The synthesis and characterization of new thermoplastic poly(carbonate-urethane) elastomers derived from HDI and aliphatic–aromatic chain extenders

New thermoplastic poly(carbonate-urethane) elastomers (TPCUs) were prepared by a one-step melt polymerization from 20–80 mol% poly(hexane-1,6-diyl carbonate) diol of as a soft segment, hexane-1,6-diyl diisocyanate and 2,2′-[methylenebis(1,4-phenylenemethylenethio)]diethanol, 3,3′-[methylenebis(1,4-phenylenemethylenethio)]-dipropan-1-ol or 6,6′-[methylenebis(1,4-phenylenemethylenethio)]dihexan-1-ol (H) as new chain extenders at the NCO/OH molar ratio of 1 in the presence of dibutyltin dilaurate as a catalyst. The structures of the TPCUs were examined by FTIR spectroscopy, X-ray diffraction analysis, scanning electron microscopy and atomic force microscopy (AFM). The TPCUs were also characterized by physicochemical, thermal (by differential scanning calorimetry (DSC) and thermogravimetry) and tensile properties as well as Shore A/D hardness. The resulting TPCUs were colorless polymers, showing ordered structures including semicrystalline, with the highest ability to crystallize exhibited by the polymers derived from diol H. The polymers with the soft-segment content of 40–80 mol% (56.4–25.7 wt% of hard segments) exhibited a microphase separation shown by DSC and AFM. The TPCUs showed tensile strength in the range of 8.8–23.3 MPa and elongation at break in the range of 240–670%.     

Surface characteristics of chitin-based shape memory polyurethane elastomers

Shape memory polyurethanes (SMPUs) were prepared from polycaprolactone diol 4000 (PCL 4000), 1,4-butanediol (BDO), chitin, dimethylol propionic acid (DMPA), triethylamine (TEA) and 4,4′-diphenylmethane diisocyanate (MDI), and the structures of the synthesized materials were verified by infrared spectroscopy. The effects of chitin and DMPA contents in the polyurethane formulation on surface properties were investigated. DMPA provides function of making hydrophilic polyurethanes. The crystalline structure of chitin enhanced the hydrophobicity of the synthesized materials. Contact angle, water absorption, surface free energy, work of water adhesion and swelling behavior of the synthesized polyurethanes were affected by varying the DMPA and chitin contents. The interactions of the PU films with solvents on the surface were clearly related to the contents of DMPA and chitin in the final polyurethane formulation.     

Biodegradability study of polylactic acid/ thermoplastic polyurethane blends

Blends with varied ratio of polylactic acid (PLA) and thermoplastic polyurethane (TPU) were prepared by melt blending. The PLA content in blends was 20, 40, 60 and 80 wt%. Samples of pure PLA and TPU that underwent the same thermal treatment were also prepared. Biodegradation was examined by respirometry. Pure TPU started to degrade immediately due to degradation of the low molecular weight plasticizer in the polymer. Pure PLA, on the other hand, exhibited an incubation period after which degradation progressed rapidly and was almost complete after 70 days. The degradation profile of the blends can be correlated to their morphology. Samples with a co-continuous morphology initially degrade at a higher rate than the rest of the samples due to the higher exposure of the TPU phase in these blends.     

Thermal Degradation,Flame Retardance and Mechanical Properties of Thermoplastic Polyurethane Composites Based on AluminumHypophosphite简

Aluminum hypophosphite （AP） was used to prepare flame-retarded thermoplastic polyurethane （FR-TPU） composites, and their flame retardancy, thermal degradation and mechanical properties were investigated by limiting oxygen index （LOI）, vertical burning test （UL-94）, thermogravimetric analysis （TGA）, cone calorimeter （CC） test, Fourier transform infrared （FTIR） spectroscopy, scanning electron microscopy （SEM） and tensile test. TPU containing 30 wt% of AP could reach a V-0 rating in the UL-94 test, and its LOI value was 30.2. TGA tests revealed that AP enhanced the formation of residual chars at high temperatures, and slightly affected the thermal stability of TPU at high temperatures. The combustion tests indicated that AP affected the burning behavior of TPU. The peak of heat release rate （PHRR）, total heat release （THR） and mass loss rate （MLR） greatly reduced due to the incorporation of AP. The tensile test results showed that both the tensile strength and the elongation at break slightly decreased with the addition of AP. The digital photos and SEM micrographs vitrified that AP facilitated the formation of more compact intumescent char layer. Based on these results mentioned above, the flame-retarding mechanism of AP was discussed. Both the self-charring during the decomposing process of AP and its facilitation to the charring of TPU led to the great improvement in the flame retardancy of TPU.     

