Polyisobutylene‐based polyurethanes. III. Polyurethanes containing PIB/PTMO soft co‐segments

The synthesis, characterization, and structure–property behavior of polyurethanes containing polyisobutylene (PIB)/poly(tetramethylene oxide) (PTMO) soft co‐segments and bis(4‐isocyanatocyclohexyl)methane (HMDI)/hexanediol (HDO) hard segments is presented. The mechanical (stress/strain, hardness, and hysteresis) properties of these novel polyurethanes were investigated over a broad composition range. PIB‐based polyurethanes with HMDI/HDO hard segments showed better mechanical properties than earlier polyurethanes containing highly crystalline hard segments. The addition of moderate amounts (20% by weight) of PTMO significantly increased both tensile strengths and elongation. In the presence of larger amounts of PIB, these polyurethanes are expected to possess oxidative/hydrolytic/enzymatic stabilities superior to commercially available polyurethanes. These polyurethanes are softer and exhibit hysteresis superior to or comparable with conventional polyurethanes. According to initial thermal studies, these materials show good melt processibility. Overall, the mechanical properties of PIB based hybrid polyurethanes are similar to commercially important polyurethane type biomaterials. Our results show that the incorporation of PTMO segments to PIB‐based polyurethanes significantly improves elastomeric properties. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5278–5290, 2009     

PIB‐based polyurethanes. IV. The morphology of polyurethanes containing soft co‐segments*

Novel polyurethanes consisting of polyisobutylene (PIB)/poly(tetramethylene oxide) (PTMO) or PIB/poly(hexamethylene carbonate) (PC) soft co‐segments in combination with 4,4′‐methylene‐bis(cyclohexyl isocyanate)/1,6‐hexanediol, 1,4‐butanediol, or 1,6‐hexamethylene diamine hard segments exhibit excellent mechanical properties (upto 31 MPa tensile strength with 700% elongation) together with unprecedented oxidative/hydrolytic stability. A structural model of the morphology of these polyurethanes was developed that reflects this combination of properties. The key new elements of our model are H bridges between the PTMO and PC type soft and urethane hard segments, which compatibilize the soft and hard domains, and the presence of large quantities of chemically resistant PIB soft segments that protect the other oxidatively/hydrolytically vulnerable constituents. A variety of FTIR, DSC, SAXS, AFM, and DMTA experiments strongly support the proposed morphological model. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6180–6190, 2009     

Morphology and tensile properties of model thermoplastic polyurethanes with MDI/butanediol based monodisperse hard segments

Morphology and tensile properties of model thermoplastic polyurethanes (TPUs) containing polyisobutylene (PIB) or poly(tetramethylene oxide) (PTMO) based soft segment and 4,4‐methylene bis(phenyl isocyanate) (MDI) and 1,4‐butanediol (BDO) based monodisperse hard segments (HSs), consisting of exactly two to four MDI units extended by BDO, were investigated. Using FT‐IR spectroscopy, increased hydrogen bonded C?O fraction was observed in model TPUs as the HS size increased. The hydrogen bonded C?O fraction was higher in PIB based TPUs compared with PTMO based TPUs, indicating higher phase separation in PIB based TPUs. The morphology of TPUs was investigated using AFM phase imaging, which showed ribbon‐like or interconnected hard domains in PTMO based model TPUs and randomly dispersed hard domains in PIB based model TPUs. SAXS revealed that the degree of phase separation in the model TPUs was higher than in their polydisperse analogues. Domain spacing as well as interfacial thickness increased with the increasing HS size, and both values were higher in PTMO based TPUs. The tensile analysis indicated that model TPUs exhibited higher modulus and slightly higher elongation compared with their polydisperse analogues. Only in PTMO based model TPUs, strain induced crystallization was observed above 300% elongation. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2485–2493     

Pi‐conjugated chain extenders for the synthesis of optoelectronic segmented polyurethanes

