Segmented block copolymers of natural rubber and propylene glycol-toluene diisocyanate oligomers

Segmented block copolymers were synthesized from hydroxyl terminated liquid natural rubber (HTNR) and polyurethane oligomers based on 1,2-propylene glycol and toluene diisocyanate (TDI) by one-shot and two-shot processes in solution. They were completely phase segregated. Structural features were characterized by infrared and nuclear magnetic resonance spectroscopies. The two-phase morphology was deducted from thermal analysis and dynamic mechanical analysis (DMA). The soft segment glass transition temperature was about ?64°C and the hard segment glass transition was between 70°C and 100°C depending on the polyurethane content. The two-phase morphology was corroborated by a two-stage thermal decomposition of the products. The morphology consisted of a heterogeneous dispersion of beads in a continuous matrix. The large size and the nature of the beads suggest that they are independent of the block copolymer structure and are formed by the agglomeration of the polyurethane homopolymers, which remain unbonded to the rubber chains during chain extension. At lower hard segment contents the materials behaved like quasi-elastomers, and at higher hard segment contents, they were like tough plastics. At intermediate compositions they behaved as rigid elastomers. Variations in hardness and tear strength were consistent with this behavior.     

Block copolymers of polycarbonates with several hydroxy-terminated elastomers to yield thermoplastic elastomers for higher service temperature

The synthesis of block copolymers and the study of their morphology were undertaken to find improved thermoplastic rubbers for service at elevated temperatures. The basis was the extraordinary properties possessed by ABA-type block copolymers in which the terminal blocks are polystyrene and the central block is either polyisoprene or polybutadiene. In these systems it has been well established that the unusual properties are a result of domain formation in which the hard and the soft blocks aggregate separately into distinct phases. The hard segment is thought to act both as a crosslink and as a filler. Block copolymers were synthesized with different soft and hard segments. The effects of these segments and of their properties on the morphology and the stress-strain properties of the block copolymers were measured and evaluated. Electron microscopy and birefringence were used to determine the morphology. It was found that the glass transition temperatures of the segments, the bulk of the monomer unit in the glassy segment, and the morphology determined the strength of the material. Some of the materials prepared have tensile strengths of 0.1 kg/cm² or more at temperatures in excess of 180°C and therefore appear promising as elastomers for service at elevated temperatures.     

Thermal and mechanical properties of linear segmented polyurethanes with butadiene soft segments

A series of segmented polyurethanes based on a hydroxyl terminated polybutadiene soft segment (HTPBD) have been prepared with varying hard segment content between 20 and 60 weight percent. These materials are linear and amorphous and have no potential for hydrogen bonding between the “hard” and “soft” segments. The existence of two-phase morphology was deduced from dynamic mechanical behavior and thermal analysis. Both techniques showed a soft segment glass transition temperature, T_gs, at ?56°C and hard segment transitions between 20 and 100°C, depending on the urethane content. The low value of T_g, only 8° higher than the T_g of free HTPBD and independent of hard segment concentration indicated nearly complete phase segregation. Depending on the nature of the continuous and dispersed phases, the urethanes behaved as elastomers below 40 weight percent hard segment or as glasslike materials at higher hard segment contents. The effect of thermal history on transitions of the HTPBDurethanes was also investigated and the results suggest that the absence of hydrogen bonding to the soft segment must account for the extraordinary insensitivity to thermal history in dynamic mechanical, thermal and stress-strain behavior. Comparisons are made to the more common polyurethanes containing polyether and polyester soft segments.     

Ionene segmented block copolymers containing imidazolium cations: Structure-property relationships as a function of hard segment content

Imidazolium ionene segmented block copolymers were synthesized from 1,1′-(1,4-butanediyl)bis(imidazole) and 1,12-dibromododecane hard segments and 2000 g/mol PTMO dibromide soft segments. The polymeric structures were confirmed using ¹H NMR spectroscopy, and resonances associated with methylene spacers from 1,12-dibromododecane became more apparent as the hard segment content increased. TGA revealed thermal stabilities ≥250 °C for all imidazolium ionene segmented block copolymers. These ionene segmented block copolymers containing imidazolium cations showed evidence of microphase separation when the hard segment was 6-38 wt%. The thermal transitions found by DSC and DMA analysis found that the T_g and T_m of the PTMO segments were comparable to PTMO polymers, namely approximately −80 °C and 22 °C, respectively. In the absence of PTMO soft segments the T_g increased to 27 °C The crystallinity of the PTMO segments was further evidence of microphase separation and was particularly evident at 6, 9 and 20 wt% hard segment, as indicated in X-ray scattering. The periodicity of the microphase separation was well-defined at 20 and 38 wt% hard segment and found to be approximately 10.5 and 13.0 nm, respectively, for these ionenes wherein the PTMO soft segment is 2000 g/mol. Finally, the 38 and 100 wt% hard segment ionenes exhibited scattering from correlations within the hard segment on a length scale of approximately 2-2.3 nm. These new materials present structure on a variety of length scales and thereby provide various routes to controlling mechanical and transport properties.     

