Soft Segment Structure Research Articles

Impact of Block Ratio, Polymer Architecture, and Soft Segment Structure on Modified Asphalt Rheological Performance

Impact of Block Ratio, Polymer Architecture, and Soft Segment Structure on Modified Asphalt Rheological Performance

Influence of soft segment structure, hydrogen bonding, and diisocyanate symmetry on morphology and properties of segmented thermoplastic polyurethanes and polyureas.

A comprehensive review of the structure-morphology-property relations in segmented thermoplastic polyurethanes and polyureas (TPU) is provided. Special emphasis is given to the influence of the soft segment structure, polarity, and molecular weight, diisocyanate symmetry and the nature, extent, and strength of hydrogen bonding on the morphology and thermal and mechanical properties of TPUs. Experimental results obtained on composition-dependent TPU morphology and properties by various techniques were also compared by the morphology profiles generated by computational methods such as quantum mechanical calculations and molecular dynamics simulations.

Impact of Soft Segment Composition on Phase Separation and Crystallization of Multi-Block Thermoplastic Polyurethanes Based on Poly(butylene adipate) Diol and Polycaprolactone Diol

In this work, we explore the influence of soft segment structure on the crystallinity and phase separation of semicrystalline multi-block thermoplastic polyurethanes (TPUs) based on poly(butylene adipate) diol, polycaprolactone diol, and their mixture. According to thermal and structural analyses, the crystal growth rate and degree of crystallinity decrease with an increase in the PCL/PBA ratio and reach a minimum at the equimolar composition of polyesters. A reduction in crystal phase content leads to an improvement in elastomeric behavior. TPU samples with high PCL content demonstrate enhanced crystallinity but a lower melting temperature compared to TPU with PBA crystals. Crystallization of TPU below room temperature results in an enhancement of total crystallinity and a change in the phase composition of the PBA block. The difference in semicrystalline morphology and crystallization kinetics can be explained by the efficiency of phase separation and the density of hydrogen bonding between soft and hard segments. Our findings show that the ratio of the two crystallizable polyesters, combined with the choice of crystallization temperature, allows for independent control over the melting temperature and the overall degree of crystallinity of the TPUs. This significantly impacts the mechanical characteristics of the materials. The effect of adding a second crystallizable polyester on the crystallization behavior, phase composition, and mechanical properties of TPU is discussed for the first time.

The Influence of Soft Segment Structure on the Properties of Polyurethanes.

A series of polyurethanes (PU) were synthesised via one-step polymerisation without a chain extender, using toluene diisocyanate as well as a variety of soft segments composed of different macrodiols. Poly(D,L-lactide) (PDLLA) and polycaprolactone diol (PCL) were synthesised as a polyester type polyols to obtain soft segments. The process of varying the molar ratio of newly synthesised PDLLA in soft segments has been confirmed as a powerful tool for fine-tuning the final properties of PU. Fourier-transformed infrared spectroscopy was used for evaluation of molecular structures of synthesised PDLLA polyol and final PU. Nuclear magnetic resonance spectrometry was used to confirm the presumed structure of PU. The influence of soft segment composition on polyurethane thermal characteristics was examined using thermogravimetric analysis and differential scanning calorimetry. The composition of soft segments had little impact on the thermal stability of PU materials, which is explained by the comparable structures of both polyester polyols. Wide-angle X-ray scattering was utilised to evaluate the effect of amorphous PDLLA on the degree of crystallinity of PCL in soft PU segments. It was discovered that not only did the PDLLA ratio in the soft segment have a substantial influence on the degree of microphase separation in the soft and hard segments, but it also influenced the crystallisation behaviour of the materials. Furthermore, the restriction of crystallisation of the PCL soft segment has been verified to be dependent on the hard segment concentration and the ratio of PDLLA/PCL polyols. The sample with pure PCL as the polyol component achieved the highest degree of crystallinity (34.8%). The results demonstrated that the composition of soft segments directly affected the properties of obtained polyurethane films. These results can be utilised to easily achieve a desirable set of properties required for application in biomaterials.

Tailored Dynamic Viscoelasticity of Polyurethanes Based on Different Diols.

