Crystallization behaviour of random block copolymers of poly(butylene terephthalate) and poly(tetramethylene ether glycol)

The morphology and crystallization behaviour of random block copolymers of poly(butylene terephthalate) and poly(tetramethylene ether glycol) have been investigated. Single crystals have been grown in thin films crystallized from the melt. Well defined lamellae, exhibiting (hkO) single crystal electron diffraction patterns have been observed in copolymers containing down to 49 wt% (0.83 mole fraction) poly(butylene terephthalate). WAXS and electron diffraction support a model of a relatively pure poly(butylene terephthalate) crystal core with the poly(tetramethylene ether glycol) (soft segment) sequences and short hard segments being rejected to the lamellar surface and the soft segment rich matrix. The lateral dimensions of the lamellae are determined by the number of hard segment sequences long enough to traverse the stable crystal size at the crystallization temperature. This leads to an initial population of crystals formed at T_c and a second set of smaller crystals that grow from the short hard segment sequences upon cooling to room temperature. The result is fractionation by sequence length due to a coupling of the sequence distribution with the stable crystal size at the crystallization temperature.     

Characterization on mixed-crystal structure of poly(butylene terephthalate/succinate/adipate) biodegradable copolymer fibers

Biodegradable poly(butylene terephthalate/succinate/adipate) (PBTSA) pellet, an ideal random copolymer characterized by ¹H solution NMR, was melt-spun into fibers. The crystal structure and physical properties of the as-spun fibers were investigated by WAXD, solid-state ¹³C NMR, DSC and tensile test measurements. Only poly(butylene terephthalate) (PBT)-like diffraction pattern was observed in WAXD; however, two different ¹³C spin-lattice relaxation time (T_1C) components were observed for aliphatic units, in which the longer and the shorter T_1C components correspond to the crystalline and the amorphous domains, respectively. Therefore the crystal structure of PBTSA was concluded to be formed by mixed crystallization of its comonomers. Such crystallization behavior enabled the PBTSA fibers to have well developed PBT-like crystal structure despite of its ideal randomness. Furthermore, due to the introduction of soft segments (BA and BS) into BT crystal lattice, melting temperature of PBTSA fibers (115 °C) was over 100 °C lower than that of PBT.     

Carbon nanotubes induced crystallization of poly(ethylene terephthalate)

We have investigated the crystallization characteristics of melt compounded nanocomposites of poly(ethylene terephthalate) (PET) and single walled carbon nanotubes (SWNTs). Differential scanning calorimetry studies showed that SWNTs at weight fractions as low as 0.03 wt% enhance the rate of crystallization in PET, as the cooling nanocomposite melt crystallizes at a temperature 10 °C higher as compared to neat PET. Isothermal crystallization studies also revealed that SWNTs significantly accelerate the crystallization process. WAXD showed oriented crystallization of PET induced by oriented SWNTs in a randomized PET melt, indicating the role of SWNTs as nucleating sites.     

Toughening of poly(butylene terephthalate) with epoxy-functionalized acrylonitrile-butadiene-styrene

Glycidyl methacrylate (GMA) functionalized acrylonitrile-butadiene-styrene (ABS) copolymers have been prepared via an emulsion polymerization process. These functionalized ABS copolymers (ABS-g-GMA) were blended with poly(butylene terephthalate) (PBT). DMA result showed PBT was partially miscible with ABS and ABS-g-GMA, and DSC test further identified the introduction of GMA improved miscibility between PBT and ABS. Scanning electron microscopy (SEM) displayed a very good dispersion of ABS-g-GMA particles in the PBT matrix compared with the PBT/ABS blend when the content of GMA in PBT/ABS-g-GMA blends was relatively low (<8 wt% in ABS-g-GMA). The improvement of the disperse phase morphology was due to interfacial reactions between PBT chains end and epoxy groups of GMA, resulting in the formation of PBT-co-ABS copolymer. However, a coarse, non-spherical phase morphology was obtained when the disperse phase contained a high GMA content (≥8 wt%) because of cross-linking reaction between the functional groups of PBT and GMA. Rheological measurements further identified the reactions between PBT and GMA. Mechanical tests showed the presence of only a small amount of GMA (1 wt%) within the disperse phase was sufficient to induce a pronounced improvement of the impact and tensile properties of PBT blends. SEM results showed shear yielding of PBT matrix and cavitation of rubber particles were the major toughening mechanisms.     

