Effect of organoclay on thermal and dynamic mechanical properties of novel thermoplastic polyurethane nanocomposites prepared by melt intercalation technique

Polymer nanocomposites based on thermoplastic polyurethane (TPU) containing organophilic montmorillonite (OMMT) were prepared by melt compounding method followed by compression molding. Different percentage of organically modified nanoclays (1, 3, 5, 7, and 9 wt%) was incorporated into the TPU matrix in order to examine the influence of the nanofillers on nanophase morphology and materials' properties. The microstructure morphology of the nanocomposites was examined by transmission electron microscopy (TEM), energy dispersion X‐ray analysis (EDX), wide angle X‐ray diffraction (WAXD), and atomic force microscope (AFM). The observation established that the organoclay is homogeneously dispersed and preferentially embedded in the TPU soft segment phase. Significant enhancement in the thermal stability of the nanocomposites was observed with the addition of the OMMT under thermogravimetric analysis (TGA). Dynamic mechanical properties of the TPU nanocomposites were analyzed using a dynamic mechanical thermal analyzer (DMTA), which confirms that the addition of OMMT has a strong influence on the storage and loss modulus of the TPU matrix. Copyright © 2009 John Wiley & Sons, Ltd.     

环氧乙烷-四氢呋喃共聚醚基热塑性聚氨酯弹性体氢键体系的定量研究

氢键为热塑性聚氨酯弹性体内的重要键合力特征。该文基于氢键所引起基团的频移,以FTIR为主要的研究手段,并结合通过动态力学性能（DMA）研究所建立的评估硬段与软段之间混溶的定量方程,对所合成的以环氧乙烷－四氢呋喃无规共聚醚、2,4－甲苯二异氰酸酯以及1,4－丁二醇为原料的热塑性聚醚聚氨酯弹性体的氢键体系进行了定量化研究。结果表明,大约有30％的硬段混溶进入炊段相对软段的醚氧产生氢键作用,主要的氢键包括硬段羰基与硬段氨基之间的氢键以及硬段烷氧与硬段氨基之间的氢键,仍发生在硬段岛区内。     

Exploring preferential association of laponite and cloisite with soft and hard segments in TPU‐clay nanocomposite prepared by solution mixing technique

Thermoplastic polyurethane (TPU) is a versatile polymer exhibiting many engineering applications. In this article, two varieties of clay (Cloisite and Laponite RD) have been used to prepare TPU‐based nanocomposites. They differ in, chemical composition, hydrophobicity, aggregation tendency, and dispersibility in a particular solvent. A detailed investigation of the thermal, morphological, and rheological behavior reflects the affinity of Cloisite towards the soft segment, whereas it is the hard segment for modified Laponite. The maximum improvement in onset degradation temperature has been observed to be 17.5 and 8.3 °C for Cloisite and Laponite, respectively. Five percent Cloisite‐filled sample shows optimum storage modulus in the glassy region where as it is the 10% filled sample at the rubbery region. However, the trend remains indifferent both in rubbery and glassy regions for Laponite, and properties have been found optimum for 3% filled sample. To explore the behavior in the terminal and flow regions, dynamic rheological experiments were performed in low shear rate. Variation in dynamic rheological properties can be explained well on the basis of the combination of partly exfoliated, intercalated, and aggregated structures of the nano clay inside the TPU matrix, depending on their nature and preferential association with different segments. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2341–2354, 2008     

Synthesis and characterization of poly(dimethylsiloxane‐urethane) elastomers: Effect of hard segments of polyurethane on morphological and mechanical properties

A series of poly(dimethylsiloxane‐urethane) elastomers based on hexamethylenediisocyanate, toluenediisocyanate, or 4,4′‐methylenediphenyldiisocyanate hard segment and polydimethylsiloxane (PDMS) soft segment were synthesized. In this study, a new type of soft‐segmented PDMS crosslinker was synthesized by hydrosilylation reaction of 2‐allyloxyethanol with polyhydromethylsiloxane, using Karstedt's catalyst. The synthesized soft‐segmented crosslinker was characterized by FT‐IR, ¹H, and ¹³C NMR spectroscopic techniques. The mechanical and thermal properties of elastomers were characterized using tensile testing, thermogravimetric analysis, differential scanning calorimetry (DSC), and dynamical mechanical analysis measurements. The molecular structure of poly(dimethylsiloxane‐urethane) membranes was characterized by ATR‐FTIR spectroscopic techniques. Infrared spectra indicated the formation of urethane/urea aggregates and hydrogen bonding between the hard and soft domains. Better mechanical and thermal properties of the elastomers were observed. The restriction of chain mobility has been shown by the formation of hydrogen bonding in the soft and hard segment domains, resulting in the increase in the glass‐transition temperature of soft segments. DSC analysis indicates the phase separation of the hard and soft domains. The storage modulus (E′) of the elastomers was increasing with increase in the number of urethane connections between the hard and soft segments. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2980–2989, 2006     

