Phase behavior of blends containing amorphous poly(resorcinol phthalate‐block‐carbonate) and semicrystalline polyesters

The phase behavior of poly(resorcinol phthalate‐block‐carbonate) (RPC) with engineering polyesters was investigated by using differential scanning calorimeter (DSC) and dynamic mechanical analysis. RPC was found to form miscible blends with poly(ethylene terephthalate) (PET), poly(butylene terephthalate) (PBT), and poly(cyclohexylmethylene terephthalate) (PCT), but was partially miscible with poly(1,4‐cyclohexanedimethylene‐1,4‐cyclohexanedicarboxylate) (PCCD) in the melt state and below the melting temperature (T_m). The degree of melting‐point depression indicates that the RPC is most miscible with PCT followed by PET and then PBT. Furthermore, with the help of empirical DSC data and the Nishi–Wang equation, the interaction parameters between RPC and PET, PBT, and PCT were quantified to be ?0.36, ?0.33, and ?0.54, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Preparation and characterization of poly(ethylene terephthalate) powder‐filled high‐density polyethylene in the presence of silane coupling agents

Micron‐size crystalline particles of Poly(ethylene terephthalate) (PET), obtained from PET bottles by crystallization and grinding, were used as a filler in high‐density polyethylene (HDPE). The composite of PET particle‐filled HDPE was prepared by melt mixing at 190°C, which was well below the melting temperature of PET. Silane coupling agents (SCAs) were used to enhance the interaction between PET and HDPE in the composite. A chain extender (CE) and maleic anhydride (MA) were also used to provide further interaction with SCAs between these two materials. The ultimate tensile strength, especially at highest content 40% PET‐filled HDPE, and the impact strength of SCAs‐treated PET‐filled HDPE was found to be highly improved compared to untreated PET filling into HDPE. Dynamic mechanical analyses (DMA) demonstrated that T_g of the main matrix polyethylene was depressed from 3 to 10°C. Scanning electron microscopy (SEM) studies indicated a strong interaction between PET powder and HDPE when SCAs were present in the system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 827–835, 2001     

Preparation of amorphous poly(ethylene terephthalate) from U‐polymer via a copolymerization process

U‐Polymer, a kind of polyarylate, was synthesized by interfacial polycondensation method with terephthaloyl chloride (TPC), isophthaloyl chloride (IPC), and bisphenol A (BPA) as raw materials. The structure of the U‐Polymer was characterized by IR and ¹H–NMR spectra. Then, an amorphous poly(ethylene terephthalate) (APET) was prepared with the introduction of the U‐Polymer to the PET sequence to improve thermal and mechanical behaviors of PET via the polymerization process. The structure and property of the APET were characterized by DSC and DMA. The results showed that the APET exhibits amorphism, transparency, higher glass‐transition temperature (T_g), and higher storage modulus than that of PET. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1653–1657, 2001     

Glass‐transition and melting behavior of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) blends

The glass‐transition temperatures and melting behaviors of poly(ethylene terephthalate)/poly(ethylene 2,6‐naphthalate) (PET/PEN) blends were studied. Two blend systems were used for this work, with PET and PEN of different grades. It was found that T_g increases almost linearly with blend composition. Both the Gibbs–DiMarzio equation and the Fox equation fit experimental data very well, indicating copolymer‐like behavior of the blend systems. Multiple melting peaks were observed for all blend samples as well as for PET and PEN. The equilibrium melting point was obtained using the Hoffman–Weeks method. The melting points of PET and PEN were depressed as a result of the formation of miscible blends and copolymers. The Flory–Huggins theory was used to study the melting‐point depression for the blend system, and the Nishi–Wang equation was used to calculate the interaction parameter (χ₁₂). The calculated χ₁₂ is a small negative number, indicating the formation of thermodynamically stable, miscible blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 11–22, 2001     

Synthesis of novel azo‐containing polyureas derived from 4‐[4′‐(2‐hydroxy‐1‐naphthylazo)phenyl]‐1,2,4‐triazolidine‐3,5‐dione

