Low temperature solid‐state extrusion of recycled poly(ethylene terephthalate) bottle scraps

The processing of poly(ethylene terephthalate) (PET) involves thermal and hydrolytic degradation of the polymer chain, which reduces not only the intrinsic viscosity and molecular weight, but also the mechanical properties of recycled materials. A novel PET/bisphenol A polycarbonate/styrene–ethylene–butylene–styrene alloy based on recycled PET scraps is prepared by low temperature solid‐state extrusion. Hydrolysis and thermal degradation of PET can be greatly reduced by low temperature solid‐state extrusion because the extrusion temperature is between the glass‐transition temperature and cold‐crystallization temperature of PET. Modification of recycled PET by low temperature solid‐state extrusion is an interesting method; it not only provides an easy method to recycle PET scraps by blend processing, but it can also form novel structures such as orientation, crystallization, and networks in the alloy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2692–2699, 2006     

Biaxial Orientation of Poly(ethylene 2,5‐furandicarboxylate): An Explorative Study

The biaxial orientation behavior of poly(ethylene 2,5‐furandicarboxylate) (PEF) is studied in comparison to poly(ethylene terephthalate) (PET). PEF is a polyester that can be produced through similar steps as PET but using 100% biobased 2,5‐furandicarboxylic acid instead of terephthalic acid. This work highlights the stress–strain behavior of PEF during biaxial orientation at various temperatures. Strain hardening and strain‐induced crystallization in the oriented PEF samples generally appeared at higher stretch ratios for PEF than for PET at comparable molecular weight, while somewhat lower degrees of crystallinity are reached in PEF. Shrinkage in oriented PEF is found to be on par with PET in the region of the glass transition. Higher modulus and improved barrier properties, compared to PET, are found in the oriented materials when sufficiently high stretch ratios are applied in biaxial orientation.     

Isothermal crystallization kinetics of poly(ethylene terephthalate)-poly(ethylene oxide) segmented copolymer with two crystallizing blocks

The isothermal crystallization kinetics and morphology of poly(ethylene terephthalate)-poly(ethylene oxide) (PET30-PEO6) segmented copolymer, and poly(ethylene terephthalate) (PET) and poly(ethylene oxide) (PEO) homopolymers have been studied by means of differential scanning calorimetry (DSC) and a transmission electron microscope (TEM). It is found that the nucleation mechanism and growth dimension of PEO in the copolymer are different from that in the homopolymer, which is attributed to the effect of the crystallizability of PET-blocks. Furthermore, the crystallization rate of PEO-blocks in the copolymer is slower than that in the homopolymer because the PET-blocks phase is always partially solidified at the temperatures when PEO-blocks begin to crystallize. In contrast, the isothermal crystallization rate of PET-blocks in the copolymer is faster than that in the homopolymer because the lower glass transition temperature of the PEO-blocks (soft blocks) increases the mobility of the PET-blocks in the copolymer.     

The influence of fibers on the crystallization of poly(ethylene terephthalate) as related to processing of composites

The effect of fiber reinforcement on the isothermal crystallization of poly(ethylene terephthalate) (PET) was investigated using differential scanning calorimetry (DSC). Unidirectional fiber composites were prepared using glass and aramid fibers in PET. The rate of crystallization, as reflected by crystallization half-time, and the degree of crystallinity of PET are seen to depend on the type of reinforcing fiber as well as on crystallization temperature. Crystallization kinetics are also analyzed using an Avrami model for the volume of polymer crystallized as a function of time. The crystalline morphology of PET in fiber-reinforced systems was studied using polarized light microscopy. Results concerning nucleation densities and growth morphologies are used in explaining differences seen in crystallization kinetics in fiber-reinforced systems.     

