of edta or citrate chelating anions. Intercalation of [Mⁿ⁺(edta)]^(4?n)? or [La(cit)OH]^? complexes is proved by elemental analysis, XRD analysis and FT-IR spectroscopy. However, in order to satisfy the charge equilibrium in the materials, (edta)^4? and (citrate)^3? species are also co-intercalated in the nanocomposites. The basic properties of the mixed oxides obtained after thermal decomposition of the nanocomposites precursors were evaluated in the disproportionation of 2-methyl-3-butyn-2-ol (MBOH) and the transesterification of 1-phenylethanol with diethylcarbonate (DEC). The Sr- and Ba-containing mixed oxides exhibit basicity close to the one of MgO and Mg(La)O mixed oxides. A comparative study of the reactivity of La-containing mixed oxides obtained following different preparation routes, i.e. coprecipitation or anionic exchange, allows to conclude that the nanocomposite route led to the most active samples.     

Preparation and properties of new flame retardant unsaturated polyester nanocomposites based on layered double hydroxides

The preparation of new layered double hydroxides/unsaturated polyester (LDH/UP) nanocomposites was performed and the effect of LDH on the resin properties was studied. Two different organo-LDHs have been prepared, adipate-LDH (A-LDH) and 2-methyl-2-propene-1-sulfonate-LDH (S-LDH); in order to evaluate the influence of these nanofillers, samples with two different concentrations were dispersed in the matrix. The physical, thermal, mechanical and fire reaction properties of nanocomposites were studied. Intercalated layered structures were observed for the different organo-LDH loadings (1 and 5 wt%). Mechanical properties studied under flexural tests show that incorporation of organo-LDH in the resin reduces the flexural strength of polyester resin while the flexural modulus is unchanged for the S-LDH/UP composites and increased with 1 wt% of A-LDH. Adding 1 wt% of A-LDH to the resin produces an important reduction on the flexural strength, but an increase of the flexural modulus. The study of fire reaction properties, using cone calorimeter, suggested a significant reduction in the UP flammability, by 46 and 32%, by incorporating 1 wt% of A-LDH and 5 wt% S-LDH, respectively. Mass loss curves show enhanced char formation with the different loads tested while the amount of evolved smoke remains quite unchanged.     

New layered double hydroxides containing intercalated manganese oxide species: synthesis and characterization

Manganese oxide species (MnO(x)) have been intercalated within the gallery spaces of Mg-Al layered double hydroxides (LDHs). Synthesis of these materials was achieved by ion-exchange of the LDH-nitrate precursor with permanganate anion followed by reduction with organic reagents, such as glucose, ethanol, and ascorbic acid. Elemental analysis, X-ray diffraction, FT-IR spectroscopy, Raman spectroscopy, HR-TEM, and N(2) sorption analyses have been used to characterize these materials. TEM micrographs of LDH-MnO(x) materials revealed platelike morphology, characteristic of hydrotalcite-like compounds. Chemical analysis results showed that permanganate anions exchanged with nitrate anions. FT-IR and Raman spectroscopy confirmed the reduction of the permanganate anions after treatment with the organic reagents. The XRD diffraction patterns of LDH-MnO(x) revealed that the layer structure is maintained after all synthetic steps. The observed basal spacings of intercalates varied depending on the reducing agent; the largest expansion was 9.93A, corresponding to the use of ascorbic acid. The specific surface areas were also affected according to the organic reagent used, indicating that the structural modifications in the interlayer domain observed by X-ray diffraction also influence the microtextural properties.     

Synthesis and characterization of Cd-Cr and Zn-Cd-Cr layered double hydroxides intercalated with dodecyl sulfate

Cd-Cr and Zn-Cd-Cr layered double hydroxides (CdCr-LDH and ZnCdCr-LDH) containing alkyl sulfate as the interlamellar anion have been prepared through a coprecipitation technique. The resulting compounds were characterized using X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy. Magnetic property measurements indicate that antiferromagnetic interactions occur between the chromium ions in the two compounds at low temperatures. The introduction of zinc influences the ligand field of Cr^III and the Cr^III-Cr^III interactions in the LDH compound. It is found that both CdCr-LDH and ZnCdCr-LDH can be delaminated by dispersion in formamide, leading to translucent and stable colloidal solutions.     

Poly(L‐lactide)/layered double hydroxides nanocomposites: Preparation and crystallization behavior

Novel nanocomposites from poly(L ‐lactide) (PLLA) and an organically modified layered double hydroxide (LDH) were prepared using the melt‐mixing technique. The structure and crystallization behavior of these nanocomposites were investigated by means of wide‐angle X‐ray diffraction (WAXD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), and polarized optical microscopy (POM). WAXD results indicate that the layer distance of dodecyl sulfate‐modified LDH (LDH‐DS) is increased in the PLLA/LDH composites, compared with the organically modified LDH. TEM analysis suggests that the most LDH‐DS layers disperse homogenously in the PLLA matrix in the nanometer scale with the intercalated or exfoliated structures. It was found that the incorporation of LDH‐DS has little or no discernable effect on the crystalline structure as well as the melting behavior of PLLA. However, the crystallization rate of PLLA increases with the addition of LDH‐DS. With the incorporation of 2.5 wt % LDH‐DS, the PLLA crystallization can be finished during the cooling process at 5 °C/min. With the addition of 5 wt % LDH‐DS, the half‐times of isothermal melt‐crystallization of PLLA at 100 and 120 °C reduce to 44.4% and 57.0% of those of the neat PLLA, respectively. POM observation shows that the nucleation density increases and the spherulite size of PLLA reduces distinctly with the presence of LDH‐DS. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2222–2233, 2008