Solute and solvent effects on the thermorheological properties of poly(oxyethylene)–poly(oxypropylene) block copolymers: Implications for pharmaceutical dosage form design

Despite their widespread use as platforms for topical drug delivery systems, there is a relative lack of information concerning the thermorheological and viscoelastic properties of poloxamer systems and the effects of formulation components on these properties. To address this deficit, we examined the effects of the poloxamer concentration (25 and 35% w/w), molecular weight blend (poloxamer 407 and poloxamer 188), cosolvents (ethanol, propylene glycol, and glycerol), and presence of inorganic and organic electrolytes (sodium chloride and tetracaine hydrochloride, respectively) on these properties. The rheological properties were examined with a rheometer (4‐cm‐diameter, stainless steel, parallel‐plate geometry) in either thermal sweep (0.5 Hz) or frequency sweep (0.01–1.0 Hz and 37°C) modes. Increasing the poloxamer concentration increased the elasticity [i.e., increased the storage modulus (G′) and reduced the loss tangent (tan δ)] and reduced the sol–gel transition temperature (T_m) of all the formulations. Decreasing the ratio (407:188) increased T_m and reduced the elasticity of all the formulations. Increasing the concentration of ethanol, propylene glycol, or glycerol in the solvent reduced T_m. The presence of ethanol reduced G′ and increased tan δ in a concentration‐dependent fashion, whereas the viscoelastic properties of the poloxamers were more tolerant of glycerol (in particular) and propylene glycol. The elasticity of the formulations containing up to 10% glycerol and 5% propylene glycol was increased with respect to their aqueous counterparts. The presence of sodium chloride reduced T_m and, at lower concentrations (1 and 3%), increased G′ and reduced tan δ for aqueous poloxamer systems. Conversely, the addition of a model therapeutic agent, tetracaine hydrochloride (5 and 7% w/w), significantly increased T_m and altered the viscoelastic character of the poloxamer system, notably reducing G′ and increasing the loss modulus and tan δ. Alterations in the viscoelastic and thermorheological properties of aqueous poloxamer systems will have implications for their clinical performance. This study, therefore, has highlighted the need for the rational selection of components in the formulation of poloxamer systems as platforms for topical drug delivery. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1016–1026, 2003     

In situ gel forming systems of poloxamer 407 and hydroxypropyl cellulose or hydroxypropyl methyl cellulose mixtures for controlled delivery of vancomycin

Poloxamers are a family of triblock copolymers consisting of two hydrophilic blocks of polyoxyethylene separated by a hydrophobic block of polyoxypropylene, which form micelles at low concentrations and form clear thermally reversible gels at high concentrations. The objective of this study was to develop an in situ gel forming drug delivery system for vancomycin using the minimum possible ratio of poloxamer 407 (P407). Decreasing the concentration of poloxamer could reduce the risk of hypertriglyceridemia induction. Different additives were added to the poloxamer formulations. It was observed that among different additives, hydroxypropyl methyl cellulose (HPMC) and hydroxypropyl cellulose (HPC) can decrease poloxamer concentration required to form in situ gelation from 18 to 10%. The dynamic viscoelastic properties of the samples were determined. Both the storage modulus and the loss modulus of the samples increased abruptly as the temperature passed a certain point. The gelling temperature was in the order of P407 : HPC (10 : 10 w/w) < P407 : HPMC (10 : 10 w/w) < P407 : HPMC (15 : 5 w/w) < P407 : HPC (15 : 5 w/w). Drug release rate could be controlled by changing the type and ratio of additives as well as the amount of drug loaded. It can be concluded that combining P407 and cellulose derivatives could be a promising strategy for preparation of thermally reversible in situ gel forming delivery systems with low poloxamer concentration. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermoplastic hydrogel based on pentablock copolymer consisting of poly(γ‐benzyl L‐glutamate) and poloxamer

