Injection stretch blow moulding process of reactive extruded recycled PET and virgin PET blends

Reactive extruded recycled PET (RER-PET) was blended with virgin PET in order to find optimum composition for producing bottles using injection stretch blow moulding (ISBM) process. Two variables were investigated namely, RER-PET concentration in the blend with virgin PET and RER-PET intrinsic viscosity, [η]. The variability of [η] was facilitated by changing PMDA chain extender concentration in the production of RER-PET. Different molecular, mechanical, barrier and optical tests such as infrared, burst pressure, top load strength, drop impact, environmental stress cracking, liquid permeation, gas permeation, and clarity were conducted. The aim was to evaluate the properties of the bottles in response to different blends compositions. Bottles made from RER-PET and virgin PET blends showed similar and better mechanical and barrier properties at certain compositions to those made from Virgin PET. The effects of RER-PET molecular properties such as intrinsic viscosity, chain orientation and conformation on bottles mechanical, barrier and optical properties are detailed.     

Optimisation of mould surface temperature and bottle residence time in mould for the carbonated soft drink PET containers

Polyethylene terephthalate (PET) bottles, which are usually produced by injection stretch blow moulding (ISBM) are widely used for carbonated soft drinks (CSD) storage and transportation. Stretch rod movement, blow pressure, preform temperature profile, mould surface temperature and material properties are among the most important factors affecting the final product's quality in terms of the thickness distribution, burst pressure and top-load resistance of the bottles. However, the residence time of the blown bottle inside the mould is also an important factor affecting its final properties. Especially in PET bottle production for hot fillings, the residence time is a very important factor because the longer the residence time the better the crystalline structure of the PET. In this production, the lid section is desired to have a fully crystalline form so that it can withstand hot fluids. In this study, the aim was to optimise the mould surface temperature and the blown bottle's residence time inside the mould for 1 L soft drink PET bottle production based on the final properties using the ECHIP 7 design of experiment (DOE) program. The method employed through this program was a quadratic one. Optimum process parameters were determined by the response surface method (RSM) and the process settings ensuring maximum top-load, burst pressure, Tg and degree of crystallinity were regarded to be optimum. It was found that the optimum mould surface temperature and blown bottle residence time inside the mould were 10 °C and 20 s, respectively.     

The effect of chain extension on the thermal behaviour and crystallinity of reactive extruded recycled PET

Recycled poly(ethylene terephthalate) (R-PET) was chain extended with pyromellitic dianhydride (PMDA) in a commercial size twin-screw reactive extrusion system. Temperature-modulated differential scanning calorimetry (TMDSC) was used to evaluate the effect of the chain extension process on the thermal transitions and crystallinity of R-PET. Reactive extruded recycled PET (RER-PET) samples were tested based on different PMDA concentration and reactive extrusion residence times. The glass transition temperature (T _g) did not show a significant change as a function of PMDA addition or the extrusion residence time. Melting temperature (T _m) and crystallisation temperature (T _c) decreased with increasing PMDA concentration and with increasing extrusion residence time. RER-PET samples showed double melting peaks, it is believed that different melting mechanism is the reason behind this phenomenon. The crystallinity of RER-PET samples is lower than that of R-PET. RER-PET samples at constant PMDA concentration showed a decrease in crystallinity with increasing extrusion residence time. Results suggest that the reactive extrusion process is more dependent on PMDA concentration rather than reactive extrusion process residence time.The first author would like to acknowledge Advanced Engineering Center for Manufacturing (AECM) and Visy Industries for their financial support to this study.     

Chain Extension and Foaming of Recycled PET in Extrusion Equipment

In this work industrial scraps of poly(ethylene terephthalate) (PET) were used for the production of foamed sheets. The process was performed by making use of a chemical blowing agent (CBA) in the extrusion process. Due to the low intrinsic viscosity of the recycled PET (IV=0.48dl/g), a chain extender was also used in order to increase the molecular weight of the polymer matrix. Pyromellitic dianhydride (PMDA) and Hydrocerol CT 534 were chosen as chain extender and CBA, respectively. The reactive extrusion and foaming were performed in a two step process, analyzing the feasibility regarding an eventual use in an industrial context. Rheological characterization was carried out on PET samples previously treated with PMDA, as well as the morphological study was performed to define the cellular structure of the foams produced. Moreover, in order to correlate the working conditions in the reactive and the foaming processes with the final morphology of the foams, a mathematical modelling of the foaming process was applied.     

