Structure and properties of segmented poly(urethaneurea)s with relatively short hard‐segment chains

We report the structure and properties of segmented poly(urethaneurea) (SPUU) with relatively short hard‐segment chains. The SPUU samples comprised poly(tetramethylene glycol) prepolymer as a soft segment and 4,4′‐diphenylmethane diisocyanate (MDI) units as a hard segment that were extended with ethylenediamine. To discuss quantitatively the conformation of the soft‐segment chain in the microphase‐separated domain space, we used SPUU samples for which the molecular weights of the hard‐ and soft‐segment chains are well characterized. The effects of the cohesive force in the hard‐segment chains on the structure and properties of SPUU were also studied with samples of different chain lengths of the hard segment, although the window of x_H, the average number of MDI units in a hard‐segment chain, was narrow (2.38 ≤ x_H ≤ 2.77). There were urethane groups in the soft segments and urea groups in the hard segments. Because of a strong cohesive force between the urea groups, we could control the overall cohesive force in the hard‐segment chains by controlling the chain lengths of the hard segment. First of all, microphase separation was found to be better developed in the samples with longer hard‐segment chains because of an increase of the cohesive force. It was also found that the interfacial thickness became thinner. The long spacing for the one‐dimensionally repeating hard‐ and soft‐segment domains could be well correlated with the molecular characteristics when the assumption of Gaussian conformation was employed for the soft‐segment chains. This is unusual for strongly segregated block copolymers and might be characteristic of multiblock copolymers containing rod–coil chains. The tensile moduli and thermal stability temperature, T_H, increased with an increase of the cohesive force, whereas the glass‐transition temperature, the melting temperature, and the degree of crystallinity of the soft‐segment chains decreased. The increase in T_H especially was appreciable, although the variation in the chain length of the hard segment was not profound. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1716–1728, 2000     

Calorimetric and Dielectric Study of the Segmented Biodegradable Poly(ester‐urethane)s Based on Bacterial Poly[(R)‐3‐hydroxybutyrate]

Two series of segmented poly(ester‐urethane)s were synthesized from bacterial poly[(R)‐3‐hydroxybutyrate]‐diol (PHB‐diol), as hard segments, and either poly(ε‐caprolactone)‐diol (PCL‐diol) or poly(butylene adipate)‐diol (PBA‐diol), as soft segments, using 1,6‐hexamethylene diisocyanate as a chain extender. The hard‐segment content varied from 0 to 50 wt.‐%. These materials were characterized using ¹H NMR spectroscopy and GPC. The polymers obtained were investigated calorimetrically and dielectrically. DSC showed that the T_g of either the PCL or PBA soft segments are shifted to higher temperatures with increasing PHB hard‐segment content, revealing that either the PCL or PBA are mixed with small amounts of PHB in the amorphous domains. The results also showed that the crystallization of soft or hard segments was physically constrained by the microstructure of the other crystalline phase, which results in a decrease in the degree of crystallinity of either the soft or hard segments upon increase of the other component. The dielectric spectra of poly(ester‐urethane)s, based on PCL and PHB, showed two primary relaxation processes, designated as α_S and α_H, which correspond to glass–rubber transitions of PCL soft and PHB hard segments, respectively. Whereas in the case of other poly(ester‐urethane)s, derived from PBA and PHB, only one relaxation process was observed, which broadens and shifts to higher temperature with increasing PHB hard‐segment content. It was concluded from these results that our investigated materials exhibit micro‐phase separation of the hard and soft segments in the amorphous domains.     

