Hexamethylene Oxide Research Articles

Thermochemical properties of oxepane

In this work, the vapor pressures of oxepane (CAS 592-90-5) have been determined for the first time within the temperature range 276.2–303.2 K using the transpiration method. The enthalpy of vaporization of hexamethylene oxide was evaluated from the experimental vapor pressure data measured by using this method. Values of the enthalpies of combustion and formation have been determined for the first time by combustion calorimetry in a static bomb. A conformational analysis of oxepane in the gas has been performed using methods of molecular mechanics and ab initio computations; the structure of the most stable conformer has been identified. The enthalpy of formation of oxepane in the gaseous state was calculated with the composite G4 method. The thermodynamic functions of oxepane in the ideal gas state over wide temperature range (298.15–1500 K) have been evaluated. Values of the strain energies in a series of cyclic and heterocyclic compounds have been estimated.

Living Cationic Ring-Opening Homo- and Copolymerization of Cyclohexene Oxide by “Dormant” Species Generation Using Cyclic Ethers as Lewis Basic Additives

The living cationic ring-opening polymerization of cyclohexene oxide (CHO) was demonstrated to proceed using cyclic ethers as Lewis basic additives that potentially form “dormant” species through a reaction with the CHO-derived propagating species. The polymers obtained under suitable conditions had molecular weights close to the theoretical values and narrow molecular weight distributions. The formation of the dormant species was strongly supported by the generation of chain ends consisting of a cyclic ether additive and a quencher fragment, which was confirmed by 1H NMR and ESI-MS analysis of the product polymers. The use of additives with appropriate basicity, such as hexamethylene oxide and tetrahydropyran, is of considerable importance for living polymerization. In addition, the living copolymerization of CHO and 1,4-epoxycyclohexene and the synthesis of alternating-like acid-degradable polymers with aliphatic aldehydes were also achieved.

Thermoplastic Polyurethane (TPU) / Organo- fluoromica Nanocomposites for Biomedical Applications: In Vitro Fatigue Properties

Poly(dimethylsiloxane) (PDMS) / poly(hexamethylene oxide) (PHMO)-based thermoplastic polyurethane (TPU) nanocomposite was investigated for potential use in biomedical application. Studies on the in vitro fatigue behaviour of the TPU and TPU nanocomposite (under physiological saline solution, 37°C conditions) were highlighted in this article. The data were compared with those of commercially available silicone elastomer (Nusil MED 4860). Results indicated that the TPU nanocomposite (2MED-C (2HM)) had greater fatigue properties than the virgin TPU, which provide strong evidence of its greater capacity to withstand cyclic forces than the host TPU when exposed to physiological fluid. This was caused by the presence of well dispersed and impermeable organofluoromica platelets in the TPU matrix resulted in more tortuous path for the physiological fluid diffusion, thereby decreasing the fluid permeability of the polymer. Eventhough the silicone elastomer has lesser hysteresis than the virgin TPU and TPU nanocomposite, its fatigue strength is much lower than those of the TPU nanocomposite. The findings revealed the potential of PDMS/PHMO based TPU nanocomposite to replace silicone elastomer as biomaterial, particularly for implantable biomedical device application.

In Vitro Tensile Properties, Hydrolytic and Oxidative Permeability of the Biomedical Thermoplastic Polyurethane (TPU) / Organohectorite Nanocomposites

In this work, poly(dimethylsiloxane) (PDMS) / poly (hexamethylene oxide) (PHMO)-based thermoplastic polyurethane (TPU) nanocomposites incorporating nano-organo-hectorite were studied for biomedical application.

Hard segment composition, morphology, tensile properties and biostability of linked-macrodiol based siloxane poly(urethane urea)

