Novel polyether polyurethane/clay nanocomposites synthesized with organicly modified montmorillonite as chain extenders

A kind of novel polyether polyurethane (PU)/clay nanocomposite was synthesized using poly(tetramethylene glycol), 4,4′‐diphenylmethane diisocyanate (MDI), 1,6‐hexamethylenediamine, and modified Na⁺‐montmorillonite (MMT). Here, organicly modified MMT (O‐MMT) was formed by applying 1,6‐hexamethylenediamine as a swelling agent to treat the Na⁺‐MMT. The X‐ray analysis showed that exfoliation occurred for the higher O‐MMT content (40 wt %) in the polymer matrix. The mechanical analysis indicated that, when the O‐MMT was used as a chain extender to replace a part of the 1,2‐diaminopropane to form PU/clay nanocomposites, the strength and strain at break of the polymer was enhanced when increasing the content of O‐MMT in the matrix. When the O‐MMT content reached about 5%, the tensile strength and elongation at break were over 2 times that of the pure PU. The thermal stability and the glass transition of the O‐MMT/PU nanocomposites also increased with increasing O‐MMT content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 6–13, 2006     

聚氨酯/蒙脱土纳米复合材

聚氨酯／蒙脱土(PU／MMT)纳米复合材料主要是采用插层聚合法合成的1种综合性能优越的新型材料。广角X-射线(WAXD)和透射电镜(TEM)分析结果表明蒙脱土以3～4nm的层间距分散在聚氨酯基体中，因此获得非常有序的插层结构。当PU中加入质量分数为8％的有机蒙脱土(OMMT)时，其拉伸强度提高1．5倍以上，伸长率则提高1．2倍以上；其吸水性随着有机蒙脱土含量的增加而下降，并具有较好的阻隔性。同时热失重分析(TGA)表明，PU／MMT纳米复合材料的热稳定性略有提高。因此，PU／MMT纳米复合材料具有广泛的工业应用前景。     

Synthesis and properties of polyurethane/clay nanocomposite by clay modified with polymeric methane diisocyanate

A polyurethane (PU)/clay nanocomposite was synthesized from polyol, polymeric 4,4′‐diphenyl methane diisocyanate (PMDI), and modified clay with PMDI. To achieve the modified clay with PMDI, the silanol group of the clay and the NCO group of the PMDI were reacted for 24 h at 50°C to form urethane linkage. Fourier transform IR analysis of the clay modified with the PMDI demonstrated that the NCO characteristic peak was observed in the clay after a modification reaction with PMDI. The results of the X‐ray pattern suggested that the clay layers were exfoliated from the PU/clay nanocomposite. From the results of the mechanical properties, the maximum values of the flexural and tensile strength were observed when 3 wt % clay based on PMDI was added into the PU/clay nanocomposites. The glass‐transition temperature and change in the heat capacity at glass transition temperature (ΔC_p) of the PU/clay nanocomposite decreased with an increase in the modified clay content. We suggested that the decrease in the ΔC_p with the modified clay content might be due to the increase of steric hindrance by the exfoliated clay layers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2879–2883, 2006     

PU/有机蒙脱土纳米复合材料的制备和性能研究

采用原位插层聚合法制备PU/有机蒙脱土(OMMT)纳米复合材料。通过X射线衍射和透射电镜分析发现,当OMMT质量分数为0 01和0 03时,OMMT完全剥离并较均匀地分散于PU基体中;当OMMT质量分数为0 05时,OMMT在PU基体中发生部分剥离。热重分析表明,加入OMMT可提高复合材料的耐热性。动态力学分析表明,OMMT对PU模量的影响不大。PU/OMMT复合材料的硬度、弹性模量、拉伸强度和拉断伸长率均比纯PU有所提高。     

Synthesis and characterization of poly(urethane‐benzoxazine)/clay hybrid nanocomposites

