• Bulletin of the Korean Chemical Society
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• 제23권9호
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• pp.1201-1210
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• 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.

• 한국응용과학기술학회지
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• 제23권3호
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• pp.177-184
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• 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.

• 폴리머
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• 제29권6호
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• pp.575-580
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• 2005

하이드록시 말단의 지방족 고차가지구조 폴리에스테르를 용융축합법을 이용하여 합성하였다. 말단의 하이드록시 그룹을 acryloyl chloride를 사용하여 비닐 말단으로 변환시켰으며, 말단변화에 따른 구조를 분석하고 분자량을 측정하였다. 비닐 말단의 지방족 고차가지구조 폴리에스테르는 점도가 높고 노란색의 투명한 액체이며, 하이드록시 말단의 지방족 고차가지구조 폴리에스테르에 비해 유리전이온도가 낮았다. 또한 비닐 말단으로 변형한 후에는 열안정성이 감소하였으며, 말단 작용기의 전환율 차이에 의해 불규칙적인 열분해거동을 보였다.

• 폴리머
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• 제29권3호
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• pp.314-319
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• 2005

촉매인 stannous octeate 존재 하에서 글리콜리드를 이관능성 개시제인 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol과 반응시켜 4가지 종류의 새로운 지방족 디올을 합성하였다. 이들 새로운 디올과 succinic acid, adipic acid, 혹은 suberic acid와 titanium(IV) isopropoxide 촉매하에서 170, 190, 또는 $220^{circ}C$에서 축합중합 시켜 분자구조가 규칙적으로 배열된 새로운 지방족 폴리에스테르와 무질서한 구조를 갖는 폴리에스테르를 각각 얻었다. 이들 지방족 폴리에스테르들의 유리전이온도($T_g$)는 -40에서 $30^{circ}C$ 사이였다. 또한 $170^{circ}C$에서 제조된 분자구조가 규칙적으로 배열된 폴리에스테르가 높은 온도에서 합성된 구조가 무질서한 폴리에스테르들보다 $T_g$가 $5-10^{circ}C$ 정도 높았다. 체외분해 실험 결과, 분자구조가 규칙적으로 배열된 폴리에스테르가 불규칙한 중합체보다 완충용액 속에서 가수분해속도가 느렸다.

• 한국진공학회:학술대회논문집
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• 한국진공학회 1999년도 제17회 학술발표회 논문개요집
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• pp.203-203
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• 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.

• 한국섬유공학회:학술대회논문집
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• 한국섬유공학회 2003년도 가을 학술발표회 논문집
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• pp.161-162
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• 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
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• 제19권6호
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• pp.680-685
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• 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.

• 폴리머
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• 제35권6호
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• pp.526-530
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• 2011

바이오매스에서 유래된 2,5-dihydroxymethylfuran(DHMF)을 $KMnO_4$ 산화반응으로 furan-2,5-dicarboxylic acid(FDCA)를 합성하였다. 합성한 FDCA와 다이올류를 에스테르화 반응과 축중합 반응을 진행시켜 폴리에스터를 중합하였다. 폴리에스터는 NMR을 통해 조성을 분석하였고 DSC와 TGA를 통해 열적특성을 분석하였다. 합성된 폴리에스터의 고유점도는 0.78~1.2 dL/g으로 상용화된 poly(ethylene terephthalate)(PET)와 비슷하였다. 다이올의 길이가 증가할수록 Young's modulus와 strength는 낮아지고 elongation-to-break는 높아지는 경향을 확인하였다. 합성한 poly(ethylene furandicarboxylate)(PEF)의 Young's modulus는 3551 MPa, strength는 103 MPa로 상용화된 PET와 비슷하였다.

• Bulletin of the Korean Chemical Society
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• 제33권8호
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• pp.2560-2566
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• 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.

• 한국응용과학기술학회지
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• 제22권3호
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• pp.257-269
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• 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.