聚醚氨酯的微区形态

<正> 聚醚氨酯热塑弹性体是属于(AB)n类型的线型多嵌段共聚物,包括交替的硬段和软段单元.自从1966年Cooper和Tobolsky首先提出聚氨酯具有微相分离的本体结构之假设以后,至今已有大量文献报道了这类材料结构形态与性能关系的研究结果. Wilkes和Koberstein等使用SAXS研究了聚氨酯体系的形态特征.一般认为,聚氨酯材料的微相结构包括一个叠层状或类似叠层状形态,由相分离的软段和硬段组成,平均尺寸为100A的数量级,在软硬段微区之间还存在一相混合的过渡区,其厚度可以从几个埃至几十个埃.然而,SAXS虽然能够高分辨地给出多相体系相分离情况的定     

ABS/clay nanocomposites obtained by a solution technique: Influence of clay organic modifiers

Acrylonitrile-butadiene-styrene (ABS) polymer/clay nanocomposites were produced using an intercalation-adsorption technique from polymer in solution: polymer/clay suspensions were subjected to ultrasonic processing to increase the effectiveness of mixing. Several kinds of organically modified layered silicates (OMLS) were used to understand the influence of the surfactant nature on the intercalation-exfoliation mechanism. We show that only imidazolium-treated montmorillonite (DMHDIM-MMT) is stable at the processing temperature of 200 °C, used for hot-pressing, whereas alkyl-ammonium modified clays show significant degradation.The morphology of ABS based polymer nanocomposites prepared in this work was characterized by means of wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). Dynamic-mechanical analysis (DMA) was used to determine the storage modulus and damping coefficient as a function of temperature, and to investigate the correlations between mechanical properties and morphology of the nanocomposites. The thermal stability was assessed by means of thermogravimetric analysis (TGA). DMA and TGA show that the nanocomposites based on imidazolium-modified clay out-perform the nanocomposites based on quaternary-ammonium-modified clays in terms of mechanical properties and thermal stability.     

Electrospinning‐induced shape memory effect in thermoplastic polyurethane characterization and thermoviscoelastic modeling

Electrospun thermoplastic polyurethane (TPU) nanofibers are known to contract considerably (～40%) on heating up to ～90 °C. This study investigates this thermomechanical behavior and the TPU shape memory capabilities. The shape memory effect was first studied in TPU films as a model system by applying classical thermomechanical cycles (programming and recovery). The films were able to fix the applied deformation during long‐term storage at room temperature, well above the material's calorimetric glass transition temperature and in the absence of a percolated structure of hard domains. Structural analysis (Fourier transform infrared, differential scanning calorimeter, and dynamic mechanical analysis) revealed broad thermal transitions indicating the presence of a mixed phase of hard segments dispersed in the soft segment matrix. Using a linear viscoelastic model together with time–temperature superposition, the shape memory effect was attributed to the thermoviscoelastic properties of TPU. In particular, the mixed phase was found to give rise to a very broad relaxation spectrum dominated by long relaxation times, which explains the suppression of strain recovery at room temperature. Finally, the electrospinning process was examined and was found to be similar to a programming cycle characterized by the strong elongation flow accompanied by massive solvent evaporation, whereas the contraction effect was interpreted as the recovery phase in a shape memory perspective. Thus, the contraction of electrospun TPU mats may be considered to be an electrospinning‐induced shape memory effect. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1590–1602     

TPU增韧MABS的研究

利用双螺杆挤出机制备聚氨酯和甲基丙烯酸甲酯—丙烯腈-丁二烯-苯乙烯树脂熔融共混物(合金)。研究TPU的类型以及含量对TPU/MABS合金的透光率、力学性能和缺口冲击强度影响。结果表明:TPU/MABS合金可以保持较好透明性,随TPU含量的增加,合金材料的拉伸强度和弯曲模量逐渐降低,但是合金材料的冲击强度得到明显提高。扫描电镜观察表明,随TPU含量的增加,TPU与MABS界面分离现象逐渐明显。同时发现聚醚型TPU与MABS相容性和增韧效果要优于聚酯型TPU。     

