FTIR investigation of the influence of diisocyanate symmetry on the morphology development in model segmented polyurethanes

Novel segmented polyurethanes with hard segments based on a single diisocyanate molecule with no chain extenders were prepared by the stoichiometric reactions of poly(tetramethylene oxide)glycol (M_n=1000 g/mol) (PTMO-1000) and 1,4-phenylene diisocyanate (PPDI), trans-1,4-cyclohexyl diisocyanate (CHDI), bis(4-isocyanatocyclohexyl)methane (HMDI) and bis(4-isocyanatophenyl)methane (MDI). Time dependent microphase separation and morphology development in these polyurethanes were studied at room temperature using transmission FTIR spectroscopy. Solvent cast films on KBr discs were annealed at 100 °C for 15 s and microphase separation due to self organization of urethane hard segments was followed by FTIR spectroscopy, monitoring the change in the relative intensities of free and hydrogen-bonded carbonyl (CO) peaks. Depending on the structure of the diisocyanate used, while the intensity of free CO peaks around 1720-1730 cm⁻¹ decreased, the intensity of H-bonded CO peaks around 1670-1690 cm⁻¹, which were not present in the original samples, increased with time and reached saturation in periods ranging up to 5 days. Structure of the diisocyanate had a dramatic effect on the kinetics of the process and the amount of hard segment phase separation. While PPDI and CHDI based polyurethanes showed self-organization and formation of well ordered hard segments, interestingly no change in the carbonyl region or no phase separation was observed for MDI and HMDI based polyurethanes. Quantitative information regarding the relative amounts of non-hydrogen bonded, loosely hydrogen bonded and strongly hydrogen bonded and ordered urethane hard segments were obtained by the deconvolution of CO region and analysis of the relative absorbances in CO region.     

Microdomain composition and properties differences of biodegradable polyurethanes based on MDI and HDI

The study of the effect of the diisocyanate structure on the microstructure and macroscopic properties of polyurethanes was the main aim of this work. Biodegradable segmented thermoplastic elastomeric polyurethanes based on a poly(hexamethylene carbonate‐co‐caprolactone)diol (PHM‐co‐PCL) as soft segment were synthesized using 1,4‐butanediol (BD) as chain extender and both 4,4′‐diphenylmethane diisocyanate (MDI) and 1,6‐hexamethylene diisocyanate (HDI) as components of the hard segment by the two shoot synthesis procedure. Microphase structure and properties were analyzed using Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC) as complementary techniques, used to characterize thermal transitions of the polyurethanes and to assign them to determinate functional groups interactions. Gaussian deconvolution technique was used to decompose carbonyl region in four peaks and to study the hydrogen bonding within the different polyurethanes. Both DSC and FTIR showed that MDI‐based biodegradable polyurethanes were less phase segregated than to those based on HDI, and thus that diisocyanate structure has an important role on microdomain composition and polyurethanes properties. Macroscopic properties as hardness and water‐polymer contact angles are related to polyurethanes microphase compositions. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers.     

Hydrogen bonding and morphological structure of segmented polyurethanes based on hydroquinone– bis(β-hydroxyethy)ether as a chain extender

Two series of polyether polyurethanes based on hydroquinone bis(β-hydroxyethy) ether (HQEE) or 1,4-butanediol (BDO) as a chain extender were prepared by a one-step bulk polymerization process. Their hydrogen bonding and morphological structure were studied by means of Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). Compared with BDO-based polyurethanes, HQEE-based polyurethanes showed better phase segregation and higher extent of ordering in the hard domain. Besides short-range hydrogen bonds, a considerable amount of long-range hydrogen bonds existed in amorphous phase of the hard domain. The soft segment was easier to crystallize, and the melting temperature of the hard domain was elevated in HQEE-based polyurethanes. Its hard domain displayed a banded structure, rather than spherulitic structure in BDO-based polyurethanes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 2895–2902, 1999     

Polyurethanes with monodisperse rigid segments based on a diamine–diamide chain extender

