Crystallization kinetics of poly(1,4‐butylene‐co‐ethylene terephthalate)

The crystallization kinetics of poly(butylene terephthalate) (PBT), poly(ethylene terephthalate) (PET), and their copolymers poly(1,4‐butylene‐co‐ethylene terephthalate) (PBET) containing 70/30, 65/35 and 60/40 molar ratios of 1,4‐butanediol/ethylene glycol were investigated using differential scanning calorimetry (DSC) at crystallization temperatures (T_c) which were 35–90 °C below equilibrium melting temperature . Although these copolymers contain both monomers in high proportion, DSC data revealed for copolymer crystallization behaviour. The reason for such copolymers being able to crystallize could be due to the similar chemical structures of 1,4‐butanediol and ethylene glycol. DSC results for isothermal crystallization revealed that random copolymers had a lower degree of crystallinity and lower crystallite growth rate than those of homopolymers. DSC heating scans, after completion of isothermal crystallization, showed triple melting endotherms for all these polyesters, similar to those of other polymers as reported in the literature. The crystallization isotherms followed the Avrami equation with an exponent n of 2–2.5 for PET and 2.5–3.0 for PBT and PBETs. Analyses of the Lauritzen–Hoffman equation for DSC isothermal crystallization data revealed that PBT and PET had higher growth rate constant G_o, and nucleation constant K_g than those of PBET copolymers. © 2001 Society of Chemical Industry     

Miscibility of poly(1,4‐cyclohexamethylene terephthalate) blends with polyarylate

The miscibility of poly(1,4‐cyclohexamethylene terephthalate) (PCT) having an aliphatic cyclic segment blended with Polyarylate (PAR) was investigated by means of calorimetric measurements. It was found that all the PCT/PAR blends are miscible and show a single, composition‐dependent glass transition temperature (T_g). The T_g composition dependence has been analyzed by using the Gordon–Taylor equation and the values of T_g obtained experimentally agree quite well with those calculated theoretically by using that equation. Also, the melting point depression phenomenon that occurred in miscible polymer pairs was observed up to 40 wt % PCT content. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1947–000, 2000     

Hydrolytic degradation of poly(1,4‐butylene terephthalate‐co‐tetramethylene oxalate) copolymer

Experimentally synthesized poly(1,4‐butylene terephthalate‐co‐tetramethylene oxalate) (PBT–PTMO) monofilaments were evaluated for hydrolytic stability in salt water (SW) and distilled water (DW) at temperature below and above glass transition temperature (T_g), along with commercially available poly(hexamethylene adipamide) (NY), poly(ethylene terephthalate) (PET), and polypropylene (PP) monofilaments. There was no decrease in mechanical properties in case of NY, PET, and PP in either DW or SW below their T_g. The breaking strength, ultimate elongation, and thermal shrinkage of the PBT–PTMO, however, decreased as the ageing time increased. Total strength loss occurred after approximately 300 days at 25°C in either DW and SW. This can be attributed to the chain scission that occurs in the PBT–PTMO copolymer chain. The poor hydrolytic stability of the PBT–PTMO may be attributed to the higher moisture regain. The salinity of water did not have a significant effect on the breaking strength loss of the materials. The mode of hydrolytic degradation of aged PBT–PTMO polymer was confirmed by the increasing generation of the acid carbonyl and hydroxyl groups with concomitant increasing consumption of ester groups, regardless of ageing conditions. Above T_g, the hydrolytic rate constant (k^′_H, day⁻¹) of the PBT–PTMO, estimated by the rate of formation of acid carbonyl groups, is greater at a higher ageing temperature. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 921–936, 1999     

Melting,crystallization behaviors,and nonisothermal crystallization kinetics of PET/PTT/PBT ternary blends

