Synthesis and characterization of crosslinked polyurethane/clay nanocomposites

A series of glycerin‐crosslinked polyurethane (XPU)‐clay nanocomposites were prepared by in situ polymerization followed by solution casting and thermal treatment. The weight percent (wt %) of clay in the nanocomposites was varied between 0.25 and 10. The structural, rheological and dynamic mechanical properties of the nanocomposites were investigated. X‐ray diffraction (XRD) analysis showed that well dispersed clay platelets were formed in nanocomposites containing up to 1 wt % of clay. Scanning electron microscopy (SEM) showed that poorly dispersed and non‐exfoliated clays were present in composites containing >2 wt % of clay and resulted in phase‐separated disparities within the matrix. Rheological studies demonstrated that processability of polyurethane was significantly improved after clay addition such that solution viscosity decreased by between 76 and 90%. Furthermore, the presence of chemical and physical crosslink networks within the matrix resulted in a remarkable enhancement in the rubbery plateau storage modulus. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43346.     

A study on polyurethane/acrylate crosslinked gel polymer electrolytes

2,4‐Toluene diisocyanate, poly(propylene glycol), poly(ethylene glycol) (PEG) and 2‐hydroxyethyl methacrylate were used to synthesize PEG–UA (urethane acrylate) monomer. The crosslinked polymer and gel polymer electrolytes were prepared in dioxane by free radical polymerization. The swelling behaviour, thermal degradation properties, morphology and ionic conductivity of the gel polymer electrolytes were investigated. With decrease in the proportion of dioxane used, the synthesized polymer's network density increased, its affinity with a solution of 1 M LiClO₄ in propylene carbonate (PC) decreased, and more microgel which diffused in the network. At the same time, the conductivity increased and reached 4 × 10^?4 S cm^?1 at 25 °C. Copyright © 2003 Society of Chemical Industry     

Structural characterization of hydrophilic polymer blends/montmorillonite clay nanocomposites

The nanocomposite films comprising polymer blends of poly(vinyl alcohol) (PVA), poly(vinyl pyrrolidone) (PVP), poly(ethylene oxide) (PEO), and poly(ethylene glycol) (PEG) with montmorillonite (MMT) clay as nanofiller were prepared by aqueous solution casting method. The X‐ray diffraction studies of the PVA–x wt % MMT, (PVA–PVP)–x wt % MMT, (PVA–PEO)–x wt % MMT and (PVA–PEG)–x wt % MMT nanocomposites containing MMT concentrations x = 1, 2, 3, 5 and 10 wt % of the polymer weight were carried out in the angular range (2θ) of 3.8–30°. The values of MMT basal spacing d₀₀₁, expansion of clay gallery width W_cg, d‐spacing of polymer spherulite, crystallite size L and diffraction peak intensity I were determined for these nanocomposites. The values of structural parameters reveal that the linear chain PEO and PEG in the PVA blend based nanocomposites promote the amount of MMT intercalated structures, and these structures are found relatively higher for the (PVA–PEO)–x wt % MMT nanocomposites. It is observed that the presence of bulky ester‐side group in PVP backbone restricts its intercalation, whereas the adsorption behavior of PVP on the MMT nanosheets mainly results the MMT exfoliated structures in the (PVA–PVP)–x wt % MMT nanocomposites. The crystallinities of the PEO and PEG were found low due to their blending with PVA, which further decreased anomalously with the increase of MMT concentration in the nanocomposites. The decrease of polymer crystalline phase of these materials confirmed their suitability in preparation of novel solid polymer nanocomposite electrolytes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40617.     

