• Bulletin of the Korean Chemical Society
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• v.5 no.4
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• pp.140-145
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• 1984

A theory is given for determining the molecular weights of block copolymers from the experimental elution volume in GPC. Interaction effect between a sample of block copolymer and a column packing material as well as the size effect are separately considered for the first time applying the partial exclusion mechanism proposed by Dawkins. The molecular weight determination shows 6${\%}$ standard-deviation from the molecular weights measured by an osmometric method for eight block copolymers, which is much more improved result than other methods, e.g., the universal plot method (13 ${\%}$) and the Runyon's method (12 ${\%}$). The reason which explains the better result is that our theory takes into account the interaction effect correctly.

• Journal of Hydrogen and New Energy
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• v.27 no.6
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• pp.660-669
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• 2016

A fluorinated-sulfonated, hydrophobic-hydrophilic copolymer was planed subsequently synthesized using typical nucleophilic substitution polycondensation reaction. A novel AB and ABA (or BAB) block copolymers were synthesized using sBCPSBP (sulfonated 4,4'-bis[4-chlorophenyl)sulfonyl]-1,1'-biphenyl), DHN (1,5-dihydroxynaphthalene), DFBP (decafluorobiphenyl) and HFIP (4,4'-hexafluoroisopropylidenediphenol). All block copolymers were easily cast and made into clear films. The structure and synthesized copolymers and corresponding membranes were analyzed using GPC (gel permeation chromatography), $^1H$-NMR ($^1H$ nuclear magnetic resonance) and FT-IR (Fourier transform infrared). TGA (Thermogravimetric analysis) and DSC (differential scanning calorimetry) analysis showed that the prepared membranes were thermally stable, so that elevated temperature fuel cell operation would be possible. Hydrophobic/hydrophilic phase separation and clear ionic aggregate block morpology was confirmed in both triblock and diblock copolymer in AFM (atomic force microscopy), which may be highly related to their proton transport ability. A sulfonated BAB triblock copolymer membrane with an ion-exchange capacity (IEC) of 0.6 meq/g has a maximum ion conductivity of 40.3 mS/cm at $90^{\circ}C$ and 100% relative humidity.

• Elastomers and Composites
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• v.48 no.1
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• pp.30-38
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• 2013

Polyolefin is one of the most important commodity polymers having excellent physical properties and cost competitiveness, which has continuously broadened their market in response to a heavy demand from industry. However, the lack of polarity in polyolefin has limited its applications, especially where interactions with other materials are important. In view of the above, the incorporation of polar functional groups in polyolefin has been widely attempted. Especially, the preparations of segmented modified polyolefin copolymers, such as block and graft copolymers have been extensively investigated, since the loss of the original properties of polyolefin can be minimized while the polar segments can endow interactions with other materials. Living radical polymerization (LRP) method can be one of the most attractive synthetic tools for the preparation of the modified polyolefin block or graft copolymers. In this review, progress on the preparation of the polyolefin based block or graft copolymers through LRP technique is briefly summarized.

• Polymer(Korea)
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• v.37 no.3
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• pp.332-341
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• 2013

H-shaped amphiphilic pentablock copolymers $(PSt)_2-b-PCL-b-PEO-b-PCL-b-(PSt)_2$ was synthesized via chemoenzymatic method by combining enzyme-catalyzed ring-opening polymerization (eROP) of ${\varepsilon}$-caprolactone (${\varepsilon}$-CL) and atom transfer radical polymerization (ATRP) of styrene. By this process, we obtained copolymers with controlled molecular weight and low polydispersity. The structure and composition of the obtained copolymers were characterized by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC) and infrared spectroscopy analysis (IR). The crystallization behavior of the copolymers was analyzed by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The crystallization behavior of the H-shaped block copolymers demonstrated a PCL dominate crystallization. The self-assembly behavior of the copolymers was investigated in aqueous media. The hydrodynamic diameters of the copolymer micelles in aqueous solution were measured by dynamic light scattering (DLS). The morphology of the copolymer micelles was observed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). The hydrodynamic diameters of spherical micelles declined gradually with the increase of the hydrophobic chain lengths of the copolymers. The critical micelle concentration (CMC) values were determined from fluorescence emission, and it was found that the CMCs decreased with an increase of PSt hydrophobic block lengths.

• Journal of the Korean Chemical Society
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• v.36 no.1
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• pp.87-94
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• 1992

The elution behavior of polystyrenes(PS), polymethylmethacrylates (PMMA), polybutadienes(PB), PS-PMMA(SM) block copolymers and PS-PB star shaped copolymers on the cross-linked polystyrene gels was studied. An interpretation was proposed for the plots of log hydrodynamic volume versus retention volume of solutes in the mobile phases such as tetrahydrofuran, toluene, chloroform, methylene chloride and tetrahydrofuran-cyclohexane mixture. In order to predict the retention of solutes from their physical properties, multiple stepwise regression analysis was applied to obtain the correlation. The distribution coefficients($K_p$) of solute-gel interactions in GPC for homopolymers and PS copolymers were also obtained in terms of network-limited separation mechanism. In the cases of PS and PB, $K_p$ values approach unity, while $K_p$ values for PMMA decrease as MW increase in the good solvent, but in poor solvent, $K_p$ values increase as MW increase. $K_p$ values of PS copolymers are dependent on their MW and composition, therefore, morohology of SM block copolymer is predicted to be random phase. A single universal plot of log[η]M vs. $(V_r-V_o)/K_p$

• Journal of Biomedical Engineering Research
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• v.8 no.2
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• pp.199-204
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• 1987

ABA type block copolymers composed of r benzyle L-glutamate as the A component and poly(ethylene glycol) as the B components were obtained. Platelet adhesion on their sunfaces was investigated by a column elusion method to examine the effects of microdomain and secondary structure. The number of platelets adhered from whole blood and plasma rich platelet was smaller for the block copolymer systems than for the homopolymers. In the block copolymer system, the number of platelets adrered on their surfaces increased with increasing the content of PEG, that is, with decreasing of a-helix of block copolymers. A thick thrombus formation on the PBLG homopolymer was observed than block copolymer by scanning electron micrographs. The platelets adhesion increased with increasing the critical surface tension of the block copolymer.