The melting, crystallization behaviors, and nonisothermal crystallization kinetics of the ternary blends composed of poly(ethylene terephthalate), poly(trimethylene terephthalate) (PTT) and poly(buthylene terephthalate) (PBT) were studied with differential scanning calorimeter (DSC). PBT content in all ternary blends was settled invariably to be one‐third, which improved the melt‐crystallization temperature of the ternary blends. All of the blend compositions in amorphous state were miscible as evidenced by a single, composition‐dependent glass transition temperature (T_g) observed in DSC curves. DSC melting thermograms of different blends showed different multiple melting and crystallization peaks because of their various polymer contents. During melt‐crystallization process, three components in blends crystallized simultaneously to form mixed crystals or separated crystals depending upon their content ratio. The Avrami equation modified by Jeziorny and the Ozawa theory were employed to describe the nonisothermal crystallization process of two selected ternary blends. The results spoke that the Avrami equation was successful in describing the nonisothermal crystallization process of the ternary blends. The values of the t_1/2 and the parameters Z_c showed that the crystallization rate of the ternary blends with more poly(ethylene terephthalate) content was faster than that with the lesser one at a given cooling rate. The crystal morphology of the five ternary blends investigated by polarized optical microscopy (POM) showed different size and distortional Maltese crosses or light spots when the PTT or poly(ethylene terephthalate) component varied, suggesting that the more the PTT content, the larger crystallites formed in ternary blends. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Crystallization of poly(butylene terephthalate)/poly(ethylene octene) blends: Isothermal crystallization

Poly(ethylene‐octene) (POE), maleic anhydride grafted poly(ethylene‐octene) (mPOE), and a mixture of POE and mPOE were added to poly(butylene terephthalate) (PBT) to prepare PBT/POE, PBT/mPOE, and PBT/mPOE/POE blends by a twin‐screw extruder. Observation by scanning electron microscopy revealed improved compatibility between PBT and POE in the presence of maleic anhydride groups. The melting behavior and isothermal crystallization kinetics of the blends were studied by wide‐angle X‐ray diffraction and differential scanning calorimeter; the kinetics data was delineated by kinetic models. The addition of POE or mPOE did not affect the melting behavior of PBT in samples quenched in water after blending in an extrude. Subsequent DSC scans of isothermally crystallized PBT and PBT blends exhibited two melting endotherms (T_mI and T_mII). T_mI was the fusion of the crystals grown by normal primary crystallization and T_mII was the melting peak of the most perfect crystals after reorganization. The dispersed second phase hindered the crystallization; on the other hand, the well dispersed phases with smaller size enhanced crystallization because of higher nucleation density. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Glass‐transition and melting behavior of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

The glass‐transition temperatures and melting behaviors of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) (PET/PEN) blends were studied. Two blend systems were used for this work, with PET and PEN of different grades. It was found that T_g increases almost linearly with blend composition. Both the Gibbs–DiMarzio equation and the Fox equation fit experimental data very well, indicating copolymer‐like behavior of the blend systems. Multiple melting peaks were observed for all blend samples as well as for PET and PEN. The equilibrium melting point was obtained using the Hoffman–Weeks method. The melting points of PET and PEN were depressed as a result of the formation of miscible blends and copolymers. The Flory–Huggins theory was used to study the melting‐point depression for the blend system, and the Nishi–Wang equation was used to calculate the interaction parameter (χ₁₂). The calculated χ₁₂ is a small negative number, indicating the formation of thermodynamically stable, miscible blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 11–22, 2001     

The phase behavior and the Flory-Huggins interaction parameter of blends containing amorphous poly(resorcinol phthalate-block-carbonate), poly(bisphenol-A carbonate) and poly(ethylene terephthalate)

The phase behavior of the blends of poly(ethylene terephthalate) (PET) and poly(Resorcinol Phthalate-block-Carbonate) (RPC) and the blends of PET and poly(Bisphenol-A Carbonate) (PC) was investigated by dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). Blends of high molecular weight PET and RPC copolymer with 20 mol% resorcinol phthalate (RPC20) showed two glass transition temperatures in DMA and DSC but the cold crystallization rate of PET phase was substantially lowered as compared to neat PET, indicating partial miscibility at all compositions. The RPC20 with M_w = 31,500 g/mol formed miscible blends with PET when PET has weight-average molecular weight <9500 g/mol. The Flory-Huggins interaction parameter between PET and RPC20 was calculated to be 0.029 ± 0.003 by using the Flory-Huggins equation at critical composition and molecular weight. PC with M_w = 30,000 g/mol formed miscible blends with PET only when PET had molecular weight <2800 g/mol, indicating PC/PET blends were much less miscible than RPC20/PET blends. Group contribution methods agreed well with the experimental results obtained both in the present study and a previous study [1], predicting that the addition of a resorcinol phthalate block to a PC backbone should increase the miscibility of PC and PET.     