不同软段结构聚氨酯-酰亚胺嵌段共聚物的合成及热性能研究

用二步法合成了不同软段 (PPO ,PEG ,PEPA)聚氨酯 酰亚胺 (PUI)嵌段共聚物 ,FTIR光谱表征了所有合成PUI分子主链均含有酰亚胺链段 ,并研究了PUI嵌段共聚物的热性能受软段类型及长度的影响 .DSC研究表明聚酯型PUI的软硬段之间的相容性比聚醚型PUI好 ,随相同软段分子量的增加 ,PUI体系的软硬段兼容性变差 ,并显示了相分离的特征 ;热失重 (TGA)研究得出不同软段的PUI样品的热稳定性大小顺序为 :PEPA PUI >PEG PUI>PPO PUI ;动态力学 (DMTA)研究给出了所合成的PUI样品在 5 0～ 2 0 0℃范围内均出现了较长的模量平台显示出有较好的耐热性 ,且随硬段含量的升高其储能模量不断增强     

Novel polycarbonate-based polyurethane elastomers: Composition–property relationship

Novel all-aliphatic polycarbonate-based polyurethane (PC-PU) elastomers, as well as PC-PU nanocomposites filled with organic-modified clays were synthesized, characterized and studied. It was found that they have very attractive mechanical properties (e.g., elongation at break between 600% and 800%). The prepared PC-PUs possess a distinctly segmented structure, which is the key prerequisite for their behavior as strong physical rubbery networks. All synthesized materials melt at elevated temperatures (between 110 and 200 °C) and hence can be processed like normal thermoplastics. The dispersion of the clay nanofiller was achieved by its one day swelling in the alcohol and a brief successive stirring. This procedure is very successful and leads to a partial exfoliation of the clay (documented by X-ray diffraction and TEM). The best nanocomposites with very good tensile properties, particularly with significantly increased moduli were obtained using the bentonite nanofiller. The study shows that the nanofiller interacts strongly with the hard domains and influences their melting temperature (DMTA and DSC), but it does not affect the glass transition temperature of soft domains. While Cloisite 15A was found to interact preferentially with the hard domains, the organic modified bentonite shows a strong interaction with both soft and hard segments, behaving as a blending agent. Hard domains in neat matrices, formed by hydrogen bonding of hard segments, were practically invisible by X-ray or TEM, but were successfully detected by AFM. Besides excellent mechanical properties, the prepared elastomers and their nanocomposites showed an interesting phase behavior (which was studied by combining DMTA and modulated DSC).     

Structure-property relationships in polycaprolactone-polyurethanes

The structure-property relationships of polycaprolactone-based segmented polyurethanes were studied using differential scanning calorimetry (DSC), small-angle x-ray scattering (SAXS), wide-angle x-ray diffraction (WAXD), dynamic mechanical, and stress-strain testing. The materials studied varied in hard-segment type [4,4′-diphenylmethane diisocyanate/butanediol (MDI/BD) or 4,4′-dicyclohexyl methane diisocyanate/butanediol (H₁₂MDI/BD)], soft-segment molecular weight (830 or 2000 MW polycaprolactone), hard-segment content (23–77% by weight), and thermal history. The materials with aromatic (MDI/BD) hard segments had semicrystalline hard-segment domains, while the materials with aliphatic (H₁₂MDI/BD) hard segment had mostly amorphous domains. Materials with the shorter polycaprolactone soft segment (830 MW) exhibited thermal and mechanical behavior which indicated a considerable degree of hard- and soft-segment compatibility. The materials which contained a 2000-MW polycaprolactone soft segment exhibited better-defined microphase separation. SAXS was used to characterize the microphase structure of each system. The effects of hard-segment content and soft-segment molecular weight were similar for the aromatic (MDI) and aliphatic (H₁₂MDI) hard-segment-based block copolymers. Changing the hard segment from aromatic to aliphatic gave materials with larger interfacial area and slightly higher tensile strength. A range of morphologies between isolated hard domains in a rubbery matrix and isolated rubbery domains in a hard matrix was observed.     

Preparation and characterization of waterborne polyurethane/attapulgite nanocomposites

In this paper, waterbrone polyurethane (WPU)/attapulgite (AT) nanocomposites have been prepared by direct emulsion blending. The WPU was synthesized from poly(tetramethylene glycol), 4,4-diphenylmethane diisocyanate, dimethylol butanic acid, and neutralized by triethylamine. SEM examination of fractured surfaces showed that AT particles were irregularly dispersed in the WPU matrix. FTIR analysis suggested no major chemical structural changed in the presence of a small amount of AT. DMA results showed that the storage modulus of WPU/AT nanocomposites was increased and the glass transition temperatures of both soft and hard segments shifted to higher temperature compared to the pristine WPU. Thermal resistance of the samples measured by TGA was improved with the addition of AT. The mechanical properties of the nanocomposites, examined by tensile tests, showed higher tensile strength and elongation at break than that of the pristine WPU.     

