Thermal and dynamic mechanical characterization of polyurethane–urea–imide coatings

A series of NCO terminated polyurethane (PU)–imide copolymers were synthesized by a systematic three‐step process and were chain extended with different diol/diamine chain extenders. In the first step, isocyanate terminated PU prepolymers were prepared by reacting soft segments such as polyester (PE) polyols and polyether polyols such as polypropylene glycol (PPG‐1000) with hard segments like 2,4‐tolylene‐diisocyanate (TDI) or isophorone‐diisocyanate (IPDI) with NCO/OH ratio 2:1. In the second step, thermally stable heterocyclic imide ring was incorporated using isocyanate terminated PU prepolymers by reacting with pyromellitic dianhydride (PMDA) in a excess‐NCO:anhydride ratio of 1:0.5. The surplus NCO content after imidization was both moisture cured or partially reacted with chain extender and moisture cured. The films were characterized by thermogravimetric (TG), differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA) instruments. The adhesion strength of these coatings on mild steel (MS), copper (Cu), and aluminum (Al) is dependent on the nature of the substrate. The TGA analysis show good thermal stability. The DMTA results show the microphase separation between the different hard and soft segments. Finally, a structure to property correlation was drawn based on the structure of the soft, hard, and chain extender and the observed properties are useful for understanding and design of intelligent coatings. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3158–3167, 2006     

Preparation and XPS surface chemical analysis of PS/PU nanocomposites

Aqueous emulsions of anionic polyurethane ionomers, based on polypropylene glycol as soft segment, isophorone diisocyanate as diisocyanate, dimethylolpropionic acid as chain extender and potential ionic center, and triethylamine as neutralizer, were synthesized. They were mixed with styrene monomers to prepare polystyrene–polyurethane (PS/PU) nanocomposites by an evocator. The sizes and distributions of the particles were measured by dynamic light scattering, and the microstructure of the nanocomposites was observed by transmission electron microscope. X‐ray photoelectron spectroscopy (XPS) was used to study the surface characterization of anionic PU and PS/PU nanocomposites. It could be found that the nanoparticles of PU could encapsulate the styrene monomers effectively and the leakage type of every element in PU was not affected by the introduction of Ps. There were more hard segments on the surface of crosslinking PS/PU nanocomposites because of the formation of crosslinking structure and interpenetrating polymer network between PU and PS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3889–3894, 2006     

FT-IR and XPS studies of polyurethane-urea-imide coatings

A series of polyurethane (PU)-urea-imide coatings were synthesized by a systematic three-step reaction process. Initially isocyanate terminated PU prepolymers were prepared by reacting soft segments such as polyester polyols (prepared from neopentyl glycol, adipic acid, isophathalic acid and trimethylol propane) or polyether polyols (polypropylene glycol-1000) with hard segments such as 2,4-toluene diisocyanate or isophorone diisocyanate with NCO/OH ratio of 2:1. Heterocyclic imide ring into the PU backbone was incorporated by co-polymerization with pyromellitic dianhydride (PMDA) from the excess NCO groups in the PU prepolymer with an NCO/anhydride ratio of 1:0.5 and the surplus NCO content after imidization was moisture cured. PU-urea-imide coatings were also obtained by partial chain extension of the excess NCO groups in the NCO terminated PU-imide copolymers, and the remaining excess NCO groups were completely reacted with atmospheric moisture. The obtained polymers were analyzed with Fourier transform-infrared (FT-IR) and angle resolved X-ray photoelectron spectroscopy (AR-XPS). The type and change in intermolecular H-bonding interaction in the PU-urea-imide films with structural variables was identified by deconvolution of the FT-IR spectra using Origin 6.0 software through Gaussian curve-fitting method. The FT-IR analyses of the PU-urea-imide coating films show dependence of phase separation on the nature of chain extender. Surface characterization data from AR-XPS suggests the dependence of phase segregation behaviour on the nature of the chain extender, which also supports the FT-IR observations.     

