• Journal of the Korean Applied Science and Technology
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• v.29 no.1
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• pp.19-32
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• 2012

Pharmaceutical use accounts for a great part of articles and papers on crosslinking of polymers. Crosslinking of polymers used for tissue engineering and drug delivery respects non-cytotoxicity and in situ gelling. The crosslinking of polymers is aimed not only at the improvement of modulus, chemical resistance, and thermal resistance, but also at endowing them with such functions as metal adsorption, antifouling, and ion exchange via crosslinked segments. Smart polymers responding to environmental change, and cosslinking mediated by light, enzyme, natural compound and in aqueous medium in consideration of environment are being studied. Developing new polymeric materials is essential along with the pharmaceutics aiming at the longevity of 120 years old. Functionalization and property adjustment of polymers through crosslinking will be done more delicately. Hydrogels will be focused on injectable and in situ gel forming. In the coating industry crosslinking system with low non-toxicity and low energy consumption will be developed in consideration of workers and environment.

• Macromolecular Research
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• v.14 no.3
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• pp.373-382
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• 2006

A series of crosslinkable, waterborne polyurethanes (I-WBPUs) were prepared by in-situ polymerization using isophorone diisocyanate (IPDI)/poly(tetramethylene oxide) glycol (PTMG, $M_n$=2,000)/dimethylol propionic acid (DMPA)/ethylene diamine (EDA)/triethylamine (TEA)/aminoplast[hexakis(methoxymethyl)melamine (HMMM)] as a crosslinking agent. Typical crosslinkable, waterborne polyurethanes (B-WBPUs) blended from WBPU dispersion and aqueous HMMM solution was also prepared to compare with the I-WBPUs. The crosslinking reaction between WBPU and HMMM was verified using FTIR and XPS analysis. The effect of the HMMM contents on the dynamic mechanical thermal, thermal, mechanical, and adhesion properties of the I-WBPU and B-WBPU films were investigated. The storage modulus(E'), glass transition temperatures of the soft segment ($T_{gs}$) and the amorphous regions of higher order ($T_{gh}$), melting temperature ($T_m$), integral procedural decomposition temperature (IPDT), residual weight, $T_{10%}$ and $T_{50%}$ (the temperature where 10 and 50% weight loss occurred), tensile strength, initial modulus, hardness, and adhesive strength of both I-WBPU and B-WBPU systems increased with increasing HMMM content. However, these properties of the I-WBPU system were higher than those of the B-WBPU system at the same HMMM content. These results confirmed the in-situ polymerization used in this study to be a more effective method to improve the properties of the WBPU materials compared to the simple blending process.

• Macromolecular Research
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• v.16 no.5
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• pp.424-428
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• 2008

We prepared an ionic gel polymer electrolyte for dye-sensitized solar cells (DSSCs) without leakage problem. Triiodide compound (BTDI) was synthesized by the reaction of benzene tricarbonyl trichloride with diethylene glycol monotosylate and subsequent substitution of tosylate by iodide using NaI. Bisimidazole was prepared by the reaction of imidazole with the triethylene glycol ditosylate under strongly basic condition provided by NaH. BTDI and bisimidazole dissolved in an ionic liquid were injected into the cells and permeated into the $TiO_2$ nanopores. In situ crosslinking was then carried out by heating to form a network structure of poly(imidazolium iodide), thereby converting the ionic liquid electrolytes to a gel or a quasi-solid state. A monomer (BTDI and bisimidazole) concentration in the electrolytes of as low as 30 wt% was sufficient to form a stable gel type electrolyte. The DSSCs based on the gel polymer electrolytes showed a power conversion efficiency of as high as 1.15% with a short circuit current density of $5.69\;mAcm^{-2}$, an open circuit voltage of 0.525 V, and a fill factor of 0.43.

