长支链支化制备高熔体强度PET研究进展

主要介绍了采用多官能单体以及扩链/支化剂在PET主链上引入长支链的方法,论述了长支链结构对PET熔体强度、熔体流变行为和结晶行为的影响.     

Surface modification of poly(ethylene terephthalate) by plasma polymerization of poly(ethylene glycol)

Poly(ethylene glycol) (PEG) was ‘polymerized’ onto poly(ethylene terephthalate) (PET) surface by radio frequency (RF) plasma polymerization of PEG (average molecular weight 200 Da) at a monomer vapour partial pressure of 10 Pa. Thin films strongly adherent onto PET could be produced by this method. The modified surface was characterized by infra red (IR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), cross-cut test, contact angle measurements and static platelet adhesion studies. The modified surface, believed to be extensively cross-linked, however showed all the chemical characteristics of PEG. The surface was found to be highly hydrophilic as evidenced by an interfacial free energy of about 0.7 dynes/cm. AFM studies showed that the surface of the modified PET became smooth by the plasma polymerized deposition. Static platelet adhesion studies using platelet rich plasma (PRP) showed considerably reduced adhesion of platelets onto the modified surface by SEM. Plasma ‘polymerization’ of a polymer such as PEG onto substrates may be a novel and interesting strategy to prepare PEG-like surfaces on a variety of substrates since the technique allows the formation of thin, pin-hole free, strongly adherent films on a variety of substrates.     

In situ ring-opening polymerization of hydroxyapatite/poly(ethylene adipate)-co-(ethylene terephthalate) biomimetic composites

Hydroxyapatite/poly(ethylene adipate)-co-poly(ethylene terephthalate) biomaterials (HAp/PEA-co-PET) have been prepared by ring opening polymerization (ROP) of cyclic oligo(ethylene adipate)-co-oligo(ethylene terephthalate) (C-OEA-co-C-OET) in the porous hydroxyapatite (HAp) scaffolds at 250 °C for 24 h under vacuum. The content of ROP-PEA-co-PET in the HAp/PEA-co-PET composite was about 20 wt% with the values of number average molecular weight $({\overline{M}_{{\rm n}}})$ and weight average molecular weight $({\overline{M}_{{\rm W}}})$ of 3380 and 7160 g/mol, respectively. Compressive strength and modulus of the HAp/PEA-co-PET composites were about 29 and 246 MPa, respectively. These mechanical properties were higher than those of the porous HAp templates and natural cancellous bone. In vitro bioactivity of the HAp/PEA-co-PET composites was studied by soaking in simulated body fluid (SBF) under the flowing system at the rate of 130 mL/day for 7, 14, 21 and 28 days. The formation of hydroxyapatite nanocrystals was observed on the composite surfaces through the consumption of calcium and phosphorus from the SBF solution, indicating the bioactivity of these HAp/PEA-co-PET composites. These results indicated the competency of HAp/PEA-co-PET composites for biomedical applications.     

Effect of temperature on fracture properties of an amorphous poly(ethylene terephthalate) (PET) film

Fracture behaviour of an amorphous polyethylene terephthalate (PET) film with a glass transition temperature (T _g ) of 72°C and a thickness of 0.21 mm was studied between 23 and 70°C using Double Edge Notched Tension (DENT) specimens. Within this temperature range, DENT specimens fractured by ductile tearing of the ligament region after ligament region had been fully yielded. The load-displacement curves obtained for different ligament lengths were geometrically similar to one another. On the basis of these, Essential Work of Fracture (EWF) methodology was used to determine fracture toughness of the PET film as a function of temperature. A linear relationship was obtained between the total specific work of fracture, w _f , and ligament length, L, at temperatures under consideration. Results showed that specific essential work of fracture, w _e , is independent of temperature but the specific non-essential work of fracture ( w _p ) increases with increasing temperature and drops in value near the glass-transition temperature. A linear relationship was also found for yielding (w _y ) and necking/tearing (w _nt ) components of w _f as a function of ligament length. The specific essential work components were found to be temperature dependent and whilst component w _ey decreased component w _ent increased with increasing temperature. The contribution of w _ent to w _e was substantially greater than that of w _ey at all temperatures.     