Finite strain behavior of poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate)-glycol (PETG)

Uniaxial and plane strain compression experiments are conducted on amorphous poly(ethylene terephthalate) (PET) and poly(ethylene terephthalate)-glycol (PETG) over a wide range of temperatures (25-110 °C) and strain rates (.005-1.0 s⁻¹). The stress-strain behavior of each material is presented and the results for the two materials are found to be remarkably similar over the investigated range of rates, temperatures, and strain levels. Below the glass transition temperature (θ_g=80 °C), the materials exhibit a distinct yield stress, followed by strain softening then moderate strain hardening at moderate strain levels and dramatic strain hardening at large strains. Above the glass transition temperature, the stress-strain curves exhibit the classic trends of a rubbery material during loading, albeit with a strong temperature and time dependence. Instead of a distinct yield stress, the curve transitions gradually, or rolls over, to flow. As in the sub-θ_g range, this is followed by moderate strain hardening and stiffening, and subsequent dramatic hardening. The exhibition of dramatic hardening in PETG, a copolymer of PET which does not undergo strain-induced crystallization, indicates that crystallization may not be the source of the dramatic hardening and stiffening in PET and, instead molecular orientation is the primary hardening and stiffening mechanism in both PET and PETG. Indeed, it is only in cases of deformation which result in highly uniaxial network orientation that the stress-strain behavior of PET differs significantly from that of PETG, suggesting the influence of a meso-ordered structure or crystallization in these instances. During unloading, PETG exhibits extensive elastic recovery, whereas PET exhibits relatively little recovery, suggesting that crystallization occurs (or continues to develop) after active loading ceases and unloading has commenced, locking in much of the deformation in PET.     

On the nature of multiple melting in poly(ethylene terephthalate) (PET) and its copolymers with cyclohexylene dimethylene terephthalate (PET/CT)

The multiple melting behavior of poly(ethylene terephthalate) (PET) homopolymers of different molecular weights and its cyclohexylene dimethylene (PET/CT) copolymers was studied by time-resolved simultaneous small-angle X-ray scattering/wide-angle X-ray scattering diffraction and differential scanning calorimetry techniques using a heating rate of 2 °C/min after isothermal crystallization at 200 °C for 30 min. The copolymer containing random incorporation of 1,4-cyclohexylene dimethylene terephthalate monomer cannot be cocrystallized with the ethylene terephthalate moiety. Isothermally crystallized samples were found to possess primary and secondary crystals. The statistical distribution of the primary crystals was found to be broad compared to that of the secondary crystals. During heating, the following mechanisms were assumed to explain the multiple melting behavior. The first endotherm is related to the non-reversing melting of very thin and defective secondary crystals formed during the late stages of crystallization. The second endotherm is associated with the melting of secondary crystals and partial melting of less stable primary crystals. The third endotherm is associated with the melting of the remaining stable primary crystals and the recrystallized crystals. Due to their large statistical distribution, the primary crystals melt in a broad temperature range, which includes both second and third melting endotherms. The amounts of secondary, primary and recrystallized crystals, being molten in each endotherm, are different in various PET samples, depending on variables such as isothermal crystallization temperature, time, molecular weight and co-monomer content.     

Synthesis and properties of poly(tetramethylene terephthalate-co-ethylene terephthalate)–poly(tetramethylene ether) segmented copolymers

A series of polyether–copolyester segmented copolymers ((PBT–PET)PTMG) based on hard segments of tetramethylene terephthalate–ethylene terephthalate copolyester (PBT–PET) and soft segments of poly(tetramethylene ether)(PTMG) was synthesized. The hard : soft segment weight ratio was 30 : 70 and the mole ratio of PBT : PET was 1 : 10; 1 : 6; 1 : 1; 3 : 1, respectively. Their mechanical properties, morphology, crystallization behavior and optical transparency were investigated and compared with poly(tetramethylene terephthalate)–poly(tetramethylene ether)(PBT–PTMG), as well as with poly(ethylene terephthalate)–poly(tetramethylene ether)(PET–PTMG), consisting of the equivalent composition ratio of hard and soft segments. It was found that the transparency could be improved by introducing a small amount of PBT into PET–PTMG through copolymerization. However, a decrease was observed in the transparency if more PBT was added. This is due to the fact that the copolymerization makes both crystallinity and crystallization rate decrease.     