Morphology and performance of unsaturated polyester nanocomposites modified with organoclay and thermoplastic polyurethane

<正>Unsaturated polyester(UPR)/thermoplastic polyurethane(TPU)/organoclay nanocomposites were prepared by melt compounding of thermoplastic polyurethane and unsaturated polyester prepolymer,and then mixing with the hybrids of styrene monomers and organoclay at ambient temperature.The crosslinking reaction eventually occurred through the unsaturated polyester prepolymer and styrene monomer.The morphology of the composites was investigated by scanning electron microscopy(SEM) and transmission electron microscopy(TEM).The results show that the impact strength of UPR/TPU/organoclay nanocomposites increases obviously;the cure shrinkage decreases markedly,the glass transition temperature is enhanced and an elastic response to the deformation is prominent at the temperature above 10℃.     

Compression set of thermoplastic polyurethane under different thermal-mechanical-moisture conditions

Elastomeric materials are used in the manufacture of structural dampeners due to their high damping coefficient and ease of production. However, elastomers, and in particular thermoplastic polyurethanes (TPU), are susceptible to degradation from environmental conditions. Samples of TPU were investigated, in terms of their mechanical properties, under the influence of four factors; time (up to 10 weeks thermal exposure), temperature (20-80 °C), strain (10% and 25%) and moisture (pre-soak/testing in water). Compression, hardness and compression set tests were used to determine the major contributors to the degradation process. It was found that pure thermal loading at 70 °C for 10 weeks did not result in any changes in material properties, other than an initial drying phase causing an increase in hardness of 2-3 Shore D. The compression set values were found to be heavily dependent on the test temperature, with a significant increase in compression set being seen between 70 and 80 °C. The presence of water (introduced by testing in water) acted as a plasticiser and resulted in a larger amount of compression set, than testing in the absence of water. The level of compression set was shown to be insensitive to the strain level. Overall, it was found, for the conditions tested, that temperature was the major driving force behind the compression set of the TPU material.     

A polymer network based on thermoplastic polyurethane and ethylene-propylene-diene elastomer via melt blending: morphology, mechanical properties, and rheology

Blends of thermoplastic polyurethane (TPU) and ethylene-propylene-diene elastomer (EPDM) were prepared via a melt blending, and morphology, mechanical properties, and rheology were studied. Scanning electron microscopy (SEM) micrographs demonstrated that a network of EPDM domain was formed in TPU matrix, and became finer and more perfect with addition of 8 wt% EPDM into TPU. Dynamic mechanical analysis (DMA) and Fourier transformed infrared spectroscopy (FTIR) investigation indicated that EPDM was thermodynamically miscible with the soft segments of TPU and incompatible with the hard segments. The formation of the network was resulted from the competition of compatible and incompatible segments of TPU with EPDM. The tensile strength and elongation at break achieved a significant improvement with addition of EPDM, and obtained the optimum values of 39.21 MPa and 2659%, respectively, when EPDM content was 8 wt%. PEO-g-MA as a compatibilizer was employed to improve the compatibilization between EPDM and the hard segments of EPDM, and consequently, the network became finer and more perfect. The evaluation of rheological properties revealed that the introduction of EPDM into TPU resulted in a reduction of the viscosity at high shear rate and a decrease of the flow activation energy; thus the processability of the blends was improved.     

Short Twaron aramid fiber reinforced thermoplastic polyurethane

Mechanical, dynamic mechanical, and rheological behaviors of a short p‐aramid fiber reinforced thermoplastic polyurethane (TPU) have been studied in the range of 0–30 wt% of fibers. The tensile strength of the composite is improved slightly at higher fiber content with a minimum at around 10 wt% of fibers. The addition of fibers markedly reduces elongation at break and entails a steady increase in the elastic modulus, but decreases the wear resistance of the matrix. Storage modulus (E′) is increased and the shapes of loss tangent (tan δ) peaks point to a possible fiber–matrix interaction. Rheological studies show a power law behavior for all composites and increased viscosity with fiber loading. Study of the tensile and cryogenic fracture surfaces by scanning electron microscopy (SEM) indicates good correlation between the modes of failure and strength of the composites. The micrographs reveal good interfacial adhesion and extensive peeling and fibrillation of the fibers in the compounded and fractured composites. Theoretical models have been used to fit the experimental modulus data. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface modification and aging studies of addition-curing silicone rubbers by oxygen plasma