The formation, structure and properties of urethane-diacetylene copolymers as optical strain-sensitive surface coatings

Segmented copolyurethanes comprising ductile polyether-urethane (PE-U) and rigid diacetylene-urethane (DA-U) phases, have been prepared via a one-shot, bulk polymerisation process. Subsequent thermal treatment (100 °C/40 h) of the as-prepared linear copolymers effected solid-state topochemical reactions within the DA-U phase, producing crosslinked and intensely coloured materials. The cross-polymerised copolymers had values of T_g between −32°C and 70°C depending on composition, and were elastically isotropic with tensile moduli and strengths ranging, respectively, from 20–1800 MPa, and 8–67 MPa. The copolymers exhibited optical properties similar to those of polydiacetylene single crystals, and produced intense resonance Raman spectra. In particular, the CC triple bond stretching Raman band at ˜ 2080 cm⁻¹ was well defined and shifted to lower frequency under the application of tensile stress/strain. The copolyurethanes may be readily applied as surface coatings to various substrates, and their use as optically stress/strain-sensitive materials (optical strain sensors) is demonstrated.     

Structure and mechanical properties of thermoplastic polyurethane,based on hyperbranched polyesters

A series of hyperbranched polyurethane (HB‐PU) were synthesized using hyperbranched polyester as a precursor. Morphology of these HB‐PU films was investigated using atomic force microscopy and wide‐angle X‐ray diffraction; it's molecular dynamics was studied by dynamic mechanical analysis. FTIR studies showed that hard segments get more aggregated to form domains in the HB‐PU block copolymer as hard segment content increases. Such domain formation has a significant influence on the mechanical and thermomechanical properties of HB‐PU, such as maximum stress and elongation at break. Especially, maximum stress and elongation at break increased significantly at 25 wt % of hard segment content, and the highest loss tangent was observed at the same composition. Heat of crystallization as measured by differential scanning calorimetry is also dependent on the hard segment content, and the control of hard segment content in PU block copolymers is very important in determining their physical properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5266–5273, 2006     

Structure–property relationships of poly(urethane urea)s with ultra‐low monol content poly(propylene glycol) soft segments. I. Influence of soft segment molecular weight and hard segment content

Structure–property relationships in poly(urethane urea)s synthesized with ultra‐low monol content poly(propylene glycol) soft segments were investigated as soft segment molecular weight (2000, 4000, and 8000 g/mol) and hard segment content (6.3 and 9.0 wt %) were varied. Morphological features such as interdomain spacing and interphase thickness were quantified and revealed with small‐angle X‐ray scattering (SAXS) and atomic force microscopy (AFM). The thermal and mechanical behavior was assessed with a dynamic mechanical analyzer (DMA) and by differential scanning calorimetry (DSC) and stress‐strain tests. Hard segment content, over the limited range studied, had little effect on the morphology and soft segment thermal and mechanical properties. The molecular weight of the soft segments had considerably more influence on the morphology and mechanical properties. Increasing soft segment molecular weight resulted in greater interdomain spacings, as shown by SAXS, and a noticeable change in the structure, as shown by AFM. Additionally, as soft segment molecular weight decreased the soft segment glass transition broadened and rose to higher temperatures. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 229–243, 2002; DOI 10.1002/app.10168     

热塑性聚酰胺酯的制备及结构性能关系

聚酰胺酯是一种由两种链段（硬、软段）组成的嵌段共聚物。其玻璃化转变温度（Ｔｇ），熔点（Ｔｍ），动态模量（Ｇ′）等与硬、软段的组成，含量紧密相关。硬段的链长分布影响其结晶结构从而影响其机械力学性能。先制备具有均一链长的含有酰胺键的硬段单体，然后与二元醇进行缩聚反应生成酯键是制备性能良好的聚酰胺酯的较好途径。     

Influence of ionic charge placement on performance of poly(ethylene glycol)-based sulfonated polyurethanes

