Segmented copolymers with monodisperse crystallizable hard segments: Novel semi-crystalline materials

Segmented block copolymers with short monodisperse crystallizable hard segments have interesting structures and properties. In the melt, such short monodisperse segments are miscible with the matrix segments. Moreover, upon cooling, they crystallize fast, demonstrating a very high crystallinity, and only a small crystallization window is needed. The melting temperature of the short segments is high, provided that they can H-bond and/or contain aromatic groups. The melting temperature was found to decrease with increasing matrix segment concentration, due to the solvent effect of the matrix segments. At concentrations of crystallizable segment of 4-35 wt%, good dimensional and solvent stabilities were obtained.The monodisperse segments crystallized into nano-ribbons with uniform thickness and high aspect ratio, and these dispersed nano-ribbon crystallites constituted physical crosslinks, while acting also as reinforcing fillers. At concentrations of the monodisperse segments below 20 wt% no spherulitic ordering took place, and the semi-crystalline polymers were transparent. The monodisperse crystallizable segments can be used in combination with matrix segments of either low or high glass transition temperature, and may even contain (bio)functional units.     

Synthesis and non‐isothermal crystallization behavior of poly(ethylene phthalate‐co‐terephthalate)s

A series of poly(ethylene phthalate‐co‐terephthalate)s were synthesized by melt polycondensation of ethylene glycol (EG) with dimethyl phthalate (DMP) and dimethyl terephthalate (DMT) in various proportions. The DMT‐rich polymers were obtained with reasonably high molecular weights, whereas the DMP‐rich polymers were synthesized with relatively low molecular weights due to steric effects associated with the highly kinked DMP monomer. The compositions and thermal properties of the polymers were determined. The copolymers containing DMP in amounts of ≤ 21 mol% were crystallizable, whereas the other polymers were not. All the polymers exhibited a single glass transition temperature. Analysis of the measured glass transition temperatures and crystal melting temperatures confirmed that the DMT‐rich copolymers are random copolymers. The non‐isothermal crystallization behaviors of the DMT‐rich copolymers were investigated by calorimetry and modified Avrami analysis. The Avrami exponents n were found to range from 2.7 to 3.8, suggesting that the copolymers crystallize via a heterogeneous nucleation and spherulitic growth mechanism; that is, the incorporation of DMP units as the minor component does not change the growth mechanism of the copolymers. In addition, the activation energies of the crystallizations of the copolymers were determined; the copolymers were found to have higher activation energies than the PET homopolymer. Polym. Eng. Sci. 44:1682–1691, 2004. © 2004 Society of Plastics Engineers.     

Glass transition and exclusion model in crystallization of polyether-polyester block copolymers with amide linkages

Polyether-polyester block copolymers having various polyetheramide contents were synthesized. Single glass transition intermediated in temperature between the glass transition temperatures of polyester and polyetheramide components was found for all of polyether-polyesters. The compositional variation of glass transition exhibited a similar trend to the predicted result of thermodynamic theory for compatible polymer blends. The incompatible pair of homopolyester and homopolyether was forced to be compatible after copolymerization. A modified theoretical prediction for the glass transition of copolymers based on the thermodynamic theory is proposed. Consistent results between theoretical prediction and experimental measurements were found. Unlike homopolyesters, the glass transition temperature of copolymer amorphous domains gradually decreases with crystallization time. An exclusion model for the crystallization of polyester segments in copolymers is proposed. The temperature width of the glass transition increases with crystallization time. The broadening towards the low temperature side in glass transition is interpreted as the evidence of crystallization-induced partial phase separation. Instead of forming macroscopic segregation, the excluded polyether segments resided in-between crystalline polyester lamellae and mix with amorphous polyesters to generate amorphous domains exhibiting concentration gradient along the lamellar basal surface normal. Further increasing the polyetheramide segment content brings the excluded polyetheramide segments to form domains among the crystallized polyester spherulites so as to inhibit the occurrence of spherulitic impingement.     