Polyether(bisurethane‐bisurea‐bisamide)s (PEUUA) based on poly(tetramethylene oxide) (PTMO) were synthesized by chain extension of PTMO endcapped with a diisocyanate (DI), and a diamine–diamide extender. The prepolymers were PTMOs with molecular weights between 1270 and 2200 g mol^?1, either endcapped with 4,4′‐diphenylmethane diisocyanate (MDI), 2,4‐toluene diisocyanate (2,4‐TDI), or 1,6‐hexane diisocyante (HDI) and with a low content of free diisocyanate (<0.1 wt %). The diamine–diamide (6A6) extender was based on hexamethylene diamine (6) and adipic acid (A). In this way, segmented polyurethanes with monodisperse rigid segments (DI‐6A6‐DI) were obtained. The PEUUAs were characterized by DSC as well as temperature‐dependent FTIR and DMTA. The mechanical properties of the polymers were evaluated by compression set and tensile test measurements. The polyurethanes with monodisperse rigid segments displayed low glass transition temperatures, almost temperature‐independent rubbery plateaus and sharp melting temperatures. The crystallinities of the hard segments were 70–80% upon heating and 40–60% upon cooling. The rate of crystallization was moderately fast as the supercooling (T_m ? T_c) was in the order 36–54°C. The polyurethanes based on HDI had a much higher rubber modulus as compared to the MDI and 2,4‐TDI‐based polymers, because of a higher degree of crystallinity and/or a higher aspect ratio of the crystallites. The HDI residues are flexible and not sterically hindered and could therefore be more easily packed than MDI or 2,4‐TDI residues. Polyurethanes with monodisperse DI‐6A6‐DI hard segments have interesting properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

浇注型聚氨酯弹性体耐酸碱性能研究

以不同种类二异氰酸酯和各种多元醇为主要原料,通过预聚法合成了一系列结构不同的聚氨酯弹性体(PUE),研究了软硬链段的化学结构及硬段含量对PUE耐酸碱性能的影响。结果表明,聚四氢呋喃醚多元醇作为软段具有更加稳定的化学结构,有利于PUE耐酸碱性的提高。选用刚性较大的二异氰酸酯4,4’-二苯基甲烷二异氰酸酯(MDI-100),以刚性对称的氢醌-双(β-羟乙基)醚(HQEE)为扩链剂,有利于聚氨酯分子链硬段的规整排列从而产生结晶,可提高PUE的耐酸碱性。     

Morphology–properties relationship in high‐renewable content polyurethanes

The effect of diisocyanate nature and hard segment content on the morphology and properties of high‐renewable content segmented thermoplastic polyurethanes was studied. Vegetable oil‐based polyether diol and corn sugar derived chain extender were used as renewable reactants together with an aliphatic (1,6‐hexamethylene diisocyanate, HDI) or aromatic (4,4′‐diphenylmethane diisocyanate, MDI) diisocyanate as hard segment. Segmented thermoplastic polyurethanes were synthesized by two‐step bulk polymerization. Morphology and physicochemical, thermal and mechanical properties were analyzed by Fourier‐transform infrared spectroscopy, differential scanning calorimetry, dynamic mechanical analysis, atomic force microscopy, and mechanical testing. The effect of mechanical deformation over the microstructure was also analyzed. Changes in crystallinity and hard segment hydrogen bonding after mechanical testing were evaluated by Fourier‐transform infrared spectroscopy and differential scanning calorimetry. The increase of physical crosslinking sites by aromatic diisocyanate and chain extender ratio in the polyurethane results in hard segment crystalline domains with spherulitic morphology, which enhance the stiffness and hardness whereas percentage elongation at break diminish. The flexible, linear aliphatic nature of HDI favors the arrangement of urethane groups thus creating strong hard segment interactions and hard segment crystal microdomains composed of fibrillar morphology are observed. POLYM. ENG. SCI., 54:2282–2291, 2014. © 2013 Society of Plastics Engineers     