Dynamic compression response of self-reinforced poly(ethylene terephthalate) composites and corrugated sandwich cores

A novel manufacturing route for fully recyclable corrugated sandwich structures made from self-reinforced poly(ethylene terephthalate) SrPET composites is developed. The dynamic compression properties of the SrPET material and the out-of-plane compression properties of the sandwich core structure are investigated over a strain rate range 10⁻⁴–10³ s⁻¹. Although the SrPET material shows limited rate dependence, the corrugated core structures show significant rate dependence mainly attributed to micro-inertial stabilisation of the core struts and increased plastic tangent stiffness of the SrPET material. The corrugated SrPET cores have similar quasi-static performance as commercial polymeric foams but the SrPET cores have superior dynamic compression properties.     

All-poly(ethylene terephthalate) composites by film stacking of oriented tapes

Self-reinforced polymer or all-polymer composites have been developed to replace traditional fibre reinforced plastic (FRP) with good interfacial adhesion and enhanced recyclability. Poly(ethylene terephthalate) (PET) is one of the most attractive polymers to be used in these fully recyclable all-polymer composites, in terms of cost and properties. In this work, all-PET composites were prepared by film stacking of oriented PET tapes. A processing temperature window was determined by a series of tests on PET tapes and co-PET films, including DSC and T-peel tests. Tensile properties of PET tape, co-PET film and all-PET composites are reported and compared with a commercial co-extruded PURE^® polypropylene tape. The effect of compaction temperatures and pressures on tensile properties of all-PET composites was investigated to explore the optimum processing parameters for balancing good interfacial adhesion between tapes and residual tensile properties of PET tapes.     

Forensic analysis of poly(ethylene terephthalate) fibers by infrared spectroscopy

Poly(ethylene terephthalate) (PET) is one of the most commonly employed polymers in the textile industry. Its relevance as a source of evidence in the reconstruction of criminal cases is nevertheless very limited because the properties and morphologies of fibers from different producers tend to be very similar. By integrating bands, obtained on single fibers by infrared (IR) microscopy, associated with trans and gauche conformation and to the O-H end-groups of the molecules, a method is proposed that can discriminate otherwise similar PET fibers. The absorbancies at 1370 and at 846 cm(-1) relative, respectively, to the gauche and trans conformation, were measured and ratioed. The end-group content was evaluated by ratioing the absorbancies of the signals at 3440 and at 874 cm(-1). Relative standard deviation (R. S. D.) was 1% for repetitive analyses on the same location of the same single fiber. Precision was reduced if the ratios were measured along the length of a single fiber (R. S. D. = 3%) and even further when different fibers of the same sample were examined (R. S. D. varied from 2 to 10%). This simple method can greatly enhance the evidential value of PET fibers by subclassifying them, thus helping the Court to better assess their significance.     

Crazing behaviour in oriented poly(ethylene terephthalate)

A study has been made of the two types of crazes formed in oriented sheets of poly(ethylene terephthalate). The crazes have been termed tensile crazes and shear crazes. The tensile crazes formed parallel to the initial draw direction (IDD) whereas the shear crazes formed in a direction close to that of the deformation bands observed when the material yields.The possibility of applying a yield criterion to shear craze formation has been examined and there appears to be fairly good agreement between theory and experiment. Measurements of crazing stress on the tensile crazes indicated that the criterion for tensile craze formation is not purely dependent on the component of stress normal to the extended chains.It is concluded that the two types of crazes are formed by two quite different mechanisms, although the exact nature of these mechanisms is still uncertain.     

