Preparation and properties of transparent thermoplastic segmented polyurethanes derived from different polyols

Various segmented polyurethanes with a hard segment content of about 50 wt% were prepared from 4,4′‐diphenylmethane diisocyanate (MDI), a poly(tetramethylene adipate) glycol with an Mn of 2000, and various combinations of aliphatic diols as chain extenders by a one‐shot, hand‐cast bulk polymerization method. The segmented polyurethanes were characterized by gel permeation chromatography (GPC), ultraviolet‐visible spectrometry, differential scanning calorimetry (DSC), and X‐ray diffraction, and their tensile properties and Shore A hardness were determined. The DSC data indicate rather good miscibility between the soft segments and the hard segments that accounts for the good transparency. The incorporation of a small amount of a second chain extender into MDI and 1‐4‐butanediol‐based segmented polyurethanes decreases the crystallinity of the hard segment, thus enhancing the transparency. A segmented polyurethane derived from MDI and 1,6‐hexanediol exhibits better transparency due to its relatively lower crystallinity of the hard segment. © 2007 Wiley Periodicals, Inc. Adv Polym Techn 26:33–40, 2007; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/adv.20086

A series of polyurethane networks were prepared from MDI (4,41-diphenyl methane diisocyanate), ethylene glycol and a polyoxyethylene-tipped polyoxypropylene triol. The phase separation and phase inversion phenomena of these polyurethane networks were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and measurement of their tensile properties. The DSC and DMA data indicate that the segmented copolyurethanes possess a two-phase morphology comprising soft and hard segments. It can be found from DSC data that the polyether soft segments exhibit a Tg (glass transition temperature) of −60 °C, and the aromatic hard segments display a Tg of about 128 °C. Two Tgs corresponding to the comprised segments can also be found by DMA for some segmented polyurethanes. Varying the content of aromatic hard segments over the range from 0 to 80 wt% changes the material behavior from a soft rubber through a highly extensible elastomer to a brittle semi-ductile glassy material. Based on the property-composition plots, phase inversion appears to occur at a hard segment content of about 50 wt%.

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

Effect of intersegmental interactions on the morphology of segmented polyurethanes with mixed soft segments: A coarse-grained simulation study

New thermoplastic nonsegmented thiopolyurethanes were obtained from the low-melting aliphatic–aromatic thiodiols 4,4′-bis(2-hydroxyethylthiomethyl)benzophenone (BHEB), 4,4′-bis(3-hydroxypropylthiomethyl)benzophenone (BHPB), and 4,4′-bis(6-hydroxyhexylthiomethyl)benzenophenone(BHHB) as well as hexamethylene diisocyanate (HDI), both by melt and solution polymerization with dibutyltin dilaurate as the catalyst. The effect of various solvents on molecular-weight values was examined. The polymers with the highest reduced viscosities (0.63–0.88 dL/g) were obtained when the polymerization was carried out in a solution of tetrachloroethane, N,N-dimethylacetamide, and N,N-dimethylacetamide or N,N-dimethylformamide for BHEB-, BHPB-, and BHHB-derived polyurethanes, respectively. These polymers with a partially crystalline structure showed glass-transition temperatures (Tg) in the range of −1 to 39 °C, melting temperatures (Tm) in the range of 107 to 124 °C, and thermal stabilities up to 230 to 240 °C. The BHEB-derived polyurethane is a low-elasticity material with high tensile strength (ca. 50 MPa), whereas the BHPB- and BHHB-derived polyurethanes are more elastic, showing yield stress at approximately 16 MPa. We also obtained segmented polyurethanes by using BHHB, HDI, and 20 to 80 mol % poly(oxytetramethylene) glycol (PTMG) of M̄n = 1000 as the soft segment. These are high-molecular thermoplastic elastomers that show a partially crystalline structure. Thermal properties were investigated by thermogravimetric analysis and differential scanning calorimetry. The increase in PTMG content decreases the definite Tg and increases the solubility of the polymers. These segmented polyurethanes exhibit the definite Tg (−67 to −62 °C) nearly independent of the hard-segment content up to approximately 50 wt %, indicating the existence of mainly phase-separated soft and hard segments. Shore A/D hardness and tensile properties were also determined. As the PTMG content increases, the hardness, modulus of elasticity, and tensile strength decrease, whereas elongation at break increases. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 4140–4150, 1999