Modelling of PET Quality Parameters for a Closed-Loop Recycling System for Food Contact

Summary: A rigorous process model has been developed which describes a closed-loop recycling system for PET beverage bottles. The reaction / mass transport model is aimed at the dominant quality parameters such as intrinsic viscosity, concentration of acetaldehyde, concentration of carboxylic end-groups, and concentration of vinyl end-groups, respectively. The model covers the main process steps being preform production (injection moulding), drying, solid-state polycondensation, and melt filtration. The simulation reveals that after a single recycling loop all the relevant quality parameters achieve the specification, if certain temperatures, residence times, and surface areas for degassing are provided during the recycling process. Another simulation showed the evolution of quality parameters in PET being subjected to an “infinite” number of recycling loops in a closed system. In this case, the concentration of acetaldehyde and vinyl end-groups decreases with the number of recycling loops, which is a desired effect. On the other hand, the concentration of carboxylic end-groups increases with every completed recycling loop. Higher concentrations of carboxylic end-groups make the polymer more susceptible to hydrolysis and increase the SSP process time needed to achieve the specified intrinsic viscosity for carbonated soft drink bottles. To overcome this problem, the recycled PET has to be blended with a certain amount of virgin PET in industrial processes.     

PET/LDPE REACTIVE COMPATIBILIZATION THROUGH THE CARBAMATE FUNCTIONALIZED EPM

ABSTRACT

To investigate the effect of reactive compatibilization in the immiscible poly(ethylene terephthalate) (PET)/low-density polyethylene (LDPE) blend, ethylene-propylene copolymer-g-methacryloyl carbamate (MEPM) was prepared and used as a reactive compatibilizer. The inter-facial reaction of carbamate group in MEPM with OH/COOH in PET was confirmed by measuring the interfacial tension between the PET and LDPE using the breaking thread method. The two-step blending process strongly influenced the blend morphology at high concentration of the dispersed phase in the blend. The MEPM showed a discrepancy in the reactive compatibilization ability with a blend sequence in the blends of different dispersed phase concentration.     

低温固相反应挤出PET/PC合金中的多重网络增韧结构

以聚对苯二甲酸乙二酯(PET)瓶片为主要原料, 加入聚碳酸酯(PC)、热塑性弹性体及扩链剂, 采用低温固相反应挤出制备了具有良好强度与韧性的新型合金. 在加工过程中产生PET相和PC相互穿的网络结构的同时, 反应性扩链剂在PET相中发生交联反应, 形成了次级网络结构. 由于这些网络结构的存在, 使合金材料的力学性能得到明显提高, 特别是缺口冲击性能有了明显的改善.     

三元共聚液晶聚酯酰亚胺/PET共混体系结构与性能研究

通过熔融共混的方式,将实验室自行设计合成的三元共聚热致液晶聚酯酰亚胺(PPDI)与聚对苯二甲酸乙二酯(PET)进行共混,制备一系列不同液晶聚合物含量的共混体系.采用示差扫描量热仪(DSC)、广角X-射线衍射仪(WAXD)和动态力学性能分析仪(DMA)对共混体系的结构与性能进行表征.结果表明,共混体系中两组份之间具有良好...     

Transesterification kinetics of poly(ethylene terephthalate) and poly(ethylene 2,6‐naphthalate) blends with the addition of 2,2′‐bis(1,3‐oxazoline)

The kinetics of the transesterification reaction between poly(ethylene terephthalate) (PET) and poly(ethylene 2,6‐naphthalate) (PEN) with and without the addition of a chain extender were studied with ¹H NMR. Different kinetic approaches were considered, and a second‐order, reversible reaction was accepted for the PET/PEN reactive blend system. The addition of 2,2′‐bis(1,3‐oxazoline) (BOZ) promoted the transesterification reaction between PET and PEN in the molten state. The activation energy of the transesterification reaction for the PET/PEN reactive blend with BOZ (94.0 kJ/mol) was lower than that without BOZ (168.9KJ/mol). The rate constant k took an almost constant value for blend samples with different compositions mixed at 275 °C. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2607–2614, 2001     

Fire retardant poly(ethylene terephthalate)/polycarbonate/triphenyl phosphite blends

Flame retardant recycled PET blends containing PC and triphenyl phosphite (TPP) have been designed using the following sequential processing strategy: PET and PC are first melt blended with a transesterification catalyst, allowing the compatibilisation of the blend, before adding TPP. The presence of this last component was shown to stop the transesterification reaction between PET and PC, avoiding chain breaking. In addition, TPP acts as a chain extender of PET, allowing the average chain length to be increased. The optimized blends obtained present “V-0” UL94 rating due to a better thermal stability leading to low flammability and to the development of an important, stable and covering char layer, resulting in self-extinguishability and very low Heat Release Rates during combustion.     