Poly(urethane‐benzoxazine)/clay hybrid nanocomposites (PU/Pa–OMMTs) were prepared from an in situ copolymerization of a polyurethane (PU) prepolymer and a monofunctional benzoxazine monomer, 3‐phenyl‐3,4‐dihydro‐2H‐1,3‐benzoxazine (Pa), in the presence of an organophilic montmorillonite (OMMT), by solvent method using DMAc. OMMT was made from cation‐exchange of Na‐montmorillonite (MMT) with dodecyl ammonium chloride. The formation of the exfoliated nanocomposite structures of PU/Pa‐OMMT was confirmed by XRD from the disappearance of the peak due to the basal diffraction of the layer‐structured clay found in both MMT and OMMT. DSC showed that, in the presence of OMMT, the curing temperature of PU/Pa lowered by ca. 60°C for the onset and ca. 20°C for the maximum. After curing at 190°C for 1 h, the exothermic peak on DSC disappeared. All the obtained films of PU/Pa–OMMT were deep yellow and transparent. As the content of OMMT increased, both the tensile modulus and strength of PU/Pa–OMMT films increased, while the elongation decreased. The characteristics of the PU/Pa–OMMT films changed from plastics to elastomers depending on OMMT content and PU/Pa ratio. PU/Pa–OMMT films also exhibited excellent resistance to the solvents such as tetrahydrofuran, N,N‐dimethylformamide and N‐methyl‐2‐pyrrolidinone. The thermal stability of PU/Pa were enhanced remarkably even with small amount of OMMT. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 4075–4083, 2003     

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     

Constitutive modeling of HDPE polymer/clay nanocomposite foams

A constitutive model for tensile behavior of high density polyethylene (HDPE)/clay nanocomposite foams was proposed. The elastic modulus of HDPE/clay nanocomposite was developed using micromechanics theory, and the modulus for foams was obtained by using representative volume element (RVE) concept. In order to describe the tensile behavior of the foams, a constitutive equation obtained from a viscoelastic model was proposed. The constitutive model was expressed in terms of microstructural properties of polymer, and physical properties of the foams. The effects of the material parameters and processing conditions on the foam morphologies and mechanical properties of HDPE/clay nanocomposite foams were investigated. Microcellular closed-cell nanocomposite foams were manufactured with HDPE, where the nanoclay loadings of 0.5, 1.0, and 2.0 wt% were used. The effect of clay loading and foaming conditions on the volume expansion ratio, elastic modulus, tensile strength, and elongation at break was investigated. Except for the elongation at break, the mechanical properties were improved with nanoclay loading. The tensile experimental data of the foams were compared with the prediction by the theoretical model. It was demonstrated that the tensile behaviors of HDPE/clay nanocomposite foams were well described by the constitutive model.     

Toughening of polylactide via in situ formation of polyurethane crosslinked elastomer during reactive blending

Polylactide (PLA)/polyurethane (PU) composites were prepared by reactive blending method with in situ formation of PU particles via the reaction between polyester polyol (PPG) and toluene‐2,4‐diisocyanate (TDI). The interfacial compatibility and adhesion between the PLA and PU phases were greatly improved by the reaction of the terminal hydroxyl groups of PLA and N?C?O groups of TDI forming graft copolymer, as confirmed by FTIR spectroscopy. The elongation at break and notch impact strength of PLA/PU composites increased considerably with increasing PU content, and the tensile strength of PLA/PU composites decreased slightly compared with that of pure PLA. Upon addition of 12 wt % PU, the elongation at break and notch impact strength increased to 175.17% and 10.96 kJ/m², respectively, about 27 times and 5.4 times greater than the corresponding values for the pure PLA. The tensile strength decreased only slightly to 48.65 MPa. The excellent interfacial adhesion, the dispersed PU elastomeric particles acting as stress concentration areas, and the triggering of large matrix shear yield as well as many fibrils by internal cavitation were the main mechanical toughening mechanisms. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44383.     

Epoxy/acrylonitrile-butadiene-styrene copolymer/clay ternary nanocomposite as impact toughened epoxy

Epoxy resins have low impact strength and poor resistance to crack propagation, which limit their many end use applications. The main objective of this work is to incorporate both acrylonitrile-butadiene-styrene copolymer (ABS) and organically modified clay (Cloisite 30B) into epoxy matrix with the aim of obtaining improved material with the impact strength higher than neat epoxy, epoxy/clay and epoxy/ABS hybrids without compromising the other desired mechanical properties such as tensile strength and modulus. Impact and tensile properties of binary and ternary systems were investigated. Tensile strength, elongation at break and impact strength were increased significantly with incorporation of only 4 phr ABS to epoxy matrix. For epoxy/clay nanocomposite with 2.5% clay content, tensile modulus and strength, and impact strength were improved compared to neat epoxy. With incorporation of 2.5% clay and 4 phr ABS into epoxy matrix, 133% increase was observed for impact strength. Ternary nanocomposite had impact and tensile strengths greater than values of the binary systems. Morphological properties of epoxy/ABS, epoxy/clay and epoxy/ABS/clay ternary nanocomposite were studied using atomic force microscopy (AFM) phase imaging, scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD). New morphologies were achieved for epoxy/ABS and epoxy/ABS/clay hybrid materials. Exfoliated clay structure was obtained for epoxy/clay and epoxy/ABS/clay nanocomposite.     