The development of damping and tire materials has led to a growing need to customize the dynamic viscoelasticity of polymers. In the case of polyurethane (PU), which possesses a designable molecular structure, the desired dynamic viscoelasticity can be achieved by carefully selecting flexible soft segments and employing chain extenders with diverse chemical structures. This process involves fine-tuning the molecular structure and optimizing the degree of micro-phase separation. It is worth noting that the temperature at which the loss peak occurs increases as the soft segment structure becomes more rigid. By incorporating soft segments with varying degrees of flexibility, the loss peak temperature can be adjusted within a broad range, from -50 °C to 14 °C. Furthermore, when the molecular structure of the chain extender becomes more regular, it enhances interaction between the soft and hard segments, leading to a higher degree of micro-phase separation. This phenomenon is evident from the increased percentage of hydrogen-bonding carbonyl, a lower loss peak temperature, and a higher modulus. By modifying the molecular weight of the chain extender, we can achieve precise control over the loss peak temperature, allowing us to regulate it within the range of -1 °C and 13 °C. To summarize, our research presents a novel approach for tailoring the dynamic viscoelasticity of PU materials and thus offers a new avenue for further exploration in this field.

Effect of crystalline structure on water resistance of waterborne polyurethane

A series of solvent-free waterborne polyurethanes (WPUs) with different soft segment structure were prepared by respectively using different number-average molecular weight (Mn) of polytetramethylene glycol (PTMG, Mn = 1000, 2000, 3000) and poly (1,4-butylene adipate) (PBA, Mn = 1000, 2000 3000) as main diol in this paper. Effect of soft segment crystallization on water resistance of WPUs was discussed. The crystallization properties of WPU films were investigated by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The water resistance was determined by water absorption ratio. DSC and XRD results confirm that there are no crystalline structures in the WPU films which are synthesized with PTMG (Mn = 1000, 2000, 3000) and PBA (Mn = 1000), while the WPU films synthesized with PBA (Mn = 2000 and 3000) have obvious crystalline structures at room temperature. Meanwhile, the WPU films synthesized with PBA (Mn = 2000 and 3000) possess excellent water resistance because the existence of crystalline structure.

Recyclable Shape-Memory Waterborne Polyurethane Films Based on Perylene Bisimide Modified Polycaprolactone Diol.

Currently, much attention is given to the functionality and recyclability of waterborne polyurethane (WPU). Herein, ε-caprolactone was used as a chain extender for grafting onto perylene bisimide (PBI) and 1,4-butanediol (BDO) via ring-opening reactions to obtain PBI-PCL and BDO- PCL. Then, two kinds of WPU, namely PBI-WPU (PWPU) and BDO-WPU (BWPU), were fabricated using PBI-PCL/polytetrahydrofuran ether glycol (PTMG) and BDO-PCL/PTMG, respectively, as mixed soft segments. The properties and appearance of PWPU and BWPU emulsions were analyzed in terms of particle size, zeta potential and TEM images, and the results showed that PWPU emulsions had uniform particle size distribution and decent storage stability. AFM and DMA results revealed that PWPU films possessed a more significant degree of microphase separation and a higher glass transition temperature (Tg) than BWPU films. The PWPU films displayed good shape-memory and mechanical properties, with tensile strength up to 58.25 MPa and elongation at break up to 1241.36%. TGA analysis indicated that PWPU films had better thermal stability than BWPU films. More importantly, the PWPU films could be dissolved in a mixed solvent of acetone/ethanol (v/v = 2:1) at room temperature. The dissolved PWPU could be dispersed in deionized water to prepare waterborne polyurethane again. After the recycling process was repeated three times, the recycled PWPU emulsion still exhibited good storage stability. The recycled PWPU films maintained their original thermal and mechanical properties. Comparing the properties of BWPU and PWPU showed that the soft segment structure had important influence on waterborne polyurethane performance. Therefore, PWPU may have great potential applications in making recycling and shape-memory coating or paint.

Synthesis and Characterization of IPDI Based Shape Memory Polyurethane

Various polyurethane-based shape memory polymer was synthesized using polycaprolactone (PCL) as soft segment and, hexamethylene diisocyanate (HMDI) and isophorone diisocyanate (IPDI) as the hard segments. Palm kernel oil-based polyol was used to replace part of the petroleum-based polyol due to the increasing demand on renewable resources as a result of environmental awareness. The synthesis has been carried out using two step polymerization method. The effects of varying the molar ratio of IPDI/HMDI on material properties such as crystallinity, transition temperature, morphology, shape memory effect and tensile strength were investigated by using Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), shape memory test and tensile test. A high IPDI content in SMPU results in better shape memory effect, whereas increasing HMDI content leads to a better chain flexibility. In this work, the incorporation of IPDI contributes to the formation of phase separation which enhance the formation of crystalline soft segment structure while the incorporation of HMDI as isocyanate tend to promote phase mixing which enhance the chain flexibility of the SMPU backbone.

