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.     

Structure-property behavior of poly(dimethylsiloxane) based segmented polyurea copolymers modified with poly(propylene oxide)

Poly(propylene oxide) (PPO) was incorporated in a controlled manner between poly(dimethylsiloxane) (PDMS) and urea segments in segmented polyurea copolymers and their solid state structure-property behavior was investigated. The copolymers contained PDMS segments of MW 3200 or 7000 g/mol and an overall hard segment content of 10-35 wt%. PPO segments of MW 450 or 2000 g/mol were utilized. Equivalent polyurea copolymers based on only PDMS as the soft segment (SS) component were used as controls. The materials (with or without PPO) utilized in this study were able to develop microphase morphology as determined from dynamic mechanical analysis (DMA) and small angle X-ray scattering (SAXS). DMA and SAXS results suggested that the ability of the PPO segments to hydrogen bond with the urea segments results in a limited inter-segmental mixing which leads to the formation of a gradient interphase, especially in the PPO-2000 co-SS containing copolymers. DMA also demonstrated that the polyureas based on only PDMS as the SS possessed remarkably broad and nearly temperature insensitive rubbery plateaus that extended up to ca. 175 °C, the upper temperature limit depending upon the PDMS MW. However, the incorporation of PPO resulted in more temperature sensitive rubbery plateaus. A distinct improvement in the Young's modulus, tensile strength, and elongation at break in the PPO-2000 and PDMS-7000 containing copolymers was observed due to inter-segmental hydrogen bonding and the formation of a gradient interphase. However, when PPO was incorporated as the co-SS, the extent of stress relaxation and mechanical hysteresis of the copolymers increased relative to the segmented polyureas based on the utilization of only PDMS as the soft segment component.     

The effect of the length of the oxyethylene chain on the conductivity of the polyurethaneurea electrolyte

Polyurethaneureas (PUU), which were synthesized from 4,4′-diphenylmethane diisocyanate (MDI), poly(ethylene glycol) (PEG), and 3,5-diaminobanzoic acid (DABA), were used as polyelectrolytes in this study. Differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FT-IR) were used to monitor the effect of the various kinds of PEG on the changes in morphology of PUU electrolytes corresponding to the concentration of lithium perchlorate (LiClO₄) dopants. The results of DSC and FT-IR indicate the Li⁺ ions coordinate with the soft and hard segments. Additionally, the crystallinity of the PEG soft segment and the ordered hydrogen-bonded urea carbonyl groups decreased with increasing salt concentration. Impedance spectroscopy (IS) measurements show that the PUU electrolyte with the high phase separation degree has the high ionic conductivity. The hard-segment T_g and the soft-segment T_m influence the conductivity behavior of polyelectrolytes with increasing measurement temperature.     

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

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

Structure-property relations of segmented block copolymers with liquid-liquid demixed morphologies

Poly(propylene oxide) based polyether(ester-amide)s (PEEA) with non-crystallisable amide segments were synthesized and their structure-property relations studied. These model segmented block copolymers were used to gain insight in the structure-property relations of block copolymers with liquid-liquid demixed morphologies, also present in segmented polyurethanes. The poly(propylene oxide) used had a molecular weight of 2300 g/mol and was end capped with 20 wt% ethylene oxide. The non-crystallisable amide segments are based on an amorphous polyamide: poly(m-xylylene isophthalamide) and the repetitive length (x) of the amide segment was varied from 1 to 10. Phase separation in these PEEA's occurred by liquid-liquid demixing when the length (x) of the non-crystallisable amide segment was higher than 2 (x>2). TEM experiments showed spherical structures at two size scales, 5-10 nm domains (nano-domains) and 30-500 nm domains (sub-micron domains), both dispersed in a polyether matrix. The size and volume fraction of these spherical domains were found to increase with increasing the amide segment length. The modulus of the materials increased moderately with increasing amide segment content (increasing amide segment length x). The compression and tensile sets values of these PEEA's were found to decrease with increasing amide segment length, thus these PEEA's behave also more elastic at longer amide contents (thus also at higher modulus). Giving time these liquid-liquid demixed segmented block copolymers recovered completely.     