Influence of chain extension on the compatibilization and properties of recycled poly(ethylene terephthalate)/linear low density polyethylene blends

Polymeric methylene diphenyl diisocyanate (PMDI) was added as chain extender to a blend of recycled poly(ethylene terephthalate) (R-PET) and linear low density polyethylene (LLDPE) with compatibilizer of maleic anhydride-grafted poly(styrene-ethylene/butadiene-styrene) (SEBS-g-MA). Hydroxyl end groups of PET can react with both isocyanate groups of PMDI and maleic anhydride groups of SEBS-g-MA, which are competing reactions during reactive extrusion. The compatibility and properties of the blends with various contents of PMDI were systemically evaluated and investigated. WAXD results and SEM observations indicated that chain extension inhibits the reaction between PET and SEBS-g-MA. As the PMDI content increased, the morphology of dispersed phase changed from droplet dispersion to rodlike shape and then to an irregular structure. The DSC results showed that the crystallinity of PET decreased in the presence of PMDI, and the glass transition temperature (T_g) of PET increased with addition of 0-0.7 w% PMDI. The impact strength of the blend with 1.1 w% PMDI increased by 120% with respect to the blend without PMDI, accompanied by only an 8% tensile strength decrease. It was demonstrated that the chain extension of PET with PMDI in R-PET/LLDPE/SEBS-g-MA blends not only decreased the compatibilization effect of SEBS-g-MA but also hindered the crystallization of PET.     

A new approach to obtain Kevlar-49 from PET waste bottles

Non-biodegradable polyethylene terephthalate (PET) bottles have attracted increasing attention due to environmental concern in today’s world. In order to reduce the amount of solid wastes generated and the dependency on fossil resources, a new approach has been conducted to prepare Kevlar-49 from PET waste bottles. Terephthalic acid, the main raw material used for preparation of Kevlar, was regenerated from PET waste bottles via subjection to a saponification process, whereas p-phenylenediamine was prepared from PET waste bottles via the Hoffmann rearrangement method. Kevlar was synthesized from the reaction of terephthalic acid and p-phenylenediamine by polycondensation reaction. The structures of terephthalic acid, p-phenylenediamine and Kevlar were characterized by FT-IR, ¹H NMR, ¹³C NMR, and elemental analysis (CHN). In this study, thermogravimetric analysis and differential scanning calorimetry, X-ray diffraction (XRD), as well as the mechanical properties (tensile strength, modulus, and percentage elongation at break) of the synthesized Kevlar-49, were compared with commercial Kevlar-49, prepared from the same raw materials, for better understanding of their properties.     

Chain extension of polyesters PET and PBT with N,N′-bis (glycidyl ester) pyromellitimides. I

Three N,N′-bis (glycidyl ester imide) of pyromellitic acid (diepoxides) were prepared and were used as chain extenders for poly (ethylene terephthalate) (PET) and poly (butylene terephthalate) (PBT). The typical reaction conditions for the coupling of the polyester macromolecules were heating with the chain extender under argon atmosphere above the melting temperature (280°C for PET and 250°C for PBT) for several minutes. The Characterization of the samples, obtained at variable residence times in the reactor, was based on solution viscosity measurements and carboxyl and hydroxyl end-group determinations. Two of the diepoxides used gave satisfactory results. Starting from a PET having intrinsic viscosity [η] = 0.60 dL/g, and carboxyl content CC = 42 eq/10⁶ g, one could obtain PET with [η] = 1.15 dL/g and CC = 16 eq/10⁶ g within 30 min at 280°C. Analogous results were observed for PBT. The hydroxyl content of polyester in all cases was increased. When the quantity of the chain extender used was higher than that theoretically required for its reaction with all carboxyl end groups of the polyester, this resulted in some gel formation indicative of crosslinking. © 1995 John Wiley & Sons, Inc.     

聚酯／聚醚酯高分子混合系的凝集状态和结晶化机理

研究了结晶性高分子聚对苯二甲酸乙二酯（ＰＥＴ）聚二苯氧乙烷（１,２）二甲酸（Ｐ．Ｐ′）乙二酯（ＰＥＥＴ）混合系的热结晶化机理．用ＤＳＣ,Ｘ光,偏光显微镜观测研究发现,ＰＥＴ与ＰＥＥＴ的熔融混合并未发生酯交换和共聚合等化学反应,各组分独立结晶,它们的结晶度、结晶速度、球晶结构受到结晶化温度和混合组成两因子的影响,提出了表征这种效果的综合结晶化阻碍因子值．     

