聚(对苯二甲酸乙二醇酯-co-对苯二甲酸异山梨醇酯)等温结晶行为研究

以对苯二甲酸(PTA)、乙二醇(EG)、异山梨醇(ISB)为原料,通过直接熔融缩聚法合成聚(对苯二甲酸乙二醇酯-co-对苯二甲酸异山梨醇酯)(PEIT)共聚酯。利用差示扫描量热法(DSC)研究了共聚酯的结晶行为,采用Avrami方程分析了共聚酯的等温结晶动力学。结果表明,PEIT共聚酯结晶行为受共聚组成和结晶温度影响。随着ISB用量的增加或结晶温度的降低,共聚酯半结晶周期t1/2增加、结晶速率变慢;ISB摩尔分数超过20%,共聚酯无法结晶。     

Preparation and properties of poly(ethylene terephthalate)/ATO nanocomposites

Antimony doped tin oxide (ATO) nanoparticles modified poly(ethylene terephthalate) (PET) composites used for manufacturing antistatic PET fiber were synthesized by in situ polymerization. The crystallization and multiple melting behavior of the nanocomposites were systemically investigated by means of Differential Scanning Calorimeter (DSC), Fourier Transform Infrared (FTIR), X‐ray Diffraction (XRD) techniques. The degree of crystallinity in nanocomposites increased with increasing ATO content. Smaller and more incomplete crystals are presented in the crystalline regions of the nanocomposites with increasing the content of ATO, which could be attributed to heterogeneous nucleation effects of ATO nanoparticles. Dynamic Mechanical Analysis (DMA) measurements showed that the storage moduli of the nanocomposites increased with increasing the content of ATO, due to formation of immobilized layer between polymer and filler. The interactions between ATO and PET molecules result in high tan δ for the PET/ATO nanocomposites. Percolation threshold of PET/ATO hybrid fibers prepared by the nanocomposites at room temperature was as low as 1.05 wt %, much lower than that of the composites filled with conventional conductive particles. Adding ATO nanoparticles obviously improves the conductivity of PET. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

PEN/PET共混物结晶行为研究

用差示扫描量热法(DSC)研究了不同共混比例PEN/PET共混物的熔体结晶行为,并进行了等温结晶动力学测定。结果表明:随着两种组分向中间比例(50/50)靠近,共混物的熔融温度越低,结晶速率也越慢。     

Crystallization behavior and morphology of double crystalline poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) copolymers

Double crystalline poly(trimethylene terephthalate)/poly(ethylene oxide terephthalate) copolymers (PTT/PEOT), with PTT content ranging from 16.5 to 65.5 wt%, were synthesized by melt copolycondensation. The morphological transformation of samples from microphase separation to macrophase separation was investigated by gel permeation chromatography and transmission electron microscopy. Differential scanning calorimetry and in situ wide‐angle X‐ray diffraction suggested that all copolycondensation samples displayed double crystalline behavior. The melt‐crystallization peak temperatures (T_{m, c} values) of PTT chains monotonously increased with increasing PTT content and were higher than that of homo‐PTT when the content of PTT was above 30.6 wt%. Interestingly, T_{m, c} values of PEOT chains were also increased with increasing PTT content. Polarized optical microscopy revealed that all copolycondensation samples studied could form ring‐banded spherulites and band spacing increased with increasing T_c values. In addition, band spacing decreased with increasing PTT content at a given T_c. Strangely, although PEOT was the main component in all copolycondensation samples, spherulitic morphology formed by the advance crystallization of PTT did not change after PEOT crystallization. Only a subtle change of quadrant tones was detected. © 2012 Society of Chemical Industry     

Blends of poly(ethylene terephthalate) and poly(butylene terephthalate)