Poly(ethylene glycol) (PEG)-based sulfonated polyurethanes bearing either sulfonated soft segments (SSSPU) or sulfonated hard segments (SHSPU) were synthesized using sulfonated monomers. Differential scanning calorimetry (DSC) revealed that sulfonate anions either in the soft segments or hard segments both increased the glass transition temperatures (T_g’s) of the soft segments and suppressed their crystallization. Moreover, dynamic mechanical analysis (DMA) and tensile analysis demonstrated that SSSPU possessed a higher modulus and tensile strength relative to SHSPU. Fourier transform infrared (FTIR) spectroscopy revealed that hydrogen bonding interactions in SHSPU were suppressed compared to SSSPU and noncharged PU. This observation suggested a high level of phase-mixing for SHSPU. In addition, atomic force microscopy (AFM) phase images revealed that both SSSPU and noncharged PU formed well-defined microphase-separated morphologies, where the hard segments phase-separated into needle-like hard domains at the nanoscale. However, SHSPU showed a phase-mixed morphology, which was attributed to increased compatibility of polar PEG soft segments with sulfonated ionic hard segments and disruption of hydrogen bonds in the hard segment. The phase-mixed morphology of SHSPU was further demonstrated using small angle X-ray scattering (SAXS), which showed a featureless X-ray scattering profile. In contrast, SAXS profiles of SSSPU and noncharged PU demonstrated microphase-separated morphologies. Moreover, SSSPU also displayed a broad ionomer peak ranging in q = 1–2 nm^?1, which resulted from the sodium sulfonate ion pair association in the polar PEG soft phase. Morphologies of sulfonated polyurethanes correlated well with thermal and mechanical properties.     

含能聚氨酯热塑性黏合剂GAP/PBAMO的性能

以聚双叠氮甲基氧杂环丁烷(PBAMO)为硬段,聚缩水甘油醚(GAP)为软段,采用一锅法扩链合成了含能聚氨酯黏合剂(GAP/PBAMO).实验中合成了不同硬段含量的黏合剂,并采用FT-IR、NMR、GPC、XRD、DSC和SEM等对其结构和性能进行了表征.结果表明,硬段质量分数为66.7%时,该热塑性黏合剂具有较好的耐热...     

Synthesis and characterization of block copolymers based on natural rubber and polypropylene oxide

Segmented block copolymers from different grades of hydroxyl terminated liquid natural rubber (HTNR) (M _n 3000, 8800, 10,000, and 17,000) and polypropylene oxide (PPO) (M _n 1000, 2000, 3000, and 4000) have been synthesized and characterized by spectral analysis, thermal analysis, scanning electron microscopy (SEM), and mechanical testing. The glass transition temperature of NR block was found to be at about ?64°C, which is independent of the PPO whose transition is around 15°C. The thermogravimetric analysis (TGA) shows that the thermal degradation of the samples proceeded in two steps characteristic of the immiscible components. The inability of PPO segments to provide physical crosslinking and the subsequent formation of hard domains is reflected in the low tensile properties and tear properties. The amorphous nature of the PPO phase and its immiscibility with NR phase are evidenced by the SEM studies. The effect of molecular weight of PPO as well as HTNR on the properties of the block copolymers has also been discussed. © 2006 Wiley Periodicals, Inc. JAppl Polym Sci 103: 909–916, 2007     

Photoactivity of anatase–rutile TiO2 nanocrystalline mixtures obtained by heat treatment of homogeneously precipitated anatase

Nanosized titanium dioxide photocatalysts with varying amount of anatase and rutile phases have been synthesized. Homogeneous precipitation of aqueous solutions containing TiOSO₄ with urea was used to prepare porous spherical clusters of anatase TiO_2. Photoactive titania powders with variable amount of anatase and rutile phases were prepared by heating of pure anatase in the temperatutre range 800–1150 °C. The structure evolution during heating of the starting anatase powders was studied by XRD analysis in overall temperature range of phase transformation. The morphology and microstucture characteristics were also obtained by HRTEM, BET and BJH. The spherical particle morphology of TiO₂ mixtures determined by SEM was stable in air up to 900 °C. The photocatalytic activity of the sample titania TIT85/825 heated to 825 °C in air, contained 77.4% anatase and 22.6% rutile was higher than that nanocrystalline anatase powder. Titania sample TIT85/825 reveals the highest catalytic activity during the photocatalyzed degradation of 4-chlorophenol in aqueous suspension.     