Supermolecular structure and thermal properties of poly(ethylene terephthalate)/lignin composites

Poly(ethylene terephthalate) (PET) has been compounded with lignin (L) by a single-screw extruder. The influence of L presence and its content on the thermal properties and crystalline structure of PET has been studied. Morphological analyses evidenced good dispersion of the L particles in the PET matrix. Polarizing optical microscopy (POM) and small-angle X-ray scattering (SAXS) techniques were employed to measure the L particles dimension. The influence of L on the overall isothermal crystallization of PET was investigated by using differential scanning calorimetry (DSC). L particles acting as nucleating agent in the composite increased the crystallization rate. The crystallization process was composed of primary and secondary stages. As the L content was increased in the composite, the primary crystallization progressively proceeded toward higher percentage of the crystallizable PET fraction. As evidenced by SAXS and wide angle X-ray diffraction (WAXD), the L presence produced a noticeable enhancement of PET crystallinity and crystal dimensions.     

Micromechanical modelling of the viscoelastic behaviour of an amorphous poly(ethylene)terephthalate (PET) reinforced by spherical glass beads

Homogenization micromechanical models are applied to predict the linear viscoelastic properties of an amorphous poly(ethylene)terephthalate (PET) composite in the range of glass transition by using the elastic-viscoelastic superposition principle defined by Hashin [1]. An amorphous PET is reinforced by glass beads and is submitted to dynamic mechanical tests at temperatures surrounding its quasi-static glass transition temperature. The viscoelastic properties of the matrix and the elastic properties of the beads are measured experimentally. The micromechanical models predictions of the linear viscoelastic behaviour in the glassy state are acceptable. In the rubbery state, the beads seem to reduce the molecular mobility of the matrix driving to a large change in the viscoelastic properties of the materials. Thus, this paper aims to emphasize that classical homogenization micromechanical models, which depend only on the constituent behaviour, shape and distribution, cannot predict this change in the linear viscoelastic behaviour of the beads/PET composites.     

Orientation in poly(ethylene terephthalate) drawn by solid state coextrusion

The development of uniaxial orientation by solid-state extrusion at 60 to 90° C has been evaluated for both the amorphous and crystalline components of a polyethylene terephthalate). Analyses involved X-ray diffraction, birefringence and visable dichroism. The dichroism was evalulated from a host dye molecule. The initial PET film for draw was amorphous and isotropic. Orientation functions for the amorphous and the developed crystalline phases are reported at a series of draw ratios up to 4.4.     

Structural changes during photodegradation of poly(ethylene terephthalate)

An investigation has been conducted into the effects of photodegradation on the structure of poly(ethylene terephthalate) (PET). Films, with and without ultraviolet absorbers and prepared by biaxial orientation after extrusion, have been exposed in the laboratory for periods of up to 1020 hours. The samples were investigated by differential scanning calorimetry (DSC), X-ray diffraction and size exclusion chromatography. The appearance of a cold crystallization peak during DSC heating scans was noted for exposed samples and this was considered to be a result of released molecules in the amorphous region that could rearrange into a crystalline phase. From X-ray analysis, a loss of crystalline orientation was observed after degradation and an interpretation was given based on relaxation in the mesophase region. In samples containing the photostabilizer additive the magnitude of changes in structure was lower, possibly due to segregation effects during film production making the non-crystalline region relatively immune to degradation effects.     

Nonisothermal crystallization kinetics of poly(ethylene terephthalate) nanocomposites

This article reports the nonisothermal crystallization kinetics of poly(ethylene terephthalate) (PET) nanocomposites. The non-isothermal crystallization behaviors of PET and the nanocomposite samples are studied by differential scanning calorimetry (DSC). Various models, namely the Avrami method, the Ozawa method, and the combined Avrami-Ozawa method, are applied to describe the kinetics of the non-isothermal crystallization. The combined Avrami and Ozawa models proposed by Liu and Mo also fit with the experimental data. Different kinetic parameters determined from these models prove that in nanocomposite samples intercalated silicate particles are efficient to start crystallization earlier by nucleation, however, the crystal growth decrease in nanocomposites due to the intercalation of polymer chains in the silicate galleries. Polarized optical microscopy (POM) observations also support the DSC results. The activation energies for crystallization has been estimated on the basis of three models such as Augis-Bennett, Kissinger and Takhor methods follow the trend PET/2C20A < PET/1.3C20A < PET, indicating incorporation of organoclay enhance the crystallization by offering large surface area.     

