Synthesis of unsaturated polyesters of increased solubility in styrene

The present study presents the synthesis of unsaturated polyester resins using only one glycol i.e., ethylene glycol. Polyesters of inorganic solubility in styrene were prepared. Properties of the resins in the noncrosslinked state in the process of crosslinking and after curing were studied. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3143–3150, 2006     

Low surface energy films based on partially fluorinated isocyanates: the effects of curing temperature

Self-stratification strategy can be used to prepare films in which both bulk and surface properties can be optimized. By using this approach, only a very small quantity of fluorinated species is needed to generate a surface with low surface energy. When cross-linking is involved during film formation, we are dealing with a competition behavior between the diffusion of fluorinated species and the formation of cross-linked network. In this study low surface energy polymeric films were prepared on the basis of partially fluorinated polyisocyanates, in combination with hydroxyl-end-capped three-armed solventless liquid oligoesters and modified hyperbranched polyesters. At a fluorine concentration of only 0.5 wt.%, contact angles of water and hexadecane can reach 120° and 80°, respectively. A surface energy as low as 10–15 mN/m can be obtained upon the addition of less than 1 wt.% of fluorine in the films. It was shown, from real time ATR-FTIR and contact angle measurements, that the curing temperatures demonstrated significant effects on the cross-linking rate as well as on the wettability of the films.     

New intramolecular effect observed for polyesters: An anomeric effect

A series of polyesters was prepared to evaluate hydrolytic stability as a function of cyclohexyl dibasic acid content. The three cyclohexyl dibasic acids: 1,2; 1,3; and 1,4 were formulated into polyesters with two glycols. The proportion of cis and trans isomers was evaluated via ¹H NMR. The hydrolytic stability of short chain polyesters was evaluated in an acetone/water mixture which solubilized the polyesters to mimic oligoester behavior within a thermosetting polyester coating environment. The rate of hydrolysis was monitored by acid titration and corroborated by GPC. Surprisingly, 1,2-cylohexyl diacid-based polyesters were robust, and 1,3-cyclohexyl diacid-based polyesters were the most susceptible to hydrolysis. Evidently, a 1,2-anchimeric effect for cyclohexyl dibasic acid polyesters was not an important consideration, while the 1,3-cyclohexyl ester interaction was. Consequently, an anomeric effect was proposed. Presented at the 81st Annual Meeting of the Federation of Societies for Coatings Technology, November 12–14, 2003, in Philadelphia, PA.     

Surface modification of starch nanocrystals through ring‐opening polymerization of ε‐caprolactone and investigation of their microstructures

Bionanoparticles of starch obtained by submitting native potato starch granules to acid hydrolysis conditions. The resulted starch nanoparticles were used as core or macro initiator for polymerization of ε‐caprolactone (CL). Starch nanoparticle‐g‐polycaprolactone was synthesized through ring‐opening polymerization (ROP) of CL in the presence of Sn(Oct)₂ as initiator. The detailed microstructure of the resulted copolymer was characterized with NMR spectroscopy. Thermal characteristic of the copolymer was investigated using DSC and TGA. By introducing PCL, the range of melting temperature for starch was increased and degradation of copolymer occurred in a broader region. X‐ray diffraction and TEM micrographs confirmed that there was no alteration of starch crystalline structure and morphology of nanoparticles, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Nondegradative microextrusion of resorbable polyesters for pharmaceutical and biomedical applications: The cases of poly‐lactic‐acid and poly‐caprolactone

In recent years biodegradable polymers, particularly polyesters such as the poly(lactic acid) (PLA) and polycaprolactone (PCL), have gained high interests for their applicability in the biomedical and pharmaceutical fields where they're used for manufacturing various different resorbable devices, from tissue engineering scaffolds to controlled drug release systems. Despite many positive characteristics, processability of these materials still remains a critical issue as they easily tend to degrade during manufacturing. In this article we aimed to assess microextrusion as a nondegradative process for manufacturing PLA and PCL. The results we experimentally obtained, that are hereby presented, set a new point in the on‐going debate on degradation during processing of resorbable polymers as they allow to affirm that microextrusion leaves unmodified molecular weight distributions without producing any evident reductions in mean molecular weight. Microextrusion thus represents a risk‐free high molecular weight polymer processing solution for obtaining nondegraded products within pharmaceutical and biomedical production lines, such as for scaffolds for tissue engineering applications or drug delivery. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Semiflexible random thermotropic copolymers from 8‐(3‐hydroxy phenyl) octanoic acid and 3‐chloro‐4‐hydroxy benzoic acid/3,5‐dibromo‐4‐hydroxy benzoic acid

Two series of semiflexible random thermotropic copolymers containing 8‐(3‐hydroxy phenyl) octanoic acid (HPOA) with either 3‐chloro‐4‐hydroxy benzoic acid or 3,5‐dibromo‐4‐hydroxy benzoic acid were prepared by melt polycondensation techniques. The copolyesters were characterized with Fourier transform infrared spectroscopy, dilute solution viscometry, hot‐stage polarized light microscopy, differential scanning calorimetry, thermogravimetric analysis, and wide‐angle X‐ray diffraction. Studies revealed that the amount of HPOA as a disruptor incorporated into the backbone of substituted 4‐hydroxy benzoic acids had a detrimental effect on the liquid‐crystalline behavior. Mesophase‐transition temperatures were observed between 210 and 250°C, and the optical textures were of typical nematic phases. The degree of crystallinity decreased with an increase in the HPOA content. The thermal stability of the copolymers was in the range of 310–370°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Effects of processing conditions on the curing of a vinyl ester resin