Commercial grade poly(ethylene terephthalate), (PET, intrinsic viscosity = 0.80 dL/g) and poly(butylene terephthalate), (PBT, intrinsic viscosity = 1.00 dL/g) were melt blended over the entire composition range using a counterrotating twin‐screw extruder. The mechanical, thermal, electrical, and rheological properties of the blends were studied. All of the blends showed higher impact properties than that of PET or PBT. The 50:50 blend composition exhibited the highest impact value. Other mechanical properties also showed similar trends for blends of this composition. The addition of PBT increased the processability of PET. Differential scanning calorimetry data showed the presence of both phases. For all blends, only a single glass‐transition temperature was observed. The melting characteristics of one phase were influenced by the presence of the other. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 75–82, 2005     

Synthesis and properties of poly(ethylene terephthalate)/clay nanocomposites by in situ polymerization

Poly(ethylene terephthalate) (PET)/clay nanocomposites (PCNs) with N‐methyl diethanol amine (MDEA)‐based organoclays are synthesized by using in situ polymerization. Four kinds of MDEA‐based materials are prepared and used as organifiers of pristine montmorillonite. The clay treated with the organifiers has a d‐spacing range that is about 14–21 Å. The PCNs with these organoclays are characterized by using wide‐angle X‐ray diffraction, scanning and transmission electron microscopy, atomic force microscopy, capillary rheometry, and tensile and barrier testing. The PCNs form an intercalated and delaminated structure. The well‐stacked nanoclays are broken down into small pieces in the PET matrix and the thickness of the clay bundle decreases to 20 nm. The melt viscosity and tensile strength of these PCNs increases with only 0.5 wt % clay. In oxygen barrier testing, the PCN with 1 wt % well‐dispersed organoclay shows a twofold higher barrier property than pure PET. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1262–1271, 2007     

Spinning and properties of poly(ethylene terephthalate)/organomontmorillonite nanocomposite fibers

By in situ polycondensation, a intercalated poly(ethylene terephthalate)/organomontmorillonite nanocomposite was prepared after montmorillonite (MMT) had been treated with a water‐soluble polymer. This nanocomposite was produced to fibers through melt spinning. The resulting nanocomposite fibers were characterized by X‐ray diffraction (XRD), differential scanning calorimeter (DSC), and transmission electron microscopy (TEM). The interlayer distance of MMT dispersed in the nanocomposite fibers was further enlarged because of strong shear stress during processing of melt spinning. This was confirmed by XRD test and TEM images. DSC test results showed that incorporation of MMT accelerated the crystallization of poly(ethylene terephthalate) (PET), but the crystallinity of the drawn fibers just had a little increasing compared with that of neat PET drawn fibers. Also compared with pure PET drawn fibers, tensile strength at 5% elongation and thermal stability of the nanocomposite fibers were improved. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1443–1447, 2005     

Morphology and properties of polymer/organoclay nanocomposites based on poly(ethylene terephthalate) and sulfopolyester blends

Poly(ethylene terephthalate) (PET) nanocomposite films containing two different organoclays, Cloisite 30B^® (C30B) and Nanomer I.28E^® (N28E), were prepared by melt blending. In order to increase the gallery spacing of the clay particles, a sulfopolyester (PET ionomer or PETi) was added to the nanocomposites via a master‐batch approach. The morphological, thermal and gas barrier characteristics of the nanocomposite films were studied using several characterization techniques such as scanning electron microscopy, transmission electron microscopy, X‐ray diffraction, differential scanning calorimetry, dynamic mechanical analysis, rheometry and oxygen permeability. PET and PETi were found to form immiscible polymer blends and the nanoparticles were preferentially located in the PETi dispersed phase. A better dispersion of clay was obtained for nanocomposites containing N28E with PETi. On the contrary, for nanocomposites containing C30B and PETi, the number of tactoids increased and the clay distribution and dispersion became worse than for C30B alone. Overall, the best properties were obtained for the PET/C30B nanocomposite without PETi. Higher crystallinity was found for all nanocomposite films in comparison to that of neat PET. © 2012 Society of Chemical Industry     

Crystallization and unusual rheological behavior in poly(ethylene oxide)-clay nanocomposites