A thermoplastic hydrogel based on a pentablock copolymer composed of poly(γ‐benzyl L ‐glutamate) (PBLG) and poloxamer was synthesized by polymerization of BLG N‐carboxyanhydride, which was initiated by diamine‐terminated groups located at the ends of poly(ethylene oxide) (PEO) chains of the poloxamer, to attain a new pH‐ and temperature‐sensitive hydrogel for drug delivery systems. Circular dichroism measurements in solution and IR measurements in the solid state revealed that the polypeptide block existed in the α‐helical conformation, as in the PBLG homopolymer. The intensity of the wide‐angle X‐ray diffraction patterns of the polymers depended on the poloxamer content in the copolymer and showed basically similar reflections to the PBLG homopolymer. The melting temperature (T_m) of the poloxamer in the copolymer was reduced with an increase of the PBLG block in comparison with the T_m of the poloxamer, which is indicative of a thermoplastic property. The water contents of the copolymers were dependent on the poloxamer content in the copolymers, for example, those for the GPG‐2 (48.7 mol % poloxamer) and GPG‐1 (57.5 mol % poloxamer) copolymers were 31 and 41 wt %, respectively, indicating characteristics of a polymeric hydrogel. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2649–2656, 2003     

The effect of urea bond on structure and properties of toughened epoxy resins

In this article, modified poly(oxypropylene) diamines were synthesized and used as a new flexible curing agent for epoxy resins. The purpose of modification is to introduce urea group into epoxy resins. The reaction rate, mechanical properties, glass transition temperature (T_g), and fracture surface morphology of these toughened epoxy resins were investigated. Because of urea groups, the reactivity between poly(oxypropylene) diamines and epoxy resins was significantly enhanced. At the same time, the urea groups resulted in strong intersegmental hydrogen bonding between modified poly(oxypropylene) chain, which reduced the compatibility of poly(oxypropylene) with epoxy resins and resulted in higher T_g of toughened epoxy. The modified sample had tensile strength of 15.8 MPa and ultimate elongation of 118% at room temperature, whereas the unmodified sample only had 6.2 MPa and 70%. The scanning electron microscope analysis showed that the modified system displayed tough fracture feature, whereas the unmodified system showed typical brittle fracture. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Novel polyurethane‐based thermosensitive hydrogels as drug release and tissue engineering platforms: design and in vitro characterization

Poloxamer P407 (P407) is a Food and Drug Administration approved triblock copolymer; its hydrogels show fast dissolution in aqueous environment and weak mechanical strength, limiting their in vivo application. In this work, an amphiphilic poly(ether urethane) (NHP407) was synthesized from P407, an aliphatic diisocyanate (1,6‐hexanediisocyanate) and an amino acid derived diol (N‐Boc serinol). NHP407 solutions in water‐based media were able to form biocompatible injectable thermosensitive hydrogels with a lower critical gelation temperature behavior, having lower critical gelation concentration (6% w/v versus 18% w/v), superior gel strength (G′ at 37 °C about 40 000 Pa versus 10 000 Pa), faster gelation kinetics (<5 min versus 15–30 min) and higher stability in physiological conditions (28 days versus 5 days) compared to P407 hydrogels. Gel strength and PBS absorption at 37 °C increased whereas dissolution rate (in phosphate‐buffered saline (PBS) at 37 °C) and permeability to nutrients (studied using fluorescein isothiocyanate–dextran model molecule) decreased as a function of NHP407 hydrogel concentration from 10% to 20% w/v. By varying the concentration, NHP407 hydrogels were thus prepared with different properties which could suit specific applications, such as in situ drug/cell delivery or bioprinting of scaffolds. Moreover, deprotected amino groups in NHP407 could be exploited for the grafting of bioactive molecules obtaining biomimetic hydrogels. © 2016 Society of Chemical Industry     

Effects of salts in the Hofmeister series and solvent isotopes on the gelation mechanisms for hydroxypropylmethylcellulose hydrogels