4‐[4′‐(2‐Hydroxy‐1‐naphthylazo)phenyl]‐1,2,4‐triazolidine‐3,5‐dione ( HNAPTD ) ( 1 ) has been reacted with excess amount of n‐propylisocyanate in DMF (N,N‐dimethylformamide) solution at room temperature. The reaction proceeded with high yield, and involved reaction of both N? H of the urazole group. The resulting bis‐urea derivative 2 was characterized by IR, ¹H‐NMR, elemental analysis, UV‐Vis spectra, and it was finally used as a model compound for the polymerization reaction. Solution polycondensation reactions of monomer 1 with Hexamethylene diisocyanate ( HMDI ) and isophorone diisocyanate ( IPDI ) were performed in DMF in the presence of pyridine as a catalyst and lead to the formation of novel aliphatic azo‐containing polyurea dyes, which are soluble in polar solvents. The polymerization reaction with tolylene‐2,4‐diisocyanate ( TDI ) gave novel aromatic polyurea dye, which is insoluble in most organic solvents. These novel polyureas have inherent viscosities in a range of 0.15–0.22 g dL^?1 in DMF at 25°C. Some structural characterization and physical properties of these novel polymers are reported. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 3177–3183, 2001     

How Hydrogen Bond Interactions Affect the Flame Retardancy and Anti‐Dripping Performances of PET

To systematically study how the H‐bonding interaction affect the flame retardancy and anti‐dripping behavior of poly(ethylene terephthalate) (PET), two series of PET‐based copolyesters are prepared by introducing two benzimidazole monomers with similar structure. One (2‐(4‐methoxycarbonyl‐phenyl)‐1H‐benzimidazole‐5‐carboxylic acid methyl ester, PBM) contains H‐bonding donor, the other (2‐(4‐methoxycarbonyl‐phenyl)‐1‐methylbenzimidazole‐5‐carboxylic acid methyl ester, PNM) weeds out the H‐bonding donor by replacing ? NH group with ? N? CH₃. The dynamic rheological behavior, fire resistance and fire‐retardant mechanism of the PET‐co‐PBMs and PET‐co‐PNMs are contrastively investigated. PET‐co‐PNMs have flow behaviors similar to neat PET. While, for PET‐co‐PBMs, the movements of the molecular chains are restricted due to the H‐bonding interaction, leading to higher melt viscosity, which is conducive to the anti‐dripping property. It can be proved that benzimidazole groups promote the carbonization of substrates to form more stable charred layers in combustion, showing an obvious barrier action in condensed phase. Unfortunately, the enhancement of carbonization alone is not enough to inhibit the dripping behavior satisfactorily, and PET‐co‐PNMs fail to pass UL‐94 V‐0 rating. While, PET‐co‐PBMs exhibit better self‐extinguishing and anti‐dripping performances benefiting from strong H‐bonding interactions. The revealed effects of H‐bonding interactions on the fire resistance and anti‐dripping behavior of polymers will guide further design of flame retardants.     

Surface grafting polymerization of N‐vinyl‐2‐pyrrolidone onto a poly(ethylene terephthalate) nonwoven by plasma pretreatment and its antibacterial activities

The objective of this research was the surface grafting polymerization of biocompatible monomer N‐vinyl‐2‐pyrrolidone (NVP) onto a plasma‐treated nonwoven poly(ethylene terephthalate) (PET) substrate with ultraviolet (UV)‐induced methods. The effects of various parameters, such as the monomer concentration, reaction time, initiator (ammonium peroxodisulfate) concentration, and crosslinking agent (N,N′‐methylene bisacrylamide) concentration, on the grafting percentage were studied. The grafting efficiency of the modified nonwoven PET surfaces reached a maximum at 50 min of UV irradiation and with a 30 wt % aqueous NVP solution. After the plasma activation and/or grafting, the hydrophobic surface of the nonwoven was modified into a hydrophilic surface. NVP was successfully grafted onto nonwoven PET surfaces. The surface wettability showed that the water absorption of NVP‐grafted nonwoven PET (NVP‐g‐nonwoven PET) increased with increasing grafting time. NVP‐g‐nonwoven PET was verified by Fourier transform infrared spectra and scanning electron microscopy measurements. An antibacterial assessment using an anti‐Staphylococcus aureus test indicated that S. aureus was restrained from growing in NVP‐g‐nonwoven PET. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 803–809, 2006     

