Effects of Temperature on Morphology and Properties of Films Prepared from Poly(ester‐urethane) and Nitrochitosan

Summary: Novel elastic materials were prepared by mixing semicrystalline polyester‐based polyurethane (PU) synthesized at 100 °C with nitrochitosan (NCH) and 1,1,1‐tris(hydroxylmethyl)propane as crosslinker, and then by curing the mixture at 18, 25, 40, 60, and 80 °C. The effects of cure temperature on the crystallization behavior, miscibility, and mechanical properties of the PUNCH materials were studied by attenuated total reflection Fourier transform IR, wide‐angle X‐ray diffraction, scanning electron microscopy, dynamic mechanical analysis, X‐ray photoelectron spectroscopy, and tensile test. The results indicated that the crystalline structure of the blend films was more easily interrupted as the cure temperature increased, leading to a decrease of the degree of crystallinity. With an increase of cure temperature, the blend films exhibited high crosslinking density and tensile strength, and the phase separation between hard and soft segments of PU enhanced, resulting in a decrease in the glass transition temperature (T_g) of soft segment. Interestingly, the composite films keeping high elongation at break possessed tensile strength higher than that of the native poly(ester‐urethane). The enhanced mechanical properties of the blend films can be attributed to the relatively dense crosslinking network and strong intermolecular hydrogen bonding between NCH and PU. Therefore, this study not only provided a novel way by adding NCH into PU matrix to prepare elastic materials, which would remain functional characteristic of chitosan, but also expanded the application field of chitosan.

The cure temperature dependence of the tensile strength and elongation at break for the PEPU‐100 and PUNCH‐100 films.     

Biodegradable polyurethane based on random copolymer of L‐lactide and ϵ‐caprolactone and its shape‐memory property

A series of biodegradable polyurethanes (PUs) are synthesized from the copolymer diols prepared from L ‐lactide and ε‐caprolactone (CL), 2,4‐toluene diisocyanate, and 1,4‐butanediol. Their thermal and mechanical properties are characterized via FTIR, DSC, and tensile tests. Their T_gs are in the range of 28–53°C. They have high modulus, tensile strength, and elongation ratio at break. With increasing CL content, the PU changes from semicrystalline to completely amorphous. Thermal mechanical analysis is used to determine their shape‐memory property. When they are deformed and fixed at proper temperatures, their shape‐recovery is almost complete for a tensile elongation of 150% or a compression of 2‐folds. By changing the content of CL and the hard‐to‐soft ratio, their T_gs and their shape‐recovery temperature can be adjusted. Therefore, they may find wide applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4182–4187, 2007     

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     

Mechanical and thermal properties of functionalized multiwalled carbon nanotubes and multiwalled carbon nanotube–polyurethane composites

Multiwalled carbon nanotube (MWNT)–polyurethane (PU) composites were obtained by an in situ polycondensation approach. The effects of the number of functional groups on the dispersion and mechanical properties were investigated. The results showed that the functionalized MWNTs had more advantages for improving the dispersion and stability in water and N,N′‐dimethylformamide. The tensile strength and elongation at break of the composites exhibited obvious increases with the addition of MWNT contents below 1 wt % and then decreases with additions above 1 wt %. The maximum values of the tensile strength and elongation at break increased by 900 and 741%, respectively, at a 1 wt % loading of MWNTs. Differential scanning calorimetry measurements indicated that the addition of MWNTs resulted in an alteration of the glass‐transition temperature of the soft‐segment phase of MWNT–PU. Additionally, new peaks near 54°C were observed with differential scanning calorimetry because of the microphase‐separation structures and alteration of the segment molecular weights of the hard segment and soft segment of PU with the addition of MWNTs. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Thermal and surface characterization of polyurethane–urea clay nanocomposite coatings