The effects of various inorganic salts and isotopic solvents on the thermal gelation behavior of hydroxypropylmethylcellulose (HPMC) in aqueous solutions were examined by micro-differential scanning calorimetry and rheological measurements. It was found that salting-out salts, such as NaCl, promoted the sol–gel transition of HPMC at a lower temperature. An analysis of solvent isotope effects on the changes in the temperature at maximum heat capacity (T_m) with salt concentration showed that interchain hydrogen bonding (hydrogen bonding between the hydroxyl groups of different HPMC chains) was involved in the sol–gel transition, and its strength depended on the temperature and salt concentration. It was demonstrated that the effectiveness of anionic species in changing the T_m of the HPMC solutions was in the sequence of the Hofmeister series. Anionic species play a role in reducing T_m by their influence on the structure of the water, which in turn affects interactions between hydroxyl groups and water molecules, interchain hydrogen bonding, and the strength of the water cages prohibiting hydrophobic association. Rheological and microcalorimetric results indicated that the change in the thermodynamics of gelation of the HPMC aqueous solution was determined by the salt types and concentration, and the effect of monovalent salts was found to be more cooperative than that of multivalent salts on the sol–gel transition. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Development of a poloxamer analogs/bioadhesive polymers‐based in situ gelling ophthalmic delivery system for tiopronin

The purpose of this study was to develop a poloxamer analogs/bioadhesive polymers‐based in situ gelling ophthalmic delivery system aiming at enhancing bioavailability and anticataract effect. The effect of poloxamer 407 (P407), poloxamer 188 (P188), carbopol 934P (C934), and sodium hyaluronate (NaHA) concentration on the gelation temperature (GT) was examined. The GT of P407 based in situ gel increased with an increase in the P188 concentration. NaHA and C934 lowered the GT of poloxamer analogs based in situ gel. Correlation analysis demonstrated that in vitro drug release from in situ gel was controlled by gel dissolution and followed zero‐order kinetics. Tiopronin in vitro transcorneal transit accorded with zero‐order kinetics. Twenty‐two percent P407 and 6% P188 containing 0.2% NaHA based formulation can be chosen as in situ gel matrix of tiopronin because of proper GT and sustained releasing ability. In vivo study showed that the area under the aqueous humor–concentration time curve of tiopronin increased by 1.6 folds for in situ gel, compared with tiopronin aqueous solution. High‐dose tiopronin in situ gel and solution delayed the development of selenite cataract 6 d and 4 d, respectively. The results showed that tiopronin in situ gel exhibits higher bioavailability and therapeutical effect. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Studies on crystallization kinetics of nylon 6-polyoxypropylene-nylon 6 copolymers

The crystllization kinetics of anionic-prepared nylon6-poly(oxypropylene) 1000-nylon 6 (NPN) block copolymers containing 1.20 to 8.76 wt% poly(oxypropylene)(POP) were studied. The thermograms of isothermal and nonisothermal differential scanning calorimetry of NPN block copolymers obtained were used for the study. The Avrami equation was used to analyze the isothermal crystallization of NPN nylon block copolymers. The Avrami exponent n obtained in the temperature range of 180 to 200 °C was 2.0 to 2.5. It was not similar to that for nylon 6 reported in literature. The activation energies of crystallization for the nylon block copolymers were smaller than that of nylon 6, and showed a minimum with POP content. The equilibrium melting point increased as the POP content decreased. For the nylon block copolymers with lower POP content, the slopes of T_c vs. T_m plots were higher than the values reported elsewhere. The Ozawa plot was used to analyze the data of nonisothermal crystallization. The obvious curvature in the plot indicated that the Ozawa model could not fit our system well, and there was an abrupt change of the slope in the Ozawa plot at a critical cooling rate.     

