Effects of aggregation structure on rheological properties of thermoplastic polyurethanes

The effects of the molecular aggregation structure on the rheological properties of thermoplastic polyurethane (TPU) were investigated. The TPU was composed of poly{(tetramethylene adipate)-co-(hexamethylene adipate)} glycol as the soft segments, 4,4′-diphenylmethane diisocyanate and 1,4-butanediol as the hard segments. The TPU sheets prepared by injection molding were annealed at various temperatures from 23 to 120 °C to vary the molecular aggregation structure. Glass transition temperature of the soft segment and melting points of the hard segment domains of the TPUs decreased and increased, respectively, with increasing annealing temperature. The results of DSC, solid-state NMR spectroscopy and dynamic viscoelastic measurements revealed that the degree of micro-phase separation of the TPUs becomes stronger with increasing annealing temperature due to the progress of formation of well-organized hard segment domains. The dynamic temperature sweep experiments for molten TPUs revealed that the temperature at critical gel point, which is defined as the temperature at which the dynamic storage modulus coincides with the loss storage modulus, in the cooling process increased with the progress of aggregation of the hard segments in the TPUs observed in the solid state. The uniaxial elongational viscosity measurements showed that TPUs exhibited an obvious strain hardening behavior with strain rate owing to residual hard segment domains at an operating temperature. It was revealed that the formation of well-organized hard segment domains had a profound effect on the rheological properties of TPUs, in particular on their elongational viscosity.     

Structure,composition, and adhesion properties of thermoplastic polyurethane adhesives

The composition and hard segment content of 13 commercial thermoplastic polyurethane elastomers (TPUs) were obtained using 1H-nuclear magnetic resonance (¹H-NMR). The properties of the TPUs were studied using differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WAXD), dynamic mechanical thermal analysis (DMTA), and contact angle measurements. Solventbased adhesives were prepared by dissolving the TPUs in 2-butanone. Films of the TPUs were obtained by solvent evaporation, and their properties were studied. Adhesion properties were determined from T-peel tests on solvent-wiped poly(vinyl chloride) (PVC)/polyurethane adhesive joints. The influence of the segmented structure on the properties of the TPUs was assessed. The increase in the hard segment content in TPUs favoured the incompatibility (i.e. reduced phase separation) between hard and soft domains. TPUs with a high hard segment content had a low crystallinity, a low wettability, and a high joint strength. The storage and loss moduli obtained using DMTA decreased as the hard segment content in the TPUs increased. Furthermore, the TPUs prepared using ε-polycaprolactone as the macroglycol had a slower crystallization rate than those prepared using the polyadipate of 1,4-butanediol or the polyadipate of 1,6-hexanediol. The increase in the length of the hydrocarbon chain of the macroglycol improved both the rheological and the thermal properties of the TPUs. Finally, TPUs prepared using MDI as the isocyanate showed a higher crystallinity and a higher degree of crosslinking than those prepared using TDI.     

Synthesis and characterization of poly(propylene glycol) polytrioxamide and poly(urea oxamide) segmented copolymers

This report describes the synthesis and characterization of unprecedented poly(propylene glycol) (PPG) polytrioxamide and poly(urea oxamide) (UOx) segmented copolymers containing monodisperse hard segments. Synthesis of the segmented copolymers relied on an efficient two‐step end‐capping sequence, which resulted in novel difunctional oxamic hydrazide‐terminated polyether oligomers. Polymerization with oxalyl chloride or 4,4′‐methylenebis(cyclohexyl isocyanate) provided the desired segmented copolymers displaying thermoplastic elastomeric behavior. Variable‐temperature Fourier transform infrared and ¹H NMR spectroscopies confirmed the presence of hard segment structures and revealed ordered hydrogen bonding interactions with thermal dissociation profiles similar to those of polyurea and polyoxamide copolymer analogs. Dynamic mechanical analysis of PPG‐UOx exhibited a longer, rubbery plateau with increased moduli compared to PPG polyurea, and tensile analysis revealed a dramatic increase in copolymer toughness due to enhanced hydrogen bonding. A new step‐growth polymerization strategy is described that is capable of producing tunable hydrogen bonding segmented copolymer architectures. © 2013 Society of Chemical Industry     