Synthesis and properties of nanosilica‐reinforced polyurethane for grouting

A polyurethane/nanosilica (PU/SiO₂) hybrid for grouting was prepared in a two‐step polymerization using poly(propylene glycol) diols as the soft segment, toluene 2,4‐diisocyanate (TDI) as the diisocyanate, 3,3′‐dichloro‐4,4′‐diaminodiphenylmethane (MOCA) as the chain extender, and acetone as the solvent. The size and dispersion of nanosilica, the molecular structure, mechanical properties, rheological behavior, thermal performance, and the UV absorbance characteristic of the PU/SiO₂ hybrid were investigated by transmission electron microscopy (TEM), FTIR, mechanical tests, viscometry, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and UV spectroscopy. Nanosilica dispersed homogeneously in the PU matrix. The maximum values of mechanical properties such as tensile strength, elongation break, and adhesive strength showed an addition of nanosilica of about 2 wt %. Resistance to both high and low temperatures was better than with PU. And the UV absorbance of the PU/SiO₂ hybrid increased in the range of 290–330 nm with increasing nanosilica content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4333–4337, 2006     

Structure–thermomechanical property correlation of moisture cured poly(urethane-urea)/clay nanocomposite coatings

A series of poly(urethane-urea)/clay nanocomposite coatings were prepared by moisture curing of isophorone diisocyanate (IPDI) capped hydroxyl terminated polybutadiene (HTPB)/clay dispersions in a relative humidity (RH) of 50% at 25 °C. The curing progress was studied by periodic measurement of gel fraction of the coating samples. The studies revealed tortuosity effects of clay toward moisture diffusion, thus delaying the induction period of gelation, time for complete cure and rate of gel formation of the nanocomposite coatings. The clay platelets were found to be intercalated in the poly(urethane-urea) matrix, evidenced from wide angle X-ray diffraction (WAXD) and transmission electron microscopy (TEM). Effects of nanoclay on state of the hard and soft segments were investigated by WAXD, differential scanning calorimetry (DSC), temperature modulated DSC (MDSC) and solid-state nuclear magnetic resonance spectroscopy (NMR). WAXD studies revealed unusually ordered hard segment morphology of the moisture cured poly(urethane-urea) and its nanocomposites. Slower soft segment dynamics upon clay addition was evident from concentration dependant broadening of the line widths of the NMR peaks, and decreasing reversible heat capacity changes at soft segment glass transition. The volume fraction of immobilized soft segments of the nanocomposites was determined from MDSC and was found to increase linearly with clay loading. The mechanical property analysis showed simultaneous reinforcement and toughening effect of nanoclay on the MCPU matrix. The increment in mechanical property of the nanocomposites varied proportionately with the volume fraction of immobilized soft segments.     

The effects of soft‐segment molecular weight and organic modifier on properties of organic‐modified MMT‐PU nanocomposites

The effects of soft‐segment molecular weight and organic modification of montmorillonite (MMT) on thermal and mechanical properties of segmented polyurethane (PU) elastomers were investigated. The PU/MMT nanocomposites were prepared by in situ polymerization, and the compositions included soft segments with number average molecular weights of 1000, 2000, and 2900, and organic‐modified MMT (including MMT‐30B and MMT‐I30E). The nanocomposites produced were characterized using wide‐angle X‐ray diffraction (WAXD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and mechanical testing. The TEM and XRD results revealed that both MMT‐30B and MMT‐I30E were intercalated, and partially exfoliated by the PU. Mechanical tests showed that the PU1000 series in soft‐segment molecular weight yielded superior tensile properties compared with the PU2000 and PU2900 series. Also, for a given molecular weight of soft segment in PU, the MMT‐30B nanocomposites exhibited greater increases in Young's modulus, tensile strength, and elongation at break than the MMT‐I30E counterpart, and the crystallinity of PU was enhanced by the clays. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and properties of polyurethane/montmorillonite nanocomposites cured under room temperature

The polyurethane/C₁₆C₁₈‐MMT (the montmorillonite modified with cetyloctadecyldimethyl ammonium bromide) nanocomposites were synthesized by intercalative polymerization and cured under room temperature. The d‐spacing and the dispersion of the C₁₆C₁₈‐MMT in the nanocomposites were measured by X‐ray Diffraction (XRD) and Transmission Electron Microscope (TEM). The mechanical and thermal properties of the nanocomposites were measured by Universal Testing System, Electric Anti‐fold Instrument, Thermogravimetric Analysis (TGA), and Differential Scanning Calorimetry (DSC). It was found out that introducing C₁₆C₁₈‐montmorillonite (MMT) in the polyurethane (PU) displayed good mechanical properties and thermal stability. Rheology behavior in liquid state showed that the addition of the C₁₆C₁₈‐MMT to PU resulted in low gel time and high viscosity. POLYM. COMPOS. 27:470–474, 2006. © 2006 Society of Plastics Engineers.     