Structure‐property and swelling behavior of electron beam irradiated poly(vinyl alcohol)/acrylamide/sodium montmorillonite clay composites

Composites based on poly(vinyl alcohol) (PVA), acrylamide monomer (AM) and sodium montmorillonite clay (MMT) were prepared, in the form of thin films, by solution casting. The PVA/AM/MMT composites films were then exposed to electron beam irradiation to form crosslinked network structure. The structure‐property behavior of PVA/AM/MMT hybrids was demonstrated by x‐ray diffraction (XRD), scanning electron microscopy, gel content, color intensity, thermogravimetric analysis (TGA) and swelling behavior in aqueous solutions. The results indicated that the introduction of MMT clay ratio up to 5% decreased the gel content of PVA/AM hydrogels. The color measurements indicated that the introduction of MMT clay ratio up to 5% was shown to affect the color intensity of composite films. It was found that both PVA/AM hydrogels and PVA/AM/MMT composites reached the equilibrium swelling state in water after four hours; however PVA/AM/MMT composites displayed higher swelling than PVA/AM hydrogels. However, the swelling of PVA/AM hydrogels or their composites at the equilibrium state increased with increasing temperature up to 60°C. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of electric field on polymer/clay nanocomposites depending on the affinities between the polymer and clay

Applying an electric field is an efficient way to fabricate polymer/clay nanocomposites. It helps to achieve a good dispersion of nanoclays which improves the performance of the polymeric system. In this study, the effect of an alternating current (A.C.) electric field was investigated on clay exfoliation with various combinations of polymer/clay nanocomposites. Three different types of organoclays (Cloisite 10A, 20A, 30B) were introduced in polypropylene (PP) and poly(lactic acid) (PLA) matrices. Their rheological properties showed that the A.C. electric field was effective in enhancing the dispersion of organoclays in both the PP/clay and PLA/clay composites. The efficiency of the A.C. field varied depending on the combination of polymer and clay nanoparticles. In the case of PP, the best combination was PP/C20A followed by PP/C10A and PP/C30B. In contrast, PLA/clay showed an opposite trend. This difference arises from the different affinities between the polymers and the functional groups of the clays. The Hansen solubility parameter was introduced to quantify the affinities between the polymer and clay. The electric field was more effective for polymer/clay combinations that had less difference in the Hansen solubility parameter. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43582.     

Effects of swelling agents on the crystallization behavior and mechanical properties of polyamide 6/clay nanocomposites

Montomorillonite was organically modified with three different swelling agents: n‐dodecylamine, 12‐aminolauric acid, and 1,12‐diaminodecane. These organoclays and polyamide 6 (PA6) were blended in a formic acid solution. X‐ray diffraction analysis showed that the clay still retained its layer structure in the PA6/clay nanocomposite. Consequently, these materials were intercalated nanocomposites. The effects of the swelling agent and organoclay content on the crystallization behavior of the PA6/clay nanocomposites were studied with differential scanning calorimetry. The results showed that the position and width of the exothermic peak of the PA6/clay nanocomposites were changed during the nonisothermal crystallization process. The clay behaved as a nucleating agent and enhanced the crystallization rate of PA6.The crystallinity of PA6 decreased with an increasing clay content. Different swelling agents also affected the crystallization behavior of PA6. The effects of the type and content of the swelling agent on the tensile and flexural properties of PA6/clay nanocomposites were also investigated. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1686–1693, 2003     

Morphology and ionic conductivity of thermoplastic polyurethane electrolytes

Thermoplastic polyurethane (TPU) with a mixture of soft segments [poly(ethylene glycol) (PEG) and poly(tetramethylene glycol) (PTMG)], denoted TPU‐M, was prepared as an ion‐conducting polymer electrolyte. TPUs with PEG and PTMG as soft segments were also synthesized individually as polymer electrolytes. The changes in the morphology and ion conductivity of the phase‐segregated TPU‐based polymer electrolytes as a function of the lithium perchlorate concentration were determined with differential scanning calorimetry, Fourier transform infrared spectroscopy, alternating‐current impedance, and linear sweep voltammetry measurements. Both solid and gelatinous polymer electrolytes were characterized in this study. The effect of temperature on conductivity was studied. The conductivity changes revealed the combined influence of PTMG and PEG units in TPU‐M. The swelling characteristics in a liquid electrolyte and the dimensional stability were evaluated for the three TPUs. Because of its dimensional stability and ionic conductivity, the TPU system containing both PEG and PTMG as soft segments was found to be more suitable for electrolyte applications. A room‐temperature conductivity of approximately 1 × 10^?4 was found for TPU‐M containing 50 wt % liquid electrolyte. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1154–1167, 2004     