This paper reports synthesis and characterization of polyurethane–urea (PU‐urea) and the nanocomposites derived from the PU‐urea with silicate clays. Organophilic montmorillonite cotreated by cetyl trimethyl ammonium bromide (CTAB) was synthesized and used to prepare PU‐urea/montmorillonite nanocomposites coatings. PU‐ureas were prepared from polyethylene glycol (PEG), polypropylene glycol (PPG), trimethylol propane (TMP), and 4,4′‐diphenylmethane diisocyanate (MDI) by reacting excess diisocyanate with polyether glycols. The excess isocyanate of the prepolymers was cured with atmospheric moisture. The synthesized moisture cured PU‐urea and nanocomposites were characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), differential scanning calorimetric (DSC), and angle resolved X‐ray photoelectron spectroscopy (AR‐XPS). The thermal stability of the PU‐urea nanocomposites was higher relative to the mother PU‐urea films. DSC results showed a slight enhancement in the soft segment glass transition temperature after 3 wt % clay loading. The surface properties showed an enrichment of the soft segment toward the surface. An enhancement in the hard segment composition in the nanocomposite coatings has resulted in enhancing the phase mixing process. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2393–2401, 2006     

Comparison of the effects of linking diglycidyl ether‐terminated PDMS and BPA onto polyurethane with respect to the tensile and thermal properties

Flexible poly(dimethylsiloxane) (PDMS) or rigid bisphenol A (BPA) with diglycidyl ether end groups was linked to polyurethane (PU), which was composed of 4,4′‐methylenebis(phenyl isocyanate) as a hard segment and poly(tetramethylene ether)glycol as a soft segment. A control PDMS (CPDMS) series was prepared with an additional deprotonation step by NaH. The spectroscopic, thermal, tensile, shape memory, and low‐temperature flexibility properties were compared with those of plain PU to investigate the effects of linking the flexible PDMS or the rigid BPA on PU. The soft segment melting peaks were not affected by the PDMS content for the PDMS series but disappeared as the BPA content increased in the BPA series. The soft segment crystallization of PU was completely disrupted as the linked BPA content increased in the differential scanning calorimetry results and disappeared in the dynamic mechanical analysis results. The glass transition temperature (T_g) of the BPA series increased with increasing BPA content, whereas that of the PDMS series remained the same. The tensile strength of the PDMS series sharply increased with increasing PDMS content. The shape retention of the BPA series at ?25 °C sharply decreased as the BPA content increased. Finally, the BPA series linked with rigid aromatic BPA demonstrated excellent low‐temperature flexibilities compared with the PDMS series and plain PU. Compared with PUs linked with PDMS, PUs linked with rigid BPA demonstrated a significant change in the cross‐link density, thermal properties, shape retention, and low‐temperature flexibility. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43284.     

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     

Preparation and characterization of hydrophilic temperature‐dependent polyurethane containing the grafted poly(N‐isopropylacrylamide)

The polyurethane (PU) structure is modified with dimethylolpropionic acid (DMPA) and poly(N‐isopropylacrylamide; poly[IPA]) to prepare hydrophilic temperature‐dependent PU that is investigated with reference to the degree of crosslinking, thermal properties of soft segment, tensile and shape memory performance, hydrophilic conversion of surface, and temperature‐dependent water swelling and water vapor permeability (WVP). The thermal properties of soft segment (melting, crystallization, and glass transition) are significantly affected by poly(IPA). Breaking tensile stress also increases with increasing IPA monomer content due to crosslinking effect but breaking tensile strain does not significantly decrease with increasing IPA monomer content. Shape recovery capability at 10°C steeply inclines to over 90% from 46.9% for unmodified PU by the grafting of poly(IPA), whereas shape retention at ?25°C does not decrease below 90% with the increase in IPA content. Poly(IPA)‐grafted PU can display temperature‐dependent control of water swelling and WVP due to transformation of the grafted poly(IPA) depending on the surrounding temperature. POLYM. ENG. SCI., 59:1719–1728 2019. © 2019 Society of Plastics Engineers     

Shape memory effect of poly(L‐lactide)‐ based polyurethanes with different hard segments