Novel polyether polyurethane/clay nanocomposites synthesized with organicly modified montmorillonite as chain extenders

A kind of novel polyether polyurethane (PU)/clay nanocomposite was synthesized using poly(tetramethylene glycol), 4,4′‐diphenylmethane diisocyanate (MDI), 1,6‐hexamethylenediamine, and modified Na⁺‐montmorillonite (MMT). Here, organicly modified MMT (O‐MMT) was formed by applying 1,6‐hexamethylenediamine as a swelling agent to treat the Na⁺‐MMT. The X‐ray analysis showed that exfoliation occurred for the higher O‐MMT content (40 wt %) in the polymer matrix. The mechanical analysis indicated that, when the O‐MMT was used as a chain extender to replace a part of the 1,2‐diaminopropane to form PU/clay nanocomposites, the strength and strain at break of the polymer was enhanced when increasing the content of O‐MMT in the matrix. When the O‐MMT content reached about 5%, the tensile strength and elongation at break were over 2 times that of the pure PU. The thermal stability and the glass transition of the O‐MMT/PU nanocomposites also increased with increasing O‐MMT content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 6–13, 2006     

Effects of reaction and cure temperatures on morphology and properties of poly(ester‐urethane)

Poly(ester‐urethane) was synthesized from poly(ethylene glycol adipate) (PEG) and 2,4‐toluene diisocyanate (TDI) to study the effects of reaction temperature and cure temperature on the crystallization behavior, morphology, and mechanical properties of the semicrystalline polyurethane (PU). PEG as soft segment was first reacted with TDI as hard segment at 90, 100, and 110°C, respectively, to obtain three kinds of PU prepolymers, coded as PEPU‐90, PEPU‐100, and PEPU‐110. Then the PU prepolymers were crosslinked by 1,1,1‐tris (hydroxylmethyl) propane (TMP) and were cured at 18, 25, 40, 60, and 80°C. Their structure and properties were characterized by attenuated total reflection Fourier transform infrared, wide‐angle X‐ray diffraction, scanning electron microscopy, dynamic mechanical analysis, and tensile testing. With an increase of the reaction temperature from 90 to 100°C, the crystallinity degree of soft segment decreased, but interaction between soft and hard segments enhanced, leading to the increase of the glass transition temperature (T_g) of soft domain and tensile strength. When the cure temperature was above 60°C, miscibility between soft and hard segments of the PEPU films was improved, resulting in relatively low crystallinity and elongation at break, but high soft segment T_g and tensile strength. On the whole, all of the PEPU‐90, PEPU‐100, and PEPU‐110 films cured above 60°C possessed higher tensile strength and elongation at break than that of the films cured at other temperatures. The results revealed that the reaction temperature and cure temperature play an important role in the improvement of the crosslinking structure and mechanical properties of the semicrystalline PU. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 708–714, 2006     

Effect of organophilic montmorillonite on polyurethane/montmorillonite nanocomposites

Different kinds of organophilic montmorillonite cotreated by cetyltrimethyl ammonium bromide (CTAB) and aminoundecanoic acid (AUA) were synthesized and applied to prepare polyurethane/montmorillonite nanocomposites via solution intercalation. The results of wide‐angle X‐ray diffraction (WAXD) and transmission electron microscopy showed that, for the montmorillonite modified with CTAB and CTAB/AUA (molar ratio of 1/2), an ordered intercalated nanostructure was derived, while for the montmorillonite treated with AUA, a disordered nanostructure was derived. The tensile properties of the polyurethane (PU) nanocomposites showed higher enhancement relative to PU matrix. TG showed that there is some enhancement in degradation behavior between the nanocomposites and PU matrix. DMTA results showed that nanocomposites from some organophilic montmorillonites showed a much higher storage modulus below and above glass transition temperature, while the nanocomposites from montmorillonite treated by AUA show an even lower storage modulus. The loss curves showed that the main glass transition temperature of PU was improved to some extent for the nanocomposites. The water absorption of PU and nanocomposites was also studied and the difference in reduction was thoroughly analyzed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2536–2542, 2004     

