Synthesis and properties of star-like wholly aromatic polyester fibers

Novel star-like wholly aromatic copolyesters having four arms based on a tetraamine star core, p- and m- hydroxybenzoic acids and 6-hydroxy-2-naphthoic acid have been successfully synthesized and spun into fibers for the investigation of the effect of the star-like structure on improving compressive properties of the fiber. The reactivity of the star core was demonstrated using a model compound with FTIR, ¹H and ¹³C NMR spectroscopy. The ¹³C NMR spectrum of the star-like terpolymer having a molar ratio of 10:1 of the monomers to star core showed a characteristic peak at around δ62 ppm which corresponds to a tetra-substituted carbon and thereby demonstrates that the star core was really incorporated into the polymer. The star-like copolyester exhibited a clear stir opalescence and liquid crystalline morphology in the temperature range of 150-280 °C. However, no transition was observed in the DSC thermogram except a clear T_g at 110 °C. The star-like terpolymer fiber, prepared from a polymer with a molar ratio of 500:1 for the monomers to imide core, was spun in the liquid crystalline state at 180 °C. Fiber structure and properties have been studied.     

Synthesis and characterization of aromatic copolyesters containing siloxane linkages in the polymer backbone

A new series of aromatic copolyesters containing siloxane linkages were prepared by the melt polymerization of bisphenol A (BPA) with eugenol end‐capped siloxane (EuSi), diphenyl terephthalate (DPT), and diphenyl isophthalate (DPI) in varying ratio in the temperature range 220–290°C under reduced pressure in the presence of dibutyl tin dilaurate (DBTL) catalyst. The siloxane copolyesters prepared were characterized by FTIR, ¹H‐NMR spectroscopy, solution viscosity, thermogravimetric analysis, differential scanning calorimetry, and X‐ray diffraction. The effect of incorporation of eugenol end‐capped siloxane was studied on the properties of BPA/DPI/DPT copolyesters. The glass‐transition temperature of copolyester was decreased from 184 to 70°C by incorporation of 20% of eugenol end‐capped siloxane. All copolyesters were found to be soluble in commonly used aprotic polar solvents and had film‐forming properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3222–3228, 2006     

Improving oxygen barrier properties of poly(ethylene terephthalate) by incorporating isophthalate. I. Effect of orientation

The present study examined poly(ethylene terephthalate) (PET) and a series of statistical and blocky copolymers in which up to 30% of the terephthalate was replaced with isophthalate by copolymerization and melt blending, respectively. Some level of transesterification during processing of melt blends resulted in blocky copolymers, as confirmed by NMR. Random and blocky copolymers exhibited similar properties in the glassy state, including a single glass transition, due to miscibility of the blocks. However, random copolymerization effectively retarded cold‐crystallization from the glass whereas blocky copolymers readily cold‐crystallized to a crystallinity level close to that of PET. The polymers were oriented at four temperatures in the vicinity of the T_g and characterized by oxygen transport, wide‐angle X‐ray diffraction, positron annihilation lifetime spectroscopy, and infrared spectroscopy. Orientation of all the copolymers resulted in property changes consistent with strain‐induced crystallization. However, blocky copolymers oriented more easily than random copolymers of the same composition and after orientation exhibited slightly lower oxygen permeability, higher density, and higher fraction trans conformers. Analysis of oxygen solubility based on free volume concepts led to a two‐phase model from which the amount of crystallinity and the amorphous phase density were extracted. Dedensification of the amorphous phase correlated with the draw temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1615–1628, 2005     

Biobased poly(butylene 2,5-furandicarboxylate) and poly(butylene adipate-co-butylene 2,5-furandicarboxylate)s: From synthesis using highly purified 2,5-furandicarboxylic acid to thermo-mechanical properties

To synthesize high quality (co)polyesters derived from 2,5-furandicarboxylic acid (FA), an acetic acid refluxing/pH-swing method was proposed to purify FA. 2-Carboxyl furfural and other impurities were removed completely from FA with this method. Using highly purified FA, biobased polyester poly(butylene furnadicarboxylate) (PBF) and aliphatic-aromatic copolyesters poly(butylene adipate-co-butylene 2,5-furandicarboxy-late)s (PBAFs) were synthesized via melt (co)polycondensation. The (co)polyesters were characterized with GPC, FTIR, ¹H NMR, DSC and TGA, and their tensile mechanical properties were also assessed. The copolyesters possess random chain structure, monomer feed ratio-controlled copolymer composition and excellent thermal stability (T_d,5% > 340 °C) in full composition range. Both BA-rich and BF-rich PBAFs are crystalline polymers. The crystallizability decreases with composition, up to nearly amorphous at moderate ?_BF (40–60%). PBAFs with ?_BF no more than 50% exhibit obvious high-elastic deformation and rebound resilience, and possess tensile properties (E 18–160 MPa, σ_b 9–17 MPa, ε_b 370–910%) comparable to poly(butylene adipate). PBAFs with higher ?_BF behave like nonrigid plastics with low tensile moduli (42–110 MPa), moderate strength (30–42 MPa) and high elongation at break (310–470%). In comparison, PBF is a strong and tough thermoplastic having balanced mechanical properties, namely, much higher tensile modulus (1.9 GPa) and strength (56 MPa) and high elongation at break (260%). It seems necessary and effective to use highly purified FA for synthesizing high performance FA-derived (co)polyesters.     