We report a systematic study of the crystallization and rheological behavior of poly(ethylene oxide) (PEO)-clay nanocomposites. To that end a series of nanocomposites based on PEOs of different molecular weight (10³ < MW < 10⁵ g/mol) and clay surface modifier was synthesized and characterized. Incorporation of organoclays with polar (MMT-OH) or aromatic groups (MMT-Ar) suppresses the crystallization of polymer chains in low MW PEO, but does not significantly affect the crystallization of high MW matrices. In addition, the relative complex viscosity of the nanocomposites based on low MW PEO increases significantly, but the effect is less pronounced at higher MWs. The viscosity increases in the series MMT-Alk < MMT-OH < MMT-Ar. In contrast to the neat PEO which exhibits a monotonic decrease of viscosity with temperature, all nanocomposites show an increase after a certain temperature. This is the first report of such dramatic enhancements in the viscoelasticity of nanocomposites, which are reversible, are based on a simple polymer matrix and are true in a wide temperature range.     

Crystalline and thermal behavior of poly(ethylene terephthalate)/polyphenoxy blends

Poly(ethylene terephthalate) (PET)/polyphenoxy blends were prepared by melt blending. Crystalline and thermal behaviors of PET/polyphenoxy blends were verified by use of DSC. The experiment results show that the initial temperature, peak temperature, and ending temperature of cold crystallization increase with increasing phenoxy content. On the contrary, the onset melting temperature, finishing melting temperature, and peak temperature in the first heating and the secondary heating processes decrease with increasing phenoxy content. The crystallization enthalpy and melting enthalpy, as well as the crystallization rate, decrease with increasing phenoxy content. Avrami exponents of the blends are slightly higher than that of pure PET and almost independent of phenoxy content. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 878–885, 2005     

Synthesis and characterization of poly(ethylene terephthalate)/attapulgite nanocomposites

A kind of clay with fibrous morphology, attapulgite (AT), was used to prepare poly (ethylene terephthalate) (PET)/AT nanocomposites via in situ polymerization. Attapulgite was modified with Hexadecyltriphenylphosphonium bromide and silane coupling agent (3‐glycidoxypropltrimethoxysilane) to increase the dispersion of clay particles in polymer matrix and the interaction between clay particles and polymer matrix. FTIR and TGA test of the organic‐AT particles investigated the thermal stability and the loading quantity of organic reagents. XRD patterns and SEM micrographs showed that the organic modification was processed on the surface of rod‐like crystals and did not shift the crystal structure of silicate. For PET/AT nanocomposites, it was revealed in TEM that the fibrous clay can be well dispersed in polymer matrix with the rod‐like crystals in the range of nanometer scale. The diameter of rod‐like crystal is about 20 nm and the length is near to 500 nm. The addition of the clay particles can enhance the thermal stability and crystallization rate of PET. With the addition of AT in PET matrix, the flexural modulus of those composites was also increased markedly. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1279–1286, 2007     

Effect of shearing on crystallization behavior of poly(ethylene terephthalate)

The shear‐induced crystallization behavior of PET was investigated by measuring the time‐dependent storage modulus (G′) and dynamic viscosity (η′) with a parallel‐plate rheometer at different temperatures and shear rate. The morphology of shear‐induced crystallized PET was measured by DSC, X‐ray, and polarizing optical microscopy. When a constant shear rate was added to the molten polymer, the shear stress increased with the time as a result of the orientation of molecular chains. The induction time of crystallization is decreased with frequency. Moreover, the rate of isothermal crystallization of PET was notably decreased with increasing temperature. The shape of spherulites is changed to ellipsoid in the direction of shear. In addition, aggregation of spherulites is increased with increasing frequency. Particularly, the row nucleation morphology could be observed under polarized light for ω = 1. From the results of DSC, the melting point and enthalpy have a tendency to decrease slightly with increasing frequency. The crystallite size and perfectness decreased with frequency, which was confirmed with X‐ray data. The unit length of the crystallographic unit cell of the PET increased and the (1 0 3) plane peak increased with increasing frequency. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2640–2646, 2001     