Preparation of silicon dioxide/polyurethane nanocomposites by a sol–gel process

Aqueous emulsions of cationic polyurethane ionomers, based on poly(?‐caprolactone glycol) as soft segment, isophorone diisocyanate as hard segment, 3‐dimethylamino‐1,2‐propanediol as chain extender and potential ionic center, and hydrochloric acid as neutralizer, were mixed with tetraethoxysilane to prepare silicon dioxide–polyurethane (SiO₂/PU) nanocomposites by a sol–gel process during which the inorganic mineral is deposited in situ in the organic polymer matrix. The sizes and distributions of the particles were measured by dynamic light scattering, and the structure and morphology of the nanocomposites were observed by transmission electron microscope and FTIR spectrum. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2013–2016, 2004     

Structure and Property of PU/MMT Nanocomposites by In-Situ Polymerization

A montmorillonite modified by octadecylammonium salt (OMMT) was prepared. A polyurethane (PU)/montmorillonite nanocomposite was synthesized by in-situ polymerization using the OMMT, poly(propylene glycol), 4,4-diphenylmethylate diisocyanate, and 1,4-butanediol. The MMT platelets were dispersed in PU matrix on a 10 ～ 50 nm scale. Compared to that of pure PU, the tensile strength and tear strength of the PU/OMMT nanocomposites increased, respectively, and the MMT platelets dispersed on a nanometer scale enhanced the PU. The temperature of initial weight loss of the PU/OMMT nanocomposites was lower than that of pure PU because of the acid catalytic action of protonated MMT platelets in the first thermodegradation step. But its temperature of initial weight loss was higher than that of pure PU because of the barrier effect of the MMT platelets in the second thermodegradation step.     

Study on the influence of thermal characteristics of hyperbranched polyurethane phase change materials for energy storage

A series of hyperbranched polyurethane (HB‐PU) phase change induced energy storage materials were prepared by polyethylene glycol (PEG), methylene diphenyl 4,4′‐diisocyanate (MDI), and hyperbranched polyester polyalcohol via a two‐step process. The influence of thermal characteristics of HB‐PU was investigated using differential scanning calorimetry (DSC) and wide‐angle X‐ray diffraction (WAXD). It has been found that the thermal characteristics of HB‐PU are affected by some factors. Such as the molecular weight and content of soft segment, once the M_n of PEG soft segments is larger than the critical M_n (2000 g/mol), both the phase change enthalpy and temperature increase as M_n of PEG soft segment and soft segment content (SSC) increase. The influence of the microstructure of hard segment originates from diisocyanate and hyperbranched polyester polyalcohol, HB‐PUs with regular microstructure and lower generation of hyperbranched polyester polyalcohol have high energy storage capability. Furthermore, the conditions of measurement affect the thermal characteristics of materials. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects on the structure and properties of membranes formed by blending polydimethylsiloxane polyurethane into different soft‐segment waterborne polyurethanes