Epoxy thermosetting systems: Dynamic mechanical analysis of the reactions of aromatic diamines with the diglycidyl ether of bisphenol A

Dynamic mechanical behavior during the reactions of four aromatic diamines (m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfone, and benzidine) with the diglycidyl ether of bisphenol A was studied by torsional braid analysis under isothermal conditions. Depending on the cure temperature, three types of behavior were observed: (I) below T_gg (the glass transition temperature of the reactive systems at the gel point); (II) between T_gg and T_g∞ (the glass transition temperature of the ultimately cured polymers); (III) above T_g∞. Overall activation energies and apparent overall rate constants of the cure reactions based on third-order overall kinetics were determined before gelation, after gelation but before vitrification, and after vitrification, using gelation time, relative rigidity, and glass transition temperature T_g(t) of the polymers as kinetic terms. The influence of cure temperature and structure of the diamines on the kinetic parameters is discussed.     

Carbon black‐filled poly(ethylene‐co‐alkyl acrylate) composites: Calorimetric studies

The calorimetric characteristics of carbon black (CB)/poly(ethylene‐co‐alkyl acrylate) composites depend on both the CB and acrylate contents. An increase of the acrylate content in the pure copolymers tends to decrease all the crystalline characteristics: T_c,n, the nonisothermal crystallization temperature; T_m, the melting temperature, and ΔH_m, the melting enthalpy. CB modifies the crystallization kinetics of poly(ethylene‐co‐ethyl acrylate) (EEA) alone and in blends with poly(ethylene‐co‐24% w/w methyl acrylate) (24EMA) and poly(ethylene‐co‐35% w/w methyl acrylate) (35EMA). In the presence of CB, T_c,n, the nonisothermal crystallization temperature of EEA, increases and t_1/2, the half‐crystallization time, decreases for a given isothermal crystallization temperature, T_c,i. The thermograms obtained during the melting of EEA after isothermal crystallization show multiple endotherms, suggesting that crystalline‐phase segregation has occurred. The existence of different crystalline species can be explained by the presence of fractions of different acrylate content in the copolymers as shown by SEC. Therefore, CB does not seem to have much effect on the subsequent melting temperature of EEA, T_m,s. CB also induces a lower melting enthalpy, Δ H_m, in the blends. This decrease of ΔH_m appears to be constant whatever the compound, but when reported to the melting enthalpy of the polymer without CB, δΔH_m/ΔH_m increases with the acrylate content. A slight increase of the amorphous phase stiffness after CB introduction is noticed: The T_g of EEA/24EMA and EEA/35EMA blends increases by several degrees. Therefore, plotting ΔH_m versus ΔC_p shows that for the same ΔH_m the ΔC_p is lower in CB‐filled samples, suggesting there is some kind of rigid amorphous phase not contributing to the glass transition. We propose to explain the CB activity during the crystallization process by the existence of molecular interactions between CB and acrylate groups rather than by a pure nucleating effect. Thus, the increase of T_c,n and the decrease of ΔH_m could be explained by the fact that CB separates acrylate‐rich chains from the crystallization medium, accelerating the crystallization of the acrylate‐poor chains. During such a crystallization process, CB may be preferentially localized in the more polar amorphous phase and scattered between the two crystalline phases of EEA and EXA. These blends of poly(ethylene‐co‐alkyl acrylate) copolymers with CB provide interesting materials with adjustable properties depending on the acrylate and CB contents and on the thermomechanical treatments. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 779–793, 2001     

The relationship between the equilibrium melting temperature and the supermolecular structure of several polyoxetanes and polyethylene oxide

The relationships between equilibrium melting temperatures (T_m*) and crystalline morphology of poly[3,3bis(ethoxymethyl)oxetane], (polyBEMO), poly[3,3-bis (azidomethyl)oxetane], (polyBAMO), and poly(ethylene oxide), (PEO), were characterized. The Hoffman-Weeks extrapolation procedure led to T_m* values of 92, 102, and 69°C for these three polymers, respectively. The gross morphologies of polyBEMO, polyBAMO, and PEO were studied as a function of melt-liquid temperature (T_i) and isothermal crystallization temperature (T_c) by visible light microscopy. Spherulitic morphologies were observed for polyBEMO, polyBAMO, and PEO when T_i was above T_m*, while nonspherulitic (hedritic) morphologies were observed at T_ls below T_m*. Mixed morphologies were observed when T_l was approximately equal to T_m*.     