The optical properties of mechanochromic materials change under mechanical stress. Segmented polyurethanes are elastomers composed of amorphous, saturated chain soft segments, and rigid pi‐conjugated hard domains. Within aggregates of hard domains pi–pi interactions may form and result in perturbation of the optoelectronic properties of the system. Disruption and restoration of these electronic interactions within the material may lead to observable mechanochromic response. A series of oligothiophene diols and diamines, as well as a naphthalene diimide diol, have been synthesized for incorporation into the hard domains of segmented polyurethanes and polyureas using long poly(tetramethylene oxide) chains as soft segments. The resulting polymers were evaluated to determine their extent of polymerization and their thermal stability. The optical properties of the materials were studied in solution and as thin films. Where possible the electrochemical properties of the polymers were also explored. The length of the soft segment chains in the segmented polyurethanes hindered electronic coupling of hard domains. Future work involving smaller, more solubilizing soft segments may allow for easier material characterization and mechanochromic response. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.     

Polyisobutylene‐based polyurethanes. II. Polyureas containing mixed PIB/PTMO soft segments

The design, synthesis, characterization, and structure–property behavior of polyureas containing novel soft segments of mixed polyisobutylene (PIB)/poly(tetramethylene oxide) (PTMO) chains and conventional hard segments is presented. Modest amounts (12%) of PTMO in the soft PIB phase significantly increase both the tensile strength and elongation of the polyureas. These polyureas exhibit not only oxidative/hydrolytic stabilities far superior to Bionate® and Elast‐Eon® considered the most oxidatively stable polyurethanes on the market but also display mechanical properties (29 MPa tensile strength and 200% elongation) approaching those of conventional thermoplastic polyurethanes. The surfaces of these polyureas are covered/protected by PIB segments, which will lead to excellent biocompatibility. Our results demonstrate that the PTMO segments facilitate stress transfer from the continuous mixed soft phase to the dispersed hard phase, which strengthens and flexibilizes PIB‐based polyureas and thus significantly improves elastomeric properties without compromising oxidative and hydrolytic stability. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2787–2797, 2009     

Temperature‐dependent changes in the hydrogen bonded hard segment network and microphase morphology in a model polyurethane: Experimental and simulation studies

Hydrogen bonding between hard segments has a critical effect on the morphology and properties of polyurethanes. Influence of temperature on hydrogen bonded urethane network and melting behavior of a model semicrystalline segmented polyurethane was investigated by experiments and simulations. Polyurethane was synthesized by the stoichiometric reaction between p‐phenylene diisocyanate and poly(tetramethylene oxide) (PTMO) with a molecular weight of 1000 g/mol. Simulations were carried out using dissipative particle dynamics (DPD) and molecular dynamics (MD) approaches. Experimental melting behavior obtained by various techniques was compared with simulations. DPD simulations showed a room temperature microphase morphology consisting of a three‐dimensional hydrogen‐bonded urethane hard segment network in a continuous and amorphous PTMO matrix. The first‐order melting transitions of crystalline urethane hard segments observed during the continuous isobaric heating in DPD and MD simulations (340–360 K) were in reasonably good agreement with those observed experimentally, such as AFM (320–340 K), WAXS (330–360 K), and FTIR (320–350 K) measurements. Quantitative verification of the melting of urethane hard segments was demonstrated by sharp discontinuities in energy versus temperature plots obtained by MD simulations due to substantial decrease in the number of hydrogen bonds above 340 K. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 182–192     

Synthesis and thermal transition behavior of model thermoplastic polyurethanes containing MDI/butanediol‐based monodisperse hard segments

Amine‐terminated monodisperse hard segments (MDHSs) containing two to four 4,4′‐methylenebis (phenyl isocyanate) extended by 1,4‐butanediol have been synthesized using carboxybenzyl protecting‐deprotecting strategy. Pure MDHSs in large scale were obtained in good yield and their structures were confirmed by ¹H‐, ¹³C‐NMR spectroscopy and GPC‐MALLS. Differential scanning calorimetry (DSC) showed that as the hard segment (HS) size increased, the melting and glass transition temperature and the change of heat capacity at glass transition of ethyl capped MDHSs increased. Model thermoplastic polyurethanes (TPUs) were synthesized using the reaction of bischloroformate of poly (tetramethylene oxide) (PTMO) diol or polyisobutylene (PIB) diol with amine‐terminated MDHSs. X‐ray diffraction results indicated the amorphous structure of model TPUs. DSC revealed HS related endotherms, regardless of SS, which were attributed to the local ordering of the HSs. Additional endotherms in PTMO based model TPUs might arise from the dissociation of hydrogen bonding between PTMO and HSs. The lower T_g in model TPUs compared to the polydisperse analogues observed by dynamic mechanical analysis (DMA) indicated higher microphase separation of monodisperse HSs. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3171–3181     