Thermal and mechanical properties of polyisobutylene‐based thermoplastic polyurethanes

We investigated thermal and mechanical properties of thermoplastic polyurethanes (TPUs) with the soft segment comprising of both polyisobutylene (PIB) and poly(tetramethylene)oxide (PTMO) diols. Thermal analysis reveals that the hard segment in all the TPUs investigated is completely amorphous. Significant mixing between the hard and soft segments was also observed. By adjusting the ratio between the hard and soft segments, the mechanical properties of these TPUs were tuned over a wide range, which are comparable to conventional polyether‐based TPUs. Constant stress creep and cyclic stress hysteresis analysis suggested a strong dependence of permanent deformation on hard segment content. The melt viscosity correlation with shear rate and shear stress follows a typical non‐Newtonian behavior, showing decrease in shear viscosity with increase in shear rate. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 891‐897, 2013     

The effect of soft‐segment structure on the properties of novel thermoplastic polyurethane elastomers based on an unconventional chain extender

Thermoplastic polyurethane elastomers (TPUs) are now widely used because of their excellent properties that include high tensile and tear strength, and good abrasion, impact and chemical resistance. TPUs are multiblock copolymers with alternating sequences of hard segments composed of diisocyanates and simple diols (chain extenders) and soft segments formed by polymer diols. Commonly used hard segments for TPUs are derived from 4,4′‐diphenylmethane diisocyanate (MDI) and aliphatic diols. The aim of our research was to examine the possibility of obtaining TPUs with good tensile properties and thermal stability by using an unconventional aliphatic‐aromatic chain extender, containing sulfide linkages. Three series of novel TPUs were synthesized by melt polymerization from poly(oxytetramethylene) diol, poly(ε‐caprolactone) diol or poly(hexane‐1,6‐diyl carbonate) diol of number‐average molecular weight of 2000 g mol^?1 as soft segments, MDI and 3,3′‐[methylenebis(1,4‐phenylenemethylenethio)]dipropan‐1‐ol as a chain extender. The structure and basic properties of the polymers were examined using Fourier transfer infrared spectroscopy, X‐ray diffraction, atomic force microscopy, differential scanning calorimetry, thermogravimetric analysis, Shore hardness and tensile tests. It is possible to synthesize TPUs from the aliphatic‐aromatic chain extender with good tensile properties (strength up to 42.6 MPa and elongation at break up to 750%) and thermal stability. Because the structure of the newly obtained TPUs incorporates sulfur atoms, the TPUs can exhibit improved antibacterial activity and adhesive properties. Copyright © 2011 Society of Chemical Industry     

Effect of clay modifiers on the morphology and physical properties of thermoplastic polyurethane/clay nanocomposites

Thermoplastic polyurethanes (TPUs)/clay nanocomposites were prepared via melt processing using the ester type and the ether type TPUs and three differently modified organoclays (denoted as C30B, C25A and C15A) as well as pristine montmorillonite (PM). XRD and TEM results showed that the addition of C30B with hydroxyl group led to the nearly exfoliated structures in both TPUs. In the case of C25A and C15A clays, partially intercalated nanocomposites were obtained in both TPUs, where C25A showed better dispersion than C15A. Natural clay (PM) was not effectively dispersed in both TPUs. The tensile properties of nanocomposites with C30B were better than ones with the other clays. Higher tensile properties were obtained for ester type TPU than ether type TPU nanocomposites with all clays tested. Although the improvement in tensile properties decreased after the second extrusion of the nanocomposites, properties of the nanocomposite after first melt processing were still good enough for practical applications. Morphological changes induced by the addition of clays were analyzed using FTIR, DSC and rheological test results. Some clays were observed to cause demixing of hard and soft segments in the nanocomposites and location of clays in either soft segment or hard segment domains was also studied.     