Multiblock terephthalate copolymer as impact modifier for poly(propylene)/poly(butylene terephthalate) blends

The melt polycondensation method was investigated for the synthesis of a multiblock copolymer. The copolymer consisted of hard segments of poly(butylene terephthalate) (PBT) and soft segments of dimerised fatty acid. This multiblock copolymer was characterised by ¹H and ¹³C NMR and FTIR spectroscopies and differential scanning calorimetry. The ¹H NMR method was used for estimating quantitatively the amount of the hard/soft segments. The polymer morphology was characterised using light microscopy and transmission electron microscopy. The investigated polymer was used in a small amount as an additive to poly(propylene)/PBT blends in order to evaluate its influence on the morphology and impact properties of these blends.     

Phase separation in poly(butylene terephthalate)-based materials prepared by solid-state modification

The morphology of a series of poly(butylene terephthalate) (PBT)/fatty acid dimer diol (FADD)-based copolyesters prepared by solid-state modification (SSM) was studied. It was shown that in copolyesters containing less than 10 wt% FADD two different phases, i.e. a PBT crystalline phase and a PBT-rich amorphous phase, are present. The FADD residues were more or less homogeneously distributed throughout the interlamellar regions. For copolymers containing more than 10 wt% of FADD, a three-phase morphological model has to be used due to phase separation of a FADD-rich amorphous phase from the PBT-rich matrix, as confirmed by solid-state nuclear magnetic resonance spectroscopy and transmission electron microscopy. The final morphology was dependent on the morphology of the PBT/FADD-based physical mixtures prior to SSM. In addition, it was shown that FADD diffusion during SSM influences the final morphology.     

Structure-property behavior of poly(dimethylsiloxane) based segmented polyurea copolymers modified with poly(propylene oxide)

Poly(propylene oxide) (PPO) was incorporated in a controlled manner between poly(dimethylsiloxane) (PDMS) and urea segments in segmented polyurea copolymers and their solid state structure-property behavior was investigated. The copolymers contained PDMS segments of MW 3200 or 7000 g/mol and an overall hard segment content of 10-35 wt%. PPO segments of MW 450 or 2000 g/mol were utilized. Equivalent polyurea copolymers based on only PDMS as the soft segment (SS) component were used as controls. The materials (with or without PPO) utilized in this study were able to develop microphase morphology as determined from dynamic mechanical analysis (DMA) and small angle X-ray scattering (SAXS). DMA and SAXS results suggested that the ability of the PPO segments to hydrogen bond with the urea segments results in a limited inter-segmental mixing which leads to the formation of a gradient interphase, especially in the PPO-2000 co-SS containing copolymers. DMA also demonstrated that the polyureas based on only PDMS as the SS possessed remarkably broad and nearly temperature insensitive rubbery plateaus that extended up to ca. 175 °C, the upper temperature limit depending upon the PDMS MW. However, the incorporation of PPO resulted in more temperature sensitive rubbery plateaus. A distinct improvement in the Young's modulus, tensile strength, and elongation at break in the PPO-2000 and PDMS-7000 containing copolymers was observed due to inter-segmental hydrogen bonding and the formation of a gradient interphase. However, when PPO was incorporated as the co-SS, the extent of stress relaxation and mechanical hysteresis of the copolymers increased relative to the segmented polyureas based on the utilization of only PDMS as the soft segment component.     

Morphology and crystal structures of poly(2,6-naphthalene terephthalate) and poly(2,6-naphthalene naphthalate)

The morphology and crystal structures of poly(2,6-naphthalene terephthalate) (PNT) and poly(2,6-naphthalene naphthalate) (PNN), prepared by confined thin film melt/solution polymerization (CTFMP/CTFSP), were characterized by transmission electron microscopy, electron diffraction and molecular modeling. The unit cells of PNT and PNN are both monoclinic (P12₁/a1 space group) with parameters a=8.18 Å, b=5.80 Å, c=14.9 Å and β=101.9° for PNT, and a=7.85 Å, b=5.97 Å, c=17.1 Å and β=99.5 for PNN, respectively. Simulated ED patterns from the proposed unit cells agree well with the observed ED patterns. The crystal structures of PNT and PNN are also compared with those of poly (p-phenylene naphthalate) (PPN) and poly(2,6-oxynaphtalate) (PONA).     