Investigations of the practical routes,structure, and properties for poly(aryl ether ketone ketone) polymers

Different routes for preparing poly(aryl ether ketone)s (PEKKs) are presented and compared. The properties of PEKKs are related to the content of metaphenyl links in the molecular main chains, the molecular chain branching degree, the gelation content by molecular crosslinks, and, especially, the relative content of crystal form II to crystal form I of the PEKK polymorphism. When the molecular T/I ratio of 50/50 in the polymer chains is reached, the obtained PEKK has a lower melting point and gelation content (2% or so). The PEKKs prepared from the electronical substitution route (E route) often have a 0–30% content of crystal form II (relative to the mixed form I and form II), which is much more than that in PEKKs from the nucleophilic substitution route (N route, form II accounts for 0–20%). The relatively unstable crystal form II resulted in the unstable and difficultly predicted thermal properties of PEKKs. PEKKs from different routes provide samples with melting points from 360 to 397°C (T_m) and glassy transition temperatures (T_g) from 167 to 176°C and the equilibrium melting point of 411°C for para-PEKK, while the tensile strength of the homopolymer PEKK and copolymers of PEEKK (poly(aryl ether ether ketone ketone)–PEKK can reach 100 MPa prepared by the N route. The high T_g makes PEKK polymers practically useful while too high T_m and a very small difference between T_m and T_d (degradation temperature) produce obstacles to its wide application. The reaction mechanisms of both electrophilic and nucleophilic routes are investigated and discussed in detail. Results show that the molecular chain branched by solvents and monomers with many activated points may be partly reduced to some extent by the oligomer and extruding route. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67: 659–677, 1998     

Sequence analysis and fiber properties of a blend of poly(ethylene terephthalate) and poly(ethylene terephthalate‐co‐4,4′‐bibenzoate)

Blends of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate‐co‐4,4′‐ bibenzoate) (PETBB) are prepared by coextrusion. Analysis by ¹³C‐NMR spectroscopy shows that little transesterification occurs during the blending process. Additional heat treatment of the blend leads to more transesterification and a corresponding increase in the degree of randomness, R. Analysis by differential scanning calorimetry shows that the as‐extruded blend is semicrystalline, unlike PETBB15, a random copolymer with the same composition as the non‐ random blend. Additional heat treatment of the blend leads to a decrease in the melting point, T_m, and an increase in glass transition temperature, T_g. The T_m and T_g of the blend reach minimum and maximum values, respectively, after 15 min at 270°C, at which point the blend has not been fully randomized. The blend has a lower crystallization rate than PET and PETBB55 (a copolymer containing 55 mol % bibenzoate). The PET/PETBB55 (70/30 w/w) blend shows a secondary endothermic peak at 15°C above an isothermal crystallization temperature. The secondary peak was confirmed to be the melting of small and/or imperfect crystals resulting from secondary crystallization. The blend exhibits the crystal structure of PET. Tensile properties of the fibers prepared from the blend are comparable to those of PET fiber, whereas PETBB55 fibers display higher performance. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1793–1803, 2004     

A novel mucoadhesive polymer prepared by template polymerization of acrylic acid in the presence of poloxamer

A new mucoadhesive polymer was prepared by template polymerization of acrylic acid using poloxamer as a template polymer. FTIR results showed that the interpolymer complex was formed by hydrogen bonding between the carboxyl group of poly(acrylic acid) (PAA) and the ether group of poloxamer. The extent of hydrogen bonding in the PAA/poloxamer interpolymer complex increased as the ratio of PAA/poloxamer decreased. The T_g of PAA/poloxamer interpolymer complexes was matched well with the T_g calculated by Gordon‐Taylor's equation than that of their blends. This result suggests that the PAA and poloxamer in the interpolymer complexes are more compatible than their blends. The dissolution rate of PAA/poloxamer interpolymer complexes was much slower than that of their blends, and was dependent on the pH of the medium and the ratio of PAA/poloxamer. The adhesive bond strength of PAA/poloxamer interpolymer complexes to a plastic (polypropylene) plate was greater than their blends or a commercial product, Carbopol 971P NF. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1525–1530, 2001     