A series of siloxane poly(urethane urea)s (SiPUU) was synthesised to investigate variation of the molar ratio of urethane and urea linkages on morphology, tensile properties and in vitro oxidative stability. The soft segments of SiPUU were based on 20:80 (w/w) mixture of 4,4′-methylenediphenyl diisocyanate (MDI) linked poly(hexamethylene oxide) and α,ω-bis(6-hydroxyethoxypropyl) polydimethylsiloxane. The hard segment content in these formulations was 45% (w/w) and composed of MDI and a mixture of 1,2- ethanediamine (EDA) and 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane (BHTD) in varying molar ratios. Six SiPUU with 0, 20, 40, 60, 80 and 100 mol-% of BHTD in the hard segment in combination with EDA were prepared. The synthesized SiPUU were characterized using size exclusion chromatography, Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and tensile testing. The oxidative stability of the SiPUU samples was evaluated by an in vitro oxidative test method using a 20% H2O2 containing 0.1 mol/L CoCl2 solution on 150% strained dumbbells at 37 °C over a period of 60 days. The results showed that the modulus, tensile and tear strengths increased with increasing proportion of EDA in the hard segment. In SiPUU where the EDA content was 80% and above, a well-ordered hard segment was observed. Scanning electron microscopic (SEM) examination confirmed that the SiPUU containing a mixture of chain extenders were oxidatively stable independent of the chain extender compositions. The SiPUU chain extended only with either BHTD or EDA showed minor surface changes. All SiPUU samples, except the one containing 100% BHTD in the hard segment, showed high ultimate tensile strength (25–35 MPa), elongation (400–870%) and tear strength (40–93 N/mm) with very good oxidative stability.

Morphology and surface properties of high strength siloxane poly(urethane-urea)s developed for heart valve application.

A series of siloxane poly(urethane-urea) (SiPUU) were developed by incorporating a macrodiol linked with a diisocyanate to enhance mixing of hard and soft segments (SS). The effect of this modification on morphology, surface properties, surface elemental composition, and creep resistance was investigated. The linked macrodiol was prepared by reacting α,ω-bis(6-hydroxyethoxypropyl) poly(dimethylsiloxane)(PDMS) or poly(hexamethylene oxide) (PHMO) with either 4,4'-methylenediphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), or isophorone diisocyanate (IPDI). SiPUU with PHMO-MDI-PHMO and PHMO-IPDI-PHMO linked macrodiols showed enhanced creep resistance and recovery when compared with a commercial biostable polyurethane, Elast-Eon™ 2A. Small and wide-angle X-ray scattering data were consistent with significant increase of hydrogen bonding between hard and SS with linked-macrodiols, which improved SiPUU's tensile stress and tear strengths. These SiPUU were hydrophobic with contact angle higher than 101° and they had low water uptake (0.7%·w/w of dry mass). They also had much higher siloxane concentration on the surface compared to that in the bulk. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 107B: 112-121, 2019.

Development of high strength siloxane poly(urethane-urea) elastomers based on linked macrodiols for heart valve application.

Mixed macrodiol based siloxane poly(urethane-urea)s (SiPUU) having number average molecular weights in the range 87-129 kDa/mol were synthesized to give elastomers with high tensile and tear strengths required to fabricate artificial heart valves. Polar functional groups were introduced into the soft segment to improve the poor segmental compatibility of siloxane polyurethanes. This was achieved by linking α,ω-bis(6-hydroxyethoxypropyl) poly(dimethylsiloxane) (PDMS) or poly(hexamethylene oxide) (PHMO) macrodiols with either 4,4'-methylenediphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI) prior to polyurethane synthesis. The hard segment was composed of MDI, and a 1:1 mixture of 1,3-bis(4-hydroxybutyl)-1,1,3,3-tetramethyldisiloxane and 1,2-ethylene diamine. We report the effect of urethane linkers in soft segments on properties of the SiPUU. PHMO linked with either MDI or IPDI produced SiPUU with the highest tensile and tear strengths. Linking PDMS hardly affected the tensile strength; however, the tear strength was improved. The stress-strain curves showed no plastic deformation region typically observed for conventional polyurethanes indicating good creep resistance. © 2017 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 106B: 1712-1720, 2018.

Characterization of an S-nitroso-N-acetylpenicillamine–based nitric oxide releasing polymer from a translational perspective