Melting behavior,crystallization kinetics and morphology of random copolyesters of poly(2‐hydroxyethoxybenzoate) with ε‐caprolactone

The melting behavior after isothermal crystallization and the crystallization kinetics of random poly(2‐hydroxyethoxybenzoate/ε‐caprolactone) copolymers rich in 2hydroxyethoxybenzoate units were investigated by means of differential scanning calorimetry and hot‐stage optical microscopy. The observed multiple endotherms, which are commonly displayed by polyesters, were found to be influenced both by crystallization temperature and composition. By applying the Hoffman‐Weeks method to the melting temperatures of isothermally crystallized samples, the equilibrium melting temperatures of the copolymers were obtained. Furthermore, isothemal crystallization kinetics was analyzed according to the Avrami treatment. Values of the exponent n close to 3 were obtained, independently of crystallization temperature and composition, in agreement with a crystallization process originating from predeterminated nuclei and characterized by three‐dimensional spherulitic growth. Space‐filling banded spherulites were observed by hot‐stage optical polarizing microscopy at all the crystallization temperatures explored, the band spacing being affected by both crystallization temperature and composition. As expected, the introduction of ε‐caprolactone comonomeric units in the polymer chain of PHEBA was found to decrease its crystallization rate.     

Spherulitic morphology and growth of poly(vinylidene fluoride)/poly(3-hydroxybutyrate-co-hydroxyvalerate) blends by optical microscopy

Poly(vinylidene fluoride) (PVDF) and poly(3-hydroxybutyrate-co-hydroxyvalerate) (PHBV), both semicrystalline polymers, are miscible as shown by the single glass transition temperature over the entire composition range. Morphology of PVDF/PHBV blends was investigated by optical microscopy under two different crystallization conditions. PVDF showed the spherulitic morphology at 150 °C in the PVDF/PHBV blends, where PHBV acted as the noncrystallizing component. PHBV also showed the spherulitic morphology within the matrix of the pre-existing PVDF crystals when PVDF/PHBV blends were quenched from the melt to the crystallization temperature below the melting point of PHBV. The spherulitic growth of PHBV was investigated as the function of both blend composition and crystallization temperature.     

Crystallization kinetics,mechanical properties,and hydrolytic degradation of novel eco‐friendly poly(butylene diglycolate) containing ether linkages

The basic thermal properties, isothermal melt crystallization kinetics, spherulitic morphology, mechanical properties, and hydrolytic degradation behavior of a novel eco‐friendly polyester poly(butylene diglycolate) (PBDG) containing ether linkages were systematically studied with several techniques in this research. PBDG is an aliphatic polyester with high thermal stability. It had a glass transition temperature (T_g) of ?25.7 °C, a melting point temperature of 65.1 °C, and an equilibrium melting point of 73.2 °C. During the isothermal melt crystallization, PBDG crystallized slowly with increasing crystallization temperature, but the crystallization mechanism did not change. Negative spherulites were observed for PBDG. The mechanical properties of PBDG were investigated from the tensile testing. As a ductile polyester, PBDG possessed good mechanical properties. PBDG also showed a fast hydrolytic degradation rate. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44186.     

Thermal transitions of ethylene-vinyl chloride copolymers

Differential scanning calorimetry (d.s.c.) measurements were performed on a series of ethylene-vinyl chloride (E–V) copolymers for the purpose of studying the dependence of their thermal transitions upon their microstructure. The method of preparation, via reductive dechlorination of poly(vinyl chloride) with tributyltin hydride, resulted in a series of E–V copolymers differing only in comonomer content, sequence distribution and stereoregularity of adjacent V units. Chain length distribution and branching frequencies were identical for each member of the series.Extrapolation of glass transition temperatures, T_g, measured for our E–V copolymers to pure polyethylene (PE) predicted a T_g = ?85°C ± 10°C for amorphous PE. E–V copolymers with greater than 60 mol% E units exhibited melting endotherms characterized by melting temperatures from 20°C to 128°C and degrees of crystallinity from 12 to 63%. Observed melting temperatures were plotted against the composition of the E–V copolymers and compared to Flory's equation for melting point depression of random copolymers containing one crystallizable and one non-crystallizable monomer unit. The melting point depressions observed for our E–V copolymers were in agreement with Flory's theory, if the CH₂CH₂ moiety is considered to be the crystallizable unit and theCHmoiety is assumed to prevent the CH₂CH₂ units attached on either side from being incorporated into the crystal. This implies that among all possible comonomer triad sequences only the EEE triad may crystallize. Therefore only those E–V copolymers with average lengths of consecutive E units greater than 2 exhibit crystallinity.     