Electrostatic dissipation and flexibility of poly(oxyalkylene)amine segmented epoxy derivatives

A family of hydrophilic and flexible epoxy polymers was prepared from the reaction of poly(oxyalkylene)amines and diglycidyl ether of bisphenol‐A (DGEBA) at 1:1 molar ratio of N H to epoxide. The use of a high molecular weight (M_W = 1000–6000) poly(oxyethylene–oxypropylene)amine and a low M_W amine as curing agents provided epoxy materials with good properties in toughness and hydrophilicity. The hydrophilicity, probed by surface resistivity of these cured materials, was found to be affected by the nature and weight content of poly(oxyethylene) segment in the polymer backbone, and also by the degree of crystallinity. Specifically, in the presence of a water‐soluble poly(oxyethylene–oxypropylene)diamine of M_W 2000 the cured epoxies can reach surface resistivity as low as 10^8.6–9.6 Ω/□. In comparison, the water‐insoluble poly(oxypropylene)diamine of M_W 2000 afforded a higher surface resistivity of 10^10.5 Ω/□ because of the difference in hydrophilicity between oxyethylene and oxypropylene functionalities. Poly(oxypropylene)diamine of M_W 230 as the sole curing agent generated an epoxy with even higher surface resistivity of 10¹³ Ω/□ due to a highly crosslinking structure. With proper selection of mixed poly(oxyethylene–oxypropylene)diamine (25 wt%) and 2‐aminoethanol (9 wt%), the DGEBA cured polymer had an appropriate surface resistivity of 10^9.8 Ω/□ for antistatics. Moreover, this material was extremely ductile in appearance and showed over 500 % elongation at break during mechanical tests. The high flexibility is rationalized by the balanced chemical structure of poly(oxyalkylene) segments and bisphenol‐A distributed in a slightly crosslinked system. © 2000 Society of Chemical Industry     

Effect of solvent or hydrophilic polymer on the hydration melting behavior of polyacrylonitrile

The effect of solvent, DMF, and hydrophilic polymer on the hydration melting behavior of Tae Kwang polyacrylonitrile-based copolymer (T-PAN) was investigated by DSC measurement. The melting temperature (T_m) of T-PAN was sharply lowered by incorporating water under autogenous pressure, but leveled off above a critical water content: 23 wt %. However, an additional incorporation of DMF into the hydrated T-PAN further lowered the T_m, even above the critical water content. On the other hand, addition of water-soluble poly(acrylic acid), poly(vinyl alcohol), and poly(ethylene glycol) or water-swellable starch to the hydrated PAN slightly raised the T_m. © 1994 John Wiley & Sons, Inc.     

Time–temperature–transformation (TTT) cure diagram: Modeling the cure behavior of thermosets

The times to gelation and to vitrification for the isothermal cure of an amine-cured epoxy (Epon 828/PACM-20) have been measured on macroscopic and molecular levels by dynamic mechanical spectrometry (torsional braid analysis and Rheometrics dynamic spectrometer), infrared spectroscopy, and gel fraction experiments. The relationships between the extents of conversion at gelation and at vitrification and the isothermal cure temperature form the basis of a theoretical model of the time–temperature–transformation (TTT) cure diagram, in which the times to gelation and to vitrification during isothermal cure versus temperature are predicted. The model demonstrates that the “S” shape of the vitrification curve depends on the reaction kinetics, as well as on the physical parameters of the system, i.e., the glass transition temperatures of the uncured resin (T_g0), the fully cured resin (T_g∞), and the gel (_gelT_g). The bulk viscosity of a reactive system prior to gelation and/or vitrification is also described.     