ABSTRACTDue to the role of nitric oxide (NO) in regulating a variety of biological functions in humans, numerous studies on different NO releasing/generating materials have been published over the past two decades. Although NO has been demonstrated to be a strong antimicrobial and potent antithrombotic agent, NO-releasing (NOrel) polymers have not reached the clinical setting. While increasing the concentration of the NO donor in the polymer is a common method to prolong the NO release, this should not be at the cost of mechanical strength or biocompatibility of the original material. In this work, it was shown that the incorporation of S-nitroso-penicillamine (SNAP), an NO donor molecule, into Elast-eon E2As (a copolymer of mixed soft segments of polydimethylsiloxane and poly(hexamethylene oxide)), does not adversely impact the physical and biological attributes of the base polymer. Incorporating 10 wt% of SNAP into E2As reduces the ultimate tensile strength by only 20%. The inclusion of SNAP did not significantly affect the surface chemistry or roughness of E2As polymer. Ultraviolet radiation, ethylene oxide, and hydrogen peroxide vapor sterilization techniques retained approximately 90% of the active SNAP content and did not affect the NO-release profile over an 18-day period. Furthermore, these NOrel materials were shown to be biocompatible with the host tissues as observed through hemocompatibility and cytotoxicity analysis. In addition, the stability of SNAP in E2As was studied under a variety of storage conditions, as they pertain to translational potential of these materials. SNAP-incorporated E2As stored at room temperature for over six months retained 87% of its initial SNAP content. Stored and fresh films exhibited similar NO release kinetics over an 18-day period. Combined, the results from this study suggest that SNAP-doped E2As polymer is suitable for commercial biomedical applications due to the reported physical and biological characteristics that are important for commercial and clinical success.

Molecular Dynamics of Segmented Polyurethane Copolymers: Influence of Soft Segment Composition

Dielectric relaxation spectroscopy was used to investigate the molecular dynamics of model segmented polyurethane copolymers having identical hard segments and hard segment weight fractions, but with four different soft segment chemistries of particular interest in biomedical devices. All soft segments have molecular weight ∼1000 g/mol and are composed of either tetramethylene oxide, hexamethylene oxide, aliphatic carbonate, or dimethylsiloxane (PDMS) segments. These microphase-separated materials exhibit rich dielectric relaxation behavior: up to two relaxations in the glassy state, a segmental α relaxation (two for the polymer with predominately PDMS soft segments), and three slower relaxations. The slowest process arises from interfacial (MWS) polarization, and its strength decreases significantly with increasing temperature (over a few tens of degrees) and disappears at a temperature similar to that at which the small-angle X-ray scattering from the phase-separated microstructure disappears.

Effect of accelerated aging on the viscoelastic properties of Elast-Eon™: A polyurethane with soft poly(dimethylsiloxane) and poly(hexamethylene oxide) segments

The viscoelastic properties of cylinders (diameter 5 mm, height 2.2 ± 0.2 mm) of Elast-Eon™ 3, (a polyurethane with poly(dimethylsiloxane) and poly(hexamethylamine oxide) segments) were investigated before and after the specimens had undergone accelerated aging in saline solution at 70 °C for 38, 76 and 114 days (to simulate aging at 37 °C, for 1, 2 and 3 years, respectively). All sets of specimens were immersed in physiological saline solution at 37 °C during testing and the properties were measured using dynamic mechanical analysis (DMA). A sinusoidal cyclic compression of 40 N ± 5 N was applied over a frequency range, f, of 0.02–100 Hz. Values of the storage, E′, and loss, E″, moduli were found to depend on f; the dependence of E′ or E″ on the logarithm (base 10) of f was represented by a second-order polynomial. After accelerated aging, the E′ and E″ increased significantly ( p < 0.05) and the specimens became darker and more opaque. SEM images showed that accelerated aging affected the surface morphology but ATR-FTIR spectra did not show any appreciable change in surface chemistry. DSC thermograms showed some slight changes in thermal properties following accelerated aging.

Microstructural organization of polydimethylsiloxane soft segment polyurethanes derived from a single macrodiol

Segmented polyurethane (PU) block copolymers were synthesized using 4,4′-methylenediphenyl diisocyanate and 1,4-butanediol as hard segments and oligomeric ethoxypropyl polydimethylsiloxane (PDMS) as the soft segments, with hard segment contents ranging from 26 to 52 wt%. The microphase separated morphology, phase transitions, and degrees of phase separation of these novel copolymers were investigated using a variety of experimental methods. Like similar copolymers with mixed ethoxypropyl PDMS/poly(hexamethylene oxide) soft segments, PU copolymers containing only ethoxypropyl PDMS soft segments were found to consist of three microphases: a PDMS matrix phase, hard domains, and a mixed phase containing ethoxypropyl end group segments and dissolved short hard segments. Analysis of unlike segment demixing using small-angle X-ray scattering demonstrates that degrees of phase separation increase significantly as copolymer hard segment content increases, in keeping with findings from Fourier transform infrared spectroscopy measurements.