Effect of the degree of soft and hard segment ordering on the morphology and mechanical behavior of semicrystalline segmented polyurethanes

The hierarchical microstructure responsible for the unique energy-absorbing properties of natural materials, like native spider silk and wood, motivated the development of segmented polyurethanes with soft segments containing multiple levels of order. As a first step in correlating the effects of crystallinity in the soft segment phase to the hard segment phase, we chose to examine the morphology and mechanical behavior of polyurethanes containing polyether soft blocks with varying tendencies to crystallize and phase segregate and the evolution of the microstructure with deformation. A series of high molecular weight polyurethanes containing poly(ethylene oxide) (PEO) (1000 and 4600 g/mol) and poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) (1900 g/mol) soft segments with varying hard segment content were synthesized using a two-step solution polymerization method. The presence of soft segment crystallinity (PEO 1000 g/mol) was shown to improve the storage modulus of the segmented polyurethanes below the T_m of the soft block and to enhance toughness compared to the PEO-PPO-PEO soft segment polyurethanes. We postulate that this enhancement in mechanical behavior is the result of crystalline soft regions that serve as an additional load-bearing component during deformation. Morphological characterization also revealed that the microstructure of the segmented polyurethanes shifts from soft segment continuous to interconnected and/or hard domain continuous with increasing hard segment size, resulting in diminished ultimate elongation, but enhanced initial moduli and tensile strengths. Tuning the soft segment phase crystallinity may ultimately lead to tougher polyurethane fibers.     

The effect of chain extenders structure on properties of new polyurethane elastomers

Two series of polyurethane elastomers were synthesized to investigate what effect does the incorporation of various new chain extenders have on the mechanical and thermal properties of polyurethane elastomers. The polyurethane soft segments were based on poly(ε-caprolactone) polyol. The hard segment was based on 1,6-hexamethylene diisocyanate in combination with 2,5-dimethyl-3-hexine-2,5-diol (DHD), hexaethylene glycol, glycerin, or castor oil. The results showed that the degradation rate and mechanical properties of the final products can be controlled through the structure of diol chain extenders or/and hard segment cross-linking present in the polyurethane elastomers. The DHD-based polyurethane displayed a relatively low glass transition temperature of −57 °C and a tensile strength of 11–14 MPa and elongation at break of 600–700%. These kinds of materials have potential application in many domains.     

Influence of morphology on the properties of segmented block copolymers

A comparison was carried out regarding the structure and properties of segmented block copolymers with either non-crystallisable or crystallisable rigid segments. The flexible segment in the block copolymers was a linear poly(propylene oxide) end capped with poly(ethylene oxide), with a segment molecular weight of 2300 g/mol. The rigid segments were either non-crystallisable or monodisperse crystallisable polyamides of varying lengths. The morphologies were studied by TEM and AFM, the thermal mechanical properties by DMA and the elastic properties by compression set and tensile measurements. A direct comparison was made of segmented block copolymers with either liquid-liquid demixed or crystallised structures. The crystallised amide segments were more efficient in increasing the modulus and improving the elastic properties than the non-crystallisable ones. The copolymers with crystallised structures were transparent, had a low glass transition temperature of the polyether phase and a modulus that was independent of temperature between T_g and T_m. These copolymers also displayed a very low loss factor (tan δ), suggesting excellent dynamic properties. The hard phase in segmented block copolymers should thus preferably be crystalline.     

A study on synthesized hydroxylapatite bioceramics

Sodium-doped hydroxylapatite powder was synthesized by the wet chemical method. Powder behavior, thermal stability, mechanical strength and biocompatibility were investigated.

The synthesized hydroxylapatite powder consisted of needles 1800 Å in width and 260 Å in length. The particle size, specific area (BET) and Ca/P atomic ratio were 0·1–0·3 μm, 29·9 m²/g and 1·62 respectively. A large amount of absorbed water existed in the powder, and evaporated on heating to 1000°C. Differential thermal analysis showed that no phase transformation occurred during heating to 1250°C. After heating at 1250°C for 1 h, the O---H bond was still found in the synthesized powder, by IR spectrophotometry. The optimum sintering condition was heating at 1200°C for 4 and this resulted in 680 MPa compressive strength, 1-1·3 μm mean grain size and 99% T.D.

The synthesized hydroxylapatite showed no cytotoxicity and had excellent tissue compatibility. This powder possesses a high potential for bone implantation.     