Micro‐phase‐separation behavior of amphiphilic polyurethanes involving poly(ethylene oxide) and poly(tetramethylene oxide)

The temperature dependence of thermal, morphological, and rheological properties of amphiphilic polyurethanes was examined with differential scanning calorimetry (DSC), wide‐angle X‐ray scattering (WAXS), small‐angle X‐ray scattering (SAXS), rheological measurements, and Fourier transform infrared spectroscopy. Multiblock (MPU) and triblock (TPU) polyurethanes were synthesized with two crystallizable segments—poly(ethylene oxide) (PEO) as a hydrophilic block and poly(tetramethylene oxide) (PTMO) as a hydrophobic block. DSC and WAXS measurements demonstrated that the microphase of MPUs in the solid state is dominantly affected by the PEO crystalline phase. However, high‐order peaks were not observed in the SAXS measurements because the crystallization of the PEO segments in MPUs was retarded by poor sequence regularity. The microphase in the melt state was induced by the hydrogen bonding between the N? H group of hexamethylene diisocyanate linkers and the ether oxygen of PEO or PTMO blocks. As the temperature increased, the smaller micro‐phase‐separated domains were merged into the larger domains, and the liquidlike ordering was eventually disrupted because of the weakening hydrogen bonding. However, the fully homogeneous state of an MPU with a molar ratio of 5/5 PEO/PTMO (MPU55) was not confirmed even at much higher temperatures with both SAXS and rheological measurements. However, the SAXS patterns of TPU showed weak but broad second‐order peaks below the melting temperature of the PEO block. Compared with MPU55, the ordering of the TPU crystalline lamellar stacks was enhanced because of the high sequence regularity and the low hydrogen‐bonding density. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2365–2374, 2003     

Segmental orientations and deformation mechanism of a poly(ether‐block‐amide) film

Simultaneous measurements of microscopic infrared dichroism, mesoscale deformation, and macroscopic stress have been made for a microphase‐separated film of poly(ether‐block‐amide) 4033 during uniaxial stretching at temperatures between 30 and 91 °C, well below the melting point of the hard polyamide‐12 (PA) domains. Before the onset of dramatic microstructural alterations, the true stress–strain relationship on the mesoscale can be described with an interpenetrating network model, and poly(tetramethylene oxide) (PTMO) soft segments undergo affine deformation. Beyond a threshold strain at which stress from the soft network becomes larger than that from the hard network, plastic deformation occurs in the hard PA domains, and this is accompanied by the downward derivations of the true stress and molecular orientation of PTMO blocks from the model predictions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1161–1167, 2005     

Synthesis and characterization of biodegradable poly(ϵ‐caprolactone urethane)s. I. Effect of the polyol molecular weight,catalyst, and chain extender on the molecular and physical characteristics

Biodegradable polyurethanes with potential for applications in medical implants were synthesized in bulk with aliphatic hexamethylene diisocyanate, isophorone diisocyanate, poly(?‐caprolactone) diols of various molecular weights, 1,4‐butane diol, 2‐amino‐1‐butanol, thiodiethylene diol, and 2‐mercaptoethyl ether chain extenders. The catalysts used were stannous octoate, dibutyltin dilaurate, ferric acetyl acetonate, magnesium methoxide, zinc octoate, and manganese 2‐ethyl hexanoate. The synthesis reactions were second‐order. All the materials had narrow, unimodal molecular weight distributions and polydispersity indices of 1.5–1.9. The chemical structures of the polyurethanes, as assessed from ¹H NMR and ¹³C NMR spectra, were in good agreement with the monomer stoichiometric ratios. The glass‐transition temperatures of the materials ranged from ?38 to ?57 °C and were higher for polymers based on isophorone diisocyanate and with higher hard‐segment contents. For polyurethanes with the same hard‐segment content, there was no effect of the material molecular weight on the thermal properties. The tensile strengths of the materials were 12–63 MPa, and the tensile moduli were 8–107 MPa. These increased with an increasing hard‐segment content. The least effective catalyst was magnesium methoxide, and the most effective was ferric acetyl acetonate. Stannous octoate and manganese 2‐ethyl hexanoate were less effective than dibutyltin dilaurate and zinc octoate. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 156–170, 2002     