Metabolism and Cometabolism of Cyclic Ethers by a Filamentous Fungus, aGraphiumsp

The filamentous fungus Graphium sp. (ATCC 58400) grows on gaseous n-alkanes and diethyl ether. n-Alkane-grown mycelia of this strain also cometabolically oxidize the gasoline oxygenate methyl tert-butyl ether (MTBE). In this study, we characterized the ability of this fungus to metabolize and cometabolize a range of cyclic ethers, including tetrahydrofuran (THF) and 1,4-dioxane (14D). This strain grew on THF and other cyclic ethers, including tetrahydropyran and hexamethylene oxide. However, more vigorous growth was consistently observed on the lactones and terminal diols potentially derived from these ethers. Unlike the case in all previous studies of microbial THF oxidation, a metabolite, gamma-butyrolactone, was observed during growth of this fungus on THF. Growth on THF was inhibited by the same n-alkenes and n-alkynes that inhibit growth of this fungus on n-alkanes, while growth on gamma-butyrolactone or succinate was unaffected by these inhibitors. Propane and THF also behaved as mutually competitive substrates, and propane-grown mycelia immediately oxidized THF, without a lag phase. Mycelia grown on propane or THF exhibited comparable high levels of hemiacetal-oxidizing activity that generated methyl formate from mixtures of formaldehyde and methanol. Collectively, these observations suggest that THF and n-alkanes may initially be oxidized by the same monooxygenase and that further transformation of THF-derived metabolites involves the activity of one or more alcohol dehydrogenases. Both propane- and THF-grown mycelia also slowly cometabolically oxidized 14D, although unlike THF oxidation, this reaction was not sustainable. Specific rates of THF, 14D, and MTBE degradation were very similar in THF- and propane-grown mycelia.

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.

Polydimethylsiloxane-Based Polyurethanes: Phase-Separated Morphology and In Vitro Oxidative Biostability

Three series of segmented polyurethane block copolymers were synthesized using 4,4′-methylenediphenyl diisocyanate (MDI) and 1,4-butanediol (BDO) or 1,3-bis(4-hydroxybutyl)tetramethyl disiloxane (BHTD) as the hard segments, and soft segments composed of poly(dimethyl siloxane) (PDMS)-based and poly(hexamethylene oxide) (PHMO) macrodiols. Copolymers synthesized with the PDMS macrodiol and PDMS and PHMO macrodiol mixtures consist of three microphases: a PDMS phase, hard domains, and a mixed phase of PHMO (when present), PDMS ether end-group segments and some dissolved hard segments. Degrees of phase separation were characterized using small-angle X-ray scattering by applying a pseudo two-phase model, and the morphology resulting from unlike segment demixing was found to be closely related to the in vitro oxidative biostability of these segmented polyurethanes.

Microstructural Organization of Three-Phase Polydimethylsiloxane-Based Segmented Polyurethanes

Microphase separation is investigated for segmented polyurethane copolymers synthesized from 4,4‘-methylenediphenyl diisocyanate and 1,4-butanediol as the hard segments and poly(hexamethylene oxide diol) and hydroxyl-terminated polydimethylsiloxane as soft segments. The neat PDMS-based diol exhibits two segmental relaxations corresponding to the principal repeating unit, Si(CH3)2O, and to the hydroxyl end-group segments. When incorporated in the polyurethanes, the siloxane units form their own phase, while the end-group segments are mixed with the second macrodiol and some short hard segment sequences. This is demonstrated by the results of dynamic mechanical analysis and wide-angle X-ray diffraction experiments. The microdomain morphology was characterized principally by small-angle X-ray scattering, and the scattering data were analyzed with a pseudo-two-phase model as well as a modified three-phase core−shell model.

Effect of the average soft‐segment length on the morphology and properties of segmented polyurethane nanocomposites

AbstractTwo organically modified layered silicates (with small and large diameters) were incorporated into three segmented polyurethanes with various degrees of microphase separation. Microphase separation increased with the molecular weight of the poly(hexamethylene oxide) soft segment. The molecular weight of the soft segment did not influence the amount of polyurethane intercalating the interlayer spacing. Small‐angle neutron scattering and differential scanning calorimetry data indicated that the layered silicates did not affect the microphase morphology of any host polymer, regardless of the particle diameter. The stiffness enhancement on filler addition increased as the microphase separation of the polyurethane decreased, presumably because a greater number of urethane linkages were available to interact with the filler. For comparison, the small nanofiller was introduced into a polyurethane with a poly(tetramethylene oxide) soft segment, and a significant increase in the tensile strength and a sharper upturn in the stress–strain curve resulted. No such improvement occurred in the host polymers with poly(hexamethylene oxide) soft segments. It is proposed that the nanocomposite containing the more hydrophilic and mobile poly(tetramethylene oxide) soft segment is capable of greater secondary bonding between the polyurethane chains and the organosilicate surface, resulting in improved stress transfer to the filler and reduced molecular slippage. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 128–139, 2006

