• Bulletin of the Korean Chemical Society
• /
• v.23 no.9
• /
• pp.1201-1210
• /
• 2002

A new series of hyperbranched aromatic polyesters containing azoxybenzene mesogens and polymethylene spacers were prepared by polymerizing AB2 type monomers that have the isophthaloyl dicarboxylic acid terminal at one end and the p-oxyp henol terminal at the other end. The monomers contain a built-in azoxybenzene mesogen that is linked to the terminal groups through polymethylene spacers. The polyesters prepared were characterized by solution viscosity, differential scanning calorimetry, X-ray diffractometry and polarizing microscopy. All of the polyesters were found to be thermotropic (nematic). Their glass-transition temperatures and mesophase temperature ranges were very sensitive to the length of the two spacers existing in the repeating unit. The degree of branching of one of the polyesters was determined by the NMR spectroscopy and found to be 0.56.

• Journal of the Korean Applied Science and Technology
• /
• v.23 no.3
• /
• pp.177-184
• /
• 2006

Because of the difference in the relative reactivity between two hydroxyl groups of the hydroquinone due to the steric hindrance of the substituent, many combinations of the substituent direction in the polyesters derived from asymmetrical diphenol such as monosubstituted hydroquinone was expected. It was studied how the mode of the direction affected the properties of the resulting polyesters in terms of the transition temperatures of the thermotropic polyesters prepared from terephthalic acid, 2,4-dichloroterephthalic acid and phenylhydroquinone by the reaction using diphenyl chlorophosphate in pyridine. The direction was tried to control the relative reactivity by changing the reaction temperature and the addition time of hydroquinone, and by modifying it through an association of hydroquinone with LiCl.

• Polymer(Korea)
• /
• v.29 no.6
• /
• pp.575-580
• /
• 2005

The hydroxy terminated aliphatic hyperbranched polyesters having different generations were synthesized by using melt polycondensation procedure. Then, the terminal groups of hyperbranched polyesters were modified by using acryloyl chloride and characterized by $\^{1}H$-NMR and GPC techniques. As a result of the modification of terminal groups for hyperbranched polyesters, the phase of the polymers were changed from sticky solid to high viscous liquid indicating that the glass transition temperatures of modified hyperbranched polyesters were lower than the original one. The thermal stabilities of hydroxy terminated hyperbranched polyesters were higher than those of terminal group-modified polymers.

• Polymer(Korea)
• /
• v.29 no.3
• /
• pp.314-319
• /
• 2005

Four kinds of new aliphatic diols were synthesized by the ring opening reaction of glycolide with 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, or 1,4-cyclohexanedimethanol, a difunctional initiator, in the presence of stannous octoate catalyst. The resulting diols were melt-polymerized with succinic acid, adipic acid, or suberic acid at 170, 190, or $220^{circ}C$ to produce new sequentially ordered aliphatic polyesters and their corresponding polyesters with random structure. Their glass transition temperatures ($T_g$) ranged from -40 to $30^{circ}C$, The sequentially ordered polyesters prepared at $170^{cir}C$ had higher $T_g$ of 5 to $10^{circ}$ than the polyesters with rand()m structure produced at higher temperature. From in-vitro degradation test the sequentially ordered polyesters was shower in the rate of hydrolysis in a buffer solution than the polymers with random molecular structure.

• Proceedings of the Korean Vacuum Society Conference
• /
• 1999.07a
• /
• pp.203-203
• /
• 1999

Mass spectrometry technique provides the molecular weight distribution, data on the sequence of repeat units, polymer additives, and impurities, and structural information. time-of-Flight secondary Ion Mass Spectrometry (TOF-SIMS) has been used for structural characterization of various polymers1-2. the masses of repeat units and terminal groups and molecular weight distributions of polymers have been determined from their TOF-SIMS spectra. TOF-SMIS provides good sensitivity and structural specificity for high mass ions so that intact oligomers and large polymer fragments are observed. In this study, we investigated the detailed structural information on the oligomers and fragment ions of branched poly(1,3-butylene adipate) and branched poly[di(ethylene glycol) adipate] and the transesterification products of branched polyesters with trifluoroacetic acid or chloro difluoroacetic acid. Branched polyesters were chosen because they are important polymers but difficult to characterize; thus branched polyesters provide challanging test for TOF-SIMS. TOF-SIMS spectra of polyesters are obtained from thin polymer films cast from solution on a silver substrate. A good solvent for a polumer solution disrupts intermolecular forces between polymer chains but leaves the polumer intact. Transesterification reactions are potentially useful for characterization of high molecular weight and intractable polyesters. Transesterification products of polyesters and trifluoroacetic acid or an integral number of polyester repeat units and an additional diol. The progress of such reactions was monitored using peak intensities of reactants and products in TOF-SIMS spectra. The increasing abundance of tagged ions indicates that the reaction has progressed with time.