Oxygen permeability in thermoplastic polyurethanes

The thermal and oxygen transport properties of a series of thermoplastic polyurethanes (TPUs) based on 4,4′‐methylene diisocyanate (MDI) and 1,4‐butanediol (BD) as hard segments, and poly(tetramethylene glycol) (PTMG) or poly(butylene adipate) (PA) as soft segments, are studied. Oxygen permeabilities (P) of both polyester‐based and polyether‐based TPUs increase with decreasing hard segment fractions. Oxygen solubility (S) and diffusivity (D) can be derived from permeation curves. S correlates with the amount of excess free volume as determined by the difference between glass‐transition and testing temperatures (i.e., the degree of super cooling) and decreases with the increased T_g in polyester‐based TPUs. The intensity of low temperature gamma transition reflects the activation energy for D; the higher the intensity is, the lower D is annealed TPU samples exhibited higher oxygen permeabilities as well as lower storage moduli at room temperature, despite modest increases in overall crystallinity. Dedensification of the soft segment phase during annealing/crystalline phase growth is the most likely explanation for loss of mechanical and barrier properties after annealing as partially confirmed by Fourier transform infrared spectroscopy. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Synthesis and characterization of polyurethane–urea nanoparticles containing methylenedi‐p‐phenyl diisocyanate and isophorone diisocyanate

Water‐based polyurethane–urea (WPUU) nanoparticles containing 4,4′‐methylenedi‐p‐phenyl diisocyanate (MDI) and isophorone diisocyanate (IPDI) were synthesized by a stepwise prepolymer mixing process, that is, the consecutive formation of hydroxyl‐terminated and isocyanate‐terminated polyurethane prepolymers. The reaction behavior, chemical structure, and consequent morphology of the polyurethane prepolymers and WPUU were investigated with Fourier transform infrared (FTIR), gel permeation chromatography, and NMR techniques with MDI concentrations ranging from 0 (pure IPDI) to 50% with respect to the total moles of isocyanate. Wide‐angle X‐ray diffraction and differential scanning calorimetry patterns showed that the crystallinity of WPUU, which mostly originated from crystallizable poly(tetramethylene adipate) polyol, was significantly affected by the MDI content. Both the crystallinity and melting temperature of WPUU decreased as the MDI content increased. Deconvoluted relative peak areas of the carbonyl region in the FTIR spectrum revealed that the effect of hydrogen bonding among the hard segments became favorable as the MDI content increased, whereas the hydrogen bonding of the soft segments significantly decreased. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4353–4369, 2004     

Thermal and mechanical properties of mandelic acid‐copolymerized poly(butylene succinate) and poly(ethylene adipate)

Phenyl side chains were introduced to poly(butylene succinate) and poly(ethylene adipate) by the polymerization of the respective monomers in the presence of mandelic acid. The increasing content of the phenyl side chains decreased the melting temperature and the crystallinity but increased the glass‐transition temperature of the aliphatic polyesters. The phenyl side branches reduced the crystallinity of poly(butylene succinate) more significantly than the ethyl or n‐octyl side branches did. The tensile strength, elongation, and tear strength of poly(ethylene adipate) decreased with an increase in the content of mandelic acid units. However, the increasing content of mandelic acid units enhanced the elongation and tear strength of poly(butylene succinate) considerably without a notable deterioration of tensile strength. The biodegradability of the copolyesters was increased as a result of the introduction of more mandelic acid units due to the decrease in the crystallinity. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1504–1511, 2000     

Synthesis and characterization of hydrophilic thermotropic block copolyetheresters

The block copolyetheresters with a hard segment of poly (hexamethylene p,p′-bibenzoate) and a soft segment of poly (ethylene oxide) were prepared by melt polycondensation of dimethyl-p,p′-bibenzoate, 1,6-hexanediol, and polyethylene glycol (PEG) with molecular weights of 400, 1000, 2000, or 4000. These block copolyetheresters were characterized by intrinsic viscosity, GPC, FT-IR, ¹H-NMR, and water absorption. The thermotropic liquid crystalline properties were investigated by DSC, polarized microscope, and x-ray diffraction. The block copolyetheresters exhibit smectic liquid crystallinity due to the polyester segment. The transitions are dependent on the molar content and the molecular weight of PEG used. The block copolyetheresters show high water absorption due to the hydrophilic nature of the poly (ethylene oxide) segment. The water absorption increases with increasing PEG content. As the molecular weight of PEG increases, the water absorption increases significantly. The results indicate that the water absorption of the poly (ethylene oxide) segment in the block copolymers is affected by the presence of polyester segments. © 1995 John Wiley & Sons, Inc.     