Miscibility and crystallization kinetics of poly(trimethylene terephthalate)/amorphous poly(ethylene terephthalate) blends

The miscibility and crystallization kinetics of the blends of poly(trimethylene terephthalate) (PTT) and amorphous poly(ethylene terephthalate) (aPET) have been investigated by differential scanning calorimetry (DSC) and polarized optical microscopy (POM). It was found that PTT/aPET blends were miscible in the melt. Thus, the single glass transition temperature (T_g) of the blends within the whole composition range and the retardation of crystallization kinetics of PTT in blends suggested that PTT and aPET were totally miscible. The nucleation density of PTT spherulites, the spherulitic growth, and overall crystallization rates were depressed upon blending with aPET. The depression in nucleation density of PTT spherulites could be attributed to the equilibrium melting point depression, while the depression in the spherulitic growth and overall crystallization rates could be mainly attributed to the reduction of PTT chain mobility and dilution of PTT upon mixing with aPET. The underlying nucleation mechanism and growth geometry of PTT crystals were not affected by blending, from the results of Avrami analysis. POLYM. ENG. SCI., 47:2005–2011, 2007. © 2007 Society of Plastics Engineers     

The crystallization and transition behavior of poly(vinylidene fluoride)/copoly(chlorotriofluorethylene-vinylidene fluoride) blends

Thermal analysis of solution precipitated blends of two crystallizable polymers, poly(vinylidene fluoride) (PVDF) and copoly(chlorotrifluorethylene-vinylidene fluoride) (copoly(CTFE-VDF)), has been carried out to study the transition temperatures, crystallinity, and crystallization rates. PVDF crystallizes over the whole blend composition either during precipitation from solution or upon cooling from the melt. The high degree of crystallinity attained, higher than in PVDF by itself, suggests the occurrence of partial PVDF-copolymer cocrystallization. The melt crystallization temperature, decreasing with cooling rate, is lower in PVDF-rich blends than for lean blends. However, the heat of crystallization increases with cooling rate, suggesting that the crystal composition depends on crystallization rate. No significant melting temperature depression due to blending was observed. However, the blends glass transition (T_g) changes linearly with composition, but less than expected by any mixing rule applicable to compatible systems. Annealing of the blends above T_g results in an additional crystalline phase consisting mainly of the copolymer. The amount of these crystals increases with PVDF content, due to partial cocrystallization and kinetic effects. The addition of the copolymer to PVDF results in a volume-filling spherulitic structure consisting of spherulites which decrease in size with increasing copolymer content.     

Formation of lamellar structure by competition in crystallization of both components for crystalline-crystalline block copolymers

Crystallization and structure formation of poly(ethylene oxide)-poly(?-caprolactone) block copolymers (PEG-PCL) in which the melting temperatures of the components are close to each other were elucidated using differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) and wide-angle X-ray diffraction (WAXD) techniques. The diblock copolymers with 33, 46 and 59 wt% of PEG composition formed ordinary single spherulites similar to those of PCL homopolymers, while concentric double-circled spherulites appeared for the PCL-PEG-PCL triblock copolymer with 66 wt% PEG composition as observed previously. For the diblock copolymers, despite of the ordinary appearance of the single spherulites, the DSC thermograms and the WAXD patterns indicated the crystallization of PEG as well as PCL. The time-resolved SAXS profiles for the diblock copolymers showed that long spacings of the crystal lamellae decreased stepwise in the crystallization process. Synthesizing these results for the single spherulites, it was concluded that PCL crystallized first followed by the crystallization of PEG with preservation of the PCL crystal lamellar structure. This means that PEG must crystallize within confined space between the formerly formed PCL crystal lamellae. Such confined crystallization of PEG caused the suppressed melting temperature, crystallinity and crystallization rate especially in the smaller PEG compositions. In the melting process of the diblock copolymers, it was observed that the PEG component first melted with a stepwise increase in the long spacing.     

Crystallization and morphology of starch-g-poly(1,4-dioxan-2-one) copolymers

The thermal transition, crystallization and spherulitic morphology of starch-g-poly(1,4-dioxan-2-one) copolymers were studied by means of differential scanning calorimetry (DSC) and polarized optical micrographs (PM). It is found that the graft structures of copolymers have obvious effects on the thermal and crystallization behaviors. Because there were more defect sites in the crystalline phase originating from the short grafted chains of poly(1,4-dioxan-2-one) (PPDO), the crystal structure of the copolymers was much less perfect than that of PPDO. PM revealed that the spherulitic morphology of the graft copolymers depended on graft structures and crystallization temperatures. From the single polarized micrograph of the graft copolymers it was observed clearly that the starch segments acted as nucleation sites. The Avrami equation was used to analyze the overall isothermal crystallization of the graft copolymers. Avrami exponents were almost constant at crystallization temperatures T_c ranging from 45 to 60 °C. Both the PM observation and the DSC investigation (crystallization rate constant, K values) indicated that the graft copolymers crystallize faster than pure PPDO, especially at higher crystallization temperatures.     

