Synthesis and characterization of poly(ethylene‐co‐trimethylene terephthalate)s

Taking advantage of a melt polycondensation process, a series of copolyesters composed of pure terephthalate acid (PTA), ethylene glycol (EG), and 1,3‐propanediol (1,3‐PDO) were synthesized. The component, molecular weight, molecular weight distribution, and thermal properties of the copolymers were characterized. The results show that the contents of trimethylene terephthalate (TT) units in the resulting copolyesters are higher than PDO compositions in original diol. Oligomer content in the copolyesters varies with the compositions and attains a minimum value when the TT ingredient is 49.52 mol %. The glass transition temperature (T_g) of the copolyesters varies from 78.5°C for PET (polyethylene terephthalate) to 43.5°C for PTT (polytrimethylene terephthalate) and decreases monotonically with the components. The copolyesters are amorphous copolymers when TT content is in the range of 32.4–40.8 mol %, as calculated from the melting enthalpy (ΔH_m) measured via differential scanning calorimetry. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1511–1521 2006     

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.     

Thermal,rheological, mechanical,and dyeing property studies of poly(ethylene‐co‐trimethylene terephthalate) copolymer filaments

The thermal and rheological properties of poly(ethylene‐co‐trimethylene terephthalate) (PETT) copolymer are investigated. The thermal behavior of PETT copolymers is dependent on the composition. The PETT‐15 and PETT‐85 copolymers can crystallize, whereas the PETT‐30 copolymer cannot crystallize at 5°C/min cooling rate. The copolymers have a good thermal stability, even though the addition of poly(trimethylene terephthalate) (PTT) chain causes a disadvantage to the thermal stability of the copolymers. Moreover, the PETT copolymers are a typical pseudoplastic fluid exhibiting shear thinning. With increasing the shear rate or the content of PTT units, the flow activation energy decreases and the sensitivity of the shear viscosity to the melt temperature declines. The PETT copolymer filaments have intermediate elastic recovery and dyeability between poly(ethylene terephthalate) (PET) and PTT filaments. With increasing the PTT content, the elastic recovery and dyeability of PETT copolymer filaments increase. That is to say, introducing PTT units as a minor component into the macromolecular chains is an available means to improve the properties of PET filament. The obtained PETT copolymer filaments blend the advantage of the mechanical property of PET and the elastic and dyeability of PTT filament together into one polymer and possess a softer feeling and a higher extension. POLYM. ENG. SCI., 50:1689–1695, 2010. © 2010 Society of Plastics Engineers     

Enhanced dynamic mechanical and shape‐memory properties of a poly(ethylene terephthalate)–poly(ethylene glycol) copolymer crosslinked by maleic anhydride

Dimethyl terephthalate (DMT) and ethylene glycol (EG) were used for the preparation of poly(ethylene terephthalate) (PET), and poly(ethylene glycol) (PEG) was added as a soft segment to prepare a PET–PEG copolymer with a shape‐memory function. MWs of the PEG used were 200, 400, 600, and 1000 g/mol, and various molar ratios of EG and PEG were tried. Their tensile and shape‐memory properties were compared at various points. The glass‐transition and melting temperatures of PET–PEG copolymers decreased with increasing PEG molecular weight and content. A tensile test showed that the most ideal mechanical properties were obtained when the molar ratio of EG and PEG was set to 80:20 with 200 g/mol of PEG. The shape memory of the copolymer with maleic anhydride (MAH) as a crosslinking agent was also tested in terms of shape retention and shape recovery rate. The amount of MAH added was between 0.5 and 2.5 mol % with respect to DMT, and tensile properties and shape retention and recovery rate generally improved with increasing MAH. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 27–37, 2002     

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     

Synthesis and properties of poly(trimethylene terephthalate‐co‐2‐methyl‐ethylene terephthalate) random copolyesters

Poly(trimethylene terephthalate‐co‐2‐methyl‐ ethylene terephthalate) random copolymers of various compositions were synthesized via traditional two‐step polycondensation by incorporating of 1,2‐propanediol. The molar composition of trimethylene terephthalate and 2‐methyl‐ethylene terephthalate units and chemical structure were confirmed by means of ¹H‐NMR and Fourier transform infrared. The thermal properties of the copolyesters were evaluated by DSC and TGA. As far as the thermal properties is concerned, the main effect of incorporation of 1,2‐propanediol was a lowering in the melting temperature, and an increment of glass transition temperature compared to homopolymer PTT. Due to the effect of the lateral methyl groups in the polymeric chain, the thermal stability is slightly decreased as the amount of the MET units is increased. Furthermore, the crystals of PTT/MET copolyesters were observed by hot‐stage optical polarizing microscopy at the indicated crystallization temperatures. As expected, the incorporation of MET units in the polymer chain of PTT was found to decrease the dimension of the crystals. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structural investigation of Poly(ethylene terephthalate)/Poly(trimethylene terephthalate) transesterificated blends