Domain and segment orientation behavior of PBS–PTMG segmented block copolymers

Segment and domain orientation behaviors of a series of poly(butylene succinate) (PBS) –poly(tetramethylene glycol) (PTMG) segmented block copolymers containing different amounts of hard segment were studied with synchrotron small‐angle X‐ray scattering (SAXS) and infrared dichroic methods. Copolymers used in this work consist of PBS as a hard segment, and poly(tetramethylene oxide) (PTMO) of molecular weight 2000g/mol as a soft segment. As hard‐segment content increased, phase‐separated morphology changed from a phase of continuous soft matrix containing isolated hard domain to one of continuous hard matrix. Upon stretching, domains responded differently depending on their initial orientation. Based on SAXS results, two major domain deformation modes, that is, lamellar separation and shear compression, were suggested. The orientation behavior of the hard and soft segments was examined with infrared dichroic method. Upon drawing, the orientation function of the crystalline hard segment decreased at low‐draw ratios. It was interpreted in terms of rotation of long axis of hard domain along the stretching direction. The lowest value of the orientation function of PBS30 was approximately −0.5, that is, theoretical minimum. This result seems to indicate that for PBS30 containing about 30% hard segment, rotation of hard domain occurs without appreciable interdomain interaction, which is consistent with the morphological model suggested on the basis of SAXS results. Plastic deformation of the hard domain due to domain breakup was found to occur at low‐draw ratios for the sample containing higher hard‐segment content. Domain mechanical stability was tested by drawing a sample up to three different maximum draw ratios. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 699–709, 2000     

Structure-property behavior of elastomeric segmented PTMO–ionene polymers. II

A series of segmented ionene polymers based on the reaction of α,ω-bis(dimethyl amino)polytetramethylene oxide with various dihalide compounds were investigated with respect to their structure–property behavior. The placement of quaternary ammonium ions and halide counterions along the polymer chains was varied by changing the molecular weight of the PTMO soft segment and the structure of the dihalide linking agent. The techniques of dynamic mechanical spectroscopy, thermal analysis, small angle X-ray scattering, and stress–strain behavior analysis were applied. For the case when the PTMO soft segment was amorphous, the ambient temperature properties of these materials displayed low modulus, high strength, and high elongation elastomeric behavior with tensile strength enhanced by the strain-induced crystallization of the PTMO. A high level of phase separation existed between the dihalide component relative to the PTMO soft segment. Due to the Coulombic association of the ionene species, these materials displayed many similarities to the segmented urethane ionomers. In particular, distinct domain structure was noted by SAXS, whose dimensional scale was similar to the segmented urethanes. It was also shown, however, that the driving forces for the microphase separation was caused by favorable electrostatic or Coulombic interactions in contrast to segment–segment incompatibility features as in the segmented urethanes.     

Structure-property relations of poly(propylene oxide) block copolymers with monodisperse and polydisperse crystallisable segments

Segmented block copolymers with poly(propylene oxide) and crystallisable segments were synthesized and their structure-property relations studied. As crystallisable segments, amide units based on poly(p-xylylene terephthalamide), were used. The length of the amide segment was varied and these segments either had a monodisperse or random length distribution (polydisperse). The poly(propylene oxide) used was end capped with 20 wt% ethylene oxide (EO-tipped) and had a molecular weight of 2300 g/mol (M_n, incl. EO-tips). These segmented block copolymers are model block copolymers to gain insight in the structure-properties behaviour of related semi-crystalline segmented block copolymers, like polyether(urethane-urea)s. The morphology of the polyether(ester-amide)s (PEEA) was studied with TEM, the thermal properties with DSC and DMTA and the crystalline structures with WAXD. The elastic behaviour of the block copolymers was investigated in tensile and compression.Phase separation in PEEA's with crystallisable, short and monodisperse amide segments occurred by crystallisation, while with crystallisable random amide segments phase separation occurred through liquid-liquid demixing in combination with crystallisation. With short monodisperse amide segments, morphology of dispersed ribbons with a high aspect ratio was observed. PEEA's containing these monodisperse amide segments had higher moduli and better elastic properties as compared to PEEA's with random length amide segments. Increasing the length of the monodisperse amide segment increased the modulus and decreased the compression set of the corresponding blockcopolymers.     