Synthesis and characterization of thermoplastic polyurethanes as binder for novel thermoplastic propellant

Two series of thermoplastic polyurethanes (TPUs), which used nitroester plasticiable tetrahydrofuran‐ethylene oxide random copolyether as soft segment and adduction products of isophorone diisocyanate (IPDI) and toluene diisocyanate (TDI) with 1,4‐butanediol as hard segments respectively, were successfully synthesized as binders for novel thermoplastic propellant. Mechanical tests and DSC techniques were applied to make characterizations of the polymers in order to choose candidate materials. Results shown that the TPU based on IPDI with fraction of the hard segment around 45% will meet requirements of propellant in terms of mechanical properties and glass transition of the soft segment phase. The results were further manifested in detail by quantitative studies of the degree of microphase separation as well as hydrogen bonding within the hard segment domain based on the equations established through FTIR and DSC analyses. It was found that mixing of two phases, which mainly referred to the mount of the hard segment dissolving into the soft segment phase, was as little as 10% in IPDI series TPUs, whereas it was almost up to 30% in TDI series. This indicated that better phase separation was achieved in IPDI series TPU. By contrast, studies of hydrogen bonding in domain revealed that the domain of TPUs prepared with TDI was much oriented in comparison with that with IPDI, which indicated higher processing temperatures. The results were raised by the melting index results under required conditions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2961–2966, 2002; DOI 10.1002/app.2324     

Effect of Soft‐to‐Hard Segment Ratio on Viscoelastic Behavior of Model Thermoplastic Polyurethanes during Phase Transitions

Model thermoplastic polyurethanes (TPUs) are prepared with the aim of investigating the effect of soft‐to‐hard segment ratio on the phase transition and the resulting structure that forms upon isothermal exposure to temperatures near their phase transition temperature. The dynamic rheological properties of TPUs before exposure to these isothermal conditions show a phase transition at high temperatures that is directly related to the content of hard segments. The extensional viscosity data indicate a strain‐hardening behavior that becomes less pronounced with the increase of hard segments. After isothermal treatment, the DSC results show that the high‐temperature endotherm peak narrows and shifts to higher temperatures, suggesting a transition in structure. Small angle X‐ray scattering, wide angle X‐ray scattering, and atomic force microcopy results indicate a phase‐separated system in which the hard domain sizes and crystallinity change during this process. The rheological data collected after recrystallization show a significant increase in both moduli, transitioning from viscoelastic fluid‐like to glassy behavior. Concurrently, the uniaxial elongation viscosity presents a significant increase in absolute values, but with a shift from strain‐hardening to strain‐softening behavior for all strain rates. A transition from traditional phase separated viscoelastic melt behavior to more brittle rupture is also observed, marking a significant fundamental difference in properties before and after recrystallization.

     

Effect of the hydrogen bonding on the inelasticity of thermoplastic polyurethane elastomers

The effect of hydrogen bonding on the cycling tensile responses of thermoplastic polyurethane elastomers (TPUs) was followed. Hydrogen substitution was carried out by replacing the usual fully hydrogenated forms of the diol chain extender diethylene glycol (DEGh) or of the macrodiol polytetrahydrofurane (PTHFh) with their fully deuterated analogues DEGd and PTHFd. The TPUs segmental orientation was followed by means of infrared dichroic measurements. The hard segment (crystallizing or not) was varied by inclusion of a conventional rigid diisocyanate, 4,4′-diphenyl methane diisocyanate (MDI) and of an isocyanate with a large conformational mobility 4,4′-dibenzyl diisocyanate (DBDI). Inelastic effects were most pronounced when the hard segment crystallized. Irrespective of the isotopic forms of the chain extender and macrodiol used in the material synthesis, the residual strain and hysteresis energy dissipation were highest for hard segments of DBDI than of MDI. While the TPUs derived from DEGd were more resilient than the similar polymers obtained with the DEGh, there were no significant differences between the resilience of the TPUs achieved with the PTHFh and PTHFd. A quantitative correlation was found between the magnitude of the Mullins effect and the fractional energy dissipation by hysteresis under cyclic straining, giving a common relation that was approached by all the materials studied. The results provide new perspectives into the physical origin of inelastic effects in reinforced elastomers.     