Wide-Angle X-ray Diffraction (WAXD) and Small-Angle X-ray Scattering analyses were carried out to evaluate the evolution of the crystalline and supermolecular structure of poly(ethylene terephthalate) (PET) blended with poly(trimethylene terephthalate) (PTT). The conditions adopted in preparing the PET/PTT 50/50 blend induce transesterification between the polyesters; these reactions produce a new molecular characteristics based on PET/PTT copolymer that exhibits its own WAXD profile. The PET/PTT 50/50 copolymers prepared by melt mixing of the homopolymers for increasing times evidence spherulitic morphology and an evolution of the crystalline structure in terms of crystallinity and crystal dimensions. The periodicity of the transesterificated samples is intermediate between the long periods observed for pure PET and pure PTT. For the PET/PTT 50/50 copolymers the value of periodicity and lamellar thickness increase with the increasing of the processing time.     

Antielectrostatic poly(ether ester) block copolymer of poly(ethylene terephthalate‐co‐isophthalate)–poly(ethylene glycol)

Poly(ethylene terephthalate) (PET) fiber has a low moisture regain, which allows it to easily gather static charges, and many investigations have been carried out on this problem. In this study, a series of poly(ethylene terephthalate‐co‐isophthalate) (PEIT)–poly(ethylene glycol) (PEG) block copolymers were prepared by the incorporation of isophthalic acid (IPA) during esterification and PEG during condensation. PEG afforded PET with an increased moisture affinity, which in turn, promoted the leakage of static charges. However, PET also then became easier to crystallize, even at room temperature, which led to decreased antistatic properties and increased manufacturing inconveniences. IPA was, therefore, used to reduce the crystallinity of the copolymers and, at the same time, make their crystal structure looser for increased water absorption. Moreover, PET fibers with incorporated IPA and PEG showed good dyeability. In this article, the structural characterization of the copolymers and antistatic and mechanical properties of the resulting fibers are discussed. At 4 wt % IPA, the fiber containing 1 mol % PEG with a molecular weight of 1000 considerably improved antistatic properties and other properties. In addition, the use of PEIT–PEG as an antistatic agent blended with PET or modified PET fibers also benefitted the antistatic properties. Moreover, PEIT–PEG could be used with another antistatic agent to produce fibers with a low volume resistance. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1696–1701, 2003     

Molecular structures and physical properties of heat‐drawn conjugate fibers

As‐spun poly(trimethylene terephthalate) (PTT)/poly(ethylene terephthalate) (PET) side‐by‐side conjugate fibers were drawn to investigate the effects of drawing conditions on structure development and physical properties. Effects of draw ratio and heat‐set temperature were observed. In the state of an as‐spun fiber, the molecular orientation of PTT was higher than PET, whereas PET molecular orientation increased remarkably over PTT with increasing draw ratio. Crimp contraction increased sharply at a draw ratio over 2.0, where the crystalline structure of the PET developed sufficiently. A heat‐set temperature of at least 140°C was required to develop sufficient crimp contraction. The crystallinity and orientation of the PET were attributed mainly to the crimp contraction of the drawn fiber. POLYM. ENG. SCI., 2011. © 2010 Society of Plastics Engineers     

Oxygen barrier properties of PET copolymers containing bis(2‐hydroxyethyl)hydroquinones

A series of poly[ethylene‐co‐bis(2‐ethoxy)hydroquinone terephthalate], PET‐co‐BEHQ copolymers were prepared by polymerization of various substituted bis(2‐hydroxyethyl)hydroquinones (BEHQs), dimethyl terephthalate (DMT), and ethylene glycol (EG). In addition to copolymers containing 6–16.5 mol % BEHQ, the homopolymer of BEHQ with dimethyl terephthalate, p(BEHQ‐T), was also prepared. The thermal and barrier properties of amorphous materials were studied. As the amount of comonomer was increased, the T_g and T_m of the materials decreased relative to those of PET. Oxygen permeability also decreased with increasing comonomer content. This improvement in barrier‐to‐oxygen permeability was primarily due to a decrease in solubility of oxygen in the polymer. All of the copolymers tested displayed similar oxygen diffusion coefficients. The decrease in solubility correlates with the decrease in T_g. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 934–942, 2003     

The conformational changes,crystal structure and melting behavior of poly(ethylene/ trimethylene terephthalate) copolyesters