Ternary polymer mixtures: Polyarylate/phenoxy/poly(butylene terephthalate)

The intended objective of this work was to bring together two immiscible polymers, polyarylate (PAr) and Phenoxy [poly(hydroxy ether of bisphenol-A)], preparing ternary mixtures with a third component, poly(butylene terephthalate) (PBT). Experimental results showed that ternary mixtures containing 30% or more PBT gave single glass transition temperatures by DSC. Moreover, the PBT melting point depended on the composition of the mixtures. These results, which could be indicative of the existence of a single amorphous phase in these blends, have been discussed. Nevertheless, results must be considered with caution, given the peculiarities of the T_g–composition diagrams for the miscible pairs PAr/PBT and Phenoxy/PBT. Hypothetic interchange reactions during melting have been found to be unimportant.     

Random orientation of in situ composites based on liquid‐crystalline polymers by compression moulding

In this study, randomly oriented in situ composites based on liquid‐crystalline polymers (LCPs) were prepared by thermal compression moulding. The LCP employed was a semi‐flexible liquid‐crystalline copolyesteramide with 30 mol% of p‐aminobenzoic acid (ABA) and 70 mol% of poly(ethylene terephthalate) (PET). The matrices were poly(butylene terephthalate) (PBT) and polyamide 66 (PA66). The rheological properties, compatibility and morphological structures of these in situ composites were investigated. The results showed that PA66‐LCP and PBT–LCP component pairs of the composites are miscible in the molten state, but partially compatible in the solid state. The ratios of viscosity, λ₁ = η_LCP/η_PA66 and λ₂ = η_LCP/η_PBT, are all greater than 1.0. However, the melt viscosity of the LCP/PBT and LCP/PA66 blend is much lower than that of PBT and PA66, and it decreases markedly with increasing LCP content. When the LCP/PA66 or LCP/PBT blends are compression moulded, the LCP/PA66 or LCP/PBT melts and flows easily due to their low viscosity, and the LCP phases in the melts deform easily along the flow directions, which are random. It leads to uniformly dispersed LCP micro‐fibres randomly orientation in the thermoplastic matrix due to the compatibility between the blending components. © 2003 Society of Chemical Industry     

Microstructural modifications in uniaxially hot‐drawn polycyclohexylene terephthalate films

Semi‐aromatic thermoplastic polycyclohexylene terephthalate (PCT), initially wholly amorphous, was uniaxially drawn to study microstructural modifications as the appearance of the strain‐induced (S.I.) crystalline phase. Polyethylene terephthalate (PET) and poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate) (PETG) are considered as reference materials in this work. In polycyclohexylene terephthalate (PCT) the presence of a saturated ring (which is not quite as rigid as the aromatic ring) modifies the characteristics of both thermal and S.I. crystallization. Samples with various draw ratios (drawing of PCT films is performed at T > T_g) were analyzed by Modulated Differential Scanning Calorimetry, wide angle X‐ray scattering, and birefringence measurements. In drawn PCT films, an S.I. crystalline phase appears continuously with the draw ratio and reaches 35%. For this polymer and for the highest draw ratio, the “true” amorphous fraction practically disappears. The material is composed only of the S.I. crystalline phase and the “rigid” amorphous phase. Polym. Eng. Sci. 44:509–517, 2004. © 2004 Society of Plastics Engineers.     