Morphology of polyurethanes with triol monomer crosslinked on hard segments

Polyester‐based polyurethanes containing ≈60 wt % of polyester were synthesized from low molecular weight polyester (M_n ≈2000) and 4,4′‐methylene bis(phenyl isocyanate) (MDI), with butanediol as a chain extender and glycerol as a crosslinker. The triol crosslinker was used in substitution for the 1,4‐butanediol chain extender; thus, the crosslinker was chemical bonded to the hard segments of polyurethane. The morphologies of these polyurethanes were studied by differential scanning calorimetry (DSC), small‐angle X‐ray scattering (SAXS), TMA (thermal mechanical analysis), and FTIR (Fourier transform infrared spectroscopy). Owing to the highly steric hindrance, the presence of triol crosslinker in the hard segments resulted in a decrease in the aggregation of hard segments through hydrogen bonding. The experimental results revealed that the degree of phase segregation of soft and hard segments decreased with increasing the triol crosslinker content in the hard segments. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2673–2681, 1999     

Synthesis of transparent thermoplastic polyurethane elastomers

Thermoplastic polyurethanes were synthesized from poly(propylene glycol)‐block‐poly(ethylene glycol) polyols and hybrid hard segments that combined at least two different chain extenders. The combination of hard segments allowed for modification of elastomer performance and processing not achievable by any single hard segment. The combination of hard segments modulated hard‐segment energies that were directly related to elastomer performance. Special attention is paid to obtaining optically transparent elastomers with this technique. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 271–278, 2004     

Synthesis and characterization of poly(dimethylsiloxane‐urethane) elastomers: Effect of hard segments of polyurethane on morphological and mechanical properties

A series of poly(dimethylsiloxane‐urethane) elastomers based on hexamethylenediisocyanate, toluenediisocyanate, or 4,4′‐methylenediphenyldiisocyanate hard segment and polydimethylsiloxane (PDMS) soft segment were synthesized. In this study, a new type of soft‐segmented PDMS crosslinker was synthesized by hydrosilylation reaction of 2‐allyloxyethanol with polyhydromethylsiloxane, using Karstedt's catalyst. The synthesized soft‐segmented crosslinker was characterized by FT‐IR, ¹H, and ¹³C NMR spectroscopic techniques. The mechanical and thermal properties of elastomers were characterized using tensile testing, thermogravimetric analysis, differential scanning calorimetry (DSC), and dynamical mechanical analysis measurements. The molecular structure of poly(dimethylsiloxane‐urethane) membranes was characterized by ATR‐FTIR spectroscopic techniques. Infrared spectra indicated the formation of urethane/urea aggregates and hydrogen bonding between the hard and soft domains. Better mechanical and thermal properties of the elastomers were observed. The restriction of chain mobility has been shown by the formation of hydrogen bonding in the soft and hard segment domains, resulting in the increase in the glass‐transition temperature of soft segments. DSC analysis indicates the phase separation of the hard and soft domains. The storage modulus (E′) of the elastomers was increasing with increase in the number of urethane connections between the hard and soft segments. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2980–2989, 2006     