The conformational changes, crystal structure and melting behavior of poly(ethylene/trimethylene terephthalate) (ET) copolyesters were investigated using in situ Fourier transform infrared (FTIR) spectroscopy, wide‐angle X‐ray diffraction (WAXD), transmission electron microscopy (TEM) and differential scanning calorimetry (DSC) under isothermal crystallization conditions. The results show that the minimum melting temperature was observed in ET53, in which the relative amount of ethylene glycol (EG) to 1,3‐propanediol (PDO) was 52.68/47.32 and the PDO‐dimethyl terephthalate (DMT)‐PDO segments in the molecular chain dominated the crystal formation. The minimum crystallinity of ET copolyesters was found in ET66, in which the relative amount of EG/PDO was 65.91/34.09 and the EG‐DMT‐EG segments in the molecular chain dominated the crystal formation. A rapid and continuous conformational transition in ET copolyesters was observed using in situ FTIR in the first 10 min under isothermal crystallization conditions. The continuously adjusting conformation in the molecules reflects the crystallization of ET copolyesters. Based on the DSC and the X‐ray analyses of the crystallization behavior in the ET copolyesters, crystalline conformation transitions of molecules in ET copolyesters take place rapidly and early. Copyright © 2012 Society of Chemical Industry     

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     

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     

Analysis of physical properties of PET/CD‐PET polyblend hollow fiber and its kinetics of alkaline hydrolysis

Cationic dyeable poly(ethylene terephthalate) (CD‐PET) was formed by copolymerizing dimethylterephthalate (DMT),5‐sodium sulfonate dimethyl isophthalate (SIPM) with a molar ratio of 2% and ethylene glycol (EG). Blends of regular poly(ethylene terephthalate) (PET) and CD‐PET were spun into hollow fibers. The fibers were then treated with aqueous NaOH. This study investigated the physical properties of PET/CD‐PET polyblend hollow fibers and their kinetic behavior of alkaline hydrolysis using differential scanning calorimetry (DSC), wide‐angle X‐ray diffraction (WAXD), the density gradient method, a gel permeation chromatograph (GPC), a rheometer, and regression analysis of the statistical method. For the alkaline hydrolysis kinetics equation of PET, CD‐PET, and PET/CD‐PET polyblend materials: ? dW/dt = KC^αA^β, β values of chip and POY/ FOY hollow fibers are equal to 1. Moreover, R² of the kinetics equation of chip/POY/FOY for a from 1.09–1.35/1.08–1.32/1.06–1.29 were better than those of a = 1. Experimental results indicate that the rate constant of alkaline hydrolysis was CD‐PET hollow fiber > PET/CD‐PET polyblend hollow fibers > PET hollow fiber and FOY > POY > > Chip. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3601–3610, 2002     

Synthesis and characterization of poly(L‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(L‐lactic acid) copolyesters

Random copolyester namely, poly(ethylene terephthalate‐co‐sebacate) (PETS), with relatively lower molecular weight was first synthesized, and then it was used as a macromonomer to initiate ring‐opening polymerization of l ‐lactide. ¹H NMR quantified composition and structure of triblock copolyesters [poly(l ‐lactic acid)‐b‐poly(ethylene terephthalate‐co‐sebacate)‐b‐poly(l ‐lactic acid)] (PLLA‐PETS‐PLLA). Molecular weights of copolyesters were also estimated from NMR spectra, and confirmed by GPC. Copolyesters exhibited different solubilities according to the actual content of PLLA units in the main chain. Copolymerization effected melting behaviors significantly because of the incorporation of PETS and PLLA blocks. Crystalline morphology showed a special pattern for specimen with certain composition. It was obvious that copolyesters with more content of aromatic units of PET exhibited increased values in both of stress and modulus in tensile test. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Isothermal‐crystallization kinetics and melting behavior of crystalline/crystalline blends of poly(trimethylene terephthalate) and poly(ethylene 2,6‐naphthalate)

The isothermal crystallization and crystal morphology of poly(trimethylene terephthalate) (PTT)/poly (ethylene 2,6‐naphthalate) (PEN) blends were investigated with differential scanning calorimetry and polarized optical microscopy. The commonly used Avrami equation was used to fit the primary stage of isothermal crystallization. The Avrami exponents were evaluated to be in the range of 3.0–3.3 for isothermal crystallization. The subsequent melting endotherms of the blends after isothermal crystallization showed multiple melting peaks. The crystallization activation energies of the blends with 20 or 40% PTT was ?48.3 and ?60.9 kJ/mol, respectively, as calculated by the Arrhenius formula for the isothermal‐crystallization processes. The Hoffman–Lauritzen theory was also employed to fit the process of isothermal crystallization, and the kinetic parameters of the blends with 20 or 40% PTT were determined to be 1.5 × 10⁵ and 1.8 × 10⁵ K², respectively. The spherulite morphology of the six binary blends formed at 190°C showed different sizes and perfect Maltese crosses when the PTT or PEN component was varied, suggesting that the greater the PTT content was, the larger or more perfect the crystallites were that formed in the binary blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3316–3325, 2007     