Characterization and crystallization behavior of poly(ethylene‐co‐trimethylene terephthalate) copolymers

A series of poly(ethylene‐co‐trimethylene terephthalate) (PETT) copolymers were prepared by polycondensation. The synthesized PETT are block copolymers and the content of poly(trimethylene terephthalate) (PTT) units incorporated into the copolymers are always larger than that fed in the polymerization. The nonisothermal crystallization at the different cooling rates was studied by means of differential scanning calorimetry. The copolymers develop the crystallization later and show the lower melting temperature than the corresponding enriched homopolymers. The modified Avrami analysis fit well the nonisothermal crystallization of these polymers. The overall rate of crystallization of PTT is fastest and that of PET is slowest, whereas the copolymers are between them at the same cooling rate. The minor PET units incorporated into PTT polymer chains reduce the crystallization of PTT segments, but the present minor PTT units in the PET chains seem to accelerate the crystallization of PET segments. The Avrami exponent nvaries in the range of 3 – 4, indicating that the nonisothermal crystallization follows the homogeneous nucleation and two‐ to three‐dimensional growth mechanism. Wide angle X‐ray diffraction analysis explains that the PET and PTT units do not cocrystallize and it is considered as the enriched polymer segments to crystallize during crystallization. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

聚酰胺酯结晶行为研究

利用差式扫描量热法对聚酰胺酯进行结晶行为分析。结果表明:与常规PET相比,聚酰胺酯玻璃化温度、冷结晶温度、熔点、熔融结晶温度均较低,同时其熔融结晶速率也较慢;且随着共聚酯中聚酰胺成分的增加,玻璃化温度、熔点、熔融结晶温度逐渐降低并呈现一定的变化关系;在相同结晶温度下,聚酰胺成分增加,共聚酯半结晶周期t_(1/2)增加,结晶随之变慢。     

Confined crystallization of polymeric materials

The interest in confined crystallization has greatly increased with the development and progress of nanotechnology applications. Polymeric confined crystallization has been studied in droplets, ultrathin films, nanolayers, nanostructures from solutions, blends, copolymers, polymers infiltrated within AAO templates and nanocomposites. As confinement increases, the crystallization temperature first decreases, then splits into several fractions (i.e., fractionated crystallization) and finally occurs in one step at the maximum possible supercooling, near the glass transition temperature. Two factors are responsible for these effects: (a) a change in nucleation mechanism, from heterogeneous nucleation to surface nucleation (or in extreme cases, homogeneous nucleation), (b) the dependence of the crystallization temperature on the volume or the surface (or interphase) of the crystallizable micro or nanodomains. The melting point also decreases with confinement but to a lesser degree. A preferential orientation of polymeric crystals is generally induced by one or two dimensional confinement. Avrami indexes decrease with confinement until values of 1 (or even lower) are achieved in the limit of isolated domains, as the material approaches a first order crystallization kinetics. This type of kinetics reflects that nucleation is the rate determining step in the overall crystallization of ideally confined polymers.     

DSC and TGA studies of the behavior of water in native and crosslinked gelatin

Water molecules absorbed into gelatin are found to be only partially crystallizable. The fraction of noncrystallizable water depends on whether the gelatin is native or crosslinked, and on the crosslinking conditions as well. This dependence is explained by the T_g‐regulation effect newly proposed by Rault and coworkers for water‐swollen gelatin cooled below 0°C. According to this effect, a part of the frozen water cannot crystallize because during the cooling the amorphous gelatin–water phase becomes glassy before the water crystallization temperature is reached. During the heating of water‐plasticized gelatin samples in a TGA cell, the crystallizable water separates from the gelatin, mainly in the temperature interval 50–100°C, whereas the noncrystallizable water leaves the gelatin gradually over the entire temperature interval investigated, up to 300°C. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 465–470, 1999     

Morphological analysis of poly(butylene terephthalate) spherulites during fusion

Summary A detailed morphological analysis of the melting process of poly(butylene terephthalate) (PBT) is presented. Investigations were conducted by polarizing optical microscopy, coupling the measurement of depolarized light intensity with examination of morphology of PBT spherulites during their fusion. These analyses allowed to prove that the spherulitic superstructure of PBT developed upon isothermal crystallization from the melt does not vary with temperature until complete melting takes place, despite the large reorganization involved in the fusion process. It is thus shown that the double melting behavior commonly observed in PBT does not arise from the presence of various spherulitic morphologies with different thermal stabilities, and the structural changes caused by the reorganization processes do not involve variations in the spherulitic morphology. The recrystallization of PBT above the apparent melting point was also analyzed, and the role of memory effects of crystalline precursors remaining in the melt was discussed.     