Liquid-liquid phase separation and crystallization behavior of poly(ethylene terephthalate)/poly(ether imide) blend

The liquid-liquid (L-L) phase separation and crystallization behavior of poly(ethylene terephthalate) (PET)/poly(ether imide) (PEI) blend were investigated with optical microscopy, light scattering, and small angle X-ray scattering (SAXS). The thermal analysis showed that the concentration fluctuation between separated phases was controllable by changing the time spent for demixing before crystallization. The L-L phase-separated specimens at 130 °C for various time periods were subjected to a temperature-jump of 180 °C for the isothermal crystallization and then effects of L-L phase separation on crystallization were investigated. The crystal growth rate decreased with increasing L-L phase-separated time (t_s). The slow crystallization for a long t_s implied that the growth path of crystals was highly distorted by the rearrangement of the spinodal domains associated with coarsening. The characteristic morphological parameters at the lamellar level were determined by the correlation function analysis on the SAXS data. The blend had a larger amorphous layer thickness than the pure PET, indicating that PEI molecules in the PET-rich phase were incorporated into the interlamellar regions during crystallization.     

Fatigue behaviour of multiblock thermoplastic elastomers. 2. Dynamic creep of poly(aliphatic/aromatic-ester) copolymers

The ‘dynamic creep’ behaviour of poly(aliphatic/aromatic-ester) (PED) multiblock copolymers has been evaluated by the hysteresis measurements method. The effect of the hard/soft segments concentration on the microphase separation in PED copolymers was determined by means of differential scanning calorimetry. The ‘dynamic creep’ of PED copolymers has been compared with poly(ether-ester) and segmented polyurethanes indicating on the good creep behaviour of PEDs compared to those materials. It was found that the hard segment content influences the creep behaviour of PED copolymers at ambient and elevated temperature indicating that stiffer materials are less susceptible to environmental conditions than polymers containing a high amount of the soft phase. PED copolymers compare very well with commercially available poly(ester-ethers) and show much lower creep compared to poly(ether-urethanes).     

Surface control of hydrophilicity and degradability with block copolymers composed of lactide and cyclic carbonate bearing methoxyethoxyl groups

Block copolymers of L-lactide (LA) and trimethylene carbonate (TMC) derivatives bearing methoxyethyl groups [poly(TMCM-MOE1OM)-block-PLLA] were employed as spin-coated films on substrates, and their hydrophilic and degradation behaviors were investigated. Changing the solvents for film preparation, film thickness, and copolymer composition ratios varied the contact angles in the range of 84.3° ± 2.8° at 269 nm thickness and 18.2° ± 2.5° at 15 nm thickness. These contact angles showed dynamic changes from hydrophobic to hydrophilic properties, probably due to the methoxyethoxyl groups connecting the flexible TMC moieties in the copolymer. Immersion into water or hexane affected the dynamic contact angles. X-ray photoelectron spectroscopy analyses revealed that a large amount of hydrophilic groups was segregated onto the surface, although both LA and TMC units existed. Such dynamic contact angle changes were delayed by the crystallization of polylactide. The hydrolyzed behaviors of these films were examined by quartz cell microbalance, showing a slow degradation process.     

PET-PTMG聚醚酯熔融与结晶行为的研究

采用熔融缩聚法合成了一系列聚对苯二甲酸乙二醇酯(PET)-四氢呋喃聚醚(PTMG)聚醚酯，用DSC、偏光显微镜表征了材料的熔融与结晶性能，讨论了组成对聚醚酯的熔点、结晶温度、结晶度、结晶形态的影响。结果表明，PET—PTMG聚醚酯的熔点与组成的关系符合Baur公式；其结晶度随着聚醚含量的增加呈现先升高后下降的趋势；并为明显的结晶与非结晶的两相结构形态。     

Effect of self‐nucleation on the crystallization of segmented copolymer poly(ether ester)

The effect of self‐nucleation on the nonisothermal and isothermal crystallization behaviors of the segmented copolymer poly(ether ester), based on poly(ethylene glycol) as the soft segment and poly(ethylene terephthalate) as the hard segment was investigated by means of differential scanning calorimetry (DSC) and depolarization polarized light (DPL) techniques, respectively. The results demonstrated that self‐nucleation could enhance the crystallization rate in both cases. The experimental conditions of the self‐nucleation procedure studied by DSC were discussed in detail. The isothermal crystallization was analyzed by the Avrami equation, and the Avrami parameters were dependent on the melting temperature. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 498–504, 2001     