Mechanical response of dibenzyl-based polyurethanes with diol chain extension

A systematic investigation was made of the effects of varying hard and soft segment chemistry, crosslinking and preparation procedures, on the mechanical response of melt-cast polyurethane elastomers. In particular, two hard segments were compared, based on the diisocyanates: 4,4′-methylene bis(phenyl isocyanate) (MDI) and 4,4′-dibenzyl diisocyanate (DBDI). Rotation around the central -CH₂-CH₂- bridge in DBDI allows alignment of aromatic rings and hence crystallization within the hard phase, which is not available with MDI in melt-cast polyurethanes. Thus, new polymers were achieved, with a controlled ordering of copolymer hard segment blocks on the macromolecular chain. Wide angle X-ray diffraction of the as-moulded polymers revealed the presence of crystallinity in some cases, in the DBDI-based PU materials. Mechanical tests included load-unload cycles at constant rate of extension, with measurement of hysteresis and strain recovery, and stress relaxation tests. The presence of DBDI hard segments instead of MDI led systematically to increases in: the input strain energy to a given elongation, hysteresis and residual strain under cyclic loading, and stress relaxation. The results were interpreted in terms of a physically-based constitutive model framework previously proposed. This revealed that the observed effects of varying hard segment could all be explained by the hard domains having a higher flow stress in the presence of DBDI relative to MDI, associated with increased hydrogen bonding in DBDI-based polymers, which is enhanced in some cases by hard segment crystallinity. Materials with mixed MDI and DBDI hard segments were found to give the optimum combination of high input strain energy, but minimum residual strain, compared to equivalent materials based on MDI or DBDI alone.     

Synthesis and characterization of segmented polyurethanes containing aromatic diol chain extenders

A series of segmented polyurethanes (SPUs), based on hexamethylene diisocyanate (HDI) and polytetramethylene glycol (PTMG) as soft segments and then extended with alkylene di(4-hydroxybenzoate), HB as hard segments, were synthesized in this study. The effect of the number of methylene units in HB (from 2 to 6) on the microphase separation of the SPUs was evaluated by means of a differential scanning calorimeter (DSC) and a polarized optical microscope (POM). The kinetic reaction between HB and HDI was determined by Fourier transform infrared spectroscopy. The rate constants of the second-order kinetics showed that the reactions of HDI and HB with odd numbers of methylene units appeared to be faster than those with even numbers of methylene units. The results from POM showed that the SPUs with even numbers of methylene units in the HB have a higher degree of phase separation between the hard and soft segments than those with odd numbers of methylene units in HB. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 539–546, 1997     

Thermoset polyurethanes containing hydroquinone di(β-hydroxyethyl) ether

A thermoset polyurethane resin extended with hydroquinone di(β-hydroxyethyl) ether (HQEE) was found to have good thermomechanical properties suitable for external elastomeric automotive applications. A resin composed of diphenylmethane diisocyanate (MDI), ethylene glycol, and a primary polyol was found to have good mechanical properties but was too reactive for processing as a one-component resin. Replacing the liquid ethylene glycol extender with the solid HQEE substantially increased the pot life of the resin as well as improving the modulus properties. When catalyzed with zinc stearate this resin had sufficient pot life at room temperature, at least 4 hr, to be processed as a one-component system but still cure rapidly at elevated temperatures. The HQEE-extended materials required only 50% hard-block content (isocyanate plus extender) to have the same modulus at room temperature as ethylene glycol-extended materials containing 60% hard block. By using a graft or polymer polyol, the required hard-block content could be reduced to 40% The polyurethane of MDI/SAN graft polyol/HQEE containing 40% hard block had a flex modulus of 230 MPa, tensile strength of 18 MPa, and 240% elongation. The ratio of flex moduli measured at ?29 and +70°C was 2.7, which compared very favorably to conventional RIM systems. The modulus at elevated temperatures was particularly improved, which is important in painting operations.     

A small-angle X-ray scattering study of microphase separation transition of polyurethanes: Effect of hard segments

Three segmented polyurethane block copolymers PU-M, PU-X and PU-T containing different diisocynates, diphenylmethane-4,4'-diisocyanate (MDI), xylene diisocyanate (XDI) and 2,4-toluene diisocyanate (TDI) respectively with the same chain extender 1,4-butanediol (BD) and soft segment polyester-diol were investigated by small-angle X-ray scattering (SAXS). Microphase separation transition (MST) occurred due to the thermodynamic incompatibility between the soft and hard segments. The long domain spacing, interfacial thickness (or transition layer thickness), core zone, and lamellar thickness were determined for these three different polyurethanes from one dimension correlation function after the Fourier transformation of small-angle X-ray scattered intensity curve based on the Strobl and Schneider model. The structural parameters for these three polyurethanes determined from the scattering measurements indicate that the degrees of microphase separation are in the following sequence: PU-M > PU-X > PU-T.     