A series of biodegradable polylactide‐based polyurethanes (PLAUs) were synthesized using PLA diol (M_n = 3200) as soft segment, 4,4′‐diphenylmethane diisocyanate (MDI), 2,4‐toluene diisocyanate (TDI), and isophorone diisocyanate (IPDI) as hard segment, and 1,4‐butanediol as chain extender. The structures and properties of these PLAUs were studied using infrared spectroscopy, differential scanning calorimetry, tensile testing, and thermomechanical analysis. Among them, the MDI‐based PLAU has the highest T_g, maximum tensile strength, and restoration force, the TDI‐based PLAU has the lowest T_g, and the IPDI‐based PLAU has the highest tensile modulus and elongation at break. They are all amorphous. The shape recovery of the three PLAUs is almost complete in a tensile elongation of 150% or a twofold compression. They can keep their temporary shape easily at room temperature (20 °C). More importantly, they can deform and recover at a temperature below their T_g values. Therefore, by selecting the appropriate hard segment and adjusting the ratio of hard to soft segments, they can meet different practical demands for shape memory medical devices. Copyright © 2007 Society of Chemical Industry     

Influence of hard segments of polyurethane on cell growth

Polyurethanes (PU) with suitable soft segments have been found to be good blood-compatible polymers and have attracted much attention recently. In this study, various molar amounts of 4,4′-methylene bisphenyl isocyanate reacted with poly(tetramethylene oxide) were synthesized to explore the optimal ratio of hard/soft segments for cell attachment and proliferation in in vitro systems. Differential scanning calorimetry and dynamic mechanical analysis were used to determine the physical properties, hydrogen bonding index (HBI) and transmission electron microscopy to observe the phase-separation phenomena in the materials, and 3T3 fibroblast to evaluate the dependence of the cell proliferation at 37°C on the material properties. Our results show that cell attachment and proliferation are closely related to the cell growth surface, which in turn is controlled by (1) the ratio of hard to total segment concentration and (2) the recrystallization temperature (T_c) of PU. To obtain a good cell growth surface, the ratio of hard to total segment concentration is found to be between 0.4 and 0.6, and HBI is between 1.5 and 2.1. Furthermore, when the T_c of PU is near the physiology temperature, a stable surface for cell growth can be provided. The shorter molecules in the soft segment region can rearrange the molecular chain at 37°C.     

Morphology and water vapor permeability of temperature‐sensitive polyurethanes

A series of segmented polyurethanes (PUs) were prepared, in which five different polyols and hexamethylene diisocyanate were used as soft segments, and 4,4′‐diphenylmethane diisocyanate, hydrophilic segment poly (ethylene glycol) 200 (PEG 200), and chain extender 1,4‐butanediol were used as hard segment. Morphology of the PUs was investigated using differential scanning calorimetry, wide angle X‐ray diffraction, polarizing microscopy, and transmission electron microscopy. Water vapor permeability of the membranes as a function of temperature was tested accordingly. Results show that the presence of PEG200 interferes the crystallization of hard segment in these PUs, and at the same time, increases phase compatibility between soft and hard segment in the PET‐PU. It leads to a lower crystal melting temperature and degree of crystallinity of soft segment in the segmented PU than those of pure polyols, and no crystallization existing in hard segment. A morphological model is proposed, that is, aggregated soft‐segment‐rich domains can be observed clearly in the PUs with high crystallinity in soft segment, while identifiable hard domains are well‐distributed in the soft segment domains in the PU with low crystallinity. Within the temperature range of crystal melting, water vapor permeability of the PU membranes increases significantly with increase of temperature. Such temperature‐sensitive property is triggered by crystal melting of soft segment. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Annealing-induced morphological changes in segmented elastomers

Thermal analysis has been used to study annealing-induced ordering in segmented elastomers. Twelve segmented elastomers were studied each having approximately 50% by wt hard segment content. Seven general classes of materials were examined including polyether and polyester polyurethanes, polyether polyurethane-urea, and polyether-polyester. Materials were slow cooled (?10°C min^?1) from the melt to an annealing temperature (?10°, 20°, 60°, 90° or 120°C) where they were annealed (16, 12, 8, 6 or 4 days, respectively). Annealing was followed by slow cooling (?10°C min^?1) to ?120°C after which a d.s.c. experiment was run. In general, annealing resulted in an endothermic peak at a temperature 20°–50°C above that of the temperature of annealing. This phenomenon was observed in both semicrystalline and amorphous materials. The closer the annealing endotherm was to a crystalline endotherm without exceeding it in temperature, the larger its size. Annealing endotherms resulted from hard or soft segment ordering. Only one annealing endotherm was observed for a given annealing history, even though in some materials hard and soft segments could exhibit annealing-induced morphological changes. Hard segment homopolymers were studied yielding results similar to the block polymers containing shorter sequences of the same material. This suggests that annealing-induced ordering is an intradomain phenomenon not associated with the interphase between domains, or necessarily dependent on the chain architecture of segmented elastomers.     