The crystallization behaviors of copolymeric flame‐retardant poly(ethylene terephthalate) with organophosphorus

The crystallization behaviors of copolymeric flame‐retardant poly(ethylene terephthalate) (PET) with organophosphorus were studied using differential scanning calorimetry (DSC). The results indicated that the degree of tacticity of molecular chain of PET declined due to the presence of organophosphorus which had an important impact on isothermal and nonisothermal crystallization behaviors apparently. In the process of isothermal crystallization, the more organophosphorus the samples contained, the faster the samples crystallized and it resulted from the special structure of PET copolymer with organophosphorus in it. The equilibrium melting temperature of PET decreased from 284.87 to 260.72°C as the content of organophosphorus increased from 0 to 0.96 wt%, whereas in the process of nonisothermal crystallization, the Avrami exponent n decreased with the growth of the content of organophosphorus, and the addition of organophosphorus made the nucleation mechanism and the growing geometry less complicated. POLYM. COMPOS., 34:867–876, 2013. © 2013 Society of Plastics Engineers     

Crystallization kinetics and crystalline morphology of poly(ethylene naphthalate) and poly(ethylene terephthalate‐co‐bibenzoate)

Copolymers of ethylene glycol with 4,4′‐bibenzoic acid and terephthalic acid are known to crystallize rapidly to surprisingly high levels of crystallinity. To understand this unusual behavior, the isothermal crystallization of poly(ethylene bibenzoate‐co‐terephthalate) in the molar ratio 55:45 (PETBB55) was studied. Poly(ethylene naphthalate) (PEN) was included in the study for comparison. The kinetics of isothermal crystallization from the melt and from the amorphous glass was determined using differential thermal analysis. The results were correlated with the crystalline morphology as observed with atomic force microscopy (AFM). Crystallization of PEN exhibited similar kinetics and spherulitic morphology regardless of whether it was cooled from the melt or heated from the glass to the crystallization temperature. The Avrami coefficient was close to 3 for heterogeneous nucleation with 3‐dimensional crystal growth. The copolymer PETBB55 crystallized much faster than did PEN and demonstrated different crystallization habits from the melt and from the glass. From the melt, PETBB55 crystallized in the “normal” way with spherulitic growth and an Avrami coefficient of 3. However, crystallization from the glass produced a granular crystalline morphology with an Avrami coefficient of 2. A quasi‐ordered melt state, close to liquid crystalline but lacking the order of a recognizable mesophase, was proposed to explain the unusual crystallization characteristics of PETBB55. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 98–115, 2002     

Crystallization of poly(tetramethylene succinate) in blends with poly(ϵ‐caprolactone) and poly(ethylene terephthalate)

The crystallization behavior of polymer blends of poly(tetramethylene succinate) (PTMS) with poly(?‐caprolactone) (PCL) or poly(ethylene terephthalate) (PET) was investigated with differential scanning calorimetry under isothermal and nonisothermal conditions. The blends were prepared by solution casting and precipitation, respectively. The constituent polymers were semicrystalline materials and crystallized nearly independently in the blends. The addition of the second component to PTMS showed that PCL did not significantly influence the crystallinity of the constituents in the blends under isothermal conditions, whereas the crystallization of PTMS was slightly suppressed by crystalline PET. Nonisothermal crystallization under constant cooling rates was examined in terms of a quasi‐isothermal Avrami approach. In blends, the rates of crystallization were differently influenced by the second component. The rate of the constituent that crystallized at the higher temperature was barely influenced by the second component being in the molten state, whereas the rate of the second component, crystallizing when the first component was already crystalline, was altered differently under isothermal and nonisothermal conditions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 149–160, 2004     

Morphology and properties of poly(ethylene terephthalate) and thermoplastic polyester elastomer blends modified in the melt by a diisocyanate chain extender and filled with a short glass fiber

The structural features and rheological, mechanical, and relaxation properties of poly(ethylene terephthalate) (PET) blends with 7–50 wt % polyester thermoplastic polyester elastomer (TPEE), a block copolymer of poly(butylene terephthalate) and poly(tetramethylene oxide), chemically modified by a diisocyanate chain extender (CE) and reinforced with 30% glass fibers (GF) were studied. The composites were obtained by reactive extrusion with a twin‐screw reactor–mixer with a unidirectional rotation of screws. The molecular–structural changes in the materials were judged against data provided by differential scanning calorimetry, scanning electron microscopy, relaxation spectrometry, and rheological analysis of the melts. Regardless of the TPEE concentration in the blends with GF‐reinforced PET, the addition of CE resulted in the growth of the indices of the mechanical properties at straining, bending, and impact loading and an increase in the melt viscosity. In addition, an increase in the average length of short GFs in the composites and an intensification of interphase adhesion in the polyester binder–GF surface system were observed. The introduction of CE promoted a slowdown in PET crystallization in the composites and intensified the interphase adhesion in the binder–GF system at temperatures higher and lower than the PET glass‐transition temperature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45711.     