Poly(dimethyl siloxane) (PDMS) has been focused on recently due to its variety of applications specifically in microsystems technology. Many companies market two-component PDMS, which is comprised of a base component and a curing agent. Widely known and used for microsystems applications is Sylgard 184 from Dow Corning. Present work deals with two-component Room Temperature Vulcanized (RTV) PDMS from three different companies. They are Sylgard 184 from Dow Corning, RTV 615 from GE Silicones and RTV 141 from Rhodia Chemicals. Temporary increase in wettability of these three different types of PDMS by oxygen plasma by varying the plasma power and exposure time has been studied and compared with results available in literature. The hydrophobic recovery of the modified surfaces was monitored as a function of time and quantified. The surfaces were characterized using contact angle measurements and ATR-FTIR and XPS spectroscopy, their behavior analyzed in term of free surface energy and work of adhesion.     

Compositional effect on the morphology and ionic conductivity of thermoplastic polyurethane based electrolytes

Four thermoplastic polyurethanes (TPUs) were synthesized from poly(ethylene glycol) (PEG), 4,4^′-methylenebis(phenyl isocyanate) (MDI), and 1,4-butanediol (1,4-BDO) with different 1,4-BDO/PEG ratios. The effect of polymer structure on the conductivity of the polymer elelctrolytes was investigated. Fourier transform infrared spectroscopy (FT-ir) and differential scanning calorimetry (DSC) were utilized to monitor changes in the morphology of the TPUs as polymeric solid electrolyte doped with LiClO₄. The structure of the TPUs has been investigated by 1H solution nuclear magnetic resonance spectroscopy. Alternating current (AC) impedance experiments were performed to determine the ionic conductivities of TPU films and their corresponding gel type electrolytes. The conductivity depends on the soft-segment concentration and on the degree of phase separation exhibited by these materials. One of the investigated TPU gel type electrolytes exhibits an ionic conductivity as high as 3×10⁻⁴ S/cm at room temperature.     

Morphology,rheological and crystallization behavior in thermoplastic polyurethane toughed poly(l-lactide) with stereocomplex crystallites

Melt-blending poly(l-lactide) (PLLA) with elastomers has been well demonstrated to improve toughness of PLLA. Here, we show a poly(d-lactide) (PDLA) grafted thermoplastic polyurethane (TPU) (TPU-g-PDLA) toughed PLLA with simultaneous formation of few amount stereocomplex crystallites (SCs) which exhibited higher efficient toughening than that of PLLA with TPU. The TPU-g-PDLA was prepared by the in-situ melt-reaction of TPU and PDLA with 4, 4’-diphenylmethane diisocyanate (MDI). A comparative study on morphology, rheological and crystallization behavior was also carried in PLLA/TPU, PLLA/TPU-g-PDLA and PLLA/TPU/PDLA samples. The PLLA/TPU-g-PDLA samples show the highest crystallization rate, complex viscosity, impact strength and tensile strength among PLLA/TPU, PLLA/TPU-g-PDLA and PLLA/TPU/PDLA samples, indicating that the higher interfacial interaction between TPU-g-PDLA and PLLA. Furthermore, TPU chains in TPU-g-PDLA were thought to break the intermolecular interaction of PLLA and rapid its crystallization and increase crystallinity.     

Development of thermoplastic polyurethane/polyaniline-doped membranes for the separation of glycine through electrodialysis

Recently, membrane-based separation processes, particularly electrodialysis, have attracted attention for the separation and purification of organic and amino acids from animal feedstock waste. In this study, cation exchange membranes were synthesized by making a composite of thermoplastic polyurethane and polyaniline (PANI) via the doping of various aromatic sulfonic acids, such as β -naphthol sulfonic acid and phenol sulfonic acid. The PANI was prepared using a standard method, which was further used in the composite blending at varying concentrations of 10%–20%. The impact of the concentration of PANI and the nature of the dopant on the membrane characteristics were comparatively studied. The membranes were analyzed by electric conductivity, water swelling, morphological studies (SEM), and thermogravimetric analysis. The membranes were used for the separation of glycine hydrochloride via electrodialysis.     