Parameters affecting transition temperatures of poly(lactic acid‐co‐polydiols) copolymer‐based polyester urethanes and their shape memory behavior

A series of polyester urethanes (PEUs) comprising poly(lactic acid‐co‐polydiol) copolymers as a soft segment, 4,4′‐diphenylmethane diisocyanate (MDI) and 1,4‐butanediol (BDO) as a hard segment were systematically synthesized. Soft segments, which were block copolymers of L ‐lactide (LA) and polydiols such as poly(ethylene glycol) and poly(trimethylene ether glycol), were prepared via ring opening polymerization. Glass transition temperatures (T_g) of the obtained PEUs were found strongly dependent on properties of copolymer soft segments. By simply changing composition ratio, type and molecular weight of polydiols in the soft segment preparation step, T_g of PEU can be varied in the broad range of 0–57°C. The synthesized PEUs exhibited shape memory behavior at their transition temperatures. PEUs with hard segment ratio higher than 65 mole percent showed good shape recovery. These findings suggested that it is important to manipulate molecular structure of the copolymer soft segment for a desirable transition temperature and design optimal soft to hard segment ratio in PEU for good shape recovery. Copyright © 2011 John Wiley & Sons, Ltd.     

New block copolymers V. Synthesis,characterization and morphological studies of poly(pentamethylene terephthalate)-b-(acrylonitrile butadiene rubber)

A block copolymer was prepared by low temperature polycondensation between (acid chloride)-terminated poly(pentamethylene terephthalate) as the hard block, and amine-terminated acrylonitrile-butadiene rubber, as the soft block. The polymer was characterized by nitrogen analysis, IR and NMR spectroscopy. The polymer showed two glass transition temperatures (T _g ) and exhibited two-phase morphology.     

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 thermal,optical, and mechanical properties of sequence‐controlled poly(1‐adamantyl acrylate)‐block‐poly(n‐butyl acrylate) containing polar side group

We prepared the sequence‐controlled block copolymers including poly(1‐adamantyl acrylate) (PAdA) and poly(n‐butyl acrylate) sequences as the hard and soft segments, respectively, by the organotellurium‐mediated living radical polymerization. The thermal, optical, and mechanical properties of the adamantane‐containing block copolymers with polar 2‐hydroxyethyl acrylate (HEA) and acrylic acid (AA) repeating units were investigated. The microphase‐separated structures of the block copolymers were confirmed by the differential scanning calorimetry and atomic force microscopy observations as well as dynamic mechanical measurements. The α‐ and β‐dispersions due to the main‐chain and side group molecular motions, respectively, of the hard and soft segments were observed. Their transition temperatures and activation energies increased due to the formation of intermolecular hydrogen bonding by the introduction of the HEA and AA repeating units. The effects of the hydrogen bonding on their tensile elasticity, strength, and strain were also evaluated. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 2899–2910     

Synthesis and characterization of fully biobased poly(propylene succinate‐ran‐propylene adipate). Analysis of the architecture‐dependent physicochemical behavior

Fully biobased aliphatic random poly(1,3‐propylene succinate‐ran‐1,3‐propylene adipate) (PPSA) copolyesters with high molar mass were synthesized with different macromolecular architectures based on various succinic acid/adipic acid (SA/AA) molar ratio, by transesterification in melt. Titanium (IV) isopropoxide was used as an effective catalyst. All synthesized copolyesters were fully characterized by different chemical and physicochemical techniques including NMR, size exclusion chromatography, FTIR, wide angle X‐ray scattering, differential scanning calorimetry, and thermogravimetric analysis. The final copolyesters molar compositions were identical to the feed ones. The different sequences based on succinate and adipate segments were randomly distributed along the chains. All the corresponding copolyesters showed an excellent thermal stability with a degradation onset temperature higher than 290 °C, which increased with the adipate content. According to their compositions and architectures, PPSA copolyesters can exhibit or not a crystalline phase, at room temperature. T_g of copolyesters decreased with the adipate content due to the decrease in the chains mobility, following the Gordon–Taylor relation. PPSA showed a pseudo eutectic melting behavior characteristic of an isodimorphic character. Finally, PPSA copolyesters were not able to crystallize during the cooling or the second heating run, due to the 1,3‐propanediol chemical structure, which led to amorphous materials with the exception of the polyester based solely on AA. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 2738–2748     