Miscibility and melting behavior of poly(ethylene terephthalate)/poly(trimethylene terephthalate) blends

The miscibility and melting behavior of binary crystalline blends of poly(ethylene terephthalate) (PET)/poly(trimethylene terephthalate) (PTT) have been investigated with differential scanning calorimetry and scanning electron microscope. The blends exhibit a single composition‐dependent glass transition temperature (T_g) and the measured T_g fit well with the predicted T_g value by the Fox equation and Gordon‐Taylor equation. In addition to that, a single composition‐dependent cold crystallization temperature (T_cc) value can be observed and it decreases nearly linearly with the low T_g component, PTT, which can also be taken as a valid supportive evidence for miscibility. The SEM graphs showed complete homogeneity in the fractured surfaces of the quenched PET/PTT blends, which provided morphology evidence of a total miscibility of PET/PTT blend in amorphous state at all compositions. The polymer–polymer interaction parameter, χ₁₂, calculated from equilibrium melting temperature depression of the PET component was ?0.1634, revealing miscibility of PET/PTT blends in the melting state. The melting crystallization temperature (T_mc) of the blends decreased with an increase of the minor component and the 50/50 sample showed the lowest T_mc value, which is also related to its miscible nature in the melting state. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Aliphatic–aromatic poly(butylene carbonate‐co‐terephthalate) random copolymers: Synthesis,cocrystallization, and composition‐dependent properties

A series of aliphatic–aromatic poly(carbonate‐co‐ester)s poly(butylene carbonate‐co‐terephthalate)s (PBCTs), with weight‐average molecular weight of 113,000 to 146,000 g/mol, were synthesized from dimethyl carbonate, dimethyl terephthalate, and 1,4‐butanediol via a two‐step polycondensation process using tetrabutyl titanate as the catalyst. The PBCTs, being statistically random copolymers, show a single T_g over the entire composition range. The thermal stability of PBCTs strongly depends on the molar composition. Melting temperatures vary from 113 to 213°C for copolymers with butylene terephthalate (BT) unit content higher than 40 mol %. The copolymers have a eutectic melting point when about 10 mol % BT units are included. Crystal lattice structure shifts from the poly(butylene carbonate) to the poly(butylene terephthalate) type crystal phase with increasing BT unit content. DSC and WAXD results indicate that the PBCT copolymers show isodimorphic cocrystallization. The tensile modulus and strength decrease first and then increase according to copolymer composition. The enzymatic degradation of the PBCT copolymers was also studied. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41952.     

Isothermal crystallization kinetics and melting behaviors of poly(butylene terephthalate) and poly(butylene terephthalate‐co‐fumarate) copolymer

The isothermal crystallization kinetics and melting behaviors after isothermal crystallization of poly(butylene terephthalate) (PBT) and poly(butylene terephthalate‐co‐fumarate) (PBTF) containing 95/5, 90/10, and 80/20 molar ratios of terephthalic acid/fumaric acid were investigated by differential scanning calorimetry. The equilibrium melting temperatures of these polymers were estimated by Hoffman–Weeks equation. So far as the crystallization kinetics was concerned, the Avrami equation was applied and the values of the exponent n for all these polymers are in the range of 2.50–2.96, indicating that the addition of fumarate does not affect the geometric dimension of PBT crystal growth. Crystallization activation energy (ΔE) and nucleation constant (K_g) of PBTF copolymers are higher than that of PBT homopolymer, suggesting that the introduction of fumarate hinders the crystallization of PBT in PBTF. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Crystallization of poly(butylene terephthalate)/poly(ethylene octene) blends: Nonisothermal crystallization