Novel segmented thermoplastic polyurethane (TPU) copolymers were synthesized using two-step solventless bulk polymerization. 4,4'-methylenediphenyl diisocyanate (MDI) and 1,4-Butanediol (BDO) were used to form hard segment of TPU and α,ω-dihydroxy-[poly(propyleneoxide)-poly (dimethylsiloxane)-poly(propyleneoxide)] (α,ω-dihydroxy-(PPO-PDMS-PPO)) was used to form soft segment of TPU, where the molar ratio of the –N=C=O/OH was 1.02 and the hard segment weight percentage was 30%. A series of TPUs were characterized by fourier transform infrared spectroscopy (FT-IR). The investigation of triblock oligomer's PPO molecular weight impact on the derived TPU's mechanical properties, thermal performance, surface water repellency and morphology performance was carried by Instron material tester, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), water contact angles (WCA), scanning electron microscope and energy dispersive X-ray spectroscopy (SEM-EDX) and wide angle X-ray diffraction (WAXD), respectively. FT-IR confirmed α,ω-dihydroxy-(PPO-PDMS-PPO) well cooperating into urethane structure and analyzed hydrogen bonding between N-H group with hard segment C=O group and N-H group with soft segment C-O-C group. DSC and WAXD results showed α,ω-dihydroxy-(PPO-PDMS-PPO) segments crystallization. SEM-EDX results showed that the presence of a spherulitic morphology, which arose from the crystallization of the PPO segments. The thermal properties measured by TGA and DSC were slightly affected by molecular weight of PPO and microphase separation. The weight loss of TPUs started between 294°C and 300°C, and Tg was in the range of -70°C to -107°C. TPU copolymers' surface hydrophobicity property was excellent with WCA range of 95° to 112°. TPU-3 with 1000 molecular weight PPO has the optimized mechanical properties with tensile strength 16.4 MPa and the modulus at 100% elongation 6.2 MPa and elongation 398%.

The phase behavior of a set of high hard block content (50% to 100% hard segment by weight) linear thermoplastic polyurethanes has been investigated mainly via differential scanning calorimetry (DSC). The soft segment was based on a polypropylene oxide polyol end-capped with ethylene oxide and the hard segment on a 4,4‘-methylene diphenyldiisocyanate (MDI) chain extended by 2-methyl-1,3-propanediol (MP-Diol). By investigating thermal behavior of the samples, it has been possible to assign the observed high-temperature endothermic transitions to the disruption of an ordered structure appearing in the hard phase under certain annealing conditions and to the microphase mixing of the soft and hard segments. These results suggest a two-step melting process: (1) melting of the ordered structure present in the hard phase; (2) microphase mixing of the soft and hard segments. Wide-angle X-ray scattering experiments gave further support to this assignment. In addition, investigation of the melt-quenched samples ha...

Microstructure and properties of polyurethanes derived from castor oil

The author proposed the third concept in the reinforcement of elastomers for segmented polyurethane with the direct observation by microscopic techniques. The structure in segmented polyurethane elastomers fundamentally consists of three domains of different sizes, two kinds of micro-domain, cluster of 100 nm in diameter and spherulite of µm order. Of the micro-domains, one is the hard-segment (HS)-rich micro-domain consisting of hard segment (4 nm thickness) and soft segment (7 nm) and the other is the hard-segment (HS)-poor micro-domain of hard segment (4 nm) and soft segment (15∼20 nm). The HS cluster is constructed by the assembly of the HS-rich micro-domains. The spherulite seems to be composed of the dense packing of the HS cluster, growing up radially or circularly from the center to the outside surface. From physical and mechanical points of view, we can regard the above structures in the segmented polyurethane as bi-continuous structure of the HS clusters whose volume fraction is 0.2, and the matrix phase consisting of the HS-poor domains (0.8 in the volume fraction). The characteristic stress-strain relation of the segmented polyurethane is generated by the combination of both the continuous structures. That is, the initial very high stress (modulus) at small extension and the following gradual increase in stress at medium extension mainly result from the extension and the sliding of the HS cluster, respectively. The very large stress-upturn at large extension and the final great tensile strength are generated by the contribution of both the continuous structures. Thus, the third reinforcement is achieved by the formation of bicontinuous structure of the hard and strong cluster and also the strong matrix phase, in which the absolute structural defects seem not to be included.