Kinetics of alkaline hydrolysis and morphologies of novel poly(ethylene terephthalate) micro‐porous hollow fibers and functional characteristics of fabrics

This investigation explores the kinetics of the alkaline hydrolysis of regular poly(ethylene terephthalate) (PET) solid fibers and PET micro‐porous hollow fibers, using statistical regression analysis. Statistical regression analysis results concerning the kinetics of the alkaline hydrolysis of regular PET solid fibers and PET micro‐porous hollow fibers yielded a β value of 1. The R² of the kinetic equation for α values from 1.07 to 1.16 exceeded that for α = 1. The rate constants of alkaline hydrolysis followed the order PET micro‐porous hollow fibers ? regular PET solid fibers. A morphology of large pores of diameter 0.1–3.5 μm was observed following alkali treatment of the PET micro‐porous hollow fibers. The weight loss percentage of the hollow fibers was around 20%. The hollowness of the PET micro‐porous hollow fibers after alkali treatment was between 30 and 32%. The PET micro‐porous hollow fibers exhibited simultaneous water‐absorption/release and keep‐warm functions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Deep‐black‐coloring effect of fabrics made of noncircular cross‐section polyester filaments

The effects of noncircular cross‐section (NCCS) poly ethylene terephthalate (PET) filaments and its shape factor on deep‐black‐coloring of dyed fabrics were investigated by comparing to that of the circular cross‐section PET ones. Indexes such as K/S, L* and Integ values were used for characterizing the deep‐black‐coloring effect on fabrics. The results indicated that fabrics made with NCCS PET filaments exhibited good deep‐black‐coloring effects. The calculated shape factor of the NCCS PET fiber had a significant correlation with the degree of deep‐black‐coloring exhibited by the fabric made from the fibers. A qualitative optical analysis of the NCCS PET fibers was carried out to explain the causes of the deep‐coloring of the NCCS fibers. This analysis implies that the contours of the NCCS fiber composed of surfaces with varied curvature increase the scattering of light by lowering specular reflection and increasing interior reflected and refracted light. This, in turn, strengthens the deep‐coloring effect. © 2013 Wiley Periodicals, Inc. Col Res Appl, 39, 511–518, 2014     

Melt rheology of poly(ϵ‐caprolactone)/poly(styrene‐co‐acrylonitrile) blends

Dynamic viscoelastic properties for miscible blends of poly(?‐caprolactone) (PCL) and poly(styrene‐co‐acrylonitrile) (SAN) were measured. It was found that the time–temperature superposition principle is applicable over the entire temperature range studied for the blends. The temperature dependency of the shift factors a_T can be expressed by the Williams–Landel–Ferry equation: log a_T = ?8.86(T ? T_s)/(101.6 + T ? T_s). The compositional dependency of T_s represents the Gordon–Taylor equation. The zero‐shear viscosities are found to increase concavely upward with an increase in weight fraction of SAN at constant temperature, but concavely downward at constant free volume fraction. It is concluded that the relaxation behavior of the PCL/SAN blends is similar to that of a blend consisting of homologous polymers. It is emphasized that the viscoelastic functions of the miscible blends should be compared in the iso‐free volume state. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2037–2041, 2001     

Strain‐induced crystallization in uniaxially drawn PETG plates

The copolyester poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate) (PETG) is used industrially as an uncrystallizable polymer, whereas PET is an inherently crystallizable polymer. Nevertheless, a crystalline phase could appear in the material. To create a strain‐induced crystalline phase in an initially amorphous PETG material, plates were placed in the heating chamber of a tensile machine at 100°C and uniaxially drawn to obtain different samples with various draw ratios. During DSC analysis of highly drawn samples, perturbations of the baseline appear above the glass‐transition temperature, consisting of weak exothermic and endothermic phenomena. Comparison of DSC and X‐ray diffraction analysis of drawn PETG and PET shows that a strain‐induced crystalline phase appears in this copolyester. A spherulitic superstructure could also appear after lengthy annealing. Analysis of this semicrystalline material allowed estimation of the degree of crystallinity, about 3% after a drawing at high draw ratio and about 11% for undrawn annealed material. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 3405–3412, 2001     