Synthesis and characterization of non-ionic and anionic two-component aromatic waterborne polyurethane

PurposeThe purpose of this paper is to synthesize and characterize a series of two-component aromatic waterborne polyurethane (2K-WPU) which is composed of non-ionic and anionic polyisocyanate aqueous dispersion and polyurethane polyol aqueous dispersion.Design/methodology/approachThe polyisocyanate aqueous dispersion was synthesized through non-ionic and anionic hydrophilic modification procedures. The values of the hydrogen bonding index (HBI) and molecule structures of WPU were obtained by Fourier transform infrared (FTIR). The thermal, mechanical and water resistance properties of 2K-WPU films were investigated.FindingsThe appearance of non-ionic polyisocyanate aqueous dispersion and anionic polyisocyanate aqueous dispersion was colorless translucent pan blue and yellow opaque emulsions, respectively. FTIR not only showed that 2K-WPU was obtained from the polymerization of polyisocyanate component and polyhydroxy component by polymerization but also showed that the content of hydrogen bondings of anionic 2K-WPU (WPU 2) was higher than non-ionic 2K-WPU (WPU 1). The glass-transition temperature (Tg), storage modulus and water resistance of WPU 2 were higher than WPU1, whereas the thermal stability of WPU1 was better than WPU 2.Practical implicationsThe investigation established a method to prepare a series of 2K-WPU which was composed of non-ionic or anionic polyisocyanate aqueous dispersion and polyurethane polyol aqueous dispersion. The prepared 2K-WPU film could be applied as substrate resin material in the field of waterborne coating.Originality/valueThe paper established a method to synthesize a series of 2K-WPU. The effect of HBI value and the molecule structure of soft segment on the thermal stability, mechanical and water resistance properties of 2K-WPU films were studied.

Combined Effects of Carbonate and Soft-Segment Molecular Structures on the Nanophase Separation and Properties of Segmented Polyhydroxyurethane

The influence of hard-segment structure on the properties of segmented polyhydroxyurethane (PHU) was investigated using three bis-carbonate molecules: divinylbenzene dicyclocarbonate (DVBDCC), Bisphenol A dicarbonate (BPADC), and resorcinol bis-carbonate (RBC). These carbonates were formulated with poly(tetramethylene oxide) (PTMO)-based and polybutadiene-co-acrylonitrile (PBN)-based soft segments at 40 wt % hard-segment content, resulting in non-isocyanate polyurethanes (NIPUs). Small-angle X-ray scattering, dynamic mechanical analysis, and tensile testing reveal that hard-segment and soft-segment structures may cooperatively influence segmented PHU properties. With PTMO-based soft segment, BPADC yields phase-mixed PHU because of strong intersegmental hydrogen bonding from the hard-segment hydroxyl groups to the soft segment; in contrast, because of moderate intersegmental hydrogen bonding to the PTMO-based soft segment, DVBDCC and RBC lead to nanophase-separated PHUs with 15–17 nm interdomain spacings w...

The Combined Effect of the Soft Segment Structure and the Grafted Side Chains on the Thermal Properties and Low-temperature Flexibilities of Polyurethane

ABSTRACTPolyurethanes containing polycaprolactone diol or poly(tetramethylene ether)glycol as a soft segment and 4,4′-methylenebis(phenyl isocyanate) as a hard segment were used as a polymer frame. Polydimethylsiloxane was grafted onto polyurethanes to reduce the molecular interactions and to improve the mobility of polyurethanes, and the plasticizing groups, n-butyl and 2-ethylhexyl, were attached to polyurethanes by graft polymerization. With an increase in the polydimethylsiloxane content, the Tg of the polydimethylsiloxane–polyurethanes gradually increased, whereas the Tg of the n-butyl and 2-ethylhexyl-attached polyurethanes was not affected by a change in their composition. The polydimethylsiloxane-grafted polyurethanes demonstrated excellent tensile strength, shape recovery, and low-temperature flexibility.

Roles of Soft Segment Length in Structure and Property of Soy Protein Isolate/Waterborne Polyurethane Blend Films

Waterborne polyurethanes (WPUs) with varying lengths of soft segment were synthesized and used to physically modify soy protein isolate (SPI), a protein with good film-forming ability and oxygen barrier characteristic but poor toughness and water resistance, via a simple blending technique without any compatibilizer. The effects of soft segment structure of WPU on the structure and property of resultant blend films were investigated. The tensile strength, elongation at break, and water resistance of the SPI-based films were improved and modulated by adding WPUs with different lengths of soft segment. Compared with neat SPI film, the equilibrium water uptake was decreased by 138% at most for a blend film, and the tensile strength and elongation at break were improved by 96% and 82%, respectively. All the blend films possessed uniform cross-section structures due to the strong interactions between SPI and WPU. Moreover, the blend films exhibited a satisfied water vapor barrier property. It was proved that t...