The effect of sterilisation on a poly(dimethylsiloxane)/poly(hexamethylene oxide) mixed macrodiol-based polyurethane elastomer

The effect of various forms of sterilisation on a novel thermoplastic polyurethane elastomer synthesised using poly(hexamethylene oxide) (PHMO) and poly(dimethylsiloxane) (PDMS) macrodiols has been studied. The five sterilisation methods investigated were ethylene oxide (EtO) (single and multiple cycles), gas plasma, steam, vapour phase liquid chemical and gamma-irradiation (single and multiple cycles). Following sterilisation, scanning electron microscopy (SEM) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) were used to assess changes in the surface chemical structure and morphology, and gel permeation chromatography (GPC) and tensile testing were used to examine changes in bulk characteristics. Biostability was assessed using subcutaneous implantation of strained samples in sheep for 6 weeks. The results showed that the properties of the commercially available control material, Pellethane 2363-80A, were significantly affected by exposure to gamma-irradiation, steam and multiple cycles of EtO with aging and implantation compounding the effect. Exposure to a gas plasma sterilisation process resulted in significant degradation in both polyurethanes. A vapour phase liquid chemical sterilisation process caused minimal adverse effects. Sterilisation of the PDMS-based polyurethane using EtO, gamma-irradiation and autoclaving resulted in no significant changes in properties. The material's biostability was also unaffected by exposure to each of these sterilisation processes followed by short-term implantation suggesting that this material is a potential candidate for use in a wide range of implantable medical devices sterilised using commercially available processes. Further biostability studies should be performed to assess the longer-term in vivo biostability of the PDMS-based material sterilised using autoclaving and gamma-irradiation.

Long-term in vivo biostability of poly(dimethylsiloxane)/poly(hexamethylene oxide) mixed macrodiol-based polyurethane elastomers

The long-term biostability of a novel thermoplastic polyurethane elastomer (Elast-Eon TM 2 80A) synthesized using poly(hexamethylene oxide) (PHMO) and poly(dimethylsiloxane) (PDMS) macrodiols has been studied using an in vivo ovine model. The material's biostability was compared with that of three commercially available control materials, Pellethane ® 2363-80A, Pellethane ® 2363-55D and Bionate ® 55D, after subcutaneous implantation of strained compression moulded flat sheet dumbbells in sheep for periods ranging from 3 to 24 months. Scanning electron microscopy, attenuated total reflectance-Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy were used to assess changes in the surface chemical structure and morphology of the materials. Gel permeation chromatography, differential scanning calorimetry and tensile testing were used to examine changes in bulk characteristics of the materials. The results showed that the biostability of the soft flexible PDMS-based test polyurethane was significantly better than the control material of similar softness, Pellethane ® 80A, and as good as or better than both of the harder commercially available negative control polyurethanes, Pellethane ® 55D and Bionate ® 55D. Changes observed in the surface of the Pellethane ® materials were consistent with oxidation of the aliphatic polyether soft segment and hydrolysis of the urethane bonds joining hard to soft segment with degradation in Pellethane ® 80A significantly more severe than that observed in Pellethane ® 55D. Very minor changes were seen on the surfaces of the Elast-Eon TM 2 80A and Bionate ® 55D materials. There was a general trend of molecular weight decreasing with time across all polymers and the molecular weights of all materials decreased at a similar relative rate. The polydispersity ratio, M w/ M n, increased with time for all materials. Tensile tests indicated that UTS increased in Elast-Eon TM 2 80A and Bionate ® 55D following implantation under strained conditions. However, ultimate strain decreased and elastic modulus increased in the explanted specimens of all three materials when compared with their unimplanted unstrained counterparts. The results indicate that a soft, flexible PDMS-based polyurethane synthesized using 20% PHMO and 80% PDMS macrodiols has excellent long-term biostability compared with commercially available polyurethanes.

