• 한국응용과학기술학회지
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• 제29권1호
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• pp.19-32
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• 2012

가교에 관한 리뷰논문으로 특허의 다수는 의료용이다. 조직공학용 지지체나 약물전달용 매체로 쓰이는 고분자의 가교는 세포 무독성, 제 자리 겔 형성성이 있는 가교반응을 중시하고 있다. 가교를 탄성률, 내약품성, 내열성의 증대 목적 외에 가교부위에 금속 흡착성, 방오성, 항균성, 이온교환성 등의 기능을 부여하고 있다. 환경의 자극에 응답하는 스마트 가교, 환경을 고려한 광 가교, 물리적 가교, 효소가교, 천연물 가교, 수성가교가 연구되고 있다. 120세 수명을 목표로 의용재료의 발전에 고분자 소재의 개발도 필수적이다. 가교를 통한 고분자의 기능성 부여 및 물성 강화도 더욱 섬세하게 될 것이다. 고분자 가교물 중의 중요한 분야를 점하는 히드로젤은 주사용 제자리 겔 형성성의 개선 방향으로 전개될 것이다. 코팅용 고분자 가교제는 작업자, 작업환경을 고려하여 저독성-무독성의 가교제, 낮은 에너지에서 가교되는 에너지 절약형 가교제가 개발될 것이다.

• Macromolecular Research
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• 제14권3호
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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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• 제16권5호
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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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• 제1권2호
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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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• 제31권11호
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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.

• 생체재료학회지
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• 제22권4호
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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.

• 폴리머
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• 제31권2호
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• pp.117-122
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• 2007

본 연구에서는 제자리 중합에 의해 합성된 기상성장 탄소나노섬유/폴리이미드(VGCNFs/PI) 복합재료 필름의 기계적, 전기적 특성과 열안정성을 만능재료 시험기와 체적저항기, 열중량분석기를 통해 관찰하였다. 그 결과, VGCNFs 일정량 첨가되었을 때 복합재료 필름의 인장강도가 증가한 것을 관찰할 수 있었다. VGCNFs/PI 복합재료 필름의 체적저항 값은 VGCNFs 첨가량이 증가할수록 감소하였으며, 전기적 percolation threshold는 VGCNFs 함량 1과 3 wt% 형성되었는데, 이는 복합재료 내부에서 VGCNFs 상호간 네트워크의 형성으로 인하여 전기적 경로가 만들어졌기 때문이라 판단된다. VGCNFs가 PI 복합재료 필름의 열안정성은 순수한 이미드 필름보다 VGCNFs가 첨가됨에 따라 향상되었으며, 이는 충전제로 사용한 VGCNFs가 PI 수지에 잘 분간됨에 따라 복합재료의 가교화에 영향을 주어 VGCNFs/PI 복합재료 필름의 열안정성이 향상된 것으로 판단된다.

• 공업화학
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• 제26권3호
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• pp.336-340
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• 2015

단량체로 디페닐카보네이트를 이용한 세 종류의 폴리카보네이트(PC)/그래핀 옥사이드(GO) 복합체, 즉 이축압출기를 이용한 PC/GO 복합체(PC/GO), 촉매를 이용한 in-situ PC/GO 복합체(PC/GO-cat.), 그리고 -COCl로 표면 처리된 GO-COCl을 이용한 in-situ PC/GO 복합체(PC/GO-COCl)를 용융중합을 통해 제조하였다. PC/GO 복합체의 합성은 $3000cm^{-1}$와 $1750cm^{-1}$ 근처에서 나타나는 C-H 그리고 C=O 신축진동 피크를 통해 확인하였다. DSC와 TGA 분석 결과에 따르면, PC/GO와 PC/GO-cat.과 비교할 때, PC/GO-COCl의 유리전이온도가 상대적으로 낮은 값을 나타내었고, PC/GO 복합체의 열안정성이 가장 우세함을 나타내었다. 저장탄성률(G')-손실탄성률(G") 그래프의 기울기는 고분자 용융체의 비균질성의 증가와 함께 감소하는 경향이 있어, GO 분산성을 확인하는데 사용될 수 있다. G'-G" 기울기 결과로부터 PC/GO와 PC/GO-cat. 복합체의 PC 매트릭스 내 GO 분산성이 양호함을 알 수 있고, 이는 원자력현미경 사진을 통해 재확인하였다. PC/GO-COCl의 경우 분산성이 열세한 이유 중 하나는 중합과정에서 -COCl에 의해 분지구조나 가교구조 등이 발생하여 GO의 분산을 방해하기 때문으로 해석할 수 있고, 이는 복합탄성률과 위상차(${\delta}$) 그래프로부터 확인할 수 있었다.

• Fibers and Polymers
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• 제7권2호
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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.

• 멤브레인
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• 제33권5호
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• pp.257-268
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• 2023

막 축전식 탈염 공정(membrane capacitive deionization, MCDI)은 이온교환막을 다공성 전극과 함께 사용하여 탈염 효율을 향상시킬 수 있는 CDI 공정의 변형이다. 이온교환막은 MCDI의 성능에 큰 영향을 미치는 핵심 구성요소이다. 본 연구에서는 MCDI의 탈염 효율을 크게 향상시킬 수 있는 이온교환막의 최적 제조 인자를 도출하고자 하였다. 이를 위해 PE 다공성 필름의 세공에 단량체를 충진하고 in-situ 광중합을 진행하여 세공충진 이온교환막(pore-filled ion-exchange membranes, PFIEMs)을 제조하였다. 실험 결과, 제조된 PFIEMs은 다양한 탈염 및 에너지 변환 공정에 적용할 수 있는 수준의 우수한 전기화학적 특성을 나타내었다. 또한, MCDI 성능과 막 특성 인자와의 상관성 분석을 통해 막의 가교도를 제어하여 막의 전기적 저항이 충분히 낮은 범위에서 이온 선택 투과성을 최대화하는 것이 MCDI의 성능 향상을 위해 가장 바람직한 막제조 조건이라는 결론을 얻었다.