Poly(ethylene octene) (POE), maleic anhydride grafted poly(ethylene octene) (mPOE), and a mixture of POE and mPOE were added to poly(butylene terephthalate) (PBT) to prepare PBT/POE (20 wt % POE), PBT/mPOE (20 wt % mPOE), and PBT/mPOE/POE (10 wt % mPOE and 10 wt % POE) blends with an extruder. The melting behavior of neat PBT and its blends nonisothermally crystallized from the melt was investigated with differential scanning calorimetry (DSC). Subsequent DSC scans exhibited two melting endotherms (T_mI and T_mII). T_mI was attributed to the melting of the crystals grown by normal primary crystallization, and T_mII was due to the melting of the more perfect crystals after reorganization during the DSC heating scan. The better dispersed second phases and higher cooling rate made the crystals that grew in normal primary crystallization less perfect and relatively prone to be organized during the DSC scan. The effects of POE and mPOE on the nonisothermal crystallization process were delineated by kinetic models. The dispersed phase hindered the crystallization; however, the well‐ dispersed phases of an even smaller size enhanced crystallization because of the higher nucleation density. The nucleation parameter, estimated from the modified Lauritzen–Hoffman equation, showed the same results. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Study on co[poly(butylene terephthalate‐p‐oxybenzoate)] thermotropic copolyester. II. Thermal behavior and crystalline morphology

The POB/PBT copolyesters, designated B28, B46, B64, and B82, were prepared from p‐acetoxybenzoic acid (PAB) and poly(butylene terephthalate) (PBT). The polymeric products obtained were then ground and subjected to solid‐state polymerization under vaccum for 4 h. The melting and crystallization behaviors of these copolyesters haven been studied by differential scanning calorimetry (DSC). In the DSC scan of the POB‐rich composition, the endothermic peak shows obscurely, and enthalpy of fussion becomes small due to the change in the crystalline morphology from isotropic to anisotropic. In general, the melting point of the copolyester is increased by the solid‐state polymerization reaction. Also, thermogravimetric analysis (TGA) were performed with these samples obtained. It was found that the decomposition temperature (T_d ) is increased as the POB content is increased. Effects of composition and solid‐state polymerization on the decomposition temperature of copolyesters are also discussed. The crystalline morphology of copolyester was investigated with a Zeiss polarized optical microscope. It was found that the POB/PBT copolyesters with 60 mol % POB was shown to be highly anisotropic. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2363–2368, 2000     

Copolymers based on poly(butylene terephthalate) and polycaprolactone‐block‐polydimethylsiloxane‐block‐polycaprolactone

A series of novel thermoplastic elastomers, based on poly(butylene terephthalate) (PBT) and polycaprolactone‐block‐polydimethylsiloxane‐block‐polycaprolactone (PCL‐PDMS‐PCL), with various mass fractions, were synthesized through melt polycondensation. In the synthesis of the poly(ester‐siloxane)s, the PCL blocks served as a compatibilizer for the non‐polar PDMS blocks and the polar comonomers dimethyl terephthalate and 1,4‐butanediol. The introduction of PCL‐PDMS‐PCL soft segments resulted in an improvement of the miscibility of the reaction mixture and therefore in higher molecular weight polymers. The content of hard PBT segments in the polymer chains was varied from 10 to 80 mass%. The degree of crystallinity of the poly(ester‐siloxane)s was determined using differential scanning calorimetry and wide‐angle X‐ray scattering. The introduction of PCL‐PDMS‐PCL soft segments into the polymer main chains reduced the crystallinity of the hard segments and altered related properties such as melting temperature and storage modulus, and also modified the surface properties. The thermal stability of the poly(ester‐siloxane)s was higher than that of the PBT homopolymer. The inclusion of the siloxane prepolymer with terminal PCL into the macromolecular chains increased the molecular weight of the copolymers, the homogeneity of the samples in terms of composition and structure and the thermal stability. It also resulted in mechanical properties which could be tailored. Copyright © 2010 Society of Chemical Industry     

Structural investigations of poly(ethylene terephthalate)‐graft‐polystyrene copolymer films

Structural investigations of poly(ethylene terephthalate)‐graft‐polystyrene (PET‐g‐PS) films prepared by radiation‐induced grafting of styrene onto commercial poly(ethylene terephthalate) (PET) films were carried out by FTIR, X‐ray diffraction (XRD), and differential scanning calorimetry (DSC). The variation in the degree of crystallinity and the thermal characteristics of PET films was correlated with the amount of polystyrene grafted therein (i.e., the degree of grafting). The heat of melting was found to be a function of PET crystalline fraction in the grafted films. The grafting is found to take place by incorporation of amorphous polystyrene grafts in the entire noncrystalline (amorphous) region of the PET films and at the surface of the crystallites. This results in a decrease in the degree of crystallinity with the increase in the degree of grafting, attributed to the dilution of PET crystalline structure with the amorphous polystyrene, without almost any disruption in the inherent crystallinity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1949–1955, 2002; DOI 10.1002/app.10515     