Synthesis and characterization of biodegradable aliphatic copolyesters with poly(ethylene oxide) soft segments

A series of multiblock poly(ether-ester)s based on poly(butylene succinate) (PBS) as the hard segments and hydrophilic poly(ethylene oxide) (PEO) as the soft segments was synthesized with the aim of developing degradable polymers which could combine the mechanical properties of high performance elastomers with those of flexible plastics. The aliphatic poly(ether-ester)s were synthesized by the catalyzed two-step transesterification reaction of dimethyl succinate, 1,4-butanediol and α,ω-hydroxyl terminated poly(ethylene oxide) (PEO, = 1000 g/mol) in bulk. The content of soft PEO segments in the polymer chains was varied from about 10 to 50 mass%. The effect of the introduction of the soft PEO segments on the structure, thermal and physical properties, as well as on the biodegradation properties was investigated. The composition and structure of these aliphatic segmented copolyesters were determined by ¹H NMR spectroscopy. The molecular weights of the polyesters were verified by gel permeation chromatography (GPC), as well as by viscometry of dilute solutions and polymer melts. The thermal properties were investigated using differential scanning calorimetry (DSC). The degree of crystallinity was determined by means of DSC and wide-angle X-ray scattering. A depression of melting temperature and a reduction of crystallinity of the hard segments with increasing content of PEO segments were observed. Biodegradation of the synthesized copolyesters, estimated in enzymatic degradation tests in phosphate buffer solution with Candida rugosa lipase at 37 °C was compared with hydrolytic degradation in the buffer solution. The weight losses of the samples were in the range from 2 to 10 mass%. GPC analysis confirmed that there were significant changes in molecular weight of copolyesters with higher content of PEO segments, up to 40% of initial values. This leads to conclusion that degradation mechanism of the poly(ether-ester)s based on PEO segments occurs through bulk degradation in addition to surface erosion.     

Synthesis of poly(vinyl ether)‐based,ABA triblock‐type thermoplastic elastomers with functionalized soft segments and their gas permeability

The ABA‐type triblock copolymers consisting of poly(2‐adamantyl vinyl ether) [poly(2‐AdVE)] as outer hard segments and poly(6‐acetoxyhexyl vinyl ether) [poly(AcHVE)], poly(6‐hydroxyhexyl vinyl ether) [poly(HHVE)], or poly(2‐(2‐methoxyethoxy)ethyl vinyl ether) [poly(MOEOVE)] as inner soft segments were synthesized by sequential living cationic polymerization. Despite the presence of polar functional groups such as ester, hydroxyl, and oxyethylene units in their soft segments, the block copolymers formed elastomeric films. The thermal and mechanical properties and morphology of the block copolymers showed that the two polymer segments of these triblock copolymers were segregated into microphase‐separated structure. Effect of the functional groups in the soft segments on gas permeability was investigated as one of the characteristics of the new functional thermoplastic elastomers composed solely of poly(vinyl ether) backbones. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1114–1124     

Synthesis and properties of poly(ester urethanes) based on cellulose triacetate

Segmented poly(ester urethanes) were synthesized from oligomeric cellulose triacetate diols, poly(caprolactone)diols, and 1,6-hexamethylene diisocyanate. The effects of the molecular mass and structure of soft and hard segments of poly(ester urethanes) on their thermal behavior, mechanical properties, and degradation in aqueous solutions of a phosphate buffer were studied by DSC and IR spectroscopy. The combination of soft segments derived from poly(caprolactone)diols with M = (1.0–3.5) × 10³, hard segments based on depolymerized cellulose triacetate with M = (2–4) × 10³, and 1,6-hexamethylene diisocyanate makes it possible to synthesize poly(ester urethanes) with excellent mechanical characteristics. The degree of crystallinity of these polymers increases with a decrease in the molecular mass of the depolymerized cellulose triacetate block in the hard segment. As the soft segment lengthens, phase separation between domains of soft and hard segments becomes more pronounced. Upon incorporation of poly(ethylene glycol) blocks into the soft segments of poly(ester urethanes), their hydrophobicity is enhanced and biodegradability is accelerated.     