Polydimethylsiloxane polyurethane (PDMS‐PU), which was synthesized from PDMS as the soft segment, was blended into a variety of ester‐ or ether‐based soft‐segment waterborne polyurethanes with different concentrations to investigate the crystallization, thermal, and physical properties of the membrane formations. According to X‐ray analysis, the ether‐based PUs, synthesized from soft segments of poly(propylene glycol) (PPG1000) or poly(ethylene glycol) (PEG2000), were found to have maximum crystallinity at a 5% blending ratio of PDMS‐PU, but the ester‐based PU, synthesized from soft segments of polycaprolactone (PCL1250), had decreased crystallinity at a 5% blending ratio. Differential scanning calorimetric analysis revealed that the T_g,s values of PUs were highest when the blending ratio of PDMS‐PU was 5%–10%, except for PU from PCL1250. Moreover, ether‐based PUs showed maximum T_m,h values, but the T_m,h of the ester‐based PU was greatly reduced when PU with PCL1250 was blended with PDMS‐PU. In addition, the PU from PEG2000 had the highest melting entropy. Mechanical property analysis showed that the stress of ether‐based PUs would be increased when PUs were blended with a small amount of PDMS‐PU and that the stress of PU from poly(tetramethylene glycol) (PTMG1000) increased to its greatest value (20–30 MPa). On the other hand, the ester‐based PU, from PCL1250 blended with PDMS‐PU, would have reduced stress. On the whole, the stress and strain of PU from PEG1000 had excellent balance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 210–221, 2006     

Differential scanning calorimetry analysis of silicon‐containing and phosphorus‐containing segmented polyurethane. I—Thermal behaviors and morphology

This article investigated thermal transition and morphology utilizing differential scanning calorimetry (DSC), which was performed on silicon‐containing and phosphorus‐containing segmented polyurethane (Si‐PU and P‐PU). The hard segments of those Si‐PU and P‐PU polymers investigated consisted of 4,4′‐diphenylmethane diisocyanate (MDI) and diphenylsilanediol (DSiD), MDI, and methylphosponic (MPA), respectively. The soft segment of those polymers comprised polytetramethylene ether glycol, with an average molecular weight of 1000 or 2000 (PTMG 1000 and PTMG 2000, respectively). Several thermal transitions appeared for on the Si‐PU and P‐PU polymers, reflecting both the soft‐segment and hard‐segment phases. The Si‐PU and P‐PU polymers with a lower hard‐segment content exhibited a high degree of phase separating as indicated by the constancy of both the soft‐segment glass transition temperature (T_gs) and the breadth of transition zone (ΔB). The polymers in which PTMG 2000 was used as the soft segment generally exhibited a crystalline melting endotherm about 10°C, while crystallization usually disappeared upon melt quenching. The hard segments of the Si‐PU and P‐PU polymers displayed multiple endotherms. The first endotherm was related to a short‐range ordering of the hard segment domain (Region I), and the second endotherm was ascribed to a long‐range ordering of the domain (Region II). The wide‐angle X‐ray demonstrated that the structure in Region I and Region II was almost completely amorphous. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3489–3501, 2001     

Study on synthesis and thermal properties of polyurethane–imide copolymers with multiple hard segments

Different multiple hard segment polyurethane–imide copolymers (MHPUI) were synthesized and characterized. FTIR spectroscopy confirmed the characteristic absorption of the MHPUI copolymer. The difference in the imide group FTIR absorption bands in different MH segment PUI copolymers was found in this study and was explained by the different MH segment types, hard segment contents, and hard segment rigidity with different interactions of the molecular chains. The hard segment interaction in MHPUI with an increase of the structure rigidity of the short hard segments is strengthening. The DSC analysis revealed that the glass‐transition temperature of the soft segment of PUI rose in value from ?42 to ?3.4°C with the introduction of MH and different MH segments. The DSC results suggest that the soft segment is more compatible with the hard segment rigidity increase. The TGA results showed the hard segment structure symmetry has a more important role in the MHPUI thermal stability. Every sample containing symmetrical structure short hard groups (4,4′‐diphenylmethane diisocyanate or 4,4′‐diaminodiphenylmethane) is more thermally stable than that with worse symmetry structure groups (2,4‐toluene diisocyanate or 3,3′‐dichloro‐4,4′‐diamino‐diphenylmethane). The three‐step mechanism of PUI thermal degradation was further verified by the TGA study. The thermally unstable group was confirmed as urethane or a urea–urethane segment. The TGA results showed that MHPUI copolymers with higher separation of the soft–hard phase have higher thermal stability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2206–2215, 2002     