Fast scanning calorimetry clarifies the understanding of the complex melting and crystallization behavior of polyesteramide multi‐block copolymers

Fast scanning calorimetry has been applied in order to understand the phase transitions in thermoplastic elastomers (TPEs) based on well‐defined multi‐block copolymers made of ‘soft’ polytetrahydrofuran and ‘hard’ terephthalate ester diamides. The intrinsically complex chemical structure of TPEs leads to complex phase transitions. By changing their thermal history over a wide range of temperature (from ?100 °C to 200 °C) and cooling rates (from 10 to 4000 °C s^?1), we clarify the origins of the various phases present in these materials. In particular, we study the different possibilities for the hard segments to associate depending on their mobility during the quenching phase, forming either strong and stable structures or weaker and metastable ones. Besides, we demonstrate that a minimal cooling rate of 800 °C s^?1 is necessary to keep these TPEs (made of short and monodisperse hard segments) amorphous leading to a subsequent cold crystallization when heating back, at around 30 °C. Finally, we validate our interpretations by varying the copolymer composition (from 10 wt% to 20 wt% hard segments), revealing the thermal invariance of poorly organized domains. Based on these data, we also discuss the importance of chain diffusion in the crystallization process. Applying fast scanning calorimetry allows us to link fundamental understanding to industrial application. © 2018 Society of Chemical Industry     

Thermoplastic Polyurethane Elastomers with Aliphatic Hard Segments Based on Plant‐Oil‐Derived Long‐Chain Diisocyanates

Novel plant‐oil‐derived long‐chain (C₁₉ and C₂₃) α,ω‐diisocyanates, optionally in combination with the corresponding long‐chain diols, provide entirely aliphatic hard segments in segmented thermoplastic polyurethane elastomers (TPUs), with carbohydrate‐based poly(trimethylene glycol) soft segments. Compared to materials based on a mid‐chain monomer analog, phase separation is higher due to an increased flexibility of the aliphatic segments. Although melting points are slightly lower than for HDPE, the long‐chain TPU's solid‐state structure is still dominated by hydrogen‐bonding.     

Polyurethane elastomers through multi-hydrogen-bonded association of dendritic structures

A series of hydrogen bonding-rich polyurea/malonamide dendrons have been utilized as building blocks for the synthesis of novel dendritic polyurethane elastomers. Based on the resulting microstructure of soft segments reinforced by the rigid dendritic domains, the hydrogen bonding enforced phase separation of segmented polyurethanes was explored. DSC and FT-IR results indicate that a certain degree of phase separation between dendritic and poly(tetramethylene oxide) (PTMO) domains. The domain size of phase separation are less than 100 nm based on the results obtained from the atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS). The analysis of tensile measurements indicates that the incorporation of various contents of different dendrons as the hard segments allows these polymers to exhibit drastically different mechanical properties. Furthermore, low complex viscosity is observed at medium temperatures (above 130 °C) via the rheological analysis. With good mechanical properties at room temperature and low melt viscosity at medium temperatures, these thermoplastic elastomeric polyurethanes are suitable for applying in hot-melt process.     