Synthesis and characterization of biodegradable poly(butylene succinate‐co‐propylene succinate)s

Biodegradable polyesters such as poly(butylene succinate) (PBS), poly(propylene succinate) (PPS), and poly(butylene succinate‐co‐propylene succinate)s (PBSPSs) were synthesized respectively, from 1,4‐succinic acid with 1,4‐butanediol and 1,3‐propanediol through a two‐step process of esterification and polycondensation in this article. The composition and physical properties of both homopolyesters and copolyesters were investigated via ¹H NMR, DSC, TGA, POM, AFM, and WAXD. The copolymer composition was in good agreement with that expected from the feed composition of the reactants. The melting temperature (T_m), crystallization temperature (T_c), crystallinity (X), and thermal decomposition temperature (T_d) of these polyesters decreased gradually as the content of propylene succinate unit increased. PBSPS copolyesters showed the same crystal structure as the PBS homopolyester. Besides the normal extinction crosses under the polarizing optical microscope, the double‐banded extinction patterns with periodic distance along the radial direction were also observed in the spherulites of PBS and PBSPS. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Crystallization of 2‐methyl‐1,3‐propanediol substituted poly(ethylene terephthalate). I. Thermal behavior and isothermal crystallization

Differential scanning calorimetry (DSC) was used to evaluate the thermal behavior and isothermal crystallization kinetics of poly(ethylene terephthalate) (PET) copolymers containing 2‐methyl‐1,3‐propanediol as a comonomer unit. The addition of comonomer reduces the melting temperature and decreases the range between the glass transition and melting point. The rate of crystallization is also decreased with the addition of this comonomer. In this case it appears that the more flexible glycol group does not significantly increase crystallization rates by promoting chain folding during crystallization, as has been suggested for some other glycol‐modified PET copolyesters. The melting behavior following isothermal crystallization was examined using a Hoffman–Weeks approach, showing very good linearity for all copolymers tested, and predicted an equilibrium melting temperature (T_m⁰) of 280.0°C for PET homopolymer, in agreement with literature values. The remaining copolymers showed a marked decrease in T_m⁰ with increasing copolymer composition. The results of this study support the claim that these comonomers are excluded from the polymer crystal during growth. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2592–2603, 2006     

Sequence distribution,thermal properties,and crystallization studies of poly(trimethylene terephthalate‐co‐1,4‐cyclohexylene dimethylene terephthalate) copolyesters

A series of novel poly(trimethylene terephthalate‐co‐1,4‐cyclohexylene dimethylene terephthalate) (PTCT) with various compositions were synthesized by melt polycondensation of 1,3‐propanediol, 1,4‐cyclohexanedimethanol and dimethyl terephthalate. The resulting copolyesters were characterized using ¹³C and ¹H nuclear magnetic resonance. The average length of both trimethylene terephthalate (TT) and cyclohexylene dimethylene terephthalate (CT) sequences varies from 1 to 10, and the chain structure is statistically random. The crystallization was investigated using wide angle X‐ray diffractometer (WAXD) and differential scanning calorimeter. The WAXD patterns can be divided in two groups according to the composition: copolyesters with less than 35 mol % CT content exhibit PTT‐type lattice, and those with CT unit content higher than 42 mol % crystallize with the PCT‐type lattice. The crystallizability of CT sequence is higher than that of TT sequence. Thermodynamic analysis shows that the comonomer is excluded from the PTT‐type or PCT‐type crystal of the copolyesters. The thermal decomposition temperature of copolyesters increases with increasing CT content, and their thermal stability is improved as compared to that of PTT. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009