Size Exclusion Chromatography as a Method for Routine Check‐Up and Quality Control of Industrial Thermoplastic Polyurethane Systems – Correlation between Molecular Weight and Mechanical and Thermal Properties

A method has been developed which allows an accurate molecular characterization of linear prepolymers end‐capped with diisocyanates which is correlated with the properties of the finally formed thermoplastic polyurethane elastomer (TPU). Therefore, this method is suitable for a fast routine check‐up in quality control in the polyurethane (PU) processing industry. A homologous series of three toluene‐2,4‐diisocyanate (TDI) end‐capped PU prepolymers with poly(oxytetramethylene) glycol (POTM) as soft segment (number‐average degree of polymerization: 3, 4, and 7) have been characterized according to their molar mass and its distribution by means of size exclusion chromatography (SEC) calibrated with commercially available POTM standards. The validation of this method was carried out by SEC with double detection, using a combination of a concentration (differential refractive index detector, DRI) and an end group specific detector (ultraviolet detector, UV), which allows the determination of the absolute number‐average molar mass of the PU prepolymers as well as their content of soft and hard segment. The values for the number‐average molar mass were confirmed by osmometry. The PU prepolymers were reacted each with the same aromatic diamine to give the corresponding TPU elastomers which have been examined according to their thermal and dynamic behavior (transition temperature of soft and hard segment, temperature range of application) by means of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA). Also the hardness, tear strength and elongation at break could be related to the molecular structure, leading to a judgement for the efficiency of the final product for special fields of application.     

Effect of annealing on poly(urethane‐siloxane) copolymers

Poly(urethane‐siloxane) copolymers were prepared by copolymerization of OH‐terminated polydimethylsiloxane (PDMS), which was utilized as the soft segment, as well as 4,4′‐diphenylmethane diisocyanate (MDI) and 1,4‐butanediol (1,4‐BD), which were both hard segments. These copolymers exhibited almost complete phase separation between soft and hard segments, giving rise to a very simple material structure in this investigation. The thermal behavior of the amorphous hard segment of the copolymer with 62.3% hard‐segment content was examined by differential scanning calorimetry (DSC). Both the T₁ temperature and the magnitude of the T₁ endotherm increased linearly with the logarithmic annealing time at an annealing temperature of 100°C. The typical enthalpy of relaxation was attributed to the physical aging of the amorphous hard segment. The T₁ endotherm shifted to high temperature until it merged with the T₂ endotherm as the annealing temperature increased. Following annealing at 170°C for various periods, the DSC curves presented two endothermic regions. The first endotherm assigned as T₂ was the result of the enthalpy relaxation of the hard segment. The second endothermic peak (T₃) was caused by the hard‐segment crystal. The exothermic curves at an annealing temperature of above 150°C exhibited an exotherm caused by the T₃ microcrystalline growth. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5174–5183, 2006     

Synthesis and characterization of biodegradable poly(ester‐urethanes) based on bacterial poly(R‐3‐hydroxybutyrate)

A series of poly(R‐3‐hydroxybutyrate)/poly(ε‐caprolactone)/1,6‐hexamethylene diisocyanate‐segmented poly(ester‐urethanes), having different compositions and different block lengths, were synthesized by one‐step solution polymerization. The molecular weight of poly(R‐3‐hydroxybutyrate)‐diol, PHB‐diol, hard segments was in the range of 2100–4400 and poly(ε‐caprolactone)‐diol, PCL‐diol, soft segments in the range of 1080–5800. The materials obtained were investigated by using differential scanning calorimetry, wide angle X‐ray diffraction and mechanical measurements. All poly(ester‐urethanes) investigated were semicrystalline with T_m varying within 126–148°C. DSC results showed that T_g are shifted to higher temperature with increasing content of PHB hard segments and decreasing molecular weight of PCL soft segments. This indicates partial compatibility of the two phases. In poly(ester‐urethanes) made from PCL soft segments of molecular weight (M_n ≥ 2200), a PCL crystalline phase, in addition to the PHB crystalline phase, was observed. As for the mechanical tensile properties of poly(ester‐urethane) cast films, it was found that the ultimate strength and the elongation at the breakpoint decrease with increasing PHB hard segment content. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 703–718, 2002     