• Proceedings of the Korean Fiber Society Conference
• /
• 2003.10b
• /
• pp.161-162
• /
• 2003

The synthesis and properties of aromatic polyesters have been extensively studied recently following the observation of the excellent physical and mechanical properties of thermotropic aromatic polyesters noted in both academia and industry$\^$1∼3/. Most aromatic polyesters are composed entirely of rigid, linear, aromatic ester units and as a result, they have high melting temperatures. (omitted)

• Bulletin of the Korean Chemical Society
• /
• v.19 no.6
• /
• pp.680-685
• /
• 1998

Two kinds of new aliphatic diols were synthesized by the ring-opening reaction of lactide and glycolide with 1,4-butanediol, a difunctional initiator, in the presence of stannous octoate. The resulting aliphatic diols were melt-polymerized with D-tartaric acid at 150 ℃ to produce new crosslinkable polyesters. They were reacted with hexamethylene diisocyanate in THF at 65 ℃ in a teflon mold for 24 h to prepare sequentially ordered crosslinked polyesters (BD/LT/GL/D-tartarate). Degradation of the prepared yellow crosslinked films was carried out in a buffer solution in order to examine the effect of time, pH, temperature and crosslinking degree on their degradation rate and mechanism. The rate of degradation increased with an increase in pH and temperature, but it decreased with increasing degree of crosslinkage incorporated into the crosslinked polyesters. We also found that the crosslinked polymers were converted into the acidic compounds such as lactic, glycolic, and D-tartaric acids during the degradation.

• Polymer(Korea)
• /
• v.35 no.6
• /
• pp.526-530
• /
• 2011

Furan-2,5-dicarboxylic acid (FDCA) was synthesized by $KMnO_4$ oxidation of 2,5-dihydroxymethylfuran(DHMF) derived from biomass. Polyesters were synthesized by esterification and polycondensation of FDCA with various diols(ethane-1,2-diol, propane-1,3-diol, butane-1,4-diol, hexane-1,6-diol, decane-1,10-diol). The composition of polyesters was characterized by using $^1H$ NMR. Thermal properties of the polyesters were characterized by DSC and TGA. Intrinsic viscosities(IV) of the polyesters were measured to be 0.78~1.2 dL/g comparable with IV of commercial poly(ethylene terephthalate)(PET). As the chain lengths of diols increased, Young's modulus and strength decreased and elongation-to-break generally increased. Young's modulus and strength of the polyesters were measured to be 3551 MPa and 103 MPa, respectively, comparable with commercial PET.

• Bulletin of the Korean Chemical Society
• /
• v.33 no.8
• /
• pp.2560-2566
• /
• 2012

The present study investigates how the thermal stability of retinol (vitamin A) encapsulated in polyester nanoparticles is influenced by the types of polyester used for the nanoparticles. A variety of polyester-retinol nanoparticles were prepared with various polyesters like: poly(ethylene adipate), PEA; poly(butylene adipate), PBA; poly(hexamethylene adipate), PHMA; and three polycaprolactones, PCL, of different molecular weights ($M_n$ ~10, 40, and 80K). The chemical stability of retinol in these nanoparticles, monitored in an aqueous solution at $25^{\circ}C$ and $40^{\circ}C$ for 4 weeks, was high in the following order of the nanoparticles prepared with PHMA > PCL 40K > PCL 10K > PCL 80K > PBA~PEA at $25^{\circ}C$ and PCL 10K > PCL 40K > PHMA > PCL 80K > PEA > PBA at $40^{\circ}C$. More importantly, this study has also found that the thermal stability of the retinol in the nanoparticles was closely connected with the melting temperatures of polyesters and polyester nanoparticles. The results were further discussed with possible factors - such as sample preparation condition (or history) and miscibility between the polyesters and retinol - affecting $T_m$ of the polyesters and the nanoparticles.

• Journal of the Korean Applied Science and Technology
• /
• v.22 no.3
• /
• pp.257-269
• /
• 2005

This study was focused on the maximization of flame-retardancy of polyesters by a synergism of simultaneously introduced chlorine and phosphorus into polymer chains of modified polyesters. To prepare modified polyesters, reaction intermediates, TD-adduct (prepared from trimethylolpropane /2,4-dichlorobenzoic acid (2,4-DCBA)) and TMBO (prepared from tetramethlene bis (orthophosphate)), were prepared first, then condensation polymerization of the prepared intermediates, adipic acid, and 1,4-butanediol were carried out. In the condensation polymerization, the content of phosphorus was fixed to be 2wt%, and the content of 2,4-DCBA that provides chlorine component was varied to be 10, 20, and 30wt%, and we designated the prepared modified polyesters containing chlorine and phosphorus as ABTTs. The prepared intermediates and modified polyesters were characterized with FT-IR, NMR, GPC, and TGA analysis. Average molecular weight and polydipersity index of the preparation of ABTTs were decreased with increasing 2,4-DCBA content because of the incease in hydroxyl group that retards reaction. We found that the thermal stability of the prepared ABTTs increased with chlorine content at high temperatures.