• Fibers and Polymers
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• v.1 no.2
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• pp.116-121
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• 2000

It has been considered that malic acid, $\alpha$-hydroky succinic acid, could not form crosslinks in the cellulosic materials unless activated by other polycarboxylic acids such as butanetetracarboxylic acid or citric acid because there are only two carboxylic acids per molecule available fur the formation of one anhydride intermediate. However we found that the dicarboxylic malic acid with sodium hypophosphite catalyst without the addition of other crosslinkers was able to improve wrinkle resistance of cotton up to $294^{\circ}$(dry WRA) and $285^{\circ}$ (wet WRA), which is a measure of crosslinking level in cotton. $^1$H FT-NMR, FT-IR and GPC analysis indicated the in-situ formation of an trimeric $\alpha$, $\beta$-rnalic acid with a composition of 1:3 through the esterification between hydroxyl group and one of carboxylic groups in malic acid during curing. The crosslinking of cotton was attributed to the trimeric $\alpha$, $\beta$-malic acid, a tetracarboxylic acid, which can form two anhydride rings during curing. The influence of crosslinking conditions such as concentrations of malic acid and catalyst, pH of the formulation bath, and curing temperature were investigated in terms of imparted wrinkle resistance and whiteness. The addition of reactive polyurethane resin in the formulation slightly increased the mechanical strength retention of crosslinked fabric coupled with additional increase in wrinkle resistance.

• Bulletin of the Korean Chemical Society
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• v.31 no.11
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• pp.3163-3172
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• 2010

In this work, a novel method to synthesis of an acrylic superabsorbent hydrogel was reported. In the two stage hydrogel synthesis, first copolymerization reaction of acrylonitrile (AN) and acrylamide (AM) monomers using ammonium persulfate (APS) as a free radical initiator was performed. In the second stage, the resulted copolymer was hydrolyzed to produce carboxamide and carboxylate groups followed by in situ crosslinking of the polyacrylonitrile chains. The results from FTIR spectroscopy and the dark red-yellow color change show that the copolymerization, alkaline hydrolysis and crosslinking reactions have been do take place. Scanning electron microscopy (SEM) verifies that the synthesized hydrogels have a porous structure. The results of Brunauer-Emmett-Teller (BET) analysis showed that the average pore diameter of the synthesized hydrogel was 13.9 nm. The synthetic parameters affecting on swelling capacity of the hydrogel, such as AM/AN weight ratio and hydrolysis time and temperature, were systematically optimized to achieve maximum swelling capacity (330 g/g). The swollen gel strength of the synthesized hydrogels was evaluated via viscoelastic measurements. The results indicated that superabsorbent polymers with high water absorbency were accompanied by low gel strength. The swelling of superabsorbent hydrogels was also measured in various solutions with pH values ranging from 1 to 13. Also, the pH reversibility and on-off switching behavior makes the hydrogel as a good candidate for controlled delivery of bioactive agents. Finally, the swelling of synthesized hydrogels with various particle sizes obey second order kinetics.

• Biomaterials Research
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• v.22 no.4
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• pp.235-248
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• 2018

Background: Injectable hydrogels have been extensively researched for the use as scaffolds or as carriers of therapeutic agents such as drugs, cells, proteins, and bioactive molecules in the treatment of diseases and cancers and the repair and regeneration of tissues. It is because they have the injectability with minimal invasiveness and usability for irregularly shaped sites, in addition to typical advantages of conventional hydrogels such as biocompatibility, permeability to oxygen and nutrient, properties similar to the characteristics of the native extracellular matrix, and porous structure allowing therapeutic agents to be loaded. Main body: In this article, recent studies of injectable hydrogel systems applicable for therapeutic agent delivery, disease/cancer therapy, and tissue engineering have reviewed in terms of the various factors physically and chemically contributing to sol-gel transition via which gels have been formed. The various factors are as follows: several different non-covalent interactions resulting in physical crosslinking (the electrostatic interactions (e.g., the ionic and hydrogen bonds), hydrophobic interactions, ${\pi}$-interactions, and van der Waals forces), in-situ chemical reactions inducing chemical crosslinking (the Diels Alder click reactions, Michael reactions, Schiff base reactions, or enzyme-or photo-mediated reactions), and external stimuli (temperatures, pHs, lights, electric/magnetic fields, ultrasounds, or biomolecular species (e.g., enzyme)). Finally, their applications with accompanying therapeutic agents and notable properties used were reviewed as well. Conclusion: Injectable hydrogels, of which network morphology and properties could be tuned, have shown to control the load and release of therapeutic agents, consequently producing significant therapeutic efficacy. Accordingly, they are believed to be successful and promising biomaterials as scaffolds and carriers of therapeutic agents for disease and cancer therapy and tissue engineering.