Effect of soft segment length on properties of fluorinated polyurethanes

The effects of soft segment length on the variations in morphology, surface composition, and hydrophilicity have been studied in fluorinated polyurethanes (FPUs) and correlated with their preliminary blood compatibility as evidenced by in vitro platelet adhesion experiments. The fluorinated polyurethanes were obtained using hexamethylene diisocyanate (HDI) and chain extender of 2,2,3,3-tetrafluoro-1,4-butanediol (TF) as the hard segment as well as various soft segments—polytetramethyl oxides (PTMO) with molecular weights of 650, 1000, 1400, and 2000. The increased phase separation in hard-segment domains with lengthening soft segment was observed by FT-IR, which is believed to result in enhanced strength of hydrogen bonds and good hard-segment order arrangement. Thin-film XRD results indicate at least three lateral distances existing between adjacent hard segments in the crystallized hard segment. Their distribution depends strongly on the length of soft segment. Lengthening soft segment promotes the formation of dense arrangement of crystallized hard segments. Compared with the effect of phase separation, surface composition was found to exert a major influence on the preliminary blood compatibility of fluorinated polyurethanes. Increasing fluorine content by decreasing soft segment length promotes reduction in platelet adhesion and activation on polyurethane surfaces.     

Elastomeric polyurethanes modified with geminal bisphosphonate groups

Three types of elastomeric segmented polyurethanes represented by a polyether‐urethane, a polyurethane‐urea, and a polycarbonate‐urethane were introduced into a modified low‐temperature variant of base‐induced N‐alkylation of urethane hard segments with an excess of 1,6‐dibromohexane in N,N′‐dimethylacetamide (DMAc), resulting in the modification of polymers with 0.08–0.26 mmol/g of pendant 6‐bromohexyl groups. Either lithium diisopropylamide (LDA) or sodium hydride was used to initiate the reaction, although LDA was found to be more suitable for the bromoalkylation. Selected bromoalkylated polyurethanes of all three types were reacted with thiol‐containing bisphosphonates, to yield the polymers modified with 0.08–0.12 mmol/g of geminal nonesterified covalently attached bisphosphonate groups. Two thiol‐containing geminal bisphosphonates used in the modifications were prepared via reactions of nucleophilic addition to vinylidene‐bisphosphonic acid. All three types of polyurethanes were found equally suitable for the modifications. The bisphosphonate‐modified polyurethanes with nonmetallic cations on the bisphosphonate groups remain soluble in the solvents suitable for the dissolution of nonmodified polymers and can be processed into films by solvent casting. After the exchange of nonmetallic cations to sodium, the polymers become insoluble in any solvent, probably as a result of the intermolecular coordination of bisphosphonate groups with the metal cations. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 105–116, 2001     

Synthesis of novel moisture‐curable polyurethanes end‐capped with trialkoxysilane and their application to one‐component adhesives

Novel silane endcappers and novel polyurethanes end‐capped with trimethoxysilane (silylated polyurethanes) were developed as water‐curable materials in which the curing reaction occurred under humid conditions in the presence of dioctyltin diversatate as a curing catalyst. A variety of amine‐terminated trimethoxysilane compounds were synthesized by the Michael addition reaction of commercially available 3‐aminopropyltrimethoxysilane with acrylates, and the resulting silane endcappers were used to react with isocyanate‐terminated polyurethanes, providing the silylated polyurethanes. The moisture‐curable silylated polyurethanes were used for the preparation of novel one‐component and solvent‐free adhesives. The evaluated properties were the curing speed, the tensile shear bond strength, and the adherence to some substrates. The longer alkyl chains of the silane endcappers derived from various acrylates led to a slower curing speed, lower tensile strength at break, and longer elongation at break of the silylated polyurethanes. The tensile shear bond strength of the silylated polyurethane‐based adhesive decreased with decreasing the trimethoxysilane end‐capping ratio, whereas an increase in the adherence was observed. The adherence to the acrylic substrate was improved by changes in the main‐chain structure of the polyurethane based on the composition of poly(propylene oxide) and poly(ethylene oxide). © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2689–2704, 2007     

Atom transfer coupling reactions performed with benign reducing agents and radical traps