Reaction kinetics and characteristics of polyurethane/clay nanocomposites

The reaction behavior and physical properties of polyurethane (PU)/clay nanocomposite systems were investigated. Organically modified clay was used as nanofillers to formulate the nanocomposites. Differential scanning calorimetry was used to study the reaction behavior of the PU/clay nanocomposite systems. The reaction rate of the nanocomposite systems increased with increasing clay content. The reaction kinetic parameters of proposed kinetic equations were determined by numerical methods. The glass transition temperatures of the PU/clay nanocomposite systems increased with increasing clay content. The thermal decomposition behavior of the PU/clay nanocomposites was measured by using thermogravimetric analysis. X‐ray diffractometer and transmission electronic microscope data showed the intercalation of PU resin between the silicate layers of the clay in the PU/clay nanocomposites. A universal testing machine was used to investigate the tensile properties of the PU/clay nanocomposites. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1641–1647, 2005     

New solid polymer electrolytes based on PEO/PAN hybrids

Hybrid polymer dry electrolytes comprised of poly(ethylene oxide) (PEO), polyacrylonitrile (PAN), and LiClO₄ were investigated. The impedance spectroscopy showed that the effect of PAN on the ion conductivity of PEO‐based electrolytes depends on the concentration of lithium salt. When the mole ratio of lithium to oxygen is 0.062 (15%LiClO₄‐PEO), adding PAN will increase the ionic conductivity. Differential scanning calorimetry, NMR, and IR data suggested that the enhanced conductivity was due to both the decreasing of the PEO crystallinity and increasing of the degree of ionization of lithium salt. There was obviously no interaction between PAN and lithium ions, and PAN acts as a reinforcing filler, and hence contributes to the mechanical strength besides reducing the crystallinity of the polymer electrolytes. When the LiClO₄‐PEO‐PAN hybrid polymer electrolyte was heated at 200°C under N₂, PAN crosslinked partially, which further decreased the crystallinity of PEO and increased the ionic conductivity, and at the same time prevented the recrystallization of PEO upon sitting at ambient environment. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1530–1540, 2006     

Effect of the addition of hydrophobic clay on the electrochemical property of polyacrylonitrile/LiClO4 polymer electrolytes for lithium battery

In this study, an organoclay, ALA-MMT, was prepared by the ionic exchange reaction of montmorillonite (MMT) with 12-aminododecanoic acid (ALA). ALA-MMT was then used as a filler to prepare a series of composite polymer electrolytes based on polyacrylonitrile (PAN) and LiClO₄. The effect of the addition of ALA-MMT on the properties of the composite polymer electrolytes (CPEs) was investigated by XRD, FT-IR, DSC, tensile strength, AC impedance, and cyclic voltammetry measurements. It was found that the ALA-MMT particles were well dispersed in the CPEs. Owing to the incorporation of ALA-MMT, a higher fraction of the free anions was obtained, indicating that the lithium salt dissolved in the PAN matrix more effectively for the CPE than in the PAN/LiClO₄ polymer electrolyte. Moreover, the glass-transition temperature was reduced, benefiting the ion transport. The best ionic conductivity at room temperature was obtained from the CPE with 7 wt% of the modified clay and 0.6 M LiClO₄ per PAN repeat unit (CPE-7) and was more than seven times higher than that from the corresponding PAN/LiClO₄ polymer electrolyte (CPE-0). The mechanical property and the cation transference number, t₊, of CPE-7 are largely increased compared to that of CPE-0. Besides, the CPEs were electrochemically stabilized up to 4.75 V and the corresponding cell exhibited excellent electrochemical stability and cyclability over the potential range between 0 V and 4.0 V vs. Li/Li⁺.     