New segmented poly(ester‐urethane)s from renewable resources

The physical and mechanical properties of aliphatic homopolyesters from monomers obtainable from renewable resources, namely, 1,3‐propanediol and succinic acid, were improved by their combination with aromatic urethane segments capable of establishing strong intermolecular hydrogen bonds. Segmented poly(ester‐urethane)s were synthesized from dihydroxy‐terminated oligo(propylene succinate)s chain‐extended with 4,4′‐diisophenylmethane diisocyanate. The newly synthesized materials were exhaustively characterized by ¹H NMR spectroscopy, size exclusion chromatography, differential scanning calorimetry, dynamic mechanical analysis, and with respect to their main static mechanical properties, an Instron apparatus was used. The average repeat number of the hard segments, evaluated by NMR, ranged from 4 to 9, whereas that of the flexible segments was about 14. The degree of crystallinity, glass‐transition temperature, melting point, tensile strength, elongation, and Young's modulus were influenced by the ratio between hard and soft segments of the segmented copolymer in a predictable way. The results demonstrated that poly(ester‐urethane)s from 1,3‐propanediol and succinic acid are promising thermoplastics. © 2001 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 630–639, 2001     

Synthesis and properties of comb-shaped segmented poly(urethanes) based on 1,2-propanediol derivatives

Comb-shaped segmented poly(urethanes) have been synthesized from ethers via the one-step procedure with the use of glycerol monostearate, D,L-3-octadecyloxy-1,2-propanediol, 3-tert-butoxy-1,2-propanediol, 3-benzyloxy-1,2-propanediol, and 1,2-propanediol as chain extenders. The soft segment of poly(urethanes) was derived from macrodiol (poly(tetramethylene glycol) with M _n = 1000), and 1,6-hexamethylene diisocyanate and 4,4′-cyclohexylmethane diisocyanate were used as diisocyanates. The effect of the structure of side chains located at the hard segments on the formation of hydrogen bonds in comb-shaped poly(urethanes) has been studied by IR spectroscopy. On the basis of DSC measurements, the glass transition temperatures of the soft and hard segments and the temperature and enthalpy of melting of the crystalline phase have been estimated and the microphase separation of segments has been assessed. The mechanical characteristics of the polymers under study have been examined.     

Glass transition and melting behavior of poly(ether-ester) multiblock copolymers with poly(tetramethylene isophthalate) hard segments

The glass transition and melting behavior of poly(ether-ester) multiblock copolymers with poly(tetramethylene isophthalate) (PTMI) hard segments and poly(tetramethylene oxide) (PTMO) soft segments are studied by differential scanning calorimetry (DSC) and small- and wide-angle x-ray scattering (SAXS and WAXS). Thermodynamic melting parameters for the PTMI homopolymer are estimated by WAXS and from the dependence of melting point on crystallization temperature. The melting behavior of PTMI is characterized by dual endotherms which are qualitatively representative of the original morphology, although reorganization effects are present. The composition dependence of the glass transition temperature parameters after rapid quenching from the melt are well described by mixed phase correlations for copolymers in the range 30-100 wt% hard segment. Combined with SAXS characterization at melt temperatures, a single phase melt is suggested in these materials which extends to temperatures below the hard segment melting point. © 1994 John Wiley & Sons, Inc.     

