聚硅氧烷聚脲多嵌段共聚物中氢键的研究

采用多种手段研究了聚硅氧烷与聚脲嵌段共聚物中所存在的各类氢键．特别探讨在聚硅氧烷软段中引入极性氰丙基对体系成氢键能力的影响和两相间相互作用力的情况结果表明，在软段分子中引入极性氰丙基有利于增加聚硅氧烷分子与聚脲链段的相互作用，这一相间作用力使两相间界面层厚度随着硬段分子量的增加而加宽，并发现在聚硅氧烷聚脲嵌段共聚物中硬段的聚集形态随溶液浓度改变变化不大，其中氢键随着温度升高而下降．     

聚氰丙基甲基硅氧烷-聚脲嵌段共聚物的结构和性能

本文以氨丙基封端聚(氰丙基,甲基)硅氧烷(CH_2)_3CN:CH_3=1:5),MDI和EDA为原料,采用DMAC单一溶剂合成了一系列高软段分子量(Mn=3000～9000)和高硬段含量(7～30%wt)的多嵌段共聚物。产物为透明热塑性弹性体,具有良好的成膜性能和宽阔的使用温区,其杨氏模量比相应的聚二甲基硅氧烷-聚脲显著提高。通过FT-IR,WAXD,DSC,DMA等证明其硬段为近程有序结构,氰丙基与聚脲硬段有氢键作用,这一作用力使两相相溶性提高,“界面厚度”增加。氰丙基的引入和硬段含量的增加对材料相结构和力学性能有显著影响。     

氨丙基封端聚氰丙基甲基硅氧烷改性环氧树脂——两相相溶性及表界面形态研究

本文针对聚二甲基硅氧烷改性环氧树脂相溶性太差,性能不够理想等问题,提出用氰丙基替代部分甲基以减小聚硅氧烷与环氧树脂的溶度参数差,改善两相的相溶性。采用氨丙基封端的聚氰丙基甲基硅氧烷低聚体(表1)单独或与二乙烯三胺(固化剂)一同与双酚A环氧树脂反应,合成了一系列不同聚硅氧烷分子量和重量百分比的样品(表2)。并用示差扫描量热计(DSC)、动态力学谱(DMA)、光电子能谱(XPS)、接触角仪、扫描电子显微镜(SEM)、电子拉力试验机对其进行研究。结果表明在聚硅氧烷软段中引入氰丙基可提高两相的相溶性并使增韧效果明显改善。     

不同硬段含量脂肪族聚脲的结构与性能研究

通过端氨基聚醚、异佛尔酮二异氰酸酯和异佛尔酮二胺反应 ,合成了一系列不同硬段含量的脂肪族聚脲 ,并用DSC和FTIR等考察了硬段含量对聚脲的微观结构与力学性能的影响 .研究结果表明 ,聚脲呈现部分微观分相的形态 ,随硬段含量增加 ,聚脲中软段和硬段间的相容性提高 ,脲羰基的氢键化程度增加 ,但软段的玻璃化转变温度变化不大 ;此外 ,材料的拉伸强度、撕裂强度和硬度等也随着硬段含量的增加而显著提高 .     

不同硬段含量嵌段聚脲合成及性质的研究

用两步溶液聚合法合成了硬段含量不同的一系列热塑性嵌段聚脲.研究了影响反应的各种因素.所得聚脲是线性和无定形的.用DSC和DMS法初步研究了这些聚脲的性质,随硬段含量增加.聚脲从软弹性体转变为高模量的硬塑料.     

多嵌段聚硅氧烷聚脲共聚物及双离子型聚硅氨酯的表面性质的研究

本文利用光电子能谱(ESCA)和表面接触角研究了多嵌段聚硅氧烷聚脲共聚物(PUSE)和双离子型聚硅氨酯(PUSM)的表面性质,发现PUSE和PUSM中的软段聚硅氧烷均在表面富集;提高本体的相分离程度,更有利于软段的表面富集;但在50层内,硬段仍有一定的比例,表面层仍是多相结构。在PUSE中,接触角和凝血时间随聚硅氧烷软段比例增加而增加,在PUSM中,随离子化程度的提高,亲水性提高,接触角变小,凝血时间缩短。     