Polyurethanes having shape memory effects

The role of hard and soft segments in the thermal and mechanical properties of non-isocyanate polyurethanes produced via polycondensation reaction

Segmented polyurethanes (SPUs), as a class of elastomers, display a large degree of toughness and elasticity. To modify the mechanical properties of an SPU matrix, high elastic modulus fillers may be added. In this work we systematically correlated the relationship between silicon dioxide (silica) particles size and functionality on the resulting mechanical properties of the SPU-silica composites. SPU was synthesized of poly(tetramethylene glycol) soft segments, which contribute to the extensibility of the SPU, and hexamethylene diisocyanate-butanediol hard segments (HS), which contribute to the SPUs modulus and toughness. Blends of SPU with 25 wt% HS and silica nanoparticles, micrometer-sized silica particles and methyl modified silica nanoparticles were prepared. SPU-silica particle composites were also evaluated when silica particles were covalently attached to the SPU matrix. The HS concentration of in situ SPU-silica particle composites was also increased to 35 wt% and 45 wt%. Blended composites displayed poor mechanical properties due to a weak interaction of silica particles with the SPU matrix and poor control over silica particle location within the composite. Covalently attached silica particles were relegated to HS-rich domains, introduced an astonishing 10-fold increase in strain-at-break (from 200 % for the pristine SPU to >2100 % with addition of 0.5 wt% and 1.0 wt% silica nanoparticles concentrations). A decrease in elastic modulus was observed due to disruption of the HS crystallinity. In situ SPU-amine modified silica nanoparticle composites displayed the greatest increase in strain-at-break over the largest range of silica nanoparticle concentrations. The variation in properties for SPU-amine modified silica nanoparticles composites was due to a difference in reactivity and nature of the amine functional silica nanoparticles compared to that of the unmodified silica nanoparticles. Micrometer-sized silica particles and di- and octa-functional polyhedral oligomeric silsesquioxane (POSS) molecules were added to an SPU matrix in situ. Mechanical reinforcement was not observed for di-functional POSS, which did not act as a cross-linking agent. We have established a correlation between silica particle placement within an SPU matrix and the structure-properties relationship of the final polymer composites. A molecular level representation of the SPU chains near the silica fillers was proposed for the SPU-silica filler composites. A cause for the extraordinary increase in strain-at-break with in situ addition of the silica fillers at low weight concentrations is proposed.

Chemical synthesis and physical blending methods were used to prepare thermal sensitive polyurethanes (TSPU) with single or double thermal switches. In the design of the formula, polycaprolactone diol (PCL) with a molecular weight 10,000 and 4,000 and polytetramethylene glycol (PTMG) with a molecular weight 3,000 and 2,000 were used as the soft segments. The effects of the crystallinity and compatibility of the soft segments on the phase transition temperatures of the soft segments of TSPU (defined as switch temperature, Ts) were investigated in detail. To examine the thermal sensitivity of the thermal switch, water vapor permeability (WVP) experiments were performed to investigate the mass transport as a function of temperature. Differential scanning calorimetry (DSC) indicated that all the original TSPUs had a phase separated structure that was independent of the phase transition temperature of the soft and hard segments. The Ts values are determined mostly by the melting temperatures of the soft segments. On the other hand, for their blends, the Ts values are determined by the compatibility of the soft segments and the blending weight ratio. The blends of the PCL-based TSPUs showed good compatibility and single Ts due to the similar structure of the soft segments (just a difference in molecular weight), whereas for the PCL-based and PTMG-based TSPUs (the molecular structure is very different) blends, the Ts two independent values and blending weight ratio-dependent features due to the difference in the structure of the soft segments. Water vapor permeability analysis revealed the mass transport showed switching features to thermal stimuli, i.e. when the temperature reached the Ts, the WVPs of membranes showed rapid changes. On the other hand, the sensitivity of the thermal switch characterized by WVP improvement showed a dependence on the degree of crystallinity of the soft segments, i.e. well-organized soft segment structure is beneficial for improving the thermal sensitivity. Overall, TSPU membranes with a single Ts and different thermal sensitivity can be prepared using different crystalline poly-diols as the soft segments and blending two types of TSPUs with similar soft segments in the molecule structure, whereas TSPU with a double Ts can be achieved easily by blending two types of TSPUs with different soft segments.

Studies on thermoplastic polyurethanes based on new diphenylethane-derivative diols. II. Synthesis and characterization of segmented polyurethanes from HDI and MDI

Morphology and properties of thermoplastic polyurethanes with dangling chains in ricinoleate-based soft segments