• Macromolecular Research
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• v.11 no.1
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• pp.25-35
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• 2003

A series of random poly(ethylene-co-1,4-butylene terephthalate)s (PEBTs), as well as poly(ethylene terephthalate) (PET) and poly(1,4-butylene terephthalate) (PBT), were synthesized by the bulk polycondensation. Their composition, molecular weight, and thermal properties were determined. All the copolymers are crystallizable, regardless of the compositions, which may originate from both even-atomic-numbered ethylene terephthalate and butylenes terephthalate units that undergo inherently crystallization. Non-isothermal crystallization exotherms were measured over the cooling rate of 2.5-20.0 K/min by calorimetry and then analyzed reasonably by the modified Avrami method rather than the Ozawa method. The results suggest that the primary crystallizations in the copolymers and the homopolymers follow a heterogeneous nucleation and spherulitic growth mechanism. However, when the cooling rate increases and the content of comonomer unit (ethylene glycol or 1,4-butylene glycol) increases, the crystallization behavior still becomes deviated slightly from the prediction of the modified Avrami analysis, which is due to the involvement of secondary crystallization and the formation of relatively low crystallinity. Overall, the crystallization rate is accelerated by increasing cooling rate but still depended on the composition. In addition, the activation energy in the non-isothermal crystallization was estimated.

• 한국정보디스플레이학회:학술대회논문집
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• 2007.08a
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• pp.667-670
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• 2007

A new series of highly bright and efficient poly(pphenylenevinylene) s (PPV)s based on polyhedral oligomeric silsesquioxanes (POSSs) was synthesized via the Gilch polymerization method. The three POSScontaining PPVs are as follows: POSS05- PPV(containing 5 mol % POSS-appended PPV units), POSS25-PPV(containing 25 mol % POSS-appended PPV units), and POSS100-PPV(containing 100 mol % POSS-appended PPV units; this is the first ${\pi}-conjugated$ polymer composed of 100 mol % POSSsappended repeating units). The POSS-containing PPVs exhibit higher glass transition temperatures $(64-77^{\circ}C)$ than that of MEH-PPV $(58^{\circ}C)$, indicating that electroluminescence (EL) devices fabricated with these polymers should have good thermal stabilities. Light-emitting diodes (LEDs) with the configuration of ITO/PEDOT:PSS/polymer/Ca/Al were fabricated using the novel POSS-containing PPVs. Surprisingly, the luminescence efficiency (0.48 cd/A at $10540\;cd/m^2$) of the binary blend consisting 5 wt % of POSS25-PPV and 95 wt % of MEH-PPV was found to be enhanced by a factor of 6.4 with a maximum brightness of $11010cd/m^2$ (at 14.3 V).

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2342-2348
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• 2014

Poly(lactic-co-glycolic acid) (PLGA) were grafted to both ends of Pluronic$^{(R)}$ F68 ($(EO)_{75}(PO)_{30}(EO)_{75}$) triblock copolymer to produce poly{(lactic acid)$_m$-co-(glycolic acid)$_n$}-b-poly(ethylene oxide)$_{75}$-b-poly(propylene oxide)$_{30}$-b-poly(ethylene oxide)$_{75}$-b-poly{(lactic acid)$_m$-co-(glycolic acid)$_n$} (PLGA-F68-PLGA) pentablock copolymers. Molecular weights of PLGA blocks were controlled and five kinds of pentablock copolymers with different PLGA block lengths were synthesized using in-situ ring-opening polymerization of D,L-lactide and glycolide with tin(II) 2-ethylhexanoate ($Sn(Oct)_2$) catalyst. PLGA-F68-PLGA pentablock copolymers were characterized by $^1H$- and $^{13}C$-NMR, GPC, and TGA. The numbers (2m, 2n) of repeating units for lactic acid and glycolic acid inside PLGA segments were obtained as (48, 17), (90, 23), (125, 40), (180, 59), and (246, 64), with $^1H$-NMR measurement. From NMR data, the resultant molecular weights were determined in the range of 12,700-29,700, which were similar to those obtained from GPC. Polydispersity index was increased in the range of 1.32-1.91 as the content of PLGA blocks increased. TG and DTG thermograms showed discrete degradation traces for PLGA and F68 blocks, which indicate the weight fractions of PLGA blocks in pentablock copolymers can be calculated by TG profile and it is possible to remove PLGA block selectively. Hydrodynamic radius and radius of gyration of pentablock copolymer micelle were obtained in the range of 46-68 nm and 31-49 nm, respectively, in very dilute (i.e. 0.005 wt %) aqueous solution of THF:$H_2O$ = 10:90 by volume at $25^{\circ}C$.