The effects of temperature, initiator, and accelerator levels on the curing of an epoxy bisphenol‐A vinyl ester resin Derakane® 411‐45 (formulated with styrene) were investigated by gel‐time and exotherm‐peak measurements on bulk samples. It was observed that the gel time was reduced as the initiator or accelerator ratio increased. Except at higher contents of the accelerator, a small kinetic plateau was seen in the gel curve and a shift of the maximum exotherm toward high temperatures in the DSC curves. This was explained by the dual role played by the accelerator species. A regression analysis of all gel‐time data showed a dependence of 3/2 order in the accelerator and first order in the initiator concentrations. Thus, for this polymerization initiation system, the gel time can be predicted for any initiator and cobalt levels and at any temperature within the ranges studied. The effect of the initiator on the unreacted styrene and vinyl ester was also examined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1146–1154, 2002; DOI 10.1002/app.10403     

Fabrication of High Performance PET/TLCP Fibers through the Synergistic Interfacial Enhancement and Compatibilization of Functional 1D and 2D Carbon Nanomaterials

The maleic anhydride functionalized graphene oxide (GO-MA) is fabricated by an efficient and solvent-free Diels–Alder reaction. Polyethylene terephthalate (PET)/thermotropic liquid crystal polyester (TLCP), PET/TLCP/GO-MA, PET/TLCP/aminated multi-walled carbon nanotubes (MWCNTs-NH₂), and PET/TLCP/GO-MA/MWCNTs-NH₂ composite fibers are systematically melt-spun. The structure and compatibilizing effects of GO-MA and MWCNTs-NH₂ on the mechanical, thermal, and crystallization properties of the composite fibers are indicated. The non-isothermal crystallization kinetics and X-ray diffraction (XRD) data show that TLCP and nanofillers can change the crystalline morphology of PET. The mechanical properties of the fibers rise with increasing TLCP content. The tensile strength 929 MPa and modulus 17.5 GPa of the fibers with 7 wt% TLCP and 0.25 wt% nanofillers (0.1 wt% GO-MA and 0.15 wt% MWCNTs-NH₂) are significantly higher than those with 7 wt% TLCP (tensile strength 622 MPa and modulus 16.1 GPa) and even higher than those with 15% TLCP (tensile strength 836 MPa, and modulus 18.0 GPa). When the GO-MA and MWCNTs-NH₂ co-exist, the anti-dripping phenomenon is improved. Therefore, the TLCP, GO, and MWCNTs synergistically strengthens the mechanical properties. This is promising for the industrial fabrication of high-strength fibers.     

Characterization of molecular orientation in injection–stretch–blow‐molded poly(ethylene terephthalate) bottles by means of external reflection infrared spectroscopy

The molecular orientation at the outer surface of injection–stretch–blow‐molded bottles made from poly(ethylene terephthalate) was characterized and quantified by means of front‐surface reflection infrared spectroscopy based on a method developed previously. Results were obtained for two different bottle shapes (cylindrical and rectangular) molded at different injection mold temperatures (16, 38, and 60°C). For the cylindrical bottles, the preferred molecular chain orientation was found to be in the axial direction, with the Hermans orientation function near 0.3 for all three mold temperatures. For the less symmetrical rectangular bottles, a significant difference was observed between the large and small faces. For the large face, the orientation was mainly in the hoop direction; the Hermans orientation function was in the range of 0.3–0.5 and was essentially the same at all mold temperatures and positions along the bottle height. For the small face, on the other hand, the preferred orientation changed from the hoop direction near the bottom to the axial direction near the top, and the variation was more pronounced at lower mold temperatures. The utility of the front‐surface reflection technique was clearly demonstrated. It was also applied, with the use of an infrared microscope, to examine the orientation gradient across the wall thickness. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1319–1327, 2007     

Solid‐state polymerization of poly(ethylene terephthalate). I. Experimental study of the reaction kinetics and properties

The solid‐state polymerization (SSP) reaction kinetics of poly(ethylene terephthalate) were investigated in connection with the initial precursor intrinsic viscosity (IV; molecular weight). Evaluations were performed with otherwise equivalent precursors melt‐polymerized to IVs of 0.50, 0.56, and 0.64 dL/g. The changes in the molecular weight and other properties were monitored as functions of the reaction times at solid‐state temperatures of 160–230°C. Precursors with higher initial molecular weights exhibited higher rates of SSP than those with lower initial values, as discussed in connection with the levels of crystallinity and the carboxyl and hydroxyl end‐group composition. Activation energies decreased at temperatures above 200°C, and this indicated a change in the SSP reaction mechanism. At temperatures of 200–230°C, similar activation energies were required for the polymerization of all three precursors. Lower temperature polymerizations, from 160 to 200°C, required higher activation energies for all precursors, with the 0.50‐IV material requirement almost twice as high as that calculated for the higher IV precursors. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 197–212, 2003