The effect of fluorinated side chain attached on hard segment on the phase separation and surface topography of polyurethanes

It has been well established that polyurethanes exhibit a two-phase micro-structure due to the thermodynamic incompatibility between the soft segments and hard segments. In this work, we reported the effect of fluorinated side chain attached on hard segment on the phase separation and surface topography of polyurethanes. Two sets of fluorinated polyurethanes, namely, poly(ether urethane)s and poly(carbonate urethane)s containing various amounts of chain extender of fluorinated side chains, were investigated by DSC, XPS, DMA, AFM and FTIR. It was found that the phase separation in both bulk and surface increases in fluorinated poly(carbonate urethane)s and the phase mixing increases in fluorinated poly(ether urethane)s, with increasing amounts of fluorinated side chain. The increased degree of hydrogen bonding between hard segments and soft segments was observed by FTIR for fluorinated poly(ether urethane), which is believed to result in the enhanced phase mixing, and the enhanced association of domains with long-range order (hydrogen bonding) between hard segments was evident for fluorinated poly(carbonate urethane)s, which may correspond to the enhanced phase separation. The result is new and provides direct connection between surface topography and bulk phase separation of polyurethanes.     

Structure-property relationships in thermoplastic elastomers: I. Segmented polyether-polyurethanes

Segmented poly(ether-b-urethanes) have been synthesized with 2000 MW polypropylene oxide coupled with diisocyanates and diol type chain extenders. The diisocyanates used were symmetric rigid 4, 4′-diphenylmethane diisocyanate (MDI), linear aliphatic hexamethylene diisocyanate (HDI), and unsymmetric rigid toluene-2, 4-diisocyanate (TDI). The chain extenders were symmetric N, N′-bis(2-hydroxyethyl) terephthalamide (BT) and N, N′-bis(2-hydroxyethyl)-hydroquinone (BH) unsymmetric N, N′-bis(2-hydroxyethyl)isophthalamide, and linear aliphatic 1, 4-butanediol (B). Hard segment contents ranged from 20 to 40 wt percent. The thermal behavior of these materials is consistent with phase separation into separate hard and soft domains, In order of increasing temperature above the soft segment T_g, there are transitions which occur in the regions ?56 to ?36°C (T_a), 70 to 90°C (T_b), and 138 to 168°C (T_m). The former is probably associated with soft segment change from a viscoelastic to an elastomeric state. Values of T_a are ～ ?51 C and ?56°C for the MDI-BT and HDI-BT polymers, respectively, and are independent of hard segment content. Microscopy showed that the former polymers have spherulitic morphology, so these materials have good microphase separation and exhibit crosslinked elastomeric properties. The TDI-BT or BI and MDI-B polyurethane have composition-independent T_a values of ?41 and ?36°C, respectively. These materials probably have considerable “domain-bound-ary-mixing”. At low hard segment content the MDI-B polymers behave as non-crosslinked elastomers. Only the MDI-BI polymers have _Ta values, which are strongly affected by composition, increasing in magnitude with increasing of hard segment content. This is interpreted as significant “mixing-in-domains” and is supported by morphology observed by microscopy. The next higher transition, T_b, probably involves dissociation of interdomain hydrogen bonding. In the case of the MDI-BT polyurethanes, the spherulites associated with the hard domains had disappeared at 141°C and the few small spherulites in the MDI-BI polymers disappeared at 130°C. The T_b values are 70, 83 to 90, and 100°C for the MDI-B, HDI-BT, and HDI-BI polymers, respectively. The melting transitions occurred between 138 to 168°C for the various polyurethanes except for the MDI-BT systems which decompose before melting. Thermal decomposition is a two-stage process. Hard segments decompose between 200 and 300°C. The initial decomposition temperatures are lowered in the presence of strong acid. Soft segments decompose at higher temperatures. The mechanical properties of the MDI-BI polyurethanes are charateristic of crosslinked elastomer, the results of which will be presented in a subsequent paper.     

Low‐modulus siloxane–polyurethanes. Part II. Effect of chain extender structure on properties and morphology