• Bulletin of the Korean Chemical Society
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• v.24 no.4
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• pp.479-483
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• 2003

The reactions of 2,5-bis(ethynyldimethylsilyl)thiophene (1) with aromatic dihalides(1,4-dibromobenzene, 4,4'- dibromobiphenyl, 9,10-dibromoanthracene, 2,5-dibromopyridine, 2,5-dibromothiophene, and 2,6-diiodo-4- nitroaniline) were carried out in the presence of a $[(PPh_3)_2PdCl_2]$-CuI catalyst in refluxing triethylamine to give poly{[2,5-bis(ethynylenedimethylsilylene)thienylene](arylene)} (2-7) with molecular weights of 2200-7400. The oligomers reveal characteristic absorption in the UV/visible region. The thermal behavior of 2-7 was examined by thermogravimetric analysis in an argon atmosphere.

• Journal of the Korean Chemical Society
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• v.58 no.3
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• pp.289-296
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• 2014

Electrochemical copolymerization of o-chlorophenol (oCP) with o-hydroxyphenol (oHP) was carried out in aqueous $H_2SO_4$ by using cyclic voltammetry (CV) technique. In addition, CV was used to evaluate the differences in electrochemical characteristics of the copolymer in comparison with the corresponding homopolymers, poly(o-chlorophenol) (PoCP) and poly(o-hydroxyphenol) (PoHP). The variation of peak currents with respect to sweep rates was compared between copolymer and homopolymers, PoCP and PoHP, films. Further support for copolymer characterization was obtained by recording UV-visible, IR spectra and elemental analysis. The mechanism of the electrochemical polymerization has been discussed. The monomer reactivity ratios ($r_1$ and $r_2$) were calculated using Fineman-R$\ddot{o}$ss method and was found to be 0.4 and 1.3 repetitivelly and the copolymer structure is a block structure and more rich in oHP units.

• Applied Chemistry for Engineering
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• v.4 no.4
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• pp.770-775
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• 1993

Chemical structure of poly(ethylene terephthalate-co-1, 4-cyclohexylene dimethylene terephthalate), P(ET-CT) copolyesters was investigated by High Resolution NMR analysis. The copolymer composition and isomeric ratio were determined by methylene resonance peaks which were separated into three peaks corresponding to ET, trans CT and cis CT units, respectively. The copolymer sequence distribution was evaluated from the carbon resonance peaks connected to carbonyl groups in benzene, indicating died distribution. According to statistics model, these copolyesters are almost random copolymers. The copolymer sequence distribution could be simulated and its averaged length was calculated by random copolymer statistics.

• 한국신재생에너지학회:학술대회논문집
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• 2009.06a
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• pp.270-273
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• 2009

A comb-like copolymer consisting of a poly(vinylidene fluoride-co-chlorotrifluoro-ethylene) backbone and poly(hydroxy ethyl acrylate) side chains, i.e. P(VDF-co-CTFE)-g-PHEA, was synthesized through atom transfer radical polymerization (ATRP) using CTFE units as a macroinitiator. Successful synthesis and a microphase-separated structure of the copolymer were confirmed by proton nuclear magnetic resonance (1H-NMR), FT-IR spectroscopy, and transmission electron microscopy (TEM). This comb-like polymer was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the -OH groups of PHEA and the -COOH groups of IDA. Upon doping with phosphoric acid ($H_3PO_4$) to form imidazole-$H_3PO_4$ complexes, the proton conductivity of the membranes continuously increased with increasing $H_3PO_4$ content. A maximum proton conductivity of 0.015 S/cm was achieved at $120^{\circ}C$ under anhydrous conditions. In addition, these P(VDF-co-CTFE)-g-PHEA/IDA/$H_3PO_4$ membranes exhibited good mechanical properties (765 MPa of Young's modulus), and high thermal stability up to $250^{\circ}C$, as determined by a universal testing machine (UTM) and thermal gravimetric analysis (TGA), respectively.