Structure-property behaviour of segmented polyether-MDI-butanediol based urethanes: effect of composition ratio

The structure-property relationship of a systematic series of segmented polyurethanes was investigated segment was 4,4′-diphenylmethane diisocyanate (MDI) extended with 1,4-butanediol, and the soft segment was 2000 M_w poly (tetramethylene oxide) ether. X-ray studies reveal that some hard segment segment was 2000 mW poly (tetramethylene oxide) ether. X-ray studies reveal that some hard segment crystallization occurs at high hard segment content (45%). In addition, other morphological changes take place as the hard segment fraction is increased. The texture changes from that in which little such domain content exists at low hard segment levels (15%), to that in which the polymer has an interlocking domain morphology at high hard segment content (35 and 45%). Preferable elastomeric properties (low hysteresis, high extension) can be obtained when isolated hard segment domains exist (25% hard segment). Thermal treatment of the samples results in domain disruption and hard-soft segment mixing. However, this phenomenon, and the consequent time-dependent structure recovery as the material is allowed to age, is composition dependent. In general, crystalline domains, when present, are disrupted the least while the fastest recovery is displayed by samples with noncrystalline domain texture. This behaviour can be explained qualitatively in terms of kinetic diffusion effects relative to the thermodynamic driving forces for phase separation.     

Influence of soft segment molecular weight on the mechanical hysteresis and set behavior of silicone-urea copolymers with low hard segment contents

Effect of polydimethylsiloxane (PDMS) soft segment molecular weight (M_n = 3200, 10,800 and 31,500 g/mol) and urea hard segment content (2.0-11.4% by weight) on the hysteresis and permanent set behavior of segmented silicone-urea (TPSU) copolymers were investigated. In spite of very low hard segment contents, all copolymers formed self-supporting films and displayed good mechanical properties. When the mechanical hysteresis and set behavior of the silicone-urea copolymers with similar hard segment contents (around 7.5% by weight) but based on PDMS-3K, PDMS-11K and PDMS-32K were compared, it was very clear that as the PDMS molecular weight increased, hysteresis and instantaneous set values decreased significantly. Copolymers based on the same silicone soft segment (PDMS-11K or PDMS-32K) but with different hard segment contents showed a linear increase in hysteresis and a slight decrease in the instantaneous set as a function of hard segment content. Constant initial stress creep experiments also showed lower creep as the PDMS segment molecular weight increased for copolymers with similar urea contents. Since the critical entanglement molecular weight (M_e) of PDMS is stated to be 24,500 g/mol, our results tend to suggest important contribution of chain entanglements on the hysteresis and instantaneous set of these silicone-urea copolymers.     

Fouling release nanostructured coatings based on PDMS-polyurea segmented copolymers

The bulk and surface characteristics of a series of coatings based on PDMS-polyurea segmented copolymers were correlated to their fouling release performance. Incorporation of polyurea segments to PDMS backbone gives rise to phase separation with the extensively hydrogen bonded hard domains creating an interconnected network that imparts mechanical rigidity. Increasing the compositional complexity of the system by including fluorinated or POSS-functionalized chain extenders or through nanoclay intercalation, confers further thermomechanical improvements. In analogy to the bulk morphology, the surface topography also reflects the compositional complexity of the materials, displaying a wide range of motifs. Investigations on settlement and subsequent removal of Ulva sporelings on those nanostructured surfaces indicate that the work required to remove the microorganisms is significantly lower compared to coatings based on standard PDMS homopolymer. All in all, the series of materials considered in this study demonstrate advanced fouling release properties, while exhibiting superior mechanical properties and, thus, long term durability.     