Water vapor adsorption and volumetric swelling of melt‐impregnated wood–polymer composites

Wood–plastic composites were prepared through impregnation of solid wood with polyethylene. A resolution IV screening design of 16 runs for seven factors at two levels was adopted. The seven factors tested were ratio of maleated polyethylene in formulations, ratio of polyethylene of different molecular weights, four process factors (vacuum, pressure, time, and temperature), and wood species (red maple and aspen). Moisture adsorption content and volumetric changes as a function of time were investigated. This study also examined the effects of impregnation parameters and impregnants on water vapor adsorption and dimensional stability. The process parameters (pressure and temperature), polymer impregnants (polyethylene of different molecular weights), and wood species contributed significantly to the equilibrium moisture content (EMC), whereas the moisture adsorption rate was mainly affected by the polymer impregnants (polyethylene of different molecular weights). The EMC was inversely proportional to polymer retention. However, none of the variables significantly contributed to volumetric swelling; the volumetric swelling rate was mainly affected by wood species, the molecular weight of the polyethylene, and impregnation vacuum. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2668–2676, 2006     

不同聚合物基体对复合材料性能的影响

研究了以不同类型聚合物为基体的高分子夏合材料的导电性和力学强度的变化规律，并从聚合物的结晶性，对填料的粘结性及其表面张力等方面进行了分析。若基体的结晶性和极性较强，则在导电性提高的同时，冲击强度下降；若基体本身比较柔软且对填料有足够的亲和力，则在一定的填料含量范围内，导电性和冲击强度可同时提高。     

粘土/聚合物纳米复合材料制备研究现状及应用

本文综述了粘土／聚合物纳米复合材料的制备，性能，简要进行了热力学分析，并对应用前景进行了展望。     

Preparation and characterization of hyperbranched polymer modified montmorillonite/chlorinated butyl rubber damping composites

In this work, Na⁺‐montmorillonite (MMT) was modified by hyperbranched polymer (HBP) and grafted with hindered phenol to improve the damping and other properties of the chlorinated butyl rubber (CIIR) composites. The hyperbranched polymer‐modified montmorillonite (HBP‐OMMT) was prepared by organic montmorillonite (OMMT) that was obtained from the cation exchange reaction between MMT and silane quaternary ammonium salt. The main characterization methods were Fourier transform infrared spectroscopy, hydrogen nuclear magnetic resonance, X‐ray diffraction, scanning electron microscopy, energy dispersive spectrometer, and thermogravimetric (TG) analysis. The basal spacings of MMT, OMMT, and HBP‐OMMT were 1.47, 2.94, and 4.09 nm, respectively. The onset and center temperatures of decomposition (T_?5% and T_max) of HBP‐OMMT were improved from 301 and 369 °C to 332 and 398 °C, respectively. The CIIR damping composites were prepared by mechanical blending of HBP‐OMMT with pure CIIR. The tensile strength and elongation at break of the composites were improved from 5.4 MPa and 890% to 7.6 MPa and 1066%. From TG curves, T_?5% and T_max were increased from 297.4 and 406.0 °C to 323.3 and 410.5 °C, respectively. The dynamic mechanical analysis results showed that tan δ rose from the original 1.20 to 1.44 with the addition of HBP‐OMMT. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43645.     

The effect of ionic liquid fragment on the performance of polymer electrolytes

An ionic liquid 1‐methyl‐3‐[2‐(methacryloyloxy)ethyl]imidazolium bis(trifluoromethane sulfonylimide) (MMEIm‐TFSI) was synthesized and polymerized. Composite polymer electrolytes based on polymeric MMEIm‐TFSI (PMMEIm‐TFSI) and poly[(methyl methacrylate)‐co‐(vinyl acetate)] (P(MMA‐VAc)) were prepared, with lithium bis(trifluoromethane sulfonylimide) (LiTFSI) as target ions (Li⁺). DSC/TGA analysis showed good flexibility and thermal stability of the composite electrolyte membranes. The AC impedance showed that the ionic conductivity of the electrolytes increased with PMMEIm‐TFSI up to a maximum value of 1.78 × 10^?4 S cm^?1 when the composition was 25 wt% P(MMA‐VAc)/75 wt% PMMEIm‐TFSI/30 wt% LiTFSI at 30 °C. The composite electrolyte membrane (transmittance ≥ 90%) can also be used as the ion‐conductive layer material for electrochromic devices, and revealed excellent colorization performance. Copyright © 2011 Society of Chemical Industry     

凹凸棒土/聚合物复合材料研究进展

综述了凹凸棒土在聚合物中的应用研究进展。研究表明，大多数情况下，常规的聚合物加工技术不足以将凹凸棒土解离为纳米短纤维，因此只能形成凹凸棒土／聚合物微米复合材料，但将凹凸棒土进行有机改性，可以明显提高其增强效果。采用原位聚合的方法可以制备出性能优异的凹凸棒土／聚合物纳米复合材料，或在高黏度和高极性的聚合物熔体中，凹凸棒土在剪切力下可以解离为纳米单晶，从而形成纳米复合材料。利用凹凸棒土／乳液共混共凝方式也可制备出凹凸棒土／橡胶纳米复合材料。     

Equilibrium swelling behavior and elastic properties of polymer–clay nanocomposite hydrogels

Nanocomposite hydrogels were prepared by free‐radical polymerization of the monomers acrylamide (AAm), N,N‐dimethylacrylamide (DMA), and N‐isopropylacrylamide (NIPA) in aqueous clay dispersions at 21°C. Laponite XLS was used as clay nanoparticles in the hydrogel preparation. The hydrogels based on DMA or NIPA monomers exhibit much larger moduli of elasticity compared with the hydrogels based on AAm monomer. Calculations using the theory of rubber elasticity reveal that, in DMA‐clay or NIPA‐clay nanocomposites, both the effective crosslink density of the hydrogels and the functionality of the clay particles rapidly increase with increasing amount of Laponite up to 10% (w/v). The results suggest that DMA‐clay and NIPA‐clay attractive interactions are stronger than AAm‐clay interactions due to the formation of multiple layers on the nanoparticles through hydrophobic associations. It was also shown that, although the nanocomposite hydrogels do not dissolve in good solvents such as water, they dissolve in dilute aqueous solutions of acetone or poly(ethylene oxide) of molecular weight 10,000 g/mol, demonstrating the physical nature of the crosslink points. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Curing behavior,mechanical properties,intermolecular interaction,and morphology of silicone/polypyrrole/polymer electrolyte composites

The curing behavior, mechanical properties, intermolecular interaction, and morphology of silicone, polypyrrole, and polymer electrolyte composites were studied. A rigid‐body pendulum rheometer was used to determine the curing behavior of silicone/PEL blends. The polymer structure was evaluated using FTIR and Differential Scanning Calorimetery. The mechanical properties, including stress, strain, and hardness, were measured using a material testing system. The morphology of the composites was measured using scanning electron micrographs. The intermolecular interaction of the composites was measurement using dynamic mechanical analysis. The results show that the curing reaction rate is fast upon addition of 10 wt % of polymer electrolyte for silicone. The linear molecular structure of the polymer electrolyte was wound around the silicone polymer network structure forming a semi‐interpenetrating network. The intermolecular interaction was influenced by the composites, and the Ppy film effect on the surface of SP10 blends is more uniform than that of silicone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2754–2764, 2006