• Polymer(Korea)
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• v.37 no.6
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• pp.744-752
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• 2013

The miscibility between poly(L-lactide) (PLLA) and poly(methyl methacrylate) (PMMA) was investigated using thermal analyses for the purpose of developing birefringence-free material at oriented state. The effect of methyl acrylate (MA) units as comonomer of PMMA on the miscibility was also studied. All the blends prepared in this study show composition-dependent single $T_g$'s between those of blend components and high transparency over the visible region, indicating the miscibility at molecular level and no discernible effect of MA units on it. No phase separation was observed at elevated temperature of $280^{\circ}C$, higher than the degradation of PLLA and PMMA. The interaction energy density in PLLA/PMMA blends with 17 mol% of MA was measured to be $-0.74J/cm^3$ from the equilibrium melting temperature depression based on the Hoffman-Weeks method. The blends show zero-${\Delta}$n behavior at a specific mixing ratio and the drawing ratio of 3 due to compensation of intrinsic orientation birefringence. Birefringence dispersion of PLLA/PMMA5 blends was also measured to examine the possibility for quarter-wave plates or polarizer protective films.

• Polymer(Korea)
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• v.33 no.2
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• pp.144-152
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• 2009

The thermal and optical properties of poly {1-(cholesteryloxycarbonylalkanoyloxy) ethylene}s (PCALEn, n=2$\sim$8,10, the number of methylene units in the spacer) were investigated. All of the homologues formed monotropic cholesteric phases with left-handed helical structures. PCALEn with n=2 or 10, in constrast with PCALEn with $3{\leq}n{\leq}8$, did not display reflection colors over the full cholesteric range, suggesting that the helical twisting power of the cholesteryl group highly depends on the length of the spacer connecting the cholesteryl group to the polyethylene chain. The glass transition temperatures decreased with increasing n. The isotropic-cholesteric phase transition temperatures decreased with increasing n up to 7 and showed an odd-even effect. However it became almost constant when n is more than 7. This behavior is rationalized in terms of the change in the average shape of the side chain on varing the parity of the spacer. This rationalization also accounts for the observed variation of the entropy gain for the clearing transition. The thermal stability and degree of order in the mesophase and the temperature dependence of the optical pitch observed for PCALEn were significantly different from those reported for cellulose tri(cholesteryloxycarbonyl)alkanoates. The results were discussed in terms of the differences in the chemical structure and flexibility of main chain and the number of the mesogenic units per repeating unit.

• Polymer(Korea)
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• v.38 no.6
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• pp.687-693
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• 2014

Poly(ether-block-amide) 1657 (PEBAX 1657) blended membranes with molecular weight 400 poly(ethylene glycol) (PEG 400) were prepared and their permeability was tested for the gases $N_2$, $O_2$, $CH_4$, $CO_2$, and $SO_2$ by the time-lag method. The permeation characteristics were investigated in terms of diffusivity and solubility, which are dominant factors for gas transport. With the addition of PEG 400, the permeability of all the gases increased and also the ideal selectivity for several pair gases was enhanced. In particular, selectivity for $CO_2/N_2$ ranged from 53.2 (pristine PEBAX 1657 membrane) to 84.1 (50% PEG 400 added), for $SO_2/CO_2$ from 38.9 to 50.7, and for $CO_2/CH_4$ from 17.7 to 31.4. The increase of both permeability and selectivity is mainly because of the increase of solubility of the gases, especially $CO_2$ and $SO_2$. To obtain durability against water vapor, glutaraldehyde (GA) was added to the PEBAX 1657/PEG 400 blended membranes. As a result, permeability decreased owing to a reduction of the free volume and ether oxide units, which are the main factors in elevating the permeability for the blended membranes, and selectivity decrease however; we believe that the durability of the resulting membranes would be increased.