NMR analysis of poly(ethylene naphthalate) + poly(butylene terephthalate) blends

Melt blends of poly (butylene terephthalate) (PBT) and poly (ethylene naphthalate) (PEN) with 30, 40, 50, 60 and 70 wt% PEN were prepared using a single screw extruder and injection moulding machine. ¹³C and ¹H nuclear magnetic resonance (NMR) spectra were obtained with a Bruker DRX-400 instrument, on solutions prepared by dissolving samples of the homopolymers and each blend in deuterated trifluoroacetic acid + chloroform mixtures (1:1 by volume). The absence of new signals in ¹H and ¹³C spectra, that would be expected to result from transesterification reactions in the PBT + PEN blend system, provides convincing evidence that such reactions do not occur in these blends under the melt processing conditions that were used. In the light of published work on solid-state NMR studies of these and related blend systems, and our observations of partial miscibility with a very small domain size, together with substantial enhancement of the mechanical properties of PBT by blending with PEN, we conclude that the improvement in mechanical properties arises from molecular scale mixing of the homopolymers and strong but non-covalent bonding interactions over the very large interfacial area between the PBT-rich and PEN-rich phases.     

Molecular orientation of poly(ethylene terephthalate) and poly(butylene terephthalate) probed by polarized Raman spectra: a parallel study

Poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) samples uniaxially drawn above Tg and beyond the yield point exhibit significant differences in their molecular orientation behavior as probed by polarized Raman spectra. The quasi-amorphous PET samples, drawn close to the Tg, manifest considerable molecular orientation development; however, when drawn above Tg + 30 degrees C, they exhibit significant molecular orientation relaxation. The semi-crystalline PBT samples maintain prominent molecular orientation even when drawn 110 degrees C above Tg. The drawing process, in PET samples, when resulting in molecular orientation, is accompanied by a gauche-trans transformation of the glycol linkage and a concurrent initiation of crystallinity development. In PBT specimens, it gives rise to a coexistence of alpha- and beta-type crystalline phases. Phase alpha is predominant at high draw temperatures, i.e., Tg + 110 degrees C, while phase beta dominates at low draw temperatures, i.e., Tg + 10 degrees C. PBT samples, with beta-phase predominance, left at relevant draw temperatures without stress, exhibit a beta-alpha phase change though no molecular orientation relaxation occurs. A note is made of the fact that complete molecular orientation analysis of PBT segments utilizing the depol method gives more reliable results than the simplified analysis assuming a cylindrical tensor for the 1614 cm(-1) symmetric stretch of the para-disubstituted benzene ring of PBT. In this context, segments of PBT specimens rich in alpha-phase exhibit higher molecular orientation than those with beta-phase predominance.     

Viscoelastic properties of poly(butylene terephthalate)/poly(ethylene naphthalate) blends

Melt blends of poly(butylene terephalate) (PBT) and poly(ethylene naphthalate) (PEN) with 30 and 60 wt% PEN were prepared using a single screw extruder and an injection moulding machine. Stress relaxation tests for the specimens of PBT/PEN blends and the homopolymers were carried out using an Instron testing machine in an Instron environmental chamber. The Taguchi method of experimental design analysed how different levels of temperature, PEN content and initial stress affected the relaxation behaviour of PBT/PEN blends and homopolymers. From the response tables and analyses of main and interaction effects, it was shown that the most significant factor was temperature, followed by PEN content and then the initial stress. Consequently, high temperature, low PEN content and high initial stress speeded up stress relaxation rate of specimens. Interaction effects between factors were insignificant. To fit the relaxation curves of the PBT/PEN blends and the homopolymers at different temperatures, PEN contents and the initial stresses, four different equations were attempted with Matlab™, which determined the coefficients of these functions using the experimental data of stress change with time. The simulated curves from the most suitable function among them were shown using the calculated coefficients to predict the relaxation behaviour of PBT/PEN blends (50% PEN) at temperatures of 30 and 60°C with an initial stress of 7 MPa.