Monobrominated polystyrene (PSBr) was prepared by ATRP, and the resulting chain ends were activated in the presence of radical traps to induce chain end‐coupling. In atom transfer radical coupling (ATRC) with radical trap assistance, to achieve significant coupling requires excess metal catalyst, ligand, and a reducing agent that is often additional metal. In this work, activators generated by electron transfer (AGET) and radical trap assistance are used in the ATRC sequence to successfully lead to chain‐end coupling without the need for the oxidatively unstable copper (I) and with environmentally friendlier agents in place of copper metal. High extents of coupling (Xc) were achieved using ascorbic acid (AA) as the reducing agent and copper(II) bromide as the oxidized version of the catalyst, and when combined with AGET ATRP to prepare the PSBr precursor, only a fraction of the total metal was required compared to traditional atom transfer reactions, while still retaining similar Xc values. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2113–2120     

Poly(ester urethane)s with polycaprolactone soft segments: A morphological study

Two series of poly(ester urethane)s were prepared, containing polycaprolactone (PCL) as the soft segment with molecular weights of 530 and 2000. In each series, the soft‐segment/hard‐segment ratio was varied, and the morphological changes were monitored with differential scanning calorimetry, dynamic mechanical thermal analysis, wide‐angle X‐ray scattering, and scanning electron microscopy techniques. The polyurethanes with longer PCL segments retained their crystallinity, whereas those with shorter PCL segments did not. A morphological model is proposed, in which a continuous PCL‐rich matrix contains both PCL crystallites and domains of urethane hard segments. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4117–4130, 2002     

Polyurethanes containing sulfur. II. New thermoplastic nonsegmented polyurethanes with diphenylmethane unit in their structure

New thermoplastic nonsegmented thiopolyurethanes were synthesized from the new low‐melting aliphatic‐aromatic thiodiols bis[4‐(2‐hydroxyethyl)thiomethylphenyl]methane, bis[4‐(3‐hydroxypropyl)thiomethylphenyl]methane, and bis[4‐(6‐hydroxyhexyl)thiomethylphenyl]methane and hexamethylene diisocyanate both by melt and solution polyaddition with dibutyltin dilaurate as a catalyst. All the thiodiols were prepared with high yields by the condensation reaction of bis(4‐mercaptomethylphenyl)methane with 2‐chloroethanol, 3‐chloro‐1‐propanol, or 6‐chloro‐1‐hexanol. The hard‐segment‐type polyurethanes obtained were plastic materials with partially crystalline structures. Polymerization in solution produced products with higher molecular weights (η_red = 0.97–1.24 dL/g) than polymerization in melt (η_red = 0.44–1.05 dL/g). The structures of all the polyurethanes were determined with elemental analysis, Fourier transform infrared, and X‐ray diffraction analysis. Thermal properties of the polymers obtained in solution were examined by differential scanning calorimetry and thermogravimetric analysis. Shore A/D hardness and tensile properties for all the polyurethanes were also determined. Of the two kinds, the polyurethanes obtained in solution possessed better tensile properties and showed yield stress (tensile strength) in a range of 27.8–30.0 MPa at an elongation of 17.4–25.1%. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1767–1773, 2000     

Preparation and characterization of N‐methyl‐substituted polyurethane

We prepared N‐methyl‐substituted polyurethanes with different substitution degrees from sodium hydride, methyl p‐toluene sulfonate, and polyether–polyurethane containing poly(oxytetramethylene) glycol, 4,4′‐diphenylmethane diisocyanate, and 1,4‐butanediol. The chemical structures were characterized with Fourier transform infrared and ¹H NMR. To investigate the effects of the N‐substitution degree on the morphology, thermal stability, and mechanical properties, we used differential scanning calorimetry, thermogravimetric analysis, and a universal testing machine. As the substitution degree increased, the new free (1708 cm^?1) and bonded (1650 cm^?1) carbonyl peaks increased. There was no bonded carbonyl peak in fully substituted polyurethane because the urethane groups had no hydrogen. At a small substitution degree, we observed a slight increase in the glass‐transition temperature and decrease in the endotherms of soft‐segment and hard‐segment domains due to the decrease in the hard‐segment domain and the increase in the urethane groups in the soft‐segment domain. The hard‐segment domain decreased and then disappeared as the N‐methyl substitution degree increased. These changes in the morphology resulted (1) in decreased modulus and tensile strength for the films because of the decrease in physical crosslinking points and (2) improved thermal stability as the substitution degree increased. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 4077–4083, 2002