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     

Crystallization of poly(ethylene terephthalate)/polycarbonate blends. I. Unreinforced systems

The crystallization and transition temperatures of poly(ethylene terephthalate) (PET) in blends with polycarbonate (PC) is considered using thermal analysis. Additives typically used in commercial polyester blends, transesterification inhibitor and antioxidant, are found to enhance the crystallization rate of PET. Differential scanning calorimetry (DSC) reveals two glass transition temperatures in PET/PC blends, consistent with an immiscible blend. Optical microscopy observations are also consistent with an immiscible blend. Small shifts observed in the T_g of each component may be due to interactions between the phases. The degree of crystallinity of PET in PET/PC blends is significantly depressed for high PC contents. Also, in blends with PC content greater than 60 wt %, two distinct crystallization exotherms are observed in dynamic crystallization from the melt. The isothermal crystallization kinetics of PET, PET modified with blend additives, and PET in PET/PC blends have been evaluated using DSC and the data analyzed using the Avrami model. The crystallization of PET in these systems is found to deviate from the Avrami prediction in the later stages of crystallization. Isothermal crystallization data are found to superimpose when plotted as a function of time divided by crystallization half-time. A weighted series Avrami model is found to describe the crystallization of PET and PET/PC blends during all stages of crystallization. © 1996 John Wiley & Sons, Inc.     

Reaction and miscibility of two diepoxides with poly(ethylene terephthalate)

Poly(ethylene terephthalate) (PET) was melt‐blended at 270°C with two epoxy monomers, diglycidyl ether of bisphenol A (DGEBA) and 3,4‐epoxycyclohexyl‐methyl‐3,4‐epoxycyclohexyl carboxylate (ECY). Intermediate proportions of the epoxy in the range of 20–0.5 wt % were used. If the epoxy monomers were added in a high proportion (10–20%), a large fraction did not react with PET. Calorimetric experiments showed that the unreacted fractions of both epoxies were miscible with the amorphous phase of the polyester. Only one glass‐transition temperature was detected. It was depressed as the epoxy content was increased. The transition was broad when the PET component was crystalline, and it was narrow when the PET component was made amorphous by quenching of the blend. These features were confirmed by dynamic thermal mechanical analysis. As is often the case for crystalline blends, the crystallization and melting temperatures decreased when the proportion of the epoxy was increased. Concerning the reactivity of the epoxy with PET, the behavior differed according to the nature of the epoxy. The DGEBA monomer showed a low reactivity. It was not effective for the chain extension of PET, and no increase in the intrinsic viscosity was observed under the experimental conditions. However, some functionalization of the chain ends may be possible at a high concentration of the epoxy. ECY was more reactive, and the molecular weight of the processed PET increased, although the value of the commercial untreated polyester was not attained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1995–2003, 2003     

Blends of thermoplastic polyesters with amorphous polyamide. I. Thermal and crystallization behavior

The thermal and crystallization behavior of blends of three thermoplastic polyesters with different degrees of crystallizability, with an amorphous aromatic polyamide is reported. The thermoplastic polyesters used in the investigation were poly(butylene terephthalate) (PBT), poly(ethylene terephthalate) (PET) and a co-polyester of 1,4 cyclohexane-dimethanol, ethylene glydol and terephthalic acid (PETG). The blends exhibited a single glass transition temperature indicating mlseibility in the amorphous phase. The results of thermal analysis indicated that the crystallization of all the three polyesters is facilitated in the molten phase as a result of blending. The blending significantly Increased the degree of crystallinity of PET, but there was no change in the crystallinity of PBT. It is thus observed that the extent of change in both the crystallization rate and the degree of crystallinity of polyesters depend on the inherent crystallizability of the individual polyester.     