Synthesis of polyurethane–imide (PU–imide) copolymers with different dianhydrides and their properties

This study reports the synthesis of polyurethane–imide (PU–imide) copolymers using 4,4′-diphenylmethane diisocyanate (MDI) polytetramethylene glycols (PTMGs) and different aromatic dianhydrides. Differential scanning calorimetry (DSC) results indicate that PU–imide copolymers had two phase structures containing four transition temperatures (T_gs, T_ms, T_gh and T_mh). However, only PU–imide copolymers were formed by soft PTMG(2000) segments possessing a T_ms (melting point of soft segment). When different aromatic dianhydrides were introduced into the backbone chain of the polyurethane, although the T_gs (glass transition temperature of the soft segment) of some of PU–imide copolymers did not change, the copolymers with long soft segments had low T_gs values. The T_gh (glass transition temperature of hard segment) values of PU–imide copolymers were higher than that of polyurethane (PU). In addition, the high hard segment content of PU–imide copolymer series also had an obvious T_mh (melting point of hard segment). According to thermogravimetric analysis (TGA) and differential thermogravimetric analysis (DTGA), the PU–imide copolymers had at least two stages of degradation. Although the T_di (initial temperature of degradation) depended on the hard segment content and the composition of hard segment, the different soft segment lengths did not obviously influence the T_di. However, PU–imide copolymers with a longer soft segment had a higher thermal stability in the degradation temperature range of middle weight loss (about T_d 5%–50%). However, beyond T_d 50% (50% weight loss at temperature of degradation), the temperature of degradation of PU–imide copolymers increased with increasing hard segment content. Mechanical properties revealed that the modulus and tensile strength of PU–imide copolymers surpassed those of PU. Wide angle X-ray diffraction patterns demonstrated that PU–imide copolymers are crystallizable. © 1999 Society of Chemical Industry     

The temperature-sensitive water vapor permeation control of polyurethane membrane using the graft-polymerized poly(N-isopropylacrylamide) and the impact on the tensile strength and shape recovery effect

Poly(N-isopropylacrylamide) (poly(NIPAM)) was grafted onto polyurethane (PU) using a graft-polymerization method to develop a thermo-responsive PU and to investigate the impact on cross-link density, solution viscosity, soft segment thermal transitions, tensile properties, shape memory effect, and water vapor permeation through PU membrane. The soft segment crystallization peak sharply decreased with the increase in NIPAM content, whereas the glass transition temperature (T_g) slightly increased with the increase of NIPAM content. The breaking tensile stress rapidly increased with the increase in NIPAM content due to the cross-linking effect between the grafted poly(NIPAM) chains, whereas the strain at break did not significantly decreased as the NIPAM content increased. The shape recovery at 10°C rapidly increased from 46.9% for plain PU to above 90% after the grafting of poly(NIPAM) onto PU, and the shape retention at ?25°C slightly decreased with the increase in NIPAM content. Finally, the grafting of poly(NIPAM) onto PU demonstrated the temperature-responsive control of water vapor permeation through PU film due to the conformational change of the grafted poly(NIPAM) with the increase of temperature and the potential applications of the resulting PUs are discussed.     

Application of recycled polyol and benzimidazole to the enhancement of antifungal activity of polyurethane

Recycled polyol and benzimidazole were both grafted onto polyurethane (PU) to enhance the surface hydrophilicity and antifungal activity, respectively. The two grafted groups affected the viscosity, crosslink density, soft segment glass transition, breaking stress, flexibility at freezing temperature, shape recovery at ?10 °C, surface hydrophilicity, and antifungal activity. The glass transition temperature increased from ?67.5 °C for plain PU up to ?60.8 °C after the grafting of polyol. The breaking stress and shape recovery of the grafted PU increased up to 425% and 200%, respectively, relative to plain PU because of the chemical linking by the grafted polyol. The hydrophilicity of PU, evaluated by the water contact angle and water swelling ratio, increased with increasing polyol content. A PU sample demonstrated excellent low‐temperature flexibility in comparison to plain PU and control sample. Finally, the PUs modified with grafted polyol and benzimidazole completely suppressed fungal growth. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46600.     