Vibrational spectroscopic studies of laboratory scale polymer melt processing: Application to a thermoplastic polyurethane nanocomposite

A laboratory scale twin screw extruder has been interfaced with a near infrared (NIR) spectrometer via a fibre optic link so that NIR spectra can be collected continuously during the small scale experimental melt state processing of polymeric materials. This system can be used to investigate melt state processes such as reactive extrusion, in real time, in order to explore the kinetics and mechanism of the reaction. A further advantage of the system is that it has the capability to measure apparent viscosity simultaneously which gives important additional information about molecular weight changes and polymer degradation during processing. The system was used to study the melt processing of a nanocomposite consisting of a thermoplastic polyurethane and an organically modified layered silicate.     

Surface modification of high heat resistant UV cured polyurethane dispersions

To modify the surface of UV cured polyurethane dispersion (UV-PUD), fluorinated PU called surface modifying agent (SMA) was blended with base PU prior to dispersion in water. X-ray photoelectron spectroscopy (XPS) and contact angle measurements showed that surfaces of dispersion cast film are significantly enriched with fluorine groups. Atomic force microscopy (AFM) showed that surface was roughened with the addition of SMA, which provided possible mechanism of increased water resistance as well as low friction coefficient of the film. On the other hand, hardness, mechanical and dynamic mechanical properties indicated that the bulk properties are marginally altered by the additive amount of SMA.     

Surface modification of waterborne polyurethane

Fluorinated urethane oligomers (SMAs) having repeat unit identical to the hard segment of base polyurethane (PU) have been synthesized and blended with base PU prior to dispersion. XPS and static contact angle measurements showed that surfaces of dispersion cast film are significantly enriched with SMA although SMA and base PU were miscible in bulk phase showing a single glass transition temperature. AFM showed that surface roughness of the dispersion cast film increased over 13 times with the addition of SMA (15%) providing possible mechanism of increased water and oil resistance as well as low friction coefficient of the film.     

Surface and interface characterization of polyester‐based polyurethane/nano‐silica composites

Polyester‐based polyurethane/nanosilica composites were prepared via in situ polymerization and investigated by contact angle measurement, transmission electron microscopy (TEM), atomic force microscopy (AFM) and peel testing in an Instron testing machine. The contact angle and surface free energy results show that nanosilica tended to enrich at the interface between nanocomposite polymers and the substrates, TEM indicated that nanosilica particles were evenly dispersed in the bulk and AFM demonstrated that nanoparticles were located at both the surfaces and interfaces of nanocomposite polymers and that the roughness of both the surfaces and interfaces had a decreasing tendency as the nanosilica content increased, as did the adhesion strength between the nanocomposite polymers and substrates. Copyright © 2003 John Wiley & Sons, Ltd.     

Property correlations for dynamically cured rice husk ash filled epoxidized natural rubber/thermoplastic polyurethane blends: Influences of RHA loading

Novel thermoplastic vulcanizates based on thermoplastic polyurethane (TPU) and epoxidized natural rubber (ENR) were prepared with rice husk ash (RHA) filler. Therefore, two major renewable resource materials (i.e., ENR and RHA) were exploited. Influences of RHA loading on mechanical, morphological, thermal and dynamic properties of dynamically cured ENR/TPU blends were investigated. It was found that the RHA showed good dispersion and was mainly localized in the ENR phase. Increasing the RHA loading led to the formation of larger ENR domains dispersed in the TPU matrix. Also, migration of the RHA particles from ENR to TPU phases was observed, resulting in reduced strength properties. It was found that the RHA acted as a nucleating agent in the TPU matrix and could accelerate the crystallization of TPU. Additionally, stress relaxation of the blends was evaluated by temperature stress scanning relaxation (TSSR). Higher relaxation stresses or raised relaxation curves were observed with increased RHA loadings in the dynamically vulcanized ENR/TPU blends.     