Glass transition temperature in nylons

The determination of the glass transition temperature of semi-crystalline polymers is a controversial problem in the literature, because of the complexity of the phenomenon and of the different methods used for its measurement. In this work the glass transition temperatures of five commercial nylons (nylon-6, nylon-6,6, nylon-6,10, nylon-11, nylon-12) have been measured by both thermal and mechanical methods. The behaviour observed during thermal measurements is analogous to that observed by Gordon, who found that the transition detected in the heating cycle disappeared in the subsequent cooling cycle and appeared again only after a sufficient rest period of the samples, and at a temperature different from the initially measured one. He attributed this behaviour to the structure of the amorphous regions of the material, where the hydrogen bonding groups form an irregular network. The delay in reforming the above mentioned network is the main cause of the dependency of the observed transition on the thermal history imposed on the samples. Mechanical measurements give results that are quite insensitive to the thermal treatment of the materials, and thus provide very reproducible values of the transition. This feature allows the possibility of attributing to the transition obtained the character of a true glass transition where the main cause of the phenomenon is the increased mobility of the chain backbone in the amorphous regions of the materials with increasing temperature. This character was also confirmed by dilatometry, with results in agreement with Boyer's criteria for a true glass transition temperature.     

Thermal and mechanical properties of thermoplastic polyurethane elastomers from different polymerization methods

Thermoplastic polyurethane elastomers (TPUs) based on 4,4′-methylene-diphenyl diisocyanate, poly(tetramethylene glycol), diamine-terminated aliphatic nylon oligomer, and 1,4-butanediol were synthesized by two different polymerization methods, i.e. one shot and prepolymer methods. The effects of the polymerization method on the thermal and mechanical properties of the TPUs have been studied. A broader distribution of hard segment lengths in TPUs prepared by the one shot method was observed from thermal and tensile property measurements, compared with those prepared by the prepolymer method. TPUs by the one shot method showed a higher T_m of the hard segments and better tensile properties when soft-hard segment interaction was relatively small. However, inferior tensile properties were observed when the soft-hard segment interaction was high; typically when nylon oligomer was used as a soft segment.     

Characterization of thermoplastic polyurethane adhesives with different hard/soft segment ratios containing rosin as an internal tackifier

Three thermoplastic polyurethanes (TPUs) containing different hard/soft (h/s) segment ratios (1.05-1.4) were prepared using the prepolymer method. MDI (diphenylmethane-4,4′diisocyanate) and polyadipate of 1,4-butanediol (M _w = 2440) were allowed to react to produce the prepolymer. To provide the polyurethanes with high immediate adhesion to different substrates, a rosin + 1,4-butanediol mixture (1 : 1 equivalent%) was used as chain extender (TPU-Rs). These TPU-Rs had two types of hard segments: (i) Urethane hard segments, produced by reaction of the isocyanate and the 1,4-butanediol, and (ii) Urethan-amide hard segments, produced by reaction of the isocyanate and the carboxylic acid functionality of the rosin. The TPUs and TPU-Rs were characterized using FTIR spectroscopy, gel permeation chromatography, differential scanning calorimetry, stress-controlled plate-plate rheology, stress-strain measurements, and Brookfield viscosity. The TPUs and TPU-Rs were used as raw materials to prepare solvent-based polyurethane adhesives, the adhesion properties of which were obtained from T-peel tests on PVC/polyurethane adhesive/PVC joints. The addition of rosin as an internal tackifier increased the average molecular weight, more markedly in the TPU-Rs containing higher hard/soft segment ratios, but the elastic and viscous moduli decreased. An increase in the hard/soft segment ratio of the TPU-Rs retarded the kinetics of crystallization (which was determined by the soft segment content in the polyurethane), and increased the immediate T-peel strength in PVC/polyurethane adhesive/PVC joints (which was determined by the urethan-amide hard segments). Furthermore, addition of rosin to the polyurethanes decreased the final adhesion, although always reasonably high peel strength values were obtained.     