含呱嗪聚硅氧烷聚脲聚氨酸及其离聚物的研究

以氨丙基封端聚二甲基硅氧烷及脲键改性聚硅氧烷低聚体分别与4，4－二异氰酸酯二苯甲烷（MDI)反应，并用1，4二（2－羟乙基）－呱嗪（N）扩链，合成了一系列含氮杂环聚氨酯共聚物。产物为透明热塑性弹性体，具有良好的成膜性能和宽阔的使用温区，通过碘乙烷和γ－丙磺酸内酯对上述样品进行季铵化，合成了阳离子型及双离子型离聚物。用傅里叶红外光谱（FT－IR）、示差量热分析（DSC）、动态力学谱（DMTA）、力学性能等方面对样品进行了表征。结果表明，在聚硅氧烷中引入脲键，提高了软、硬段两相的相容性。体系中既有软段间的氢键作用又有两相间的氢键作用，从而使这类材料的杨氏模量、抗张强度和断裂伸长均明显高于相应的聚二甲基硅氧烷聚脲聚氨酯体系。     

含呱嗪聚硅氧烷聚脲聚氨酯及其离聚物的研究

以氨丙基封端聚二甲基硅氧烷及脲键改性聚硅氧烷低聚体分别与４，４－二异氰酸酯二苯甲烷（ＭＤＩ）反应，并用１，４二（２－羟乙基）一呱唪（Ｎ）扩链，合成了一系列含氮杂环聚氨酯共聚物，产物为透明热塑性弹性体，具有良好的成膜性能和宽阔的使用温区。通过碘乙烷和ｖ－丙磺酸内酯对上述样品进行季铵化，合成了阳离子型及双离子型离聚物。用傅里叶红外光谱（ＦＴ－ＩＲ）、示差量热分析（ＤＳＣ）、动态力学谱（ＤＭＴＡ）、力学性能等方法对样品进行了表征，结果表明，在聚硅氧烷中引人脲键，提高了软、硬段两相的相容性，体系中既有软段间的氢键作用又有两相间的氢键作用，从而使这类材料的杨氏模量、抗张强度和断裂伸长均明显高于相应的聚二甲基硅氧烷聚脲聚氨醋体系。     

侧链为光敏感基团的可生物降解聚氨酯的合成及表征

设计合成2-甲基-2-肉桂酰氧甲基-1,3-丙二醇(MCO)作为扩链剂,并以聚乳酸二醇(PLA diol)为软段,异佛尔酮二异氰酸酯(IPDI)和MCO为硬段制备了一系列侧链含有肉桂基团的可生物降解聚氨酯.结果表明MCO具有较高的反应活性,可满足制备高分子量聚氨酯的要求.聚氨酯结构中的肉桂双键可在紫外光和光引发剂的共同作用下,发生快速的交联反应,短时间内形成交联结构.软段结构相同时,凝胶含量随MCO含量的增加而增加.硬段结构相同时,凝胶含量随软段分子量的增加而减少.适度的交联可提高拉伸强度和形变回复率.     

聚对苯二甲酸丁二酯-聚四亚甲基醚多嵌段共聚物的研究

合成了硬段含量和软段分子量不同的聚对苯二甲酸丁二酯-聚四亚甲基醚(PBT-PTMG)多嵌段共聚物。研究了硬段含量和软段分子量对嵌段共聚合过程的影响。当软段分子量较大、硬段含量较高时,在嵌段共缩聚过程中有均聚物伴生。当软段分子量在2000左右,硬段含量在20％左右时,基本上不生成均聚物。硬段重量含量为 20％的低硬段 PBT-PTMG多嵌段共聚物是结晶的。由它纺成的弹体纤维有良好的力学性能和弹性回复。热处理能改进纤维的弹性回复。     

Synthesis and characterization of polydimethylsiloxane polyurea-urethanes and related zwitterionomers

A series of segmented polyurea urethane and polyurea block copolymers based on a hexane diisocyanate (HDI) modified aminopropyl terminated polydimethylsiloxane soft segment was synthesized. The hard segments consisted of 4,4′-methylene diphenylene diisocyanate (MDI) which was chain extended with 1,4-butanediol (BD), N-methyldiethanolamine (MDEA), or ethylene diamine. Zwitterionomers were prepared by quaternizing the tertiary amine of the MDEA extended material with γ-propane sultone. The effect of chemical structure on the extent of phase separation and physical properties was studied using a variety of techniques including thermal analysis, dynamic mechanical spectroscopy, tensile testing, and small-angle x-ray scattering. It was observed that the compatibility between the nonpolar polydimethylsiloxane soft segments and the polar urethane hard segments was improved by inserting HDI linkages into the polydimethylsiloxane soft segments. The aggregation of hard segments was enhanced by increasing hard-segment content or by the introduction of ionic functionality. The tensile strength and modulus of these materials was higher than those of polyurethanes containing soft segments based on polydimethylsiloxane and its derivatives.     