Light scattering studies on crystallization in polyethylene terephthalate

The light scattering from the spherulites of polyethylene terephthalate grown near the glass transition temperature has been investigated. The Hv scattering profiles can be reproduced by the sum of the ideal spherulite scattering with the distribution of spherulite radius and the isotropic scattering from randomly oriented crystallites. The ratio of optical anisotropies in the isotropic scattering to the ideal spherulite scattering is obtained by the method established to eliminate the effects of the number density of spherulites and the coefficient depending on the experimental conditions. It is found that the anisotropy ratio is almost independent of the crystallization time and of temperature above 106 °C, while it is larger at a crystallization temperature of 103 °C. The spherulitic structure is discussed in terms of the anisotropy ratio.     

Comparison of propylene/ethylene copolymers prepared with different catalysts

This study compared a series of experimental propylene/ethylene copolymers synthesized by a transition metal‐based, postmetallocene catalyst (xP/E) with homogeneous propylene/ethylene copolymers synthesized by conventional metallocene catalysts (mP/E). The properties varied from thermoplastic to elastomeric over the broad composition range examined. Copolymers with up to 30 mol % ethylene were characterized by thermal analysis, density, atomic force microscopy, and stress–strain behavior. The xP/Es exhibited noticeably lower crystallinity than mP/Es for the same comonomer content. Correspondingly, an xP/E exhibited a lower melting point, lower glass transition temperature, lower modulus, and lower yield stress than an mP/E of the same comonomer content. The difference was magnified as the comonomer content increased. Homogeneous mP/Es exhibited space‐filling spherulites with sharp boundaries and uniform lamellar texture. Increasing comonomer content served to decrease spherulite size until spherulitic entities were no longer discernable. In contrast, axialites, rather than spherulites, described the irregular morphological entities observed in xP/Es. The lamellar texture was heterogeneous in terms of lamellar density and organization. At higher comonomer content, embryonic axialites were dispersed among individual randomly arrayed lamellae. These features were characteristic of a copolymer with heterogeneous chain composition. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1651–1658, 2006     

Melting behavior and crystallization kinetics of sulfonated poly(butylene isophthalate)

The melting behavior and the crystallization kinetics of sulfonated poly(butylene isophthalate) random copolymers were investigated by means of differential scanning calorimetry. The multiple endotherms, commonly observed in polyesters, were found to be influenced both by composition and crystallization temperature. By applying the Hoffman‐Weeks method, the equilibrium melting temperatures of the copolymers under investigation were obtained. The presence of a crystal‐amorphous interphase was evidenced and its amount was found to increase as the sulfonated unit content was increased. Isothermal melt crystallization kinetics of the sample containing the lowest amount of sulfonated units was analyzed according to the Avrami treatment. The introduction of such units was found to decrease the overall crystallization rate of poly(butylene isophthalate). Values of Avrami's exponent n close to 3 were obtained, independently of crystallization temperature, in agreement with a crystallization process originating from predetermined nuclei and characterized by three‐dimensional spherulitic growth.     

The effect of end groups of PEG on the crystallization behaviors of binary crystalline polymer blends PEG/PLLA

The effect of end groups (2OH, 1OH, 1CH₃ and 2CH₃) of poly(ethylene glycol) (PEG) on the miscibility and crystallization behaviors of binary crystalline blends of PEG/poly(l-lactic acid) (PLLA) were investigated by differential scanning calorimetry (DSC) and polarizing optical microscopy (POM). A single glass-transition temperature was observed in the DSC scanning trace of the blend with a weight ratio of 10/90. Besides, the equilibrium melting point of PLLA decreased with the increasing PEG. A negative Flory interaction parameter, χ₁₂, indicated that the PEG/PLLA blends were thermodynamically miscible. The spherulitic growth rate and isothermal crystallization rate of PEG or PLLA were influenced when the other component was added. This could cause by the change of glass transition temperature, T_g and equilibrium melting point, T⁰_m. The end groups of PEG influenced the miscibility and crystallization behaviors of PEG/PLLA blends. PLLA blended with PEG whose two end groups were CH₃ exhibited the greatest melting point depression, the most negative Flory interaction parameter, the least fold surface free energy, the lowest isothermal crystallization rate and spherulitic growth rate, which meant better miscibility. On the other hand, PLLA blended with PEG whose two end groups were OH exhibited the least melting point depression, the least negative Flory interaction parameter, the greatest fold surface free energy, the greatest isothermal crystallization rate and spherulitic growth rate.