Synthesis and characterization of new thermoplastic polyurethane adhesives containing rosin resin as an internal tackifier

Three thermoplastic polyurethane elastomers (TPUs) were prepared using the prepolymer method. MDI (diphenylmethane-4,4′-diisocyanate) and the polyadipate of 1,4-butanediol (M_w = 2400) were reacted to produce a prepolymer containing unreacted isocyanate groups; chain extenders were different mixtures of 1,4-butanediol and a rosin resin (0-50%). The specific feature of this procedure was the introduction of a rosin resin as an internal tackifier to provide higher immediate adhesion to the TPUs. The new TPUs were characterized using gel permeation chromatography, wideangle X-ray diffraction, differential scanning calorimetry, stress-controlled rheology, and stress-strain measurements. The TPUs were used as raw materials to prepare solvent-based polyurethane adhesives, the adhesion properties of which were obtained from T-peel tests on PVC/polyurethane adhesive/PVC and leather/polyurethane adhesive/PVC joints. The addition of rosin resin as an internal tackifier contributed to the production of two types of hard segments, which affected the properties of the TPUs. Therefore, rosin resin as an internal tackifier produced an increase in the average molecular weight, an increase in the viscosity, and improved the rheological properties. The glass transtition temperature decreased if the TPUs contained rosin resin, due to a greater degree of incompatibility between the hard and soft segments. Consequently, slower kinetics of crystallization was obtained in the TPUs containing rosin resin. Depending on the amount of rosin resin in the TPU, different structures and properties were obtained. On the other hand, the immediate T-peel strength in all joints was improved if the TPU contained rosin resin.     

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.     

Segmented poly(urethane‐urea) elastomers based on polycaprolactone: Structure and properties

A series of segmented poly(urethane‐urea) polymers have been synthesized varying the hard segments content, based on the combination of polycaprolactone diol and aliphatic diisocyanate (Bis(4‐isocyanatocyclohexyl)methane), using diamine (1,4‐Butylenediamine) as the chain extender. The microstructure and properties of the material highly depend on the hard segments content (from 14 to 40%). These PUUs with hard segment content above 23% have elastomeric behaviors that allow high recoverable deformation. The chemical structure and hydrogen bonding interactions were studied using FTIR and atomic force microscopy, which revealed phase separation that was also confirmed by DSC, dynamic‐mechanical, and dielectric spectroscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermal and mechanical properties of poly(esterurethane) modified by copolyamide segments of various molecular weight

Thermoplastic polyurethane elastomers (TPUs) from diol-terminated poly(ethylene adipate) (PEA), 1,4-butanediol (BD) and 4,4′-diphenylmethane-diisocyanate (MDI) were modified by copolymerizing with diamine-terminated nylon-6/6,6 copolyamide (CPA) oligomers. The effects of content and molecular weight of CPA segments on the thermal and mechanical properties of TPU were studied. PEA segments showed enhanced crystallization when some of the hard segments were replaced by CPA segments, showing weaker CPA–PEA interaction. The crystallinity of the hard segments was reduced, probably due to some interaction and phase mixing between hard and CPA segments. The modulus of TPU also decreased, more markedly with CPA segments of higher molecular weight.     

Rheological study of dispersions prepared with modified soybean protein isolates

Structural modifications of modified soy protein isolates (SPI) were distinguished by rheological behavior. SPI were prepared by acidic (pH 2.5) and thermal-acidic treatment without (pH 1.6) and with neutralization (pH 8.0). Dynamic properties of dispersions were determined through the variation of storage and loss moduli with frequency, and loss tangent behavior was analyzed. Changes in viscoelastic parameters with protein concentration (10–12% wt/vol) and time of heating (15–60 min) were also determined. Flow properties of dispersions were estimated through apparent viscosity and flow and consistency index measurements. Rheological behavior of dispersions was compared with those found by experiment with commercial mayonnaise, mustard, and salad dressing. The analysis of rheological parameters showed that thermally treated isolates formed dispersions with high elastic modulus and consistency index with a structure mainly stabilized by hydrophobic interactions, although no gelation process after cooling was observed. From the rheological point of view, it was deduced that thermally treated isolates could be used as ingredients in the formulation of salad dressings. The alkaline sample would be more versatile because, depending on protein concentration and thermal treatment, the consistency of its dispersions was like that in salad dressing, or similar to those of mustard and mayonnaise.