Thermal,mechanical, and gas barrier properties of ethylene–vinyl alcohol copolymer‐based nanocomposites for food packaging films: Effects of nanoclay loading

For the application of single‐layer food packaging films with improved barrier properties, an attempt was made to prepare ethylene‐vinyl alcohol (EVOH) copolymer‐based nanocomposite films by incorporation of organically modified montmorillonite nanoclays via a two‐step mixing process and solvent cast method. The highly intercalated tactoids coexisted with exfoliated clay nanosheets, and the extent of intercalation and exfoliation depended significantly on the level of clay loadings, which were confirmed from both XRD measurements and TEM observations. It was revealed that the inclusion of nanoclay up to an appropriate level of content resulted in a remarkable enhancement in the thermal, mechanical (tensile strength/modulus), optical, and barrier properties of the prepared EVOH/clay nanocomposite films. However, excess clay loadings gave rise to a reduction in the tensile properties (strength/modulus/elongation) and optical transparency due to the formation of clay tactoids with a larger domain size. With the addition of only 3 wt % clay, the oxygen and water vapor barrier performances of the nanocomposite films were substantially improved by 59 and 90%, respectively, compared to the performances of the neat EVOH film. In addition, the presence of clay nanosheets in the EVOH matrix was found to significantly suppress the moisture‐derived deterioration in the oxygen barrier performance, implying the feasibility of applying the nanocomposite films to single‐layer food packaging films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40289.     

Relationship between mechanical properties and exfoliation degree of clay in polyurethane nanocomposites

Exfoliated and intercalated polyurethane (PU) nanocomposites were prepared by in situ polymerization of polyol/organoclay mixture, chain extender and diisocyanate. Wide‐angle X‐ray diffraction and transmission electron microscopy confirmed an exfoliated structure for clay C30B and an intercalated structure for C20A in polyol and PU. The realization of exfoliated state for clay C30B in polyol during the mixing stage can provide an effective approach for controlling the exfoliation degrees by adjusting the content of intercalated and exfoliated organoclay C20A and C30B before polymerization. The effect of exfoliation degree on the mechanical and viscoelastic properties of PU was investigated. The addition of organoclay improved the tensile strength, modulus and elongation, but the hysteresis loss ratio and relaxation rate increased, and the relaxation time distribution became broad. The effect of organoclay on PU properties varied with the hard segment content. By increasing the exfoliation degree, the tensile strength and modulus increased, whereas the elongation decreased. The exfoliated PU nanocomposite had a lower relaxation rate and hysteresis loss ratio than the intercalated PU. Copyright © 2005 Society of Chemical Industry     

A novel synthesis of reactive nano‐clay polyurethane and its physical and dyeing properties

This study is about polyurea prepolymer, which was synthesized from the extender (N‐(2‐hydroxyethyl) ethylene diamine, HEDA or ethylene diamine, EDA) with 4,4′‐diphenylmethane diisocyanate (MDI), as an intercalative agent to intercalate the organic modified montmorillonite clay. Then, it is further reacted with the polyurethane prepolymer, which is polymerized from the polytetramethylene glycol (PTMG) and MDI, to proceed the intercalative polymerization to form a polyurethane/clay nanocomposite polymer. The experimental parameters contain the use of polyurea intercalative prepolymer extender and also the contents of organo‐clay in the prepolymer etc. We expect to get better mechanical property and also to improve the dyeing properties of nano‐clay polyurethane. The polyurethane/clay polymer is synthesized using two‐step method: synthesizing the polyurethane prepolymer from PTMG and MDI and then extended with the polyurea prepolymer modified with the organo‐clay. Because the extender HEDA contains side chain of hydroxyl groups, the modified PU can further react with the reactive dye. From the experimental results of the fine structure (X‐ray and FT‐IR) and mechanical analysis, it is found that the intercalation is successfully achieved. Thedistance of interlayer spacing is manifestly enlarged. The mechanical properties are significantly improved as the content of organo‐clay is increased. Besides, although thedye up‐take is decreased with the increasing content oforgano‐clay, but the water‐resistant fastness is improved. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Synthesis and characterization of in situ sodium‐activated and organomodified bentonite clay/styrene–butadiene rubber nanocomposites by a latex blending technique