Urea hard segment morphology in flexible polyurethane foam

A series of flexible polyurethane slabstock foam samples were prepared with varying water content and studied using transmission electron microscopy (TEM), video-enhanced optical microscopy (VEM), and small-angle X-ray scattering (SAXS). A new TEM sample preparation technique was developed in which the foam is impregnated with water, frozen, and microtomed, and the polyether soft segment is selectively degraded in the electron beam. Structures of two size scales were detected. A texture with grains (“urea aggregates”) 50–200 nm in size was imaged using both VEM and low-magnification TEM for foams with formulations containing more than 2 pphp water. For the first time, images of urea hard segment microdomains in polyurethane foam (approximately 5 nm in size) were obtained using high-magnification TEM. A microdomain spacing of approximately 6–8 nm was estimated from the SAXS scattering profiles. Glycerol was added to one of the formulations in order to modify the urea microphase separation and to give insight into morphology development in molded polyurethane foam systems. No structure was observed in low-magnification TEM images of the glycerol-modified foam, although smaller structures (hard segments) were detected at high magnification and by SAXS. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 573–581, 1998     

SAXS and TEM Investigations on Thermoplastic Nanocomposites Containing Functionalized Silica Nanoparticles

Transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS) were used to characterize the morphology of thermoplastic nanocomposites. These materials were based on a thermoplastic matrix of a copolymer of methylmethacrylate (MMA) and 2-hydroxyethylmethacrylate (HEMA) with spherical 10 nm silica particles as a filler (filler content 2, 5 and 10 vol%, respectively). Depending on the surface modification of the particles, it was possible to control the aggregation tendency of the primary filler particles. With uncoated particles large aggregates about 100 nm in size could be observed by TEM. For nanocomposites containing particles coated with methacryloxypropyltrimethoxysilane (MPTS), TEM showed that the particles were better dispersed in the polymer matrix only forming aggregates comprised of two or three primary particles. In comparison to the TEM results, the volume weighted particle size distribution calculated from SAXS for the systems with uncoated particles is monomodal and shows particle sizes in the range of primary particles whereas the systems with MPTS coated particles revealed a bimodal size distribution with particle sizes comparable to those measured with TEM. To obtain complete information about the morphology of the nanocomposites above the critical upper limit of detectable scattering vectors (particle sizes >50 nm) SAXS has to be supported by TEM, whereas in the nanosize range below the critical limit both methods exhibit an excellent correspondence.     

Transmission electron microscopy observations of composite polymer colloid nucleated by functionalized silica

In this work, functionalized nanometric silica particles were engaged in emulsion polymerization of ethyl acrylate. The morphological characterization of this composite material was performed by transmission electron microscopy (TEM) and small angle X-ray scattering (SAXS). We were particularly interested in the state of encapsulation of the silica particles and their distribution in the latex film. Initialy, we successively studied both components of the composite: polymer beads and silica particles differ by their size and also by their contrast. In addition, it was possible to perfrom dark field TEM to study this system of two amorphous phases because their respective amorphous halos are not too close. Hence, we investigated the colloid material in aqueous media and after film formation. Although no ideal encapsulation is observed in the colloid in aqueous media, the distribution of silica in the latex film is good. SAXS results are in good agreement with TEM observations.     

A Study of the Emulsified Microemulsion by SAXS,Cryo‐TEM,SD‐NMR,and Electrical Conductivity

A water‐in‐oil microemulsion was further dispersed in an aqueous phase containing Pluronic F127 as a steric stabilizer, to form a specific type of double emulsion termed emulsified microemulsion (EME). The inner microemulsion phase was made from glycerol‐monooleate (GMO), R(+)‐limonene, ethanol and glycerol. SAXS (small x‐ray scattering), PGSE‐NMR (pulse gradient spin echo‐NMR), electrical conductivity, and cryo‐TEM (cryogenic‐transmission electron microscopy) imaging techniques were used to confirm the existence of inner W/O nano‐droplets after second emulsification step and upon EME aging. Spherical globules of EME without long‐range internal order were observed by the SAXS measurements and the cryo‐TEM images. The average globule size of about 200–300 nm remained intact for at least 6 months.     