Crystallization of poly(ethylene terephthalate) modified with codiols

The nucleation of poly(ethylene terephthalate) (PET) by codiols and olefinic segments was studied. The codiols 1,5‐pentanediol, 1,8‐octanediol, 2,5‐hexanediol, and 1,3‐dihydroxymethyl benzene were copolymerized into PET in a concentration range of 0–10 mol %. The melting (T_m), crystallization (T_c), and glass‐transition (T_g) temperatures were studied. These codiols were found to be able to nucleate PET at low concentrations, probably by lowering the surface free energy of the chain fold. However, the codiols also disturbed the structural order of the polymer, resulting in a decrease in both the T_m and T_c values. The optimum codiol concentration was found to be at around 1 mol %, which is lower than previously reported. A diamide segment N,N′‐bis(p‐carbo‐methoxybenzoyl)ethanediamine (T2T) was found to be a more effective nucleator than the codiols; however, no synergy was observed between the nucleating effect of the diamide segment T2T and that of the codiol. An olefinic diol (C₃₆‐diol) with a molecular weight of 540 g/mol was also copolymerized into PET in a concentration range of 0–21 wt %. Only one T_g was observed in the resulting copolymers, suggesting that the amorphous phases of PET and the C₃₆‐diol are miscible. The main effect of incorporating the C₃₆‐diol into PET was the lowering of the T_g; thus, the C₃₆‐diol is an internal plastifier for PET. The C₃₆‐diol had little effect on the T_m value; however, the T_c value actually increased in the 11.5 wt % copolymer. As the T_g decreased and the T_c increased, the crystallization window also increased and thereby the likelihood of crystallization. Therefore, the thermally stable C₃₆‐diol appears to be an interesting compound that may be useful in improving the crystallization of PET. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2676–2682, 2001     

The complicated influence of branching on crystallization behavior of poly(ethylene terephthalate)

The randomly branched poly(ethylene terephthalate) (BPET) was prepared by bulk polycondensation from dimethyl terephthalate (DMT) and ethylene glycol (EG), with 0.4–5.0 mol % (with respect to DMT) of glycerol (GL) as a branching agent. The glass transition and crystallization behavior was studied by differential scanning calorimetry (DSC). It was found that the glass transition temperature of BPET reduced with the increasing content of GL until 1.2 mol %, and then increases a little at high degrees of branching. When compared with a linear PET, the crystallization temperature of BPET from the melt shifted to higher temperature as GL content was smaller than 1.2 mol %, and then became lower while GL load was added. Nonisothermal crystallization kinetics was studied through the modified Avrami analysis. It was revealed that the overall crystallization rate parameter of BPET became larger when the GL content was less than 1.2 mol %, then turned to lower at higher branching degree. This indicated that low degree of branching could enhance the overall crystallization of poly(ethylene terephthalate) (PET), whereas high degree of branching in the range of 3.5–5.0 mol % would block the development of crystallization. On the basis of Hoffman's secondary crystallization theory, the product σσ_e of the free energy of formation per unit area of the lateral and folding surface was calculated. According to the change of the product σσ_e with the degree of branching, a possible explanation was presented to illuminate this diverse effect of different degrees of branching on crystallization. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of poly(ethylene tetrasulfide)/graphene oxide nanocomposites by in situ polymerization method

Poly(ethylene tetrasulfide) (PSP) is synthesized via interfacial polycondensation of 1,2 dichloroethane and sodium tetrasulfide, in the presence of graphene oxide (GO). This process resulted in homogeneously dispersed PSP/GO nanocomposites. Nanocomposites of 0.3 and 0.5?wt% of GO are synthesized and their morphology, chemical characteristics behavior are studied employing field emission scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray diffraction techniques. Thermal characterization of composites is performed by differential scanning calorimetry and thermogravimetry analysis. Results indicate that the addition of only small amounts (0.5?wt%) of well-dispersed GO can increase the melting point more than 16°C resulting in better thermal properties for the composite. The solubility of nanocomposite is also studied and results show that the solubility depends on solvent concentration in addition to reinforcement (GO) deals.     