A series of six polyurethanes were prepared to study the effect of silicon chain extender structure on properties and morphology of siloxane–polyurethanes. Polyurethanes were prepared by a two‐step bulk polymerization without a catalyst. The soft segment of the polyurethanes was based on an 80:20 (w/w) mixture of α,ω‐bis(6‐hydroxyethoxypropyl) polydimethylsiloxane (PDMS, MW 966) and poly(hexamethylene) oxide (MW 714). The hard segment was based on 4,4′‐methylenediphenyl diisocyanate (MDI) and a 60:40 molar mixture of 1,4‐butanediol (BDO) and a silicon chain extender. Silicon chain extenders (SCE) investigated were 1,3‐bis(4‐hydroxybutyl)1,1,3,3‐tetramethyldisiloxane (BHTD), 1,3‐bis(3‐hydroxypropyl)1,1,3,3‐tetramethyldisiloxane (BPTD), 1,4‐bis(3‐hydroxypropyl)1,1,3,3‐tetramethyldisilylethylene (HTDE), 1,3‐bis(6‐hydroxyethoxypropyl)1,1,3,3‐tetramethyldisiloxane (BETD). All polyurethanes were clear and transparent with number average molecular weights between 72,000 to 116,000. Incorporation of the silicon chain extender resulted in polyurethanes with low‐modulus and high elongation. This was achieved without significant compromise in ultimate tensile strength in all cases, except BETD. Differential scanning calorimetry (DSC) results showed that the silicon chain extenders did not significantly disrupt the hard segment crystallinity, but exhibited a unique morphological feature where SCE‐based hard segments formed separate domains, which may be the primary reason for achieving low modulus without significant compromise in strength. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1092–1100, 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

A 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     

A novel side chain liquid crystalline polyurethane

Summary Side chain liquid crystalline polyurethanes (SCLP) without flexible spacer were synthesized by a two step block copolymerization reaction. The polyurethanes were based on azobenzene-type mesogenic diol chain extender (DR-19), a poly(tetramethylene oxide) (PTMO) soft segment, and different diisocyanates, including 4,4-diphenylmethane diisocyanate (MDI) and hexamethylene diisocyanate (HDI). The polyurethane samples obtained from DR-19 or DR-19 and PTMO with HDI had mesomorphic phases as determined by DSC and polarizing microscopy. Received: 19 March 1998/Revised version: 27 May 1998/Accepted: 17 June 1998     

The effect of diisocyanate isomer composition on properties and morphology of polyurethanes based on 4,4′-dicyclohexyl methane diisocyanate and mixed macrodiols (PDMS–PHMO)

Three series of polyurethanes were prepared having 42 wt % hard segments based on 4,4′-dicyclohexyl methane diisocyanate (H₁₂MDI) with trans,trans isomer contents in the 13 to 95 mol % range and 1,4-butanediol chain extender. The soft segments were based on macrodiols poly(hexamethylene oxide) (PHMO, MW 696), α,ω-bishydroxyethoxypropyl polydimethylsiloxane (PDMS, MW 940), and two mixed macrodiol compositions consisting of 80 and 20% (w/w) PDMS. H₁₂MDI with 35, 85, and 95% trans,trans isomer contents were obtained from commercial H₁₂MDI (13% trans, trans) by fractional crystallization, and all polyurethanes were prepared by a one-step bulk polymerization procedure. The polyurethanes based on the commercial diisocyanate-produced materials soluble in DMF with molecular weights in the 53,655–75,300 range and generally yielded clear and transparent materials. The polyurethanes based on H₁₂MDI with trans,trans contents of 35% or higher yielded materials insoluble in N,N-dimethylformamide (DMF) and were generally opaque. Mechanical properties, such as tensile strength and elongation at break, decreased with increasing trans,trans content, while the Young's modulus and Shore hardness increased. The polyurethanes based on mixed macrodiols yielded higher tensile properties than those of materials based on individual macrodiols. The best mechanical properties were observed for a polyurethane consisting of a soft segment based on PDMS–PHMO (80/20) and a hard segment based on commercial H₁₂MDI and BDO. Differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR) were employed to characterize the polyurethane morphology. DSC results confirmed that the polyurethanes based on H₁₂MDI with high trans,trans isomer were very highly phase separated, exhibiting characteristic hard segment melting endotherms as high as 255°C. The other materials were generally phase mixed. FTIR spectroscopy results corroborated DSC results. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 573–582, 1999     

Thermoplastic polyurethane elastomers—thermostability in relation to composition

The dependence of thermal stability of poly(ester-urethane) elastomers on their composition was investigated. For polyurethanes of hard segment content above 3070, hydroquinone di(β-hy-droxyethyl) ether (HQEE) is the choice for good thermomechanical stability while the stability of bisphenol-A-based polymers is rather poor. The temperature sensitivity of modulus was essential in the range of -30-24OC, while in the range of 24–70°C i t is moderate. The modulus in the low temperature region depends on the nature of polyesterdiol. Its drop with temperature is lower for poly(hexamethy1ene carbonate) glycol (PHC)-based polyurethanes than poly(ethy1ene-adipate) glycol (PEAd)-based ones. In the high temperature region it also depends on the nature and amount of hard segments. The thermal stability of 4,4′-dicyclohexylmethane diisocyanate (SMD1)-based polyurethanes is inferior to the one for 4,4′-diphenylmethanediisocyanate (MD1)-derived polymers.     