Rheological behavior in blends of PET with ionomeric polyester

The rheological behavior and the morphology in blends of polyethylene terephthalate (PET) with ionomeric polyester were investigated over a wide range of different blending ratios. The ionomeric polyester is derived from PET modified through copolycondensation with sulfonate moiety, sodiosulfo isophthalate (Na-SIP), iso-phthalic acid (IPA) and polyethylene glycol (PEG). The results showed that the apparent viscosity and non-Newtonian index of the PET/ionomeric polyester blend system had a nonlinearity change with the change of the blend ratio of PET/ionomeric polyester. The anomaly of the viscous flow activation energy change was found as the content of ionomeric polyester was about 40% (w/w) in the blend system, suggesting the presence of physical cross-linked structure formed by strong polar tangling points and the phase separation owing to poor compatibility between the PET and ionomeric polyester. The morphology and thermal behavior of the blends were observed, respectively, with differential scanning calorimetry (DSC) and atomic force microscopy (AMF).     

Chain extension of polyesters PET and PBT with two new diimidodiepoxides. II

Two new diglycidyl ester compounds containing preformed imide rings for better thermal stability were prepared to be used as chain extenders for PET and PBT. The preparation of these compounds was carried out in two steps. In the first step, diimidodiacids were prepared from pyromellitic anhydride and 3-aminopropanoic acid or 4-(aminomethyl)benzoic acid. From these diimidoacids, in a second step, diimidodiepoxides were obtained by reaction with epichlorohydrin. The aforementioned diimidodiepoxides were used as chain extenders for poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) with satisfactory results. The polyester samples obtained from various residence times in the reactor, were characterized by solution viscosity measurements, carboxyl, and hydroxyl end-group determination. Starting from a PET having intrinsic viscosity ([η]) of 0.60 dL/g and carboxyl content (CC) of 42 equiv/10⁶ g, one could obtain PET with [η] of 1.16 and CC below 5 equiv/10⁶ g. The typical reaction condition for the coupling of PET was its heating with the chain extender under argon atmosphere above its melting temperature (280°C) for several minutes. Analogous results were obtained for PBT. The hydroxyl content in all cases was increased. © 1996 John Wiley & Sons, Inc.     

Toughening of Poly(ethylene terephtalate) (PET) Bottle Wastes by Modified Styrene-Butadiene Rubber (SBR) Elastomer

Summary: Modified SBR was blended with dried PET bottle wastes in an internal mixer. During the process mechanical and morphological properties were studied. When PET bottle wastes were blended with unmodified SBR, the final blend had a rough morphology and low impact strength. In contrary, blending of PET with modified SBR lead to smooth and fine morphology. Utilizing grafted SBR in PET blends creates an enormous difference in particle size and morphology, which is a result of powerful interactions and effective chemical bonding between the components of the blend. The final product had high impact strength in comparison with PET and unmodified SBR blend. These results are mainly related to formation in situ of PET/SBR graft copolymer in interface, which is produced by chemical reaction among active maleic anhydride groups and active PET groups.     

EFFECT OF EXCESS ENTHALPY RELAXATION ON PERMEATION OF CO_2 AND TOLUENE THROUGH PET FILM

Structural change in an unoriented, amorphous PET film annealed at temperatures below T_gand the effect of excess enthalpy relaxation on permeation rates of CO_2 gas and toluene liquid intreated samples have been studied. The results suggest that the amount of excess enthalpy relaxa-tion as determined from the endothermic peak in T_g interval, the T_g and density all increase withannealing time, but the trans-conformation component of samples decreases. No change of struc-ture in the amorphous phase was found other than the normal densification of the molecular chainpacking or a reduction in free volume had occurred during the annealing regimes. Therefore, thepermeation rate of CO_2 gas in treated samples reduced. While the apparent permeation rate oftoluene liquid increased with annealing time because of a creation of extensive cracks at film surfacearising from both the increase in embrittlement of polymer and the swelling action of toluene liquidon treated samples.     

Compatibility Study of Blends of Acrylic Rubber (ACM), Poly(ethyleneterephalate) (PET), and Liquid Crystalline Polymer (LCP)

The ternary blends of acrylate rubber (ACM), poly(ethyleneterephalate) (PET), and liquid crystalline polymer (LCP) were prepared by varying the amount of LCP, but fixing the ratio of ACM and PET using melt mixing procedure. The compatibility behavior of these blends was investigated with infrared spectroscopy (IR), differential scanning calorimetry (DSC), and dynamic mechanical analyzer (DMA). The IR results revealed the significant interaction between the blend components. Glass transition temperature (T_g) and melting temperature (T_m) of the blends were affected depending on the LCP weight percent in the ACM/PET, respectively. This further suggests the strong interfacial interactions between the blend components. In the presence of ACM, the nucleating effect of LCP was more pronounced for the PET. The thermogravimetric (TGA) study shows the improved thermal stability of the blends.