Thermal and mechanical properties of poly(ethylene terephthalate)/lamellar zirconium phosphate nanocomposites

The preparation of nanocomposites of poly (ethylene terephthalate) (PET) and lamellar zirconium phosphorous compounds by melt extrusion was investigated. Two types of zirconium phosphorous compounds were synthesized by the direct precipitation reaction method: α‐zirconium bis(monohydrogen orthophosphate) monohydrate (ZrP) and organic–inorganic hybrid layered zirconium phenylphosphonate (ZrPP). Composites containing 2 and 5 wt % ZrP and ZrPP were prepared in a twin‐screw extruder and specimens were obtained by injection molding. The extent of dispersion of the layered filler in the composite matrix was investigated by X‐ray diffraction and transmission electron microscopy (TEM). The crystallization and thermal properties were analyzed by differential scanning calorimetry and thermogravimetry, and the mechanical properties were evaluated by tensile tests. Whereas ZrP‐containing composites showe characteristic diffraction peaks at 2θ 11.7° (d = 7.54 Å), indicative of no delamination, ZrPP showed practically no low‐angle diffraction peak at 2θ 5.5° (d = 15.24 Å), indicating loss of the layered order. TEM images of ZrPP particles indicated the formation of an intercalated/partially delaminated nanocomposite. The behavior was attributed to the higher affinity of the polyester with phenyl groups on the platelet surface of ZrPP. In both cases, the addition of the fillers increased the crystallization rate and the modulus. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3868–3876, 2006     

Crystallization of poly(ethylene oxide) embedded with surface‐modified SiO2 nanoparticles

The crystallization of poly(ethylene oxide) (PEO) in the presence of silica nanoparticles (SiO₂ NPs) was investigated in terms of heterogeneous nucleation of SiO₂ NPs using polarizing optical microscopy and differential scanning calorimetry. The content and surface functionality of SiO₂ NPs were considered as the main factors affecting crystallization, and the effect of annealing time and temperature was also examined. The SiO₂ NPs acted as heterogeneous nucleates during the crystallization process, thereby enhancing the nucleation density and limiting the spherulitic growth rate. A kinetics study of non‐isothermal crystallization showed that the crystallization rate of 5 wt% SiO₂/PEO nanocomposite was ca 2.1 times higher than that of neat PEO. In addition, among various surface‐functionalized SiO₂ nanoparticles, alkyl‐chain‐functionalized SiO₂ NPs were favorable for achieving a higher crystallization rate due to the enhanced compatibility between the SiO₂ NPs and PEO chains. © 2012 Society of Chemical Industry     

Study of the miscibility and crystallization behavior of poly(ethylene oxide)/poly(vinyl alcohol) blends

The miscibility and crystallization behavior of poly(ethylene oxide)/poly(vinyl alcohol) (PEO/PVA) blends were investigated by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and polarizing optical microscopy. Because the glass‐transition temperature of PVA was near the melting point of PEO crystalline, an uncommon DSC procedure was used to determine the glass‐transition temperature of the PVA‐rich phase. From the DSC and DMA results, two glass‐transition temperatures, which corresponded to the PEO‐rich phase and the PVA‐rich phase, were observed. It was an important criterion to indicate that a blend was immiscible. It was also found that the preparation method of samples influenced the morphology and crystallization behaviors of PEO/PVA blends. The domain size of the disperse phase (PVA‐rich) for the solution‐cast blends was much larger than that for the coprecipitated blends. The crystallinity, spherulitic morphology, and isothermal crystallization behavior of PEO in the solution‐cast blends were similar to those of the neat PEO. On the contrary, these properties in the coprecipitated blends were different from those of the neat PEO. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1562–1568, 2004