Effects of compatibility of poly(l‐lactic‐acid) and thermoplastic polyurethane on mechanical property of blend fiber

Blending poly(l ‐lactic‐acid) (PLLA) and thermoplastic polyurethane (TPU) has been performed in an effort to toughen PLLA without compromising its biodegradability and biocompatibility. The mixing enthalpy calculation of PLLA and TPU predicted that the blend was a thermodynamic miscible system. The viscoelastic properties and phase morphologies of PLLA/TPU blends were investigated further by dynamic mechanical analysis and scanning electron microscopy. It was found that the blend was a partially miscible system. The dynamic mechanical analysis showed that T_g of PLLA and TPU shifted toward with TPU content increasing. Scanning electron microscopy photos showed that the morphologies of the blends changed from a sea island structure to a bicontinuous structure as an increment in TPU content, which suggested that the miscibility of PLLA and TPU was enhanced when the TPU increased. PLLA/TPU blend fibers were fabricated. With the TPU content increasing from 0 wt% to 30 wt%, the tensile strength and initial modulus of blend fibers decreased first then increased, while elongation at break and fracture work gradually increased. The change of tensile properties indicated the toughening effects of TPU on PLLA fibers, also suggested that the formation of blend fibers was influenced by the blend rheological behavior other than the compatibility. Copyright © 2014 John Wiley & Sons, Ltd.     

聚氯乙烯/聚丙烯酸丁酯/白泥纳米复合材料的研究

通过多步交换反应及扩散－聚合的方法,使聚丙烯酸丁酯被嵌入到改性层状结构的白泥层间,得到白泥－聚丙烯酸丁酯纳米复合物的微米粒子;然后将聚氯乙烯与白泥－聚丙烯酸丁酯进行熔融共混,制得具有一一特性的有机－无机纳米复合材料,并对复合材料的缺口冲击强度及动态力学性能进行了研究,结果表明,白泥－聚丙烯酸酯含量为5．0wt％时,复合材料的力学性能最佳;聚氯乙烯与高含量的白泥－聚丙烯酸丁酯（分别为25．0wt%和50．0wt%）形成的复合材料,在聚氯乙烯的玻璃化转变温度之前,储能模量出现先降低而后增加的过程。     

Interactions in Nanosilica-Polyurethane Composites Evidenced by Plate-Plate Rheology and DMTA

Fumed nanosilicas with different degree of silanization were used to obtain nanosilica-polyurethane (TPU) composites to modify their rheological and mechanical properties. The higher the silanol content of the nanosilica, the higher the storage modulus and the thermal stability of the silica-TPU composite. DMTA experiments confirmed that the TPU-silica interactions increased by increasing the silanol content of the nanosilica.     

Preparation and characterization of vinylidene chloride‐co‐vinyl chloride copolymer/fluorinated synthetic mica nanocomposites I thermal and mechanical properties studies

Poly(vinylidene chloride‐co‐vinylchloride)/organically modified fluorinated synthetic mica (MEE) (VDC‐VC/MEE) nanocomposites were prepared by melt blending of VDC‐VC copolymer with MEE, in the presence of dioctyl phthalate (DOP) which acted as a plasticizer and a cointercalating agent. The nanostructure, thermal, and dynamic mechanical properties of the VDC‐VC/MEE nanocomposites were studied by wide angle X‐ray diffractometer (WAXD), scanning electron microscope (SEM), transmission electron microscope (TEM), thermogravimetric analyzer (TGA), and dynamic mechanical analyzer (DMA). It was found that partially intercalated and partially exfoliated structures coexisted in VDC‐VC/MEE nanocomposities. Below 8 wt % MEE content, the intercalation effect of nanocomposites decreased with increasing the MEE content. Under a nitrogen atmosphere, VDC‐VC/MEE nanocomposites exhibited a single step thermal degradation behavior. The nanostructure of VDC‐VC/MEE can effectively prevent volatile gases from being released, and thus enhances its thermal stability. The thermal stability of VDC‐VC/MEE nanocomposites is strongly related to the morphology of nanocomposites and the degraded composites structure. DMA revealed a significant improvement in the storage modulus within the testing temperature range. The increase in storage modulus depends on the MEE content, which is attributed to the dispersed phase morphology. The glass transition temperature of VDC‐VC/MEE nanocomposites is affected by the chain mobility in the nanocomposites rather than the aggregative morphology. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1214–1225, 2008     