Dynamic mechanical signatures of a polyester‐urethane and plastic‐bonded explosives based on this polymer

The complex shear moduli of the segmented polyurethane Estane 5703p, Livermore explosive (LX)‐14, and plastic bonded explosive (PBX)‐9501, which use this polymer as a binder, have been investigated. Segmented polyurethanes, such as Estane 5703, contain microphase‐separated hard segments in a rubbery matrix of soft segments. LX‐14 is composed of 95.5% 1,3,5,7‐tetranitroazacyclooctane (HMX) explosive with 4.5% Estane 5703 binder. PBX‐9501 is composed of 94.9% HMX, 2.5% Estane 5703p binder, 2.5% nitroplasticizer (NP), and about 0.1% antioxidant Irganox 1010. In the temperature range from ?150 to 120°C, two relaxations were observed as peaks in the loss modulus and tangent delta in Estane 5703p and LX‐14. A third relaxation was found in PBX‐9501. The low temperature relaxation associated with vitrification of the poly(ester urethane) soft segment occurred in the shear loss modulus (G″) at ?29 and ?26°C in Estane and LX‐14, respectively, at 1 Hz. In PBX‐9501 the Estane soft segment glass transition peak, T_g(SS), in the loss modulus occurred at ?40 ± 3°C at 1 Hz. The reduction in soft segment glass transition in PBX‐9501 is clear evidence of plasticization of the soft segment by NP. The apparent activation energy of the maximum in the loss modulus for LX‐14 and PBX‐9501 over the frequency range from 0.1 to 10 Hz was 230 kJ/mole (55 kcal/mole). The hard segment glass transition, T_g(HS), was observed as a peak in the loss modulus at about 70°C. In LX‐14 the transition was observed at lower temperatures (56–58°C at 1 Hz) depending on thermal history. There was a low temperature shoulder on the T_g(HS) of Estane 5703 associated with soft segment crystallinity. Modulated differential scanning calorimetry (MDSC) was used to verify the T_g(HS) in Estane and 50/50 mixtures of Estane with NP. In PBX‐9501 the hard segment glass transition occurred between 65 and 72°C. The presence of NP in PBX‐9501 gave rise to a new transition, T_eu(NP), between 8 and 15°C. This peak is believed to be associated with the eutectic melting of the plasticizer. Returns of fielded PBX‐9501 that were 6 and 11 years old were also measured. Small variations in T_g(SS) and the rubber plateau modulus were observed in these aged samples, consistent with migration of plasticizer and/or very low levels of chain scission. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1009–1024, 2002     

N‐(2‐biphenylenyl)‐4‐[2′‐phenylethynyl] phthalimide: 2. Detailed study of the monomer cure and properties of the resulting polymer

A detailed study is presented of the high‐temperature cure of the difunctional monomer N‐(2‐biphenylenyl)‐4‐[2′‐phenylethynyl]phthalimide (BPP) and the thermal properties of the resulting homopolymer. Although the phenylethynyl groups are consumed within 1 h at 370 °C, other reactions continue well after this, leading to a cured polymer whose glass transition temperature (T_g) is highly dependent on cure time and temperature. A T_g of 450 °C is achieved after a 16 h cure at 400 °C. Use of chemometrics to analyse the infrared spectra of curing BPP provides evidence for changes in the aromatic moieties during cure, perhaps indicative of co‐reaction between the biphenylene and phenylethynyl groups; however, other processes also contribute to the overall complex cure mechanism. Despite the high T_g values, BPP homopolymer exhibits unacceptably poor thermo‐oxidative stability at 370 °C, showing a weight loss of about 50 % after 100 h ageing. This is perhaps a result of formation of degradatively unstable crosslink structures during elevated‐temperature cure. Copyright © 2004 Society of Chemical Industry