Morphology studies of the liquid-induced crystallization of poly(ethylene terephthalate): Effects of polymer blending,nucleating agents,and molecular weight

The morphology associated with the liquid-induced crystallization of poly(ethylene terephthalate) (PET) blended either with poly(tetramethylene terephthalate) (PTMT), atactic polystyrene (APS), or polycarbonate of bisphenol A (PC) was studied, along with the effects of nucleating agents and polymer molecular weight on this type of crystallization in PET. It was found that melt-mixed blends of PET and either PTMT or PC led to an apparent well-mixed, two-component material in which some copolymer formation may be in evidence judging from the material superstructure. Blending PET with APS appeared to produce distinctly phase-separated materials in which PET could be crystallized and APS dissolved out of the structure as a result of treatment of the blend with certain types of liquid. The incorporation of nucleating agents into PET was shown to measurably influence the spherulitic character of the subsequently liquid-induced crystallized polymer. Finally, it was determined that liquid-induced crystallized PET samples with number-average molecular weights of 18,000 and 30,000 had identical characteristic morphology and apparent crystallization kinetics.     

Efficient circumferential superdrawing

Amorphous poly(ethylene terephthalate) (PET) can be stretched at low tension without causing any observable crystallization at temperatures above the glass‐transition temperature. The resulting increased length with no measurable change in orientation is called superdrawing. Superdrawing of hollow PET fibers in the circumferential direction was demonstrated earlier. This behavior is accompanied by an increase in fiber voids caused by a combination of air expansion and water permeation. The present work describes efficient techniques for superdrawing in the circumferential direction only. The process develops large void (>65%) fibers starting from standard 15% void spun supply. It is not possible to obtain such large voids in the longitudinal direction in low denier‐per‐filament fibers via direct melt spinning. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 123–127, 2005     

PET/PTT合金结晶形态的研究

采用XP-201热台偏光显微镜研究了对苯二甲酸乙二醇酯（PET）/对苯二甲酸丙二醇酯（PTT）合金等温结晶时的结晶形态及影响因素。研究结果表明：随着等温结晶温度的升高,PET/PTT(40/60)合金的结晶诱导期变长;在观察的时间范围内各样品的球晶尺寸随着时间的延长而增大;随着PTT含量的增加,样品球晶的线生长速率增大,球晶尺寸增大;对比不同温度下等温结晶的球晶形态,PET/PTT(100/0)样品在190℃结晶时球晶尺寸最大, PET/PTT(40/60)样品和PET/PTT(100/0)样品在180℃结晶时球晶尺寸最大; PET/PTT(0/100)样品等温结晶时呈现出了复杂的条带球晶。     

Antinucleating action of polystyrene on the isothermal cold crystallization of poly(ethylene terephthalate)

The effect of polystyrene (PS) on the kinetics of the cold crystallization of poly(ethylene terephthalate) (PET) was thoroughly investigated. The PET/PS blends were essentially immiscible, as observed by dynamic mechanical thermal analysis, which showed two distinct glass‐transition temperatures, and by scanning electron microscopy. The neat PET and its blends were isothermally cold‐crystallized at various temperatures, and the kinetic parameters were determined with the Avrami approach. PET and its blends presented values of the Avrami exponent close to 2, and the kinetic constant increased with the crystallization temperature increasing. For all the crystallization temperatures studied, the presence of only 1 wt % PS significantly reduced the rate of cold crystallization of PET. A further increase in the PS concentration did not show any significant influence. The blends presented higher values of the activation energy for cold crystallization, which was estimated from Arrhenius plots. The equilibrium melting temperature of neat PET was determined on the basis of the linear Hoffman–Weeks extrapolative method to be ～ 255°C. This value decreased in the presence of PS, and this suggested limited solubility between PET and PS. From the spherulitic growth equation proposed by Hoffman and Lauritzen, the nucleation parameter was obtained, and it was shown to be higher for the neat PET than for the blends. Moreover, a transition of regimes (I → II) was observed in both PET and its blends. From the investigations conducted here, it is clear that PS in small amounts causes a reduction in the rate of PET crystallization, acting as an antinucleating agent. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Evaluation of polyesters from renewable resources as alternatives to the current fossil-based polymers. Phase transitions of poly(butylene 2,5-furan-dicarboxylate)