Effect of nano ribbons formed by the amide segment on the solvent resistivity of segmented block copolymers based on polystyrene

A segmented block copolymer is synthesized using dihydroxy terminated polystyrene (PSt) (M_W = 2,500 g/mol) and crystallizable amide segments. PSt length in the copolymer is varied from 2,500 to 10,000 g/mol using dimethylterephthalate (T). Amide segment is synthesized in situ using diamine‐diamide 6X6 (X = A or T) (synthesized by dimethylterepthalate [T], adipic acid [A], and hexamethylenediamine [6]) and T. This work is to modify the high T_g amorphous PSt to a semicrystalline copolymers (‐(PSt‐T)_y‐6X6‐T‐)‐_n). These copolymers have a very high inherent viscosity and depending on the amide concentration, the melting temperature of the polymers was ranged between 129°C and 248°C. The crystallinity of the amide segments is up to 75%. The AFM analysis showed the presence of crystalline ribbons with a high aspect ratio. All the polymers show single stage decomposition temperature centered around 420°C. The solvent resistivity of these materials is very high even at a low concentration of (5 wt%) amide content. POLYM. ENG. SCI., 58:361–368, 2018. © 2017 Society of Plastics Engineers     

Influence of chemical crosslinks on the elastic behavior of segmented block copolymers

Polyether(ester-amide)s (PEEA) segmented block copolymers with di- and tri-functional poly(propylene oxide)s and amide segments were synthesized and the elastic properties studied. The difunctional polyether used had a molecular weight of 2300 g/mol end capped with 20 wt% ethylene oxide. The trifunctional polyether had a molecular weight of 6000 g/mol of which each arm had a molecular weight of 2000 g/mol. The concentration of the trifunctional polyether of the total ether content was varied from 0 to 40 mol%. The amide segments were of a non-crystallizing type with a content in the copolymers of 27 wt%. Phase separation occurred, therefore, only by liquid-liquid demixing. The thermal mechanical properties of the polymers were analyzed by dynamic mechanical thermal analysis and the elastic properties by compression set and tensile set. The materials are model blockcopolymers for the more complex chemically crosslinked polyether(urethane-urea)s (PEUU).With increasing amounts of chemical crosslinks the glass transition temperature and the modulus did not change noticeably. However, the elastic behavior as measured by compression set and tensile set, improved dramatically. Giving time all materials recovered completely and with increasing amount of chemical crosslinks this recovery happened faster. An explanation is given for the (viscoelastic) deformation in these copolymers.     

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

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

The study on the conductivity and morphology of polyurethaneurea electrolytes based on poly(ethylene glycol) 2000 and LiClO4

Polyurethaneureas (PUU), which were synthesized from 4,4′-diphenylmethane diisocyanate (MDI), poly(ethylene glycol) (PEG, MW=2000), and 3,5-diaminobenzoic acid, were used as the matrix of the polyelectrolytes in this study. Differential scanning calorimetry (DSC), Fourier-transform infrared spectroscopy (FT-IR), and ⁷Li magic angle spinning (MAS) solid-state NMR were used to monitor changes in the morphology of PUU electrolytes corresponding to the concentration of lithium perchlorate (LiClO₄) dopants. The results of DSC and FT-IR indicate the different polymer complexes formed by the interaction of the Li⁺ ions with the different coordination sites of PUU. The ⁷Li MAS solid-state NMR investigation of the PUU electrolytes points out that two different Li⁺ environments exist at lower temperature. The results of DSC and the ⁷Li MAS solid-state NMR show that Li⁺ ions are preferentially coordinated to the ether oxygen of the PEG soft-segment when the salt concentration is below 0.1 mmol LiClO₄(gPUU)⁻¹. Impedance spectroscopy measurements show that the conductivity behavior followed the Arrhenius equation and was influenced by the hard-segment T_g. One of the PUU electrolytes under the investigation has an ionic conductivity as high as 3.0×10⁻⁵ S cm⁻¹ at 30 °C.     

Effect of mesophase separation and crystallization on the elastomeric behavior of olefin multi-block copolymers

The mesophase separation and crystallization as well as the elastomeric properties of olefin multi-block copolymers (OBCs) are studied. The solid state morphologies of the OBCs are determined by the competition between mesophase separation and crystallization of hard blocks. The OBC with lower Δ_C8 (octene content difference between soft and hard blocks) displays a spherulitic superstructure, while the OBC with higher Δ_C8 exhibits mesophase separation. The two OBCs show very different elastomeric properties. Wide-angle X-ray scattering shows that the two OBCs have different deformation mechanisms. It is proposed that the cooperative deformation of crystalline phase makes an important contribution to the elastomeric properties.     