Effect of chain extender structure on the properties and morphology of polyurethanes based on H12MDI and mixed macrodiols (PDMS–PHMO)

The effect of chain extender structure on properties and morphology of α,ω‐bis(6‐hydroxyethoxypropyl) polydimethylsiloxane (PDMS) and poly(hexamethylene oxide) (PHMO) mixed macrodiol‐based aliphatic polyurethane elastomers was investigated using tensile testing, differential scanning calorimetry (DSC), and dynamic mechanical thermal analysis (DMTA). All polyurethanes were based on 50 wt % of hard segment derived from 4,4′‐methylenecyclohexyl diisocyanate (H₁₂MDI) and a chain extender mixture. 1,4‐Butanediol was the primary chain extender, while one of 1,3‐bis(4‐hydroxybutyl)tetramethyldisiloxane (BHTD), 1,3‐bis(3‐hydroxypropyl)tetramethyldisiloxane (BPTD), hydroquinonebis(2‐hydroxyethyl)ether (HQHE), 1,3‐bis(3‐hydroxypropyl)tetramethyldisilylethylene (HTDE), or 2,2,3,3,4,4‐hexafluoro‐1,5‐pentanediol (HFPD) each was used as a secondary chain extender. Two series of polyurethanes containing 80 : 20 (Series A) and 60 : 40 (Series B) molar ratios of primary and secondary chain extenders were prepared using one‐step bulk polymerization. All polyurethanes were clear and transparent and had number‐average molecular weights between 56,000 and 122,100. Incorporation of the secondary chain extender resulted in polyurethanes with low flexural modulus and high elongation. Good ultimate tensile strength was achieved in most cases. DSC and DMTA analyses showed that the incorporation of a secondary chain extender disrupted the hard segment order in all cases. The highest disruption was observed with HFPD, while the silicon‐based chain extenders gave less disruption, particularly in Series A. Further, the silicon chain extenders improved the compatibility of the PDMS soft segment phase with the hard segment, whereas with HFPD and HQHE, this was not observed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2979–2989, 1999     

Structure–property relationships and melt rheology of segmented,non-chain extended polyureas: Effect of soft segment molecular weight

Novel, segmented non-chain extended polyureas were synthesized. Soft segments (SS) were based on poly(tetramethylene glycol) (PTMO) (average molecular weight 1000 or 2000 g/mol) and hard segments (HS) were based on a single molecule of a diisocyanate, which was either 1,6-hexamethylene diisocyanate (HDI), 1,4-phenylene diisocyanate (pPDI) or 1,4-trans-cyclohexyl diisocyanate (CHDI). An increase in the SS molecular weight was found to lead to an increased formation of SS crystallites below 0 °C, which increased the low temperature modulus. Both 1K and 2K PTMO-based polyureas showed a microphase separated morphology, where the HS formed thread-like, crystalline structures that were dispersed in the continuous SS matrix. Upon deformation, the HS were found to breakdown into distinctly smaller threads, which oriented along the direction of the strain; this effect was found to be partially reversible and time dependent. Both the 1K and 2K polyureas based on HDI HS were found to be thermally stable and potentially melt-processible.     

The properties of polyurethanes with mixed chain extenders and mixed soft segments

Series of polyurethaneurea elastomers were prepared from 4,4′-diphenylmethane diisocyanate, poly(teuramethylene ether) glycol and poly(hexamethylene carbonate) glycol for mixed soft segments, and 1,4-butanediol and isophoronediamine for mixed chain extenders. Characteristics of the copolymers related with compositions were examined. FT-IR spectra showed that most of the urea carbonyl groups associated in hydrogen bonding, while urethane carbonyls only partially did so. Thermal and mechanical properties were investigated through differential scanning calorimetry and tensile testing. These thermal and mechanical properties are discussed from the viewpoint of microphase domain separation of hard and soft segments. © 1994 John Wiley & Sons, Inc.