Poly(butylene 2,5-furan dicarboxylate) (PBF) is an alipharomatic polyester that can be prepared using monomers derived from renewable resources such as 2,5-furan dicarboxylic acid and 1,4-butanediol. In the present work the thermal behavior of PBF was studied. Multiple melting was observed during heating traces of samples isothermally crystallized from the melt using differential scanning calorimetry (DSC). The wide angle X-ray diffraction (WAXD) patterns did not reveal the presence of a second crystal population, or a crystal transition upon heating. DSC study showed that the phenomena are closely related to recrystallization. Temperature modulated DSC (TMDSC) tests indeed evidenced enhanced recrystallization. The equilibrium melting point was estimated to be 184.5 °C using the linear Hoffman–Weeks extrapolation. The heat of fusion of the pure crystalline polymer was found equal to 129 J/g or (27.35 kJ/mol), a little lower than that of PBT. The Lauritzen–Hoffman secondary nucleation theory was used and the surface energy values and the work of chain folding were found to be comparable to those of PBT, but quite lower than those of poly(ethylene terephthalate) (PET). The non-isothermal crystallization on cooling and the cold-crystallization of quenched samples were also studied. Condensed spherulites were observed on isothermal crystallization under large supercoolings by using polarized optical microscopy (POM), while the spherulites turned to ring-banded morphology at higher temperatures. In every case the nucleation density was high.     

Isothermal and non‐isothermal crystallization behavior of PET nanocomposites

Polyethylene terephthalate (PET)/clay nanocomposites (PCNs) containing 1 wt% Cloisite 30B (C30B) were prepared via melt compounding. Modulated differential scanning calorimetry (MDSC) for isothermally crystallized samples revealed that the third endotherm at the highest temperature may be attributed to the recrystalization and melting of crystals, reorganized during heating. The first and second endotherms may be associated with melting of the secondary and primary crystals, respectively. The overall isothermal crystallization rate in PCNs was faster than in the neat resin. Growth kinetics revealed that the work required for chain folding and the equilibrium melting temperature in PCNs were somewhat higher than for neat PET. During isothermal crystallization, the steric hurdles introduced by clay layers lead to a reduction in the transport of the PET chains into crystallites. The effective non‐isothermal activation energy for the PCNs was higher than for PET, possibly leading to less perfect crystals in the PCNs. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

Melting behaviors and isothermal crystallization kinetics of poly(ethylene terephthalate)/mesoporous molecular sieve composite

Isothermal crystallization and subsequent melting behavior of mesoporous molecular sieve (MMS) filled poly(ethylene terephthalate) (PET) composites have been investigated at the designated temperature by using differential scanning calorimeter (DSC). The commonly used Avrami equation was used to fit the primary stage of the isothermal crystallization. The Avrami exponents n were evaluated to be 2<n<3 for the neat PET and composites. MMS particles acting as nucleating agent in composite accelerated the crystallization rate with decreasing the half-time of crystallization. The crystallization activation energy calculated from the Arrhenius' formula was reduced as MMS content increased. It is shown that the MMS particles made the molecular chains of PET easier to crystallize during the isothermal crystallization process. Subsequent differential scanning calorimeter scans of the isothermally crystallized samples exhibited different melting endotherms. It is found that much smaller or less perfect crystals formed in composites due to the interaction between molecular chains and the MMS particles. The crystallinity of composites was enhanced by increasing MMS content.     

Improving oxygen barrier properties of poly(ethylene terephthalate) by incorporating isophthalate. II. Effect of crystallization

The present study examined crystallization of poly(ethylene terephthalate) (PET) and a series of random and blocky copolymers in which up to 30% of the terephthalate was replaced with isophthalate. Isothermal crystallization kinetics and direct observation of the spherulitic morphology revealed that the blocky copolymers crystallized more rapidly than PET, at least in part, as the result of enhanced spherulite nucleation. The statistical copolymers with 10 and 20% isophthalate achieved almost the same level of crystallinity as that of the blocky copolymers. The statistical copolymers with 10% isophthalate crystallized almost as fast as PET, although the statistical copolymer with 20% isophthalate crystallized much more slowly. Crystallization substantially reduced the oxygen permeability. Analysis of oxygen‐transport parameters in terms of a two‐phase structural model that considered a dispersion of lower‐permeability spherulites in an amorphous matrix of higher permeability revealed that dedensification of the PET interlamellar amorphous regions was responsible for the unexpectedly high oxygen solubility of crystallized PET. In contrast, copolymerization with isophthalate prevented dedensification of the interlamellar amorphous regions. As a result, crystallization was more effective in reducing the oxygen permeability. It was speculated that segregation of kinked isophthalate units to the amorphous regions of the spherulite relieved constraint on the interlamellar amorphous chain segments. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1629–1642, 2005