Effect of dialcohols on properties of poly(ethylene 2,6‐naphthalate) copolymers

Properties of poly(ethylene 2,6‐naphthalate) (PEN) and its copolymers containing diethylene glycol (DEG), propanediol (PD), butanediol (BD), and bisphenol A ethoxylate (BSA) were investigated. The copolymer composition was determined by ¹H‐NMR spectroscopy. It has a higher value than the feed composition due to the high volatility of ethylene glycol (EG). The melting temperature of the copolymers was gradually depressed with the increase of dialcohol in the composition. The complex viscosity of the copolymers did not depend on the molecular weight, but on the chemical structure. The complex viscosity of the copolymers containing 3 mol % of DEG, BD, and 5 mol % of BD was lower than that of PEN, and the mechanical properties were similar with the value of PEN. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2900–2905, 1999     

Development of active barrier systems for poly(ethylene terephthalate)

Copolymers of Poly(ethylene terephthalate) (PET) were synthesized by the melt polymerization of terephthalic acid (TPA) with ethylene glycol (EG) and with each of the active oxygen scavengers; monoolein (MO) and 3‐cyclohexene‐1,1‐dimethanol (CHEDM) in separate compositions. Proton nuclear magnetic resonance spectroscopy (¹H NMR) and 2D correlation spectroscopy (COSY) indicated that PET had reacted with both MO and CHEDM at their hydroxyl end groups. Oxygen barrier properties of the MO and CHEDM copolymers exhibited improvements of up to 40%, in comparison to an unmodified commercial PET. Effects of the oxygen scavengers on the copolymers' physical properties were investigated in terms of their crystallization, melting, and rheological behaviors. Both types of copolymers showed decreases in peak melting temperatures with increased scavenger concentrations and also crystallized more slowly as the scavenger concentrations increased. The PET/MO copolymer showed non‐Newtonian rheological behavior with higher MO concentration; while the PET/CHEDM copolymers showed Newtonian behavior within the studied range of CHEDM concentrations. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Nonisothermal crystallization kinetics and morphology of poly(ethylene terephthalate) modified with poly(lactic acid)

The nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) copolymers modified with poly(lactic acid) (PLA) were investigated with differential scanning calorimetry, and a crystal morphology of the samples was observed with scanning electron microscopy. Waste PET (P100) obtained from postconsumer water bottles was modified with a low‐molecular‐weight PLA. The PET/PLA weight ratio was 90/10 (P90) or 50/50 (P50) in the modified samples. The nonisothermal melt‐crystallization kinetics of the modified samples were compared with those of P100. The segmented block copolymer structure (PET‐b‐PLA‐b‐PET) of the modified samples formed by a transesterification reaction between the PLA and PET units in solution and the length of the aliphatic and aromatic blocks were found to have a great effect on the nucleation mechanism and overall crystallization rate. On the basis of the results of the crystallization kinetics determined by several models (Ozawa, Avrami, Jeziorny, and Liu–Mo) and morphological observations, the crystallization rate of the samples decreased in the order of P50 > P90 > P100, depending on the amount of PLA in the copolymer structure. However, the apparent crystallization activation energies of the samples decreased in the order of P90 > P100 > P50. It was concluded that the nucleation rate and mechanism were affected significantly by the incorporation of PLA into the copolymer structure and that these also had an effect on the overall crystallization energy barrier. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Surface modification of poly(ethylene terephthalate) film by coating with poly(ethylene glycol)‐grafted polystyrene

The poly(ethylene glycol) (PEG)‐grafted styrene (St) copolymer, which was formed as a nanosphere, was used as an agent to modify the surface of poly(ethylene terephthalate) (PET) film. The graft copolymer was dissolved into chloroform and coated onto the PET film by dip–coating method. The coated amount depends on the content ratios of PEG and St, the solution concentration, and the coating cycles. The graft copolymers having a low molecular weight of PEG‐ or St‐rich content was fairly stable on washing in sodium dodecyl sulfate (SDS) aqueous solution. It was confirmed that the PET surface easily altered its surface property by the coating of the graft copolymers. The contact angles of the films coated with the graft copolymers were very high (ca. 105–120°). The coated film has good antistatic electric property, which agreed with PEG content. The best condition of coating is a one‐cycle coating of 1% (w/v) graft copolymer solution. The coated surface had water‐repellency and antistatic electric property at the same time. The graft copolymer consisted of a PEG macromonomer; St was successfully coated onto PET surfaces, and the desirable properties of both of PEG macromonomer and PSt were exhibited as a novel function of the coated PE film. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1524–1530, 1999