Effect of polydimethylsiloxane macrodiol molecular weight on properties and morphology of polyurethane and polyurethaneurea

AbstractTwo series of polyurethanes and polyurethaneureas were prepared using a two‐step bulk‐solution polymerization procedure. Each series consisted of three polymers based on three molecular weights of α,ω‐bis(6‐hydroxyethoxypropyl) polydimethylsiloxane (PDMS): 940, 1913, and 2955. The soft segment in all cases was an 80:20 mixture of PDMS and poly(hexamethylene oxide) (MW 700), and the hard segment was based on 4,4′‐methylenediphenyl diisocyanate and mixed chain extenders (40 wt %). In the polyurethane (PU) series the chain extender was a 60:40 (mol) mixture of BDO and 1,3‐bis(4‐hydroxybutyl)1,1,3,3‐tetramethyldisiloxane (BHTD), whereas in the polyurethaneurea (PUU) series it was a 60:40 (mol) mixture of BHTD and 1,2‐ethylenediamine. The polymerization was carried out by preparing a prepolymer using a bulk polymerization procedure followed by chain extension in a solution of N,N‐dimethylacetamide. Polymers were characterized by size‐exclusion chromatography, tensile testing, differential scanning calorimetry (DSC), and dynamic mechanical thermal analysis (DMTA). The number‐average molecular weights of the polymers in the PU series were in the range of 114,300–124,500, whereas they were in the 78,400–103,300 range for the PUU series. Polymers with good clarity and mechanical properties were obtained with PDMS‐940 and PDMS‐1913, but those obtained from PDMS‐2955, despite having good tensile strength, had a low percentage of elongation, high modulus, and poor clarity. DSC and DMTA results indicated that regardless of the PDMS molecular weight, the siloxane segments existed as a highly phase‐separated state. This poor compatibility was consistent with the low solubility of PDMS compared to that of the hard‐segment‐forming components. The polymers in the polyurethane series exhibited multiple melting endotherms, attributed to the melting of ordered domains from different hard segments. The combined heats of fusion were similar for the materials in the PU series. In contrast, the polymers in the PUU series showed a hard‐segment order that was significantly less defined, with the heat of fusion approximately a third to a half that of the materials in the polyurethane series. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1565–1573, 2003

Low‐modulus siloxane‐based polyurethanes. I. Effect of the chain extender 1,3‐bis(4‐hydroxybutyl)1,1,3,3‐tetramethyldisiloxane (BHTD) on properties and morphology

AbstractA series of eight polyurethane elastomers was prepared using a two‐step bulk polymerization procedure to investigate the effect of the siloxane chain extender 1,3‐bis(4‐hydroxybutyl)1,1,3,3‐tetramethyldisiloxane (BHTD) on polyurethane properties and morphology. All polyurethanes were based on 40 wt % hard segment derived from 4,4′‐methylenediphenyl diisocyanate (MDI) and a mixture of 1,4‐butanediol (BDO) and BHTD in varying molar ratios. The soft segment was based on an 80 : 20 (w/w) mixture of the macrodiols α,ω‐bis(6‐hydroxyethoxypropyl)polydimethylsiloxane (PDMS, MW 965) and poly(hexamethylene oxide) (PHMO, MW 714). Polyurethanes were characterized by size‐exclusion chromatography, tensile testing, differential scanning calorimetry, dynamic mechanical thermal analysis, and FTIR spectroscopy. Clear and transparent polymers were produced in all cases with number‐average molecular weights in the range of 90,000 to 111,000. The ultimate tensile strength decreased only slightly (15%), but Young's modulus and flexural modulus decreased by 76 and 72%, respectively, compared with that of the pure BDO extended polyurethanes as the amount of BHTD was increased to 40 mol %. This change resulted in “softer” and more elastic polyurethanes. Polyurethanes with BHTD contents above 40 mol % were more elastic but had poor tensile and tear strengths. A 60 : 40 molar ratio of BDO : BHTD produced a “soft” polyurethane, which combined good tensile strength and flexibility. The DSC and DMTA results confirmed that the incorporation of BHTD as part of the hard segment yielded polyurethanes with improved compatibility between hard and soft segments. IR data indicated that the amount of hard segments soluble in the soft‐segment phase increased with increasing BHTD, contributing to the improved phase mixing. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 736–746, 2002