Morphological analysis of photocured polyurethane acrylate networks. Correlation with viscoelastic properties

In this paper, we investigate the final morphology of photocured polyurethane acrylates based on polypropylene oxide by means of Transmission Electron Microscopy (TEM), Small Angle X‐ray Scattering (SAXS), and dynamic mechanical measurements. Two interrelated structural features on two different size scales can occur in these systems. TEM analysis demonstrates the presence of inhomogeneities on the length scale of 10–200 manometers, mostly constituted by clusters of small hard units (diacrylated diisocyanate) connected by polyacrylate chains. The bimodal shape of the dynamic mechanical relaxation spectra corroborates this two‐phase structure. Besides, a suborganization of the reacted diisocyanate hard segments inside the polyurethane acrylate matrix is revealed by SAXS measurements, depending on the nature of the hydroxylacrylate used for the synthesis of the precursor. Finally, UV‐exposure time is found to induce modifications on the viscoelastic properties of the final network, even at high double‐bond conversion: this effect can be due to a postreaction and to an increase of the crosslinking density inside the hard segments domains. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 919–937, 1999     

Gold-Nickel Hydroxide Multi-Layers with Selective Absorption in the Visible Range

This work reports the growth of layered nickel hydroxide/gold films by sol-gel and dip-coating methods to obtain colored films for applications in switchable optical devices. The nickel and gold-based films were deposited on mica and glass plates from alcoholic sols. The distribution of electron density inhomogeneities (voids, nickel and gold particles) in the films was determined by means of small angle X-ray scattering (SAXS). The SAXS measurements were used to determine the nickel and gold particle sizes and to give guidelines to the appropriate chemical route to deposit homogeneous colored films. X-ray diffraction (XRD) was used to monitor the crystalline properties. Transmission electron microscopy (TEM) was used to observe the nanostructure of the gold particles and atomic force microscopy (AFM) to analyze the film surface. Spectral transmission was used to investigate the optical properties in these different layered systems, which present an absorption band in the visible region due to the gold aggregates. The composite material is deep blue. The analyses of SAXS data, TEM and AFM pictures are consistent, i.e., the formed Au particles are polydisperse in size and their clustering depends on the NiO _x H _y layer. The Au particles are polycrystalline, with [111]-preferred orientation, as determined by XRD. The nickel oxy-hydroxide matrix is amorphous.     

Local Structure of ZnO Micro Flowers and Nanoparticles Obtained by Micro‐Segmented Flow Synthesis

The micro‐segmented flow technique was applied for continuous synthesis of ZnO micro‐ and nanoparticles with short residence times of 9.4 s and 21.4 s, respectively. The obtained particles were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Small angle X‐ray scattering (SAXS) and photoluminescence spectroscopy were used to determine the size and optical properties of ZnO nanoparticles. In addition, extended X‐ray absorption fine structure (EXAFS) spectroscopy was employed to investigate local structural properties. The EXAFS measurements reveal a larger degree of structural disorder in the nanoparticles than the microparticles. These structural changes should be taken into consideration while evaluating the size‐dependent visible emission of ZnO nanoparticles.     

Crystallization behavior of P(EN‐co‐ET) copolyesters: Crystallization kinetics and morphology revealed by DSC,time‐resolved SAXS analysis,and TEM

The crystallization kinetics and morphology of PEN/PET copolyesters were investigated using differential scanning calorimetry (DSC), time‐resolved small‐angle X‐ray scattering (TR‐SAXS), and transmission electron microscopy (TEM). The Avrami exponents obtained using DSC were approximately 3 for homo PEN and 4 for all the copolyesters. The 3‐parameter Avrami model was successfully fitted to the invariants with respect to the time obtained from TR‐SAXS, and the exponent values were similar to those obtained from DSC. Moreover, the Avrami rate constants obtained from TR‐SAXS showed marked temperature‐sensitive decreases in all samples, like those obtained from DSC. This indicates that not only could changes in morphological parameters be obtained from the analysis of TR‐SAXS data but also crystallization kinetics. The changes in the morphological parameters determined from the SAXS data indicate that the minor components, dimethyl terephthalate (DMT) segments, are rejected into the amorphous phase during crystallization. In the TEM study, copolyesters crystallized at temperature above 240 °C grew into both the α‐ and β‐form, although 240 °C is the optimum condition for the β‐form crystal. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 805–816, 2005