Single- and double-ring spherulites in poly(nonamethylene terephthalate)

A new mechanism of formation of ring-banded spherulites was discovered, where three different types of spherulites were present in poly(nonamethylene terephthalate) (PNT) cast in thin film forms. The growth and morphological features in three ring-banded spherulites were compared and analyzed using polarized/non-polarized light microscopy, differential scanning calorimetry (DSC), and scanning electron microscopy (SEM) and element analysis by energy dispersive spectroscopy (EDS) on surfaces of spherulites. Three types of spherulites (labeled: Type-0, 1, and 2) are possible in PNT when crystallized at wide range of crystallization temperature (T_c); however, only two of the three types can co-exist in PNT at a given T_c. At lower T_c (<55 °C), within Regime-III, the spherulites in PNT are either of Type-0 (appearing ringless in POM) or Type-2 (double-band in POM). When crystallized at temperature of T_c = 55 °C or higher (Regime-II), the morphology is featured with Type-1 (single-ring-banded in POM) spherulites as the majority species that co-exist with Type-2 (double-ring-banded in POM) spherulites as imbedded minority. Origins and morphological differences of the single-band vs. double-band spherulites were compared. The double-band spherulites have much larger inter-ring spacing than do the single-band spherulites. By comparison, the rod-like lamellae in the double-banded spherulites (Type-2) are longer and thicker, and more ordered than those in the single-banded spherulites (Type-1).     

Synthesis and characterization of copolymers based on poly(butylene terephthalate) and ethylene oxide‐poly(dimethylsiloxane)‐ethylene oxide

A series of thermoplastic elastomers based on ethylene oxide‐poly(dimethylsiloxane)‐ethylene oxide (EO‐PDMS‐EO), as the soft segment, and poly(butylene terephthalate) (PBT), as the hard segment, were synthesized by catalyzed two‐step, melt transesterification reaction of dimethyl terephthalate (DMT) with 1,4‐butanediol (BD) and α,ω‐dihydroxy‐(EO‐PDMS‐EO). Copolymers with a content of hard PBT segments between 40 and 90 mass % and a constant length of the soft EO‐PDMS‐EO segments were prepared. The siloxane prepolymer with hydrophilic terminal EO units was used to improve the miscibility between the polar comonomers, DMT and BD, and the nonpolar PDMS. The molecular structure and composition of the copolymers were determined by ¹H‐NMR spectroscopy, whereas the effectiveness of the incorporation of α,ω‐dihydroxy‐(EO‐PDMS‐EO) into the copolymer chains was verified by chloroform extraction. The effects of the structure and composition of the copolymers on the melting temperatures and the degree of crystallinity, as well as on the thermal degradation stability and some rheological properties, were studied. It was demonstrated that the degree of crystallinity, the melting and crystallization temperatures of the copolymers increased with increasing mass fraction of the PBT segments. The thermal stability of the copolymers was lower than that of PBT homopolymer, because of the presence of thermoliable ether bonds in the soft segments. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Non-isothermal Crystallization of Poly(ethylene terephthalate) with Poly(oxybenzoate-p-trimethylene terephthalate) Copolymer

The influence of a poly(oxybenzoate-p-trimethylene terephthalate) copolymer, designated T64, on the non-isothermal crystallization process of poly(ethylene terephthalate) (PET) was investigated. All samples were prepared by solution blending in a 60/40 by weight phenol/tetrachloroethane solvent at 50°C. The solidification process strongly depended on cooling rate and composition of system. The crystallization rate of blends was estimated by crystallization rate parameter (CRP) and crystallization rate coefficient (CRC). From these results of CRP and CRC, it was predicted that the overall non-isothermal crystallization rate of PET would be accelerated by blending with 1–15 wt% of T64. The acceleration of PET crystallization rate was most pronounced in the PET/T64 blends with 5 wt% T64. The observed changes in crystallization behavior are explained by the effect of the physical state of the copolyester during PET crystallization as well as the amount of copolymer in the blends. An Ozawa plot was used to analyze the data of non-isothermal crystallization. The obvious curvature in the plot indicated that the Ozawa model could not fit the PET/T64 blend system well, and there was an abrupt change in the slope of the Ozawa plot at a critical cooling rate.