Study on Microphase Separation of Waterborne Polyurethane by the Infrared Spectroscopy Peak Fitting

A series of waterborne polyurethane (WPU) with different soft segment structures were sythesised, and the effects of the structure and molecular weight of the soft segment on the degree of PU microphase separation were evaluated by the infrared spectroscopy (FTIR) computer peak fitting. The experiment results indicated that phase separation between hard and soft segments of poly (ether–urethane) was more significant than poly (ester–urethane), based on the qualitative analysis on the N–H stretching region of the FTIR spectrum. And the qualitative analysis on the carbonyl stretching region showed that PU with lower soft segment molecular weight had a higher relative amount of hard segment, and possesses higher microphase separation degree. The addition of polyether soft segment PEG had an internal plasticization by actuating the PCD molecular chain. Therefore, it becomes easier for PU to conduct structure adjustment and increased the phase separation degree.

Thermal sensitive polyurethane membranes with desirable switch temperatures

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

Studies on thermoplastic polyurethanes based on new diphenylethane‐derivative diols. III. The effect of molecular weight and structure of soft segment on some properties of segmented polyurethanes

AbstractTwo series of poly(ether urethane)s and one series of poly(ester urethane)s were synthesized, containing, respectively, poly(oxytetramethylene) diol (PTMO) of Mn = 1000 and 2000 and poly(ε‐caprolactone) diol of Mn = 2000 as soft segments. In each series the same hard segment, i.e., 4,4′‐(ethane‐1,2‐diyl)bis(benzenethiohexanol)/hexane‐1,6‐diyl diisocyanate, with different content (∼ 14–72 wt %) was used. The polymers were prepared by a one‐step melt polymerization in the presence of dibutyltin dilaurate as a catalyst, at the molar ratio of NCO/OH = 1 (in the case of the polymers from PTMO of Mn = 1000 also at 1.05). For all polymers structures (by FTIR and X‐ray diffraction analysis) and physicochemical, thermal (by differential scanning calorimetry and thermogravimetric analysis), and tensile properties as well as Shore A/D hardness were determined. The resulting polymers were thermoplastic materials with partially crystalline structures (except the polymer with the highest content of PTMO of Mn = 2000). It was found that the poly(ether urethane)s showed lower crystallinity, glass‐transition temperature (Tg), and hardness as well as better thermal stability than the poly(ester urethane)s. Poly(ether urethane)s also exhibited higher tensile strength (up to 23.5 MPa vs. 20.3 MPa) and elongation at break (up to ∼ 1950% vs. 1200%) in comparison with the corresponding poly(ester urethane)s. Among the poly(ether urethane)s an increase in soft‐segment length was accompanied by an increase in thermal stability, tensile strength, and elongation at break, as well as a decrease in Tg, crystallinity, and hardness. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Synthesis and characterization of L‐tyrosine based polyurethanes for biomaterial applications

The use of amino acid based polymers for biomaterial applications enhance biocompatibility and ensure biodegradability. Two polyurethanes based on L-tyrosine based diphenolic dipeptide, desaminotyrosyl tyrosine hexyl ester as chain extender are synthesized with polyethylene glycol (PEG) and polycaprolactone diol (PCL) as soft segment and hexamethylene diisocyanate as diisocyanate. The chemical structure and molecular characteristics of the polymers were studied by 1H NMR, FTIR, and gel permeation chromatography. Results of DSC and TGA analysis were used for examining the thermal behavior of the polyurethanes. In addition, DSC results were used to analyze the morphology of the polymers, which shows characteristic microphase behavior of the polyurethanes. The tensile properties of the polyurethanes are primarily controlled by the soft segment and are higher in PCL based polymers. Contact angle, water vapor permeation, release of model drug, and water absorption characteristics of the polymers were studied and analyzed in terms of structure of the polyurethanes. In vitro degradation studies show that PEG based polyurethane is more degradable than PCL based polyurethane. The difference in the soft segment structure offers significant variation in the properties of the polyurethanes. These polyurethanes show the potential for use in a variety of biomaterial applications including tissue engineering.