Synthesis and thermal characterization of random poly(butylene terephthalate‐co‐2‐methyl‐ethylene terephthalate) copolyesters

Poly(butylene terephthalate‐co‐2‐methyl‐ethylene terephthalate) (PBT/MET) was synthesized by incorporating 1,2‐propandiol(1,2‐PDO) into PBT chains. The molar composition and chemical structure of PBT/MET copolyesters were confirmed by means of FT‐IR and ¹H‐NMR. To investigate the effect of 1,2‐PDO on the thermal properties of PBT/MET copolyesters, the copolymerizations were carried out by varying various contents of MET units, and the prepared materials were evaluated by differential scanning calorimetry and thermogravimetric analysis. Results suggested that with the increase of the content of 1,2‐PDO, the amount of crystallinity and the melting temperature decline, while the glass transition temperature increases and the copolyesters become more transparent and brittle with respect to PBT homopolymer. In addition, the T_g‐composition and T_m‐composition data are well subjected to the Wood equation and Flory's equation, respectively. All these copolyesters are found to consist of the general trend displayed by copolymers reported elsewhere. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Structures and properties of easily dyeable copolyesters and their fibers respectively modified by three kinds of diols

Three kinds of modified poly(ethylene terephthalate) copolyesters were synthesized, using sodium‐5‐sulfo‐bis‐(hydroxyethyl)‐isophthalate as the third monomer, 1,3‐propanediol (PDO), 2‐methyl‐1,3‐propanediol (MPD), and 2,2‐dimethyl‐1,3‐propanediol (neopentyl glycol or NPG) as the fourth monomer, respectively. The copolyester fibers were also prepared by melt spinning and drawing processes. The effect of PDO, MPD, and NPG on the synthesis and spinning process was investigated, and the structures and properties of both copolyesters and the produced fibers were characterized. The results exhibited that the structural difference of PDO, MPD, and NPG played an important role in the synthesis and spinning process, and significantly affected the structures and properties of both copolyesters and the produced fibers, which thereby resulted in the difference in terms of dyeability improvement of copolyester fibers. The dyeing at boiling temperature under normal pressure experiments of copolyester fibers in both disperse dyebath and cationic dyebath revealed that incorporation of the fourth monomer could improve the dyeability of copolyester fiber, and copolyester fiber containing MPD unit had better dyeability due to a looser, more accessible structure when compared with the fiber containing PDO or NPG unit. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Development of Micro-Debond Methods for Thermoplastics Including Applications to Liquid Crystalline Polymers

Micro-bead and related debond techniques were used to study adhesion of liquid crystalline copolyesters (LCPs) and other semi-crystalline thermoplastic polymers to glass fibers. For polymers with poor flow even at high temperatures, symmetric beads on fibers were difficult to prepare so an alternative sample preparation method was developed where glass fibers were inserted into thin sections of molten polymer. Glass fibers of widely-varying diameters were used in order to extend the dynamic range of the debond techniques in terms of debonding area, showing a significant improvement in precision over that demonstrated previously with micro debond techniques. The fibers were freshly prepared in our laboratory and silane coated when necessary, which allowed us to minimize fiber surface heterogeneity effects which are believed to influence strongly debond test results. It was found that chemical bonding of the LCPs was quite favorable as was indicated by fracture surface analysis and by comparison with the shear strength of the neat resins. The apparent poor interphase strength in fiber-reinforced LCP composites is proposed to be due to orientation of the LCP molecules near the fiber interface leading to a cohesively weak layer of LCP near the interface. Reactive silane coupling agents lead to no improvement in interface strength as compared with bare glass because chemical reaction occurs on both surfaces. This results in very strong interfaces leading to polymer cohesive failure near the interface of all thermoplastics studied here     

主链型液晶共聚酯的研究

以2,2-双(4-羟基苯基)丙烷(双酚A)、1,10-癸二醇与含液晶基元的缩聚单体2-甲基-1,4-苯撑双(4-氯甲酰)苯甲酸酯通过溶液缩聚反应合成了一系列含液晶性和非液晶性两种序列结构的共聚酯,采用DSC、偏光显微镜和X-衍射方法研究了共聚物的液晶行为,发现除共聚物10外所有的共聚物均具有较好的结晶性和热致液晶性。随双酚A用量的改变,共聚物的特性粘数和熔点呈规律性变化。     

PCT及其共聚酯的开发概况及应用

简述了PCT及其改性聚酯的工艺原理,综述了有关PCT及其共聚酯的开发现状和研究概况,并指出其应用领域。     

Preparation and thermal behavior of random poly(butylene terephthalate/azelate) copolyesters

Poly(butylene terephthalate), poly(butylene azelate), and poly(butylene terephthalate/butylene azelate) random copolymers of various compositions were synthesized in bulk using the well‐known two‐stage polycondensation procedure, and characterized in terms of chemical structure and molecular weight. The thermal behavior was examined by thermogravimetric analysis and differential scanning calorimetry. As far as the thermal stability is concerned, it was found to be rather similar for all copolymers and homopolymers investigated. All the copolymers were found to be partially crystalline, and the main effect of copolymerization was a lowering in the amount of crystallinity and a decrease of melting temperature with respect to pure homopolymers. Flory's equation was found to describe the T_m–composition data and permitted to calculate the melting temperatures (T^°_m ) and the heats of fusion (ΔH_u) of both the completely crystalline homopolymers. Owing to the high crystallization rate, the glass transition was observable only for the copolymers containing from 30 to 70 mol % of the terephthalate units; even though the samples cannot be frozen in a completely amorphous state, the data obtained confirmed that the introduction of the aromatic units gave rise to an increase of T_g, due to a chain stiffening. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2694–2702, 1999