Structural investigations of poly(ethylene terephthalate)‐graft‐polystyrene copolymer films

Structural investigations of poly(ethylene terephthalate)‐graft‐polystyrene (PET‐g‐PS) films prepared by radiation‐induced grafting of styrene onto commercial poly(ethylene terephthalate) (PET) films were carried out by FTIR, X‐ray diffraction (XRD), and differential scanning calorimetry (DSC). The variation in the degree of crystallinity and the thermal characteristics of PET films was correlated with the amount of polystyrene grafted therein (i.e., the degree of grafting). The heat of melting was found to be a function of PET crystalline fraction in the grafted films. The grafting is found to take place by incorporation of amorphous polystyrene grafts in the entire noncrystalline (amorphous) region of the PET films and at the surface of the crystallites. This results in a decrease in the degree of crystallinity with the increase in the degree of grafting, attributed to the dilution of PET crystalline structure with the amorphous polystyrene, without almost any disruption in the inherent crystallinity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1949–1955, 2002; DOI 10.1002/app.10515     

A study on novel waterproof and moisture‐permeable poly(vinylidene fluoride) micropore membrane‐coated fabrics

The feasibility of PVDF (polyvinylidene fluoride), as a novel waterproof and moisture‐permeable material, to substitute PTFE (polytetrafluoroethylene) for manufacturing civil high‐performance textiles was discussed. The work was focused on the design of casting solution composition (including solvent, additives, and polymer), possible methods to produce durably binded coated micropore membrane fabrics as well as their influences on membrane properties. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 801–807, 2001     

Durable flame‐retardant treatment of polyethylene terephthalate (PET) and PET/cotton blend using dichlorotribromophenyl phosphate as new flame retardant for polyester

Dichlorotribromophenyl phosphate (DCTBPP) was synthesized via the reaction of tribromophenol and phosphorous oxychloride and characterized by elemental analysis, IR, ¹H‐NMR, thermogravimetric analysis, and differential scanning calorimetry. To impart durable flame retardancy the poly(ethylene terephthalate) (PET) fabric was treated with DCTBPP via pad–dry–thermosol fixation and the PET/cotton (50/50) blend fabric was treated with both DCTBPP and tetrakis(hydroxymethyl) phosphonium chloride (THPC)/urea precondensate via a two‐bath sequential treatment. The treated PET fabric's increased limiting oxygen index value was proportional to the increasing DCTBPP application level and showed self‐extinguishing properties at 8.1% add‐on, even after 50 washes. The blend fabric treated with 15% DCTBPP and 30% THPC/urea precondensate became self‐extinguishable and durable to 50 washes, and the treated fabric retained over 85% of its breaking strength without excessive stiffness. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 793–799, 2001     

Polymerization of methyl methacrylate with a thermal iniferter: Diethyl 2,3‐dicyano‐2,3‐di(p‐tolyl)succinate

A hexa‐substituted ethane type compound, diethyl‐2,3‐dicyano‐2,3‐di(p‐tolyl)succinate (DCDTS), was successfully synthesized and used for initiation of methyl methacrylate (MMA) polymerization. The reaction demonstrated the characteristics of a “living” polymerization; i.e., both the yield and the molecular weight of the resulting polymers increased linearly with increasing reaction time, the molecular‐weight distribution of PMMA obtained was ～1.60 and almost unaffected by the conversion, and the resultant polymer can be chain extended by adding fresh MMA. End group analysis of the resultant PMMA confirmed that DCDTS behaves as a thermal iniferter for MMA polymerization. A block copolymer was prepared from the resultant PMMA, which contains a hexa‐substituted C? C bond functional end group. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2566–2572, 2001     

Surface graft copolymerization of 2‐hydroxyethyl methacrylate onto low‐density polyethylene film through corona discharge in air

