• Bulletin of the Korean Chemical Society
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• 제24권7호
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• pp.901-905
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• 2003

The lower critical solution temperature (LCST) of thermosensitive poly(organophosphazenes) with methoxypoly(ethylene glycol) (MPEG) and amino acid esters as side groups was studied as a function of saccharide concentration in aqueous solutions of mono-, di-, and polysaccharides. Most of the saccharides decreased the LCST of the polymers, and the LCST decrease was more prominently observed by saccharides containing a galactose ring, such as D-galactose, D-galactosamine and D-lactose, and also the polysacccharide, 1-6-linked D-dextran effectively decreased the LCST of the polymers. Such an effect was discussed in terms of intramolecular hydrogen bonding of saccharides in polymer aqueous solution. The saccharide effect was found to be almost independent on the kinds of the amino acid esters and MPEG length of the polymers. Such a result implies that the polymer-saccharide interaction in aqueous solution is clearly influenced by the structure of sacchardes rather than by that of the polymers. The acid saccharides such as D-glucuronic and D-lactobionic acid increased the LCST, which seems to be due to their pH effect.

• Bulletin of the Korean Chemical Society
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• 제35권2호
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• pp.501-504
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• 2014

A thermoresponsive polymer, poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA), was successfully synthesized by atom transfer radical polymerization (ATRP). Different amounts of 1,3-propanesultone were used as quaternization agent to transit the PDMAEMA into partially modified poly(zwitterions), resulting in p[DMAEMA-co-3-dimethyl(methacryloyloxyethyl)ammonium propanesulfonate] (PDMAEMA-co-PDMAPS). Molecular weight, molecular weight distribution, and degree of quarternization were determined by gel permeation chromatography (GPC) and 1H NMR spectroscopy. The transmission spectra of the 1.0 wt % aqueous solutions of the resulting polymers at 650 nm were measured as a function of temperature. Results showed that the lower critical solution temperature (LCST) and the upper critical solution temperature (UCST) could be easily controlled by the different composition of dimethylamino and zwitterion groups. The effect of partial quaternization on thermoresponsive properties was also studied by dynamic light scattering (DLS) with the same aqueous concentration (1.0 wt %) as employed for turbidimetry studies. The LCST and UCST values measured by DLS correlated well with those determined by turbidimetry.

• KSBB Journal
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• 제15권6호
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• pp.548-555
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• 2000

온도 및 pH에 동시에 민감한 하이드로젤 poly(N-isopropy­l lacrylamide-co-N,N-dimethylaminopropy Imethacrylamide)을 온도 (13, 15.5, 18, 20.5 및 $23^{\circ}C$)와 pH (10.3, 11.3 및 12.3)를 달리 하여 합성하고 이 젤들의 외형, 기계적 강도, 젤 표면모양, LCST, 수축 pH 및 젤의 팽윤 특성을 연구하였다. 합성온도 및 합성 pH가 낮을수록 젤의 외형은 투명하였 고 기계적 강도는 높았다. SEM 관찰 결과 단백질 보다 더 큰 pore들 때문에 분리효율이 감소되는 것으로 사료된다. 합 성온도나 합성 pH의 증가는 LCST를 낮추었다. 외부온도가 LCST보다 낮은 $25^{\circ}C$ 에 서는 모든 합성온도와 합성 pH에 대 하여 젤은 전 pH에 걸쳐 팽윤된 상태에 있었다. $40^{\circ}C$에서는 LCST보다 높은 온도임에도 불구하고 poly (NIPAAm-co­D DMAPMAAm) 하이드로젤은 pH가 중성 및 산성 영역에서 팽윤되었다. 합성온도가 증가함에 따라 젤 부피가 가장 큰 폭으로 변하는 수축 pH가 더 높아졌다.

• 대한화학회지
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• 제45권3호
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• pp.230-235
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• 2001

양 밀단에 methacryl기를 함유한 polydimethylsiloxane(PDMS)을 가교제로 하여 poly(N-isopropylacrylamide)(PNIPAAm)을 합성하여 PDMS를 함유한 PNIPAAm을 얻었다. IR, DSC를 이용하여 그것들의 성질을 조사하였으며 DSC 조사결과 PNIPAAm과 PDMS는 각각 분리된 상으로 존재하는 것이 확인되었으며, PNIPAAm의 $T_g$는 PDMS의 함량이 증가하면 약간씩 감소하였다. 또한 온도에 따른 팽윤도를 조사한 결과 PDMS의 함량이 증가하면 팽윤도는 감소하였으나 lower critical solution temperature(LCST)는 큰 변화가 없었다. 수팽윤된 중합체의 DSC 측정결과도 LCST는 PDMS의 함량에 영향을 받지 않는 다는 것을 확인하였다.

• Biomaterials and Biomechanics in Bioengineering
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• 제2권1호
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• pp.15-22
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• 2015

Poly(ethylene glycol) end-capped with pentafluorophenyl group(s) in ABA (FP-PEG-FP) and AB (mPEG-FP) types were prepared. Even though they were similar in composition, the lower critical solution temperature (LCST) of FP-PEG-FP was observed at $23^{\circ}C$, whereas that of mPEG-FP was observed at $65^{\circ}C$. To understand the large difference in solution behaviour of the two polymers, UV-VIS spectroscopy, microcalorimetry, 1H-NMR spectroscopy, and dynamic light scattering were used. FP-PEG-FP has two hydrophobic pentafluorophenyl groups at the ends of hydrophilic PEG (1000 Daltons), whereas mPEG-PF has a highly dynamic PEG (550 Daltons) block that are anchored to a hydrophobic pentafluorophenyl group. PF-PEG-PF not only has a smaller conformational degree of freedom than mPEG-PF but also can form extensive intermolecular aggregates, therefore, PF-PEG-PF exhibits a significantly lower LCST than mPEG-PF. This paper suggests that topological control is very important in designing a temperature-sensitive polymer.

• Bulletin of the Korean Chemical Society
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• 제27권12호
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• pp.1981-1984
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• 2006

Novel amphiphilic, thermo-responsive polyaspartamides which showed both LCST (lower critical solution temperature), and sol-gel transition were prepared and characterized. The polyaspartamide derivatives were synthesized from polysuccinimide, the polycondensate of aspartic acid monomer, via successive nucleophilic ring-opening reaction by using dodecylamine and N-isopropylethylenediamine (NIPEDA). At the intermediate composition ranges, the dilute aqueous solution exhibited a thermally responsive phase separation due to the presence of LCST. The phase transition temperature was controllable by changing the content of pendent groups. In addition, a physical gelation, i.e. the sol-gel transition was observed from the concentrated solutions, which was elucidated by dynamic viscoelastic measurements. These novel injectable and thermo-responsive hydrogels have potential for various biomedical applications such as tissue engineering and current drug delivery system.

• Bulletin of the Korean Chemical Society
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• 제30권7호
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• pp.1521-1525
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• 2009

Thermosensitive block copolymers of ethylene oxide and N-isopropylacrylamide (NIPAM) were synthesized. A five armed star shape oligo(ethylene oxide) initiator with a cyclotriphosphazene core was prepared and used for the atom transfer radical polymerization (ATRP) of NIPAM. The lower critical solution temperatures (LCSTs) of the copolymers were 36 to 46 ${^{\circ}C}$, higher