• Polymer(Korea)
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• v.31 no.2
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• pp.117-122
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• 2007

In this work, the mechanical and electrical properties, and thermal stability of vapor-grown carbon nanofibers/polyimide (VGCNFs/PI) composite film synthesized by in-situ polymerization were investigated in terms of tensile properties, volume resistivity and thermogravimetric analysis (TGA), respectively. From the results, the addition of VGCNFs with a certain amount into polyimide led to obvious improvement in tensile strength. The volume resistivity of the films was decreased with increasing the VGCNFs content and the electrical percolation threshold appeared between 1 and 3 wt% of VGCNFs content, which was probably caused by the formation of interconnective structures among the VGCNFs in a composite system. The thermal stability of the film was higher than that of pure PI one. This result indicated that the crosslinking of VGCNFs/PI Composites was enhanced by well-distribution of YGCNFs in PI resin, resulting in the increase of the thermal stability of the resulting composites.

• Applied Chemistry for Engineering
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• v.26 no.3
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• pp.336-340
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• 2015

Three different types of polycarbonate (PC)/graphene oxide (GO) composites using diphenyl carbonate as a monomer were fabricated by melt polymerization. Those were the PC/GO composite (PC/GO) using a twin extruder, in-situ PC/GO composite (PC/GO-cat.) using a catalyst, and in-situ PC/GO composite (PC/GO-COCl) using a GO-COCl treated by -COCl, Chemical structures of the composites were confirmed by C-H and C=O stretching peak at $3000cm^{-1}$ and $1750cm^{-1}$, respectively. The slope for the storage (G') versus loss (G") modulus plot decreased with an increase in the heterogeneous property of polymer melts. So we can check the GO dispersion of the PC/GO composites using by the slop for G'-G" plot. According to the G'- G" slopes for three different types of PC/GO composites, GO was well dispersed within PC matrix in case of PC/GO and PC/GO-cat.. It was also confirmed by atomic force microscope (AFM) photos. One of the reasons for the poor GO dispersion of PC/GO-COCl is branching and crosslinking processes occurred during polymerization, which was further confirmed by a plot for the complex modulus versus phase difference.

• Fibers and Polymers
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• v.7 no.2
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• pp.95-104
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• 2006

In order to improve the water swelling, thermal/mechanical and adhesion properties of waterborne polyurethane (WBPU), a series of the crosslinkable WBPUs containing hydrophilic ionic component, dimethylol propionic acid (20 mole%), were prepared by in-situ polymerization using a cross-linker hexakis (methoxymethyl) melamine (HMMM). Effects of the HMMM content (2, 4, and 6 wt%) and curing temperature on these properties of the crosslinked WBPUs samples were investigated. All properties were found to increase with increasing HMMM content. It was found that the optimum curing temperature of the WBPU films and adhesives was near $120^{\circ}C$, which was not dependent on the HMMM content.

• Membrane Journal
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• v.33 no.5
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• pp.257-268
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• 2023

Membrane capacitive deionization (MCDI) is a variation of the conventional CDI process that can improve desalination efficiency by employing an ion-exchange membrane (IEM) together with a porous carbon electrode. The IEM is a key component that greatly affects the performance of MCDI. In this study, we attempted to derive the optimal fabricating factors for IEMs that can significantly improve the desalination efficiency of MCDI. For this purpose, pore-filled IEMs (PFIEMs) were then fabricated by filling the pores of the PE porous support film with monomers and carrying out in-situ photopolymerization. As a result of the experiment, the prepared PFIEMs showed excellent electrochemical properties that can be applied to various desalination and energy conversion processes. In addition, through the correlation analysis between MCDI performance and membrane characteristic parameters, it was found that controlling the degree of crosslinking of the membranes and maximizing permselectivity within a sufficiently low level of membrane electrical resistance are the most desirable membrane fabricating condition for improving MCDI performance.