In vitro degradation and in vivo biocompatibility study of a new linear poly(urethane urea)

Segmented poly(urethane urea)s (PUUs) with hard segments derived only from methyl 2,6-diisocyantohexanoate (LDI) without the use of a chain extender have previously been described. These materials, which contain hard segments with multiple urea linkages, show exceptionally high strain capability (1600-4700%). In the study reported here, the rate and effect of hydrolysis of these materials were determined for gamma-sterilized and nonsterilized samples. Materials investigated contained PCL, PTMC, P(TMC-co-CL), P(CL-co-DLLA), or P(TMC-co-DLLA) as soft segments and, as well as their mechanical properties, changes in mass, inherent viscosity (I.V.), and thermal properties were studied over 20 weeks. Results showed that the degradation rate was dependant on the soft segment structure, with a higher rate of degradation for the polyester-dominating PUUs exhibiting a substantial loss in I.V. A tendency of reduction of tensile strength and strain hardening was seen for all samples. Also, loss in elongation at break was detected, for PUU-P(CL-DLLA) it went from 1600% to 830% in 10 weeks. Gamma radiation caused an initial loss in I.V. and induced more rapid hydrolysis compared with nonsterilized samples, except for PUU-PTMC. A cytotoxicity test using human fibroblasts demonstrated that the material supports cell viability. In addition, an in vivo biocompatibility study showed a typical foreign body reaction after 1 and 6 weeks.

Structure‐Morphology‐Property Behavior of Segmented Thermoplastic Polyurethanes and Polyureas Prepared without Chain Extenders

A comprehensive review of the structure‐morphology‐property relations in segmented thermoplastic elastomers (STPE) prepared by the stoichiometric reactions of soft segment oligomers and hard segment precursors is provided. Although the main focus of this study is on linear, segmented, thermoplastic polyurethanes and polyureas, other systems such as linear segmented polyamides and polyesters are also discussed for comparison. Special emphasis is made on the influence of soft segment structure and molecular weight, hard segment symmetry and crystallinity, and the strength of the hydrogen bonding on the morphology and properties of segmented, non‐chain extended thermoplastic elastomers.

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

AbstractVarious segmented polyurethanes of different soft segment structure with hard segment content of about 50 wt% were prepared from 4,4′‐diphenylmethane diisocyanate (MDI), 1,4‐butanediol and different polyols with a Mn of 2000 by a one‐shot, hand‐cast bulk polymerization method. The polyols used were a poly(tetramethylene ether)glycol, a poly(tetramethylene adipate)glycol, a polycaprolactonediol and two polycarbonatediols. The segmented polyurethanes were characterized by gel permeation chromatography (GPC), UV‐visible spectrometry, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), X‐ray diffraction, and their tensile properties and Shore A hardness were determined. The DSC and DMA data indicate that the miscibility between the soft segments and the hard segments of the segmented polyurethanes is dependent on the type of the soft segment, and follows the order: polycarbonate segments > polyester segments > polyether segments. The miscibility between the soft segments and the hard segments plays an important role in determining the transparency of the segmented polyurethanes. As the miscibility increases, the transparency of the segmented polyurethanes increases accordingly. The segmented polyurethanes exhibit high elongation and show ductile behavior. The tensile properties are also affected by the type of the soft segment to some extent. POLYM. ENG. SCI., 47:695–701, 2007. © 2007 Society of Plastics Engineers.

The phase mixing studies on moisture cured polyurethane-ureas during cure

Moisture cured polyurethane-urea (MCPU) is one of the industrially important polymers that shows good thermal, mechanical and weathering properties and is widely used in the reactive hot melt adhesives and coatings. Structural variation of the building blocks, i.e. soft, hard segment and chain extender structure on the phase mixing characteristics during cure in polyether based moisture-cured polyurethanes (MCPUs) has been investigated. Variations in the soft segment structure like polyethylene glycol (PEG), polypropylene glycol (PPG) and polytetramethylene glycol (PTMG) and hard segment like toluene diisocyanate (TDI) or isophorone diisocyanate (IPDI) were made. The effect of isocyanate content (NCO:OH ratio 1.6:1 and 2:1) as well as various aliphatic diol and aromatic diamine chain extenders were also compared. The phase mixing phenomenon during network growth was evaluated by differential scanning calorimetry (DSC) and a correlation was drawn for the degree of cure with the phase mixing property. The change in modulus and thermal stability with the cure advancement were measured by dynamic mechanical and thermal analysis (DMTA) and thermogravimetric analysis (TGA). A correlation was made for the soft, hard segment and chain extender structure to the phase mixing phenomenon during cure. The rate of phase mixing was found to be dependent on the subtle variations in molecular architecture.