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

Various new thermoplastic segmented polyurethanes were synthesized by a one-step melt polymerization from aliphatic-aromatic α,ω-diols containing sulfur in the aliphatic chain, including 4,4′-(ethane-1,2-diyl)bis(benzenethioethanol), 4,4′-(ethane-1,2-diyl)bis(benzenethiopropanol) and 4,4′-(ethane-1,2-diyl)bis(benzenethiodecanol) as chain extenders, hexane-1,6-diyl diisocyanate (HDI) or 4,4′-diphenylmethane diisocyanate (MDI) and 20-80 mol% poly(oxytetramethylene)diol (PTMO) with molecular weight of 1000 g/mol as a soft segment. The reaction was conducted at the molar ratio of NCO/OH = 1 and 1.05, and in the case of the HDI-based polyurethanes in the presence of dibutyltin dilaurate as a catalyst. The effect of the diisocyanate used on the structure and some physicochemical, thermal and mechanical properties of the segmented polyurethanes were studied. The structures of these polyurethanes were examined by FTIR and X-ray diffraction analysis. The thermal properties were investigated by differential scanning calorimetry and thermogravimetric analysis. Shore hardness and tensile properties were also determined. All the synthesized polymers showed partially crystalline structures. The MDI-based polyurethanes were products with lower crystallinity, higher glass-transition temperature (T_g) and better thermal stability in comparison with the HDI-based ones. The MDI series polymers also exhibited higher tensile strength (up to ∼36 MPa vs. ∼23 MPa) and elongation at break (up to ∼3900% vs. ∼900%), but lower hardness than the analogous HDI series polyurethanes. In both series of the polymers an increase in PTMO soft-segment content was associated with decreased crystallinity, T_g, hardness and tensile strength. An increase in PTMO content also involved an increase in elongation at break.     

Low-temperature air plasma modification of chitosan-coated PEEK biomaterials

Novel chitosan-coated PEEK biomaterials were prepared by air plasma modification. Low-temperature plasma effect on changes of specific thermal, mechanical and adhesive properties of polyetheretherketone (PEEK) was investigated. The topography and surface roughness of the prepared materials were determined using an optical profilometer. The wetting and energetic properties of biomaterials were studied by means of advancing and receding contact angles measurements and then apparent surface free energy (and its components) were evaluated applying the LWAB (Lifshitz–van der Waals Acid Base) theory and contact angle hysteresis model. After air plasma treatment a fairly hydrophobic character of PEEK was changed to strongly hydrophilic one. Significant differences in the wettability and thermal stability of samples were observed. However, hardly any differences in excellent mechanical properties were noticed. The profilometer images showed an increase in the surface roughness of PEEK modified surface due to the change of cross-link density, elasticity and formation of additional polar groups on the surface. Plasma treated polyetheretherketone surfaces had better adhesive features and stable chitosan coating was created. Modification by chitosan improved antibacterial properties, inherent haemostatics and polymer biocompatibility. These advantages allowed to obtain new attractive biomaterials from the same polymer differing in properties for a wide spectrum of applications, mainly regenerative medicine and orthopedic surgery.     

Synthesis and characterizations of silylated polyurethane from methyl ethyl ketoxime-blocked polyurethane dispersion

Water-dispersible blocked polyurethane dispersions (BPUD) were synthesized by prepolymer mixing process using toluene 2,4-diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), poly(tetramethylene glycol) (PTMG), dimethylol propionic acid (DMPA), and methyl ethyl ketoxime (MEKO). The particle size, viscosity, pH and storage stability of the BPUDs were studied and compared. The aqueous dispersions were characterized by FT-IR, GPC, DSC and TGA techniques. De-blocking temperatures of the BPUDs were measured and end-capped with phenylamino propyl trimethoxysilane (PAPTMS) at different de-blocking temperatures. The thermal analysis revealed that both MDI- and TDI-based BPUDs started to de-block at about 60–85 °C. The average molecular weights of the MDI-BPUDs were higher than that of the TDI-BPUDs due to the high reactivity of MDI. It was noticed that the tensile strength increased and elongation at break decreased in the silylated BPUD compared to pure BPUDs, which confirmed that the BPUDs were de-blocked and end-capped with PAPTMS. The T_g values of the silylated BPUD were higher than the BPUD and pure PTMG as well as thermal stability. Storage stability results showed that all BPUDs containing PAPTMS were stable. Water and xylene resistance tests and gel content studies confirmed that silylated PU cross-linked well after silylation of blocked PUDs.