二-(4-羟基丁基)聚二甲基硅氧烷改性聚氨酯/脲的合成及性能研究

以二-(4-羟基丁基)聚二甲基硅氧烷(HB-PDMS)和聚乙二醇为(PEG)软段,2,4-甲苯二异氰酸酯(TDI)为硬段,合成了一系列不同硬段含量的聚氨酯/脲(PU)和有机硅改性聚氨酯/脲(SiPU)。通过FT-IR、DSC、TG及吸水率表征了PU和SiPU的结构及性能。结果表明,相对于PU,SiPU的耐水性随SiPU中HB-PDMS含量的增大而逐渐增强,聚硅氧烷的引入虽然降低了PU的初始热降解温度,但其在高温区的热稳定性增强。     

Preparation and properties of a novel elastomeric polyurethane/organic montmorillonite nanocomposite

A novel elastomeric polyurethane (EPU)/organic montmorillonite (OMMT) nanocomposite has been synthesized. 18 Alkane‐3 methyl‐amine chloride and dihydroxethyl‐12 alkane‐3 methyl‐amine chloride were used as intercalation agents to treat Na⁺‐montmorillonite and for forming two kinds of OMMTs. The better OMMT was chosen according to fourier transform infrared spectroscopy (FTIR) and wide angle X‐ray diffraction (WAXD). Three types of EPU/OMMT nanocomposites were synthesized by in situ polymerization of EPU, with different amounts of OMMT. A combination of FTIR, WAXD, and transmission electronic microscopy (TEM) studies showed that EPU/OMMT composites were on the nanometer scale and the segmented structure of EPU was hindered by the presence of the OMMT, due to the reaction between toluene diisocyanate (TDI) and the intercalation agents. Properties such as tensile property, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA) were researched and compared. Results showed that the EPU/3% OMMT had the best physical and mechanical properties because of its uniform dispersion of the organic silicate layers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3578–3585, 2006     

Epoxy acrylate UV/PU dual‐cured wood coatings

For improving the finishing performances of complicated three‐dimensional coated wood products (e.g., furniture) with some shadow zones in the absence of ultraviolet (UV) light, resulting in incomplete curing of UV coatings, the aim of this study was to investigate the characteristics and effects of curing process on the properties of epoxy acrylate UV/PU dual‐cured resin for wood coatings when compared with traditional UV and polyurethane (PU) coatings. The epoxy acrylate oligomer was synthesized for providing a double bond of acryloyl group and a secondary hydroxyl group. The UV/PU dual‐cured coating was formulated with epoxy acrylate resin/tripropylene glycol diacrylate (TPGDA) monomer by the weight ratio of 80/20, 3% dosage of benzil dimethyl ketal as a photoinitiator, and the NCO/OH mole ratio of 1.0. The aromatic polymeric diphenylmethane diisocyanate was used as a hardener. The films of the dual‐cured coating, obtained from UV‐cured or room temperature‐cured process, showed an excellent tensile strength, elongation at break, impact resistance, and lightfastness when compared with traditional UV and PU coatings; especially, the adhesion of UV/PU dual‐cured coating by UV‐cured process was better than that of traditional UV coating. It can therefore be concluded that the epoxy acrylate oligomer‐based dual‐cured coating could readily be used for complicated wood products finishing. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis of thermoplastic polyurethane and its physical and shape memory properties

In this article, thermoplastic polyurethane (PU) with a shape memory property was synthesized. First, the PU prepolymer was prepared by reacting poly(tetramethylene glycol) with 4,4′‐diphenylmethane diisocyanate, then extended with various extenders such as linear aliphatic 1,4‐butanediol, benzoyl‐type 4,4‐bis(4‐hydroxyhexoxy)‐isopropylane and naphthalate‐type bis(2‐phenoxyethanol)‐sulfone or naphthoxy diethanol. The experimental results showed that the tensile strength, elongation at break, and initial modulus at 300% of these copolymer films were in the range of 31–64 Mpa, 42%–614%, and 8.26–11.5 MPa, respectively. Thermal analysis showed that the glass‐transition temperature of these copolymers was in the range of ?73°C to ?50°C for the soft segment (T_gs) and 70°C–106°C for the hard segment (T_gh) and that the melting point was in the range of 14.6°C–24.2°C for the soft segment and 198°C–206°C for the hard segment. The extender with a benzoyl or naphthalate group was better able to promote its shape memory property than was the regular polyurethane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 607–615, 2006