Thermomechanical characteristics of calcium aluminate cement and sand tapes prepared by tape casting

The present paper concerns the mechanical characterization of calcium aluminate cement and sand tapes prepared by tape casting, including ultrasonic measurements of Young's modulus at high temperature and evaluation of four point flexural behavior after heat treatments in the range of 20–1400 °C. It is shown that dehydration strongly affects mechanical properties in the 400–900 °C range, but that treatments at temperatures higher than 1200 °C increase both Young's modulus and strength. By correlation with thermal and X-ray diffraction analyses, the evolutions of thermomechanical properties have been related to phase and microstructural changes when heating the material after hydration: conversion of hydrates and dehydration at low temperature, then, crystallization of C–A and C–A–S phases and finally sintering at the highest temperatures. In a last part, it is shown that the reinforcement by glass fibres enhances the mechanical properties, in particular in the temperature range of dehydration, and gives to the material a non-brittle behavior.     

Morphology and mechanical properties of urethane acrylate resin networks

A series of urethane acrylate resins (UARs) having various amounts of hard segment were synthesized from poly(oxypropylene) diols (PPOs) with different molecular weights and characterized. The relationship between the morphologies and mechanical properties of these UAR (UARX‐Y‐Z, in which X means the molecular weight of PPO, Y means the content of hard segment, and Z means the content of comonomer) networks was investigated in detail. It was found that the morphology of the UARX‐Y‐Z network was related to the contents of hard segment and the comonomer (methyl methyacrylate—MMA) as well as the molecular weight of PPOs. The UAR1000‐0‐34 network synthesized from PPO210(M_n = 1000) is a homogeneous system due to the good compatibility between the PPO210 and the MMA segment. TheUAR1000‐0‐60 network exhibits the morphology of partial microphase separation resulting from increasing the length of the MMA segment, so as to decrease the miscibility between the soft and hard segment. For the UAR1000‐30‐34 network having a higher content of the hard segment, the hard segments tend to form domains with the limited short‐range and long‐range order, leading to the formation of the microcrystallites, and therefore it shows higher tensile strength and elastic modulus. For UAR400‐0‐34 network with lower molecular weight PPO204 (M_n=400), a high glass transition temperature and some microcrystallites were observed. Such a network exhibits the best mechanical properties over all UAR networks studied. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1532–1537, 2000     

Segmented block copolymers of natural rubber and bisphenol A–toluene diisocyanate oligomers

Segmented block copolymers were synthesized from hydroxyl‐terminated liquid natural rubber and polyurethane oligomers based on Bisphenol A and toluene diisocyanate by one‐shot and two‐shot processes in solution. Structural features were characterized by infrared and nuclear magnetic resonance spectroscopic analysis. The spectra of the one‐shot materials were identical with those of the two‐shot materials, indicating their chemical identity. The soft segment T_g was well defined and almost invariant around −64°C, but the hard segment T_g varied from 75 to 105°C as the hard segment content increased from 30 to 60 wt %. Two relaxation temperatures were observed for each sample in dynamic mechanical analysis (DMA). These observations and the two‐stage thermal decomposition by random nucleation mechanism, as investigated in thermogravimetric analysis unambiguously confirmed complete phase segregation in these materials. The scanning electron microscopy and optical micrographs showed well‐defined domains dispersed in a matrix, indicating the two‐phase morphology. Systematic changes in hardness and tensile properties with hard segment content were also observed. The samples behaved like soft elastomers at lower hard segment content, toughened plastics at high hard segment content, and rigid elastomers at intermediate compositions. Variations in hardness and tear strength were consistent with this behavior. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 706–721, 1999     

Influence of soft segment composition on phase-separated microstructure of polydimethylsiloxane-based segmented polyurethane copolymers

Segmented polyurethane block copolymers were synthesized using 4,4′-methylenediphenyl diisocyanate (MDI) and 1,4-butanediol (BDO) as hard segments and various soft segments derived from poly(hexamethylene oxide) (PHMO) and poly(dimethylsiloxane) (PDMS)-based macrodiols and mixtures thereof. The microstructure and degrees of phase separation were characterized using a variety of experimental methods. Copolymers synthesized with the PDMS macrodiol and from PDMS/PHMO macrodiol mixtures were found to consist of three phases: a PDMS phase; hard domains; and a mixed phase of PHMO, PDMS ether end group segments and some dissolved hard segments. Two models were used to characterize the small-angle X-ray scattering from these copolymers: pseudo two-phase and core-shell models. Analysis using both methods demonstrates that as the PDMS content in the soft segment mixture increases, the greater the fraction of hard segments involved in hard domains than are dissolved in the mixed phase. Findings from analysis of the carbonyl region of FTIR spectra are also in agreement with greater hard/soft segment demixing in copolymers containing higher PDMS contents.