The thermal transition behavior of polyorganophosphazenes

The thermal transition behavior of poly[bis(trifluoroethoxyphosphazene)] (I) and two samples of poly[bis(p-chlorophenoxyphosphazene)] (II) have been studied as representative alkoxy- and aryloxy-substituted polyorganophosphazenes. Several of the polymers of this class are reported to exhibit two first-order transitions, denoted herein as T (1) for the transition from a crystalline to mesomorphic state and T_m for the true melt. Studies of these two polymers were undertaken to gain a further understanding of this behavior. Optical microscopy on a solution-cast film of I showed that the details of spherulitic morphology persist through T(1) = 90°C and remain undisturbed through the temperature interval up to T_m = 240°C. The study of II by x-ray diffraction reveals that two sharp lines are observed above T(1) = 165°C and that orientation is not randomized upon heating to temperatures as high as 238°C. Considerable improvement in the crystalline diffraction pattern results from the thermal treatment. A detailed examination was also made by differential scanning calorimetry (DSC) of the effects of cycling through T(1), annealing in the temperature interval between T(1) and T_m and for I, the influence of controlled crystallization from the melt. The results indicate that the organization in the mesomorphic state, as influenced by thermal history, has a profound affect on the peak position, area, and sharpness of the endotherm at T(1). For I, the apparent heat of fusion at T(1) is about ten times greater than at T_m, whereas for II, no DSC peak is observed at T_m = 365°C, suggesting that the ratio of the heats of fusion at T(1) and T_m is greater than 50. However, estimated volume changes at the two transitions are nearly equal. These results are compared with those of other polymers which exhibit an intermediate state of order and with molecular liquid crystals.     

Gelation of hyaluronic acid through annealing

The effect of annealing, at a temperature higher than that of the gel‐sol transition, on the junction formation in the gelation process of sodium hyaluronate/water systems was investigated by the falling ball method (FBM) and differential scanning calorimetry (DSC). FBM measurements were carried out for 1, 2 and 3 wt% solutions. Gel formation was not observed for 1 and 2 wt% solutions, but for 3 wt% solution, gel formation was observed for annealing temperature T = 60 °C and annealing time longer than 6 h. The gel‐sol transition temperature measured by FBM was about 15 °C. Gel formation was not observed in measurements at T = 40 °C and 50 °C. However, the enthalpy of melting, ΔH_m per 1 mg of water, (determined by DSC) changed in a complex manner during annealing at 60 °C, ie ΔH_m increased in the initial stage and then decreased in the later stage. This indicates that the amount of non‐freezing water decreased in the initial stage and then increased in the latter stage. The initial stage corresponds to processes of dissociation of the assemblies of hyaluronic acid molecules by desorbing water molecules and subsequent homogenization of the system. However in the later stage, a junction structure which enables the system to form gels was thought to be formed. © 2000 Society of Chemical Industry     

Tuning the Properties of Shape-Memory Polyurethanes via the Nature of the Polyester Switching Segment

Shape-memory polymers that contain semicrystalline domains with a melting temperature (T_m) above and a crystallization temperature (T_c) below physiological temperature as fixing elements are useful to create medical devices or implants that can be custom-shaped inside or around the body. With the goal to expand the palette of materials that exhibit such properties, a series of segmented polyurethanes (PUs) containing different crystallizable polyester segments is investigated. The nature of the polyester, its molecular weight, and the ratio of hard to soft segments are systematically varied and the effect on the mechanical, thermal, and shape-memory properties of the various PUs is studied. Poly(1,12-dodecylene dodecanoate), poly(1,6-hexylene dodecanoate), and poly(ethylene sebacate) (PES) are selected as crystallizable polyester segments. The PES-based PUs display T_c values of 25–35 °C and a T_m of 60–63 °C, and allow good shape fixing at 37 °C.