Segmented polyurethanes with 4,4′-bis-(6-hydroxyhexoxy) biphenyl as chain extender. I. Synthesis and characterization of 2,4-tdi-polyurethanes

Polyurethanes composed of 2,4-toluene diisocyanate (TDI), poly (butylene adipate) diols (PBA) of different molecular weights, and 4,4′-bis-(6-hydroxyhexoxy) biphenyl (BHHBP) were prepared by a two-step solution polymerization process. The polyurethanes were char-acterized by elemental analysis, NMR, and SEC. The thermal properties were investigated by DSC, DMA, and optical polarizing microscopy. Dependent on the molecular weight of the PBA, a shift in the glass transition temperature T_g of the polyurethanes has been observed by DSC and DMA. Polyurethanes based on poly (butylene adipate)s of M_n ～ 2000 exhibited a T_g nearly independent on the hard-segment content up to 50% LC hard segments, indicating the existence of mainly phase separated soft and hard segments. By shortening the PBA chain length up to 1,000 and further to 600, the T_g of the polyester soft-segment phase increases with growing hard-segment content, a consequence of enhanced interaction between the hard and soft segments. This tendency is observed to the greatest extent at polyurethanes with the shortest, polyester diol and can be interpreted as a partial miscibility or compatibility of hard and soft segments. Although in polyurethanes with PBA 2000 the mesophase can be proven at a hard-segment content of ～ 40%, its appearance in polyure-thances prepared with PBA 1000 or PBA 600 requires a hard-segment content > 60%. © 1995 John Wiley & Sons, Inc.     

Synthesis and characterization of poly(fluorene)‐based copolymer containing triphenylamine group

The copolymers that are composed of poly(fluorene) (PF), poly(p‐phenylene), and Poly(p‐phenylenevinylene) as backbone and a large 4′‐(N,N′‐diphenylamino)diphenyl or 4′‐(N,N′‐diphenylamino)phenyl as pendent group were synthesized by the nickel(0)‐mediated polycoupling. The composition of the obtained copolymers was confirmed by H NMR. All the copolymers possessed a high weight‐average molecular weight and good solubility in common organic solvents. As the content of triphenyl amine pendants increases, the copolymers showed increased thermal stability due to increased glass transition temperature and increased hole injection ability because of decreased onset of the oxidation potential. In the photoluminescence spectra of copolymers, poly (BDAV₃₀‐co‐DHF₇₀) and poly(BDAPV₃₀‐co‐DHF₇₀) showed efficient energy transfer. indium tin oxide/poly(styrene sulfonate)‐doped poly(3,4‐ethylene dioxythiophene)/poly (BDAV₃₀‐co‐DHF₇₀)/LiF/Al device showed maximum brightness of 2267 cd/m² and efficiency of 0.80 cd/A, with turn‐on voltage at 9.1 V. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 172–182, 2006     

Synthesis of ABA‐triblock and star‐diblock copolymers with poly(2‐adamantyl vinyl ether) and poly(n‐butyl vinyl ether) segments: New thermoplastic elastomers composed solely of poly(vinyl ether) backbones

ABA‐type triblock copolymers and AB‐type star diblock copolymers with poly(2‐adamantyl vinyl ether) [poly(2‐AdVE)] hard outer segments and poly(n‐butyl vinyl ether) [poly(NBVE)] soft inner segments were synthesized by sequential living cationic copolymerization. Although both the two polymer segments were composed solely of poly(vinyl ether) backbones and hydrocarbon side chains, they were segregated into microphase‐separated structure, so that the block copolymers formed thermoplastic elastomers. Both the ABA‐type triblock copolymers and the AB‐type star diblock copolymers exhibited rubber elasticity over wide temperature range. For example, the ABA‐type triblock copolymers showed rubber elasticity from about ?53 °C to about 165 °C and the AB‐type star diblock copolymer did from about ?47 °C to 183 °C with a similar composition of poly(2‐AdVE) and poly(NBVE) segments in the dynamic mechanical analysis. The AB‐type star diblock copolymers exhibited higher tensile strength and elongation at break than the ABA‐type triblock copolymers. The thermal decomposition temperatures of both the block copolymers were as high as 321–331 °C, indicating their high thermal stability. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013