Polyether-polyester and HMDI Based Polyurethanes:Effect of PLLA Content on Structure and Property

Thermoplastic poly(ether-ester-urethane)s were synthesized from poly(L-lactide) diols (PLLA diols),polytetrahydrofuran diol(PTMG diols),4,4'-dicyclohexylmetlhane diisocyanate (HMDI),and 1,4-butanediol (BDO) by a two-step reaction,and the morphology and property of the resultant TPU could be adjusted by varying the PLLA contents.The soft segment was composed of PLLA and PTMG diols.By controlling the percentage of PLLA in the soft segment,the glass transition temperature and mechanical properties of the polyurethanes could be regulated.Based on the FTIR spectrum,we found that two kinds of hydrogen bonding existed individually in soft matrix and hard domain.The hydrogen bonding in soft matrix was unstable,which could be destroyed during elongation.With in situ stretching WAXS and SAXS experiments,we found that the PLLA crystal was destroyed and the PLLA domain oriented along the stretch direction.Finally,we proposed a schematic model to illustrate the microstructures of these elastomers before and after stretch.     

TEMPERATURE EFFECTED STRUCTURAL TRANSITIONS IN POLYURETHANES SATURATED WITH SOLVENTS STUDIED BY SAXS SYNCHROTRON METHOD

ABSTRACT

A set of segmented polyurethanes (PU) differing in the hard-segment structure was saturated with solvents and after the equilibrium saturation was reached, put to temperature-dependent SAXS investigations. The time-resolved mode of SAXS measurements with a linear increase of temperature from ?70°C to +70°C, i.e., within the temperature range between T_g of soft and hard segments, was applied. The order-order transition leading to a greater degree of order was found at higher temperatures for almost all systems investigated. Some of the PUs exhibit two kinds of microphase separated domains. The results obtained are discussed with respect to the mean-field theory of copolymers and Koberstein and Stein model for hard microdomain structure in PUs, and correlated with temperature dependence of membrane permeability in pervaporation process.     

Microstructure and properties of polyurethanes derived from castor oil

The goal of this work was the synthesis of novel segmented polyurethanes with a high percentage of components derived from renewable sources. The soft segment was a polyol derived from castor oil and the hard segment structure was varied by means of different chain extenders, petrochemical-based 1,4-butanediol (BD) and corn sugar-based 1,3-propanediol (PD). The synthesis was carried out in bulk and without catalyst via a two-step polymerization varying hard segment ratio. Physico-chemical, mechanical and morphological characterization was performed by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), atomic force microscopy (AFM), mechanical testing and termogravimetric analysis (TGA). Properties have been discussed from the viewpoint of hard/soft microdomain phase separation and also the hard segment nature and formed structure. An increase in hard segment content was accompanied by an increase in hard domain order, crystallinity, and stiffness. The hard segment structures, in addition to the elastic nature of soft segment, provide enough physical crosslink sites to impart properties ranging from elastomeric to rigid behaviour with the increase of hard segment content. Polyurethanes synthesized from bio-based chain extender showed a slightly lower crystallinity in the hard segment structure than that synthesized from BD as the chain extender. This lower crystallinity avoids strength concentrations at the soft/crystalline hard segment interface, thus improving the mechanical properties at high hard segment content. The slightly higher thermal stability observed for BD based polyurethanes is related with their more packed structures and crystallinity observed in the hard segment structure.     

Biomimetic chitosan‐treated clay–elastomer composites with water‐responsive mechanically dynamic properties

Biomimetic hydrophobic polymer composites with water‐responsive mechanically adaptive behaviors were successfully prepared using hydrophilic chitosan‐treated clay (chi‐clay) as the water‐activated, pH‐sensitive and reinforcing phase and elastomeric thermoplastic polyurethane (TPU) as the matrix. Structural characterization, swelling tests in three representative solutions with different pH values, and dynamic mechanical analysis under wet and dry conditions were performed on the resultant chi‐clay‐TPU composites with varying chi‐clay contents. The results showed that the equilibrium swelling degree of TPU increased significantly with increasing chi‐clay content and that water transportation in all the composites followed Fickian diffusion mechanism. The presence of chi‐clay provided remarkable enhancement of the storage modulus of TPU and offered water‐responsive changes of the modulus. Such changes increased with chi‐clay content and were pH‐sensitive, with the acidic condition rendering the largest modulus difference. These water‐responsive polymer composites may find potential applications in biomedical fields and beyond. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 55–62