• Macromolecular Research
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• v.10 no.6
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• pp.359-364
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• 2002

A series of PLA-PEO-PLA triblock stereo-copolymers with varying PLA/PEO and L-DL-LA ratios were synthesized via ring opening pelymerizations. Aqueous solutions of these copolymers undergo thermo-responsive phase transitions as the temperature monotonically increases. Further study shows that there is a critical gel concentration (CGC), and also lower and upper critical gel temperatures (CGTs), at which the thermo-responsive phase transition occurs. The CGC and CGTs are affected by various factors such as block length, as well as the compositions of the PLA blocks and of the additives. In particular, the changes in the phase diagram produced by varying the L-/DL-LA ratio in the PLA blocks were determined to be mainly due to consequent stereo-regularity changes in the PLA blocks.

• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1800-1808
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• 2013

Dual-responsive amphiphilic block copolymers were synthesized by combining enzymatic ring-opening polymerization (eROP) of ${\varepsilon}$-caprolactone (CL) and ATRP of N,N-dimethylamino-2-ethyl methacrylate (DMAEMA). The obtained block copolymers were characterized by gel permeation chromatography (GPC), $^1H$ NMR and FTIR-IR. The critical micelle concentration (CMC) of copolymer was determined by fluorescence spectra, it can be found that with hydrophilic block (PDMAEMA) increasing, CMC value of the polymer sample increased accordingly, and the CMC value was 0.012 mg/mL, 0.025 mg/mL and 0.037 mg/mL for $PCL_{50}$-b-$PDMAEMA_{68}$, $PCL_{50}$-b-$PDMAEMA_{89}$, $PCL_{50}$-b-$PDMAEMA_{112}$, $PCL_{50}$-b-$PDMAEMA_{89}$ was chosen as drug carrier to study in vitro release profile of anti-cancer drug (taxol). The temperature and pH dependence of the values of hydrodynamic diameter (Dh) of micelles, and self-assembly of the resulting block copolymers in water were evaluated by dynamic light scattering (DLS). The result showed that with the temperature increasing and pH decreasing, the Dh decreased. Drug-loaded nanoparticles were fabricated using paclitaxel as model. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) had been explored to study the morphology of the hollow micelles and the nanoparticles, revealing well-dispersed spheres with the average diameters both around 80 nm. In vitro release kinetics of paclitaxel from the nanoparticles was also investigated in different conditions (pH and temperature, etc.), revealing that the drug release was triggered by temperature changes upon the lower critical solution temperature (LCST) at pH 7.4, and at $37^{\circ}C$ by an increase of pH.

• Journal of Biomedical Engineering Research
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• v.9 no.2
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• pp.215-224
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• 1988

Block copoly(L-lactide-${\gamma}$-benzyl-L-glutamate)was synthesized from L-lactide by cationic ring opening polymerization and ${\gamma}$-benzyl-L-glutamate N-carboxy anhydride by introducing amino group terminated poly(L-lactide). L-lactide was polymerized in the presence of stannous octate at $110^{\circ}C$ and ${\gamma}$-benzyl- L-glutamate was polymerized in the presence of NaH at room temperature. The synthesized monomers and copolymers were identified by IR and NMR. The Itermal properties of the copolymers were characterized by differential scanning calorimetry and thermogravimetry. The thermal stability and melting temperature(Tm) of the block copolymers were measured and discussed. The activation energies of thermal decomposition for the block copoly(L-lactide-${\gamma}$ benzyl-L-glutamate) were evaluated from the thermogravimetric data by Freeman and Carroll method.

• Macromolecular Research
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• v.15 no.4
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• pp.385-391
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• 2007

Block copolymer micelles are generally formed via the self-assembly of amphiphilic block copolymers in an aqueous medium. The hydrophilic and hydrophobic blocks form shell and core micelles, respectively. The block copolymers of methoxy poly(ethylene glycol) (MPEG)-b-poly(2-diisopropylamino)ethyl methacrylate (PDPA) were synthesized via atom transfer radical polymerization, with the macro initiator synthesized by the coupling of 2-bromoisobutyryl bromide with MPEG in the presence of a triethyl amine base catalyst. The atom transfer radical polymerization of 2-diisopropylamino)ethyl methacrylate was performed in conjunction with an N,N,N',N",N"-pentamethyl-diethylenetriamine/copper bromide catalyst system, in DMF, at $70^{\circ}C$. The pH induced micellization/demicellization was studied using fluorescence, with a pyrene probe. Furthermore, the pH dependent micellization was confirmed using the microviscosity method, with a dipyme fluorescence probe. The pH dependant micelle size distribution was studied using dynamic light scattering. The characterization of the synthesized polymers was established using gel permeation chromatography and from the $^1H-nuclear$ magnetic resonance spectroscopy.