Synthesis and characterization of hexafluoroisopropylidene bisphenol poly(arylene ether sulfone) and polydimethylsiloxane segmented block copolymers

A series of hexafluoroisopropylidene bisphenol poly(arylene ether sulfone) (BAF PAES) segmented block copolymers with varying fractions of polydimethylsiloxane (PDMS) were synthesized by a condensation reaction of hydroxyl-terminated BAF PAES and dimethylamino endcapped PDMS. The segmented block copolymers have high thermal stability. The BAF PAES homopolymer exhibits a tensile modulus of 1700 MPa and an elongation at break of 16%. Copolymerizing BAF PAES with increasing molecular weight amounts of PDMS results in tensile properties ranging from plastic to elastomeric where the elongation is 417% for a segmented block copolymer with 64 wt% PDMS incorporated. The morphological properties of these segmented block copolymers were characterized by atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). AFM and TEM images show the segmented block copolymers were microphase separated, and comparison with bisphenol A (BA) PAES-b-PDMS segmented block copolymers revealed complex differences between the morphological behavior of the two systems. SAXS data of the segmented block copolymers supports AFM and TEM images, indicating microphase separation but little long-range order.     

Effect of silica nanoparticles on morphology of segmented polyurethanes

Two series of segmented polyurethanes having soft segment concentration of 50 and 70 wt%, and different concentrations of nanometer-diameter silica were prepared and tested. Atomic force microscopy revealed a strong effect of nanoparticles on the large-scale spherulitic morphology of the hard domains. Addition of silica suppresses fibril formation in spherulites. Filler particles were evenly distributed in the hard and soft phase. Nano-silica affected the melting point of the hard phase only at loadings >30 wt% silica. A single melting peak was observed at higher filler loadings. There is no clear effect of the filler on the glass transition of soft segments. Wide-angle X-ray diffraction showed decreasing crystallinity of the hard domains with increasing filler concentration in samples with 70 wt% soft segment. Ultra small-angle X-ray scattering confirms the existence of nanometer phase-separated domains in the unfilled sample. These domains are disrupted in the presence of nano-silica. The picture that emerges is that nano-silica suppresses short-scale phase separation of the hard and soft segments. Undoubtedly, the formation of fibrils on larger scales is related to short-scale segment segregation, so when the latter is suppressed by the presence of silica, fibril growth is also impeded.     

Aliphatic poly(oxytetramethylene) ionenes: effect of counter-anion on the properties and morphology

Effect of counter-anion on the properties and morphology of aliphatic poly(oxytetramethylene) ionenes was investigated, and the relationship between the properties and morphology was elucidated. The ionenes possess elastic properties at low elongations whereas they predominantly exhibit a plastic deformation at high elongations. The morphology of the ionenes was analysed in the nanometer scale by fitting a cascade model for randomly branched f-functional polycondensates incorporated in Debye-Bueche random-two-phase model and the interference term by the interdomain interaction on their small-angle X-ray scattering profiles. The size of ionic domains and distance between the domains were smaller and shorter in the ionene with bromide counter-anion than those in the ionene with chloride counter-anion, respectively. The formation of crystallite of poly(oxytetramethylene) (POTM) segments was detected in the ionene with chloride counter-anion at room temperature. These characteristics of aliphatic POTM ionenes gave the difference in their mechanical and thermal properties.     

Morphology and micromechanical behavior of binary blends comprising block copolymers having different architectures

Morphology and deformation behavior of binary blends comprising styrene/butadiene block copolymers (polystyrene content, Φ_PS∼0.70) having different molecular architectures were studied by means of transmission electron microscopy and tensile testing. In contrast to the binary diblock copolymer blends discussed in literature, the phase separation behavior of the blends investigated was found to be strongly affected by asymmetric molecular architecture. The blends showed macrophase separated grains, in which the structures resembled the microphase morphology of none of the blend components. Unlike the classical rubber-modified or particle-filled thermoplastics, neither debonding at the particle/matrix interface nor the particle cavitation was observed in these nanostructured blends. The microdeformation of the blends revealed plastic drawing of polystyrene lamellae or PS struts dispersed in rubbery matrix and orientation of the whole deformation structures along the strain direction.