The corona discharge technique was explored as a means of forming chemically active sites on a low‐density polyethylene (LDPE) film surface. The active species thus prepared at atmospheric pressure in air was exploited to subsequently induce copolymerization of 2‐hydroxyethyl methacrylate (HEMA) onto LDPE film in aqueous solution. The results showed that with the corona discharge voltage, reaction temperature, and inhibitor concentration in the reaction solution the grafting degree increased to a maximum and then decreased. As the corona discharge time, reaction time, and HEMA concentration in the reaction solution increased, the grafting degree increased. With reaction conditions of a 5 vol % HEMA concentration, 50°C copolymerization temperature, and a 2.0‐h reaction time, the degree of grafting of the LDPE film reached a high value of 158.0 μg/cm² after treatment for 72 s with a 15‐kV voltage at 50 Hz. Some characteristic peaks of the grafted LDPE came into view at 1719 cm^?1 on attenuated total reflectance IR spectra (C?O in ester groups) and at 531 eV on electron spectroscopy for chemical analysis (ESCA) spectra (O_1s). The C_1s core level ESCA spectrum of HEMA‐grafted LDPE showed two strong peaks at ～286.6 eV (? C ? O? from hydroxyl groups and ester groups) and ～289.1 eV (O?C ? O? from ester groups), and the C atom ratio in the ? C? O? groups and O?C? O groups was 2:1. The hydrophilicity of the grafted LDPE film was remarkably improved compared to that of the ungrafted LDPE film. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2881–2887, 2001     

Solid‐state polymerization of poly(trimethylene terephthalate)

The solid‐state polymerization (SSP) of poly(trimethylene terephthalate) (PTT) has been studied and compared with that of poly(ethylene terephthalate) (PET). Because PTT and PET share the same SSP mechanism, the modified second‐order kinetic model, which has successfully been used to describe the SSP behaviors of PET, also fits the SSP data of PTT prepolymers with intrinsic viscosities (IVs) ranging from 0.445 to 0.660 dL/g. According to this model, the overall SSP rate is ?dC/dt = 2k_a(C ? C_ai)², where C is the total end group concentration, t is the SSP time, k_a is the apparent reaction rate constant, and C_ai is the apparent inactive end group concentration. With this equation, the effects of all factors that influence the SSP rate are implicitly and conveniently incorporated into two parameters, k_a and C_ai. k_a increases, whereas C_ai decreases, with increasing SSP temperature, increasing prepolymer IV, and decreasing pellet size, just as for the SSP of PET. Therefore, the SSP rate increases with increasing prepolymer IV and increasing SSP temperature. The apparent activation energy is about 26 kcal/mol, and the average SSP rate about doubles with each 10°C increase in temperature within the temperature range of 200–225°C. The SSP rate increases by about 30% when the pellet size is decreased from 0.025 to 0.015 g/pellet. Compared with PET, PTT has a much lower sticking tendency and a much higher SSP rate (more than twice as high). Therefore, the SSP process for PTT can be made much simpler and more efficient than that for PET. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3188–3200, 2003     

Structure–property relation in varieties of silk fibers

Crystallite shape ellipsoid in different varieties of silk fibers namely (i) Chinese (ii) Indian, and (iii) Japanese, has been computed using wide‐angle X‐ray data and Hosemann's one‐dimensional paracrystalline model. The estimated microcrystalline parameters are correlated with the observed physical property of the silk fibers. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1979–1985, 2001     

Morphology and Tensile Strength Prediction of in situ Microfibrillar Poly(ethylene terephthalate)/Polyethylene Blends Fabricated via Slit‐Die Extrusion‐Hot Stretching‐Quenching

Summary: In situ microfibrillar poly(ethylene terephthalate) (PET)/polyethylene blends (MRB) were successfully fabricated by slit‐die extrusion‐hot stretching‐quenching. The morphology of this new material is mainly influenced by the composition and the hot stretching. Appropriate PET concentrations and a comparatively high hot stretching ratio could facilitate the fibrillation of PET domains during processing. The expression employed for prediction of the tensile strength for the microfibrillar blend was proved to be desirable. The prediction was, generally, in agreement with the experimental results, although the values of some parameters were approximated.

SEM micrograph of the cryofractured surface of the in situ microfibrillar PET/PE blend after injection molding.