In this article, we describe a method used to prepare an in situ sodium‐activated, organomodified bentonite clay/styrene–butadiene rubber nanocomposite master batch via a latex blending technique. The clay master batch was used for compound formulation. Octadecyl amine was used as an organic intercalate. The clay was purchased from local suppliers and was very cheap. Sodium chloride was used for in situ activation of the clay. The wide‐angle X‐ray diffraction data indicated that the in situ sodium activation helped to increase the intergallery distance from 1.28 to 1.88 nm. A transmission electron micrograph indicated intercalation and partial exfoliation. The thermal properties were relatively better in the case of the sodium‐activated, organomodified bentonite‐clay‐containing compound. A substantial improvement in physical properties such as the modulus, tensile strength, tear strength, and elongation at break was observed in the case of the in situ sodium‐activated compound. A cation‐exchange capacity equivalent (of the clay) of 1.5 times the octadecyl amine was the optimum dose for the modification. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Strain‐induced crystallization behavior of phenolic resin crosslinked natural rubber/clay nanocomposites

Nanocomposites of natural rubber (NR) and unmodified clay were prepared by latex compounding method. Phenolic resin (PhOH) was used to crosslink NR. Crosslinked neat NR was also prepared for comparison. The structure–property relationship of uncrosslinked and crosslinked NR/clay nanocomposites was examined to verify the reinforcement mechanism. Microstructure of NR/clay nanocomposites was studied by using transmission electron microscopic (TEM), X‐ray diffraction (XRD), wide angle X‐ray diffraction (WAXD), and small angle X‐ray scattering (SAXS) analyses. The results showed the evidence of intercalated clay together with clay tactoids for the nanocomposite samples. The highest tensile strength was achieved for the crosslinked NR/clay nanocomposite. The onset strain of deformation induced the crystallization of NR for nanocomposites was found at almost the same strain, and furthermore their crystallization was developed at lower strain than that of the crosslinked neat NR because of the clay orientation and alignment. However, at high strain region, the collaborative crystallization process related to the clay dispersion and conventional crosslink points in the NR was responsible to considerably high tensile strength of the crosslinked NR/clay nanocomposite. Based on these analyses, a mechanistic model for the strain‐induced crystallization and orientational evolution of a network structure of PhOH‐crosslinked NR/clay nanocomposite was proposed. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42580.     

A novel castor oil-based polyurethane/layered zirconium phosphonate nanocomposites: preparation,characterization, and properties

A new type of layered zirconium glycine-N,N-dimethylphosphonate (ZGDMP), with the functional groups –COOH, has been prepared and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscopy (TEM). Situ polymerization method was employed to prepare castor oil-based polyurethane/layered zirconium phosphonate (PU/ZGDMP-n) nanocomposite films. The structure and morphology of ZGDMP in PU matrix have been characterized by XRD, SEM, TEM, and Fourier transform infrared spectroscopy. The results show that the morphology and properties of PU-based nanocomposites greatly depend on the functional groups –COOH because of the chemical reactions and physical interactions involved. The tensile test shows that the tensile strength and elongation at break for the nanocomposite films increase with the loading of ZGDMP as compared to those of the virgin PU.     

蒙脱土插层对聚氨酯复合材料的结构和性能影响

用聚氧化丙烯醚二元醇插层有机蒙脱土，再与二异氰酸酯、扩链剂进行原位聚合反应，制备了聚氨酯插层纳米蒙脱土复合材料。该复合材料经X衍射、红外光谱和热分析测定．证明了复合物中的蒙脱土已被基本剥离，并形成了蒙脱土与聚氨酯硬段结合的微相有序结晶结构。复合材料的力学性能测试结果说明，当质量分数为1％的有机蒙脱土加入聚氨酯后，拉伸强度和拉断伸长率分别是未用蒙脱土的1．7倍和1．8倍。     

Synthesis and characterization of elastomeric polyurethane and PU/clay nanocomposites based on an aliphatic diisocyanate

This investigation reports preparation of polyurethane and polyurethane/clay nanocomposites based on polyethylene glycol, isophorone diisocyanate (IPDI), an aliphatic diisocyanate and 1,4‐ Butanediol as chain extender by solution polymerization. In this case PU/clay nanocomposites were prepared via ex‐situ method using 1, 3, and 5 wt % of Cloisite 30B. Thermogravimetric analysis showed that the maximum decomposition temperature (T_max) of the PU/clay nanocomposite is much higher than the pristine PU. The tensile properties improved upon increasing the organoclay (Cloisite 30B) content upto 3 wt %, and then decreased to some extent upon further increasing the nanoparticle loading to 5 wt %. Optical properties of the nanocomposites were studied by UV‐vis spectrophotometer. X‐ray diffraction (XRD) and transmission electron microscopy (TEM) were used to study the morphology of the nanocomposites. It was observed that with the incorporation of 3 wt % nanoclay the crystallinity in PU nanocomposite increases, then diminishes with further loading. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3328–3334, 2013     

Effect of blend composition and organoclay loading on the nanocomposite structure and properties of miscible poly(methyl methacrylate)/poly(styrene‐co‐acrylonitrile) blends

Organically‐modified montmorillonite clay nanocomposites of poly(styrene‐co‐acrylonitrile) (SAN), poly(methyl methacrylate) (PMMA) and SAN/PMMA miscible blend are investigated. Structure characteristics at the nanoscale and microscale and thermal and tensile properties are studied as a function of polymer blend composition and filler loading fraction. Blend miscibility and T_g are unaffected by up to 10% by wt. organoclay. Thermal degradation stability increases with SAN content and exhibits an optimum value of clay loading. Stiffness shows significant improvement. Tensile strength and elongation‐at‐break suffer as a result of nanocomposite formation. Modulus shows a maximum enhancement of 57% (5 ± 0.06 GPa at 10 wt% filler, 20/80 SAN/PMMA) and varies linearly with clay fraction for all compositions of matrix phase. Predictions of Halpin–Tsai composite model are in excellent agreement with the experimental behavior over full range of polymer blend composition. Fundamental aspects of a polymer blend–clay nanocomposite are clarified, such as lack of additional synergy between clay platelets and matrix, and tensile ductility reduction, compared with polymer–clay system. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Influence of structure of organic modifiers and polyurethane on the clay dispersion in nanocomposites via in situ polymerization

Influence of polyurethane (PU) structure on the nature of PU/clay nanocomposite was studied using varying amounts of trimethylol propane (TMP) as branching agent. The effect of hydroxyl groups in the modifier of organoclays on the structure of PU/clay nanocomposites was studied. Nanocomposites were characterized using wide‐angle X‐ray diffraction measurements (WAXD) and transmission electron microscopy (TEM). The results show that formation of completely exfoliated and well dispersed polyurethane/clay nanocomposites via in situ polymerization, is facilitated by the presence of tethering groups on the clay surface and an ability to form branched and crosslinked structures. Incorporation of long alkyl chains in addition to tethering hydroxyl groups in the modifier structure of the clay did not significantly improve the compatibility of linear PU with the clay. Intercalated thermoplastic polyurethane/clay nanocomposites, prepared using poly(caprolactone diol) as soft segment and isophorone diisocyanate and 1,4‐butanediol as hard segments show increase in storage tensile moduli at temperatures before glass transition temperature when functional groups capable of chemically reacting with the growing polymer chains are present in the clay modifier. This is indicative of improved interaction of the polymer with the clay surface when the modifier has larger number of hydroxyl groups. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(lactic acid)/low‐density polyethylene blends and its nanocomposites based on sepiolite

Poly(lactic acid) (PLA) nanocomposite ternary blends based on unmodified sepiolite were prepared by melt blending using a corotating twin‐screw extruder. Two grafted polymers were used as compatibilizer agents, in an effort to increase the PLA tensile toughness. The influence of incorporating a low‐cost commodity low‐density polyethylene, as dispersed phase to the composites on thermal degradation, and rheological and tensile properties was studied. The morphology of the blends and composites was determined through transmission and scanning electron microscopy techniques. Results showed that the compatibilized blends prepared without clay have higher thermal degradation susceptibility and tensile toughness than those prepared with sepiolite and significant changes in complex viscosity and melt elasticity values were observed between them. The nanocomposite blends exhibited similar thermal degradation, lower tensile strength, and Young's modulus values and increased elongation at break and tensile toughness, complex viscosity, and storage modulus compared with those of the nanocomposite of PLA. These results are related to the clay dispersion, to the type of morphology of the different blends, to the localization of the sepiolite in the different phases, the thermomechanical degradation of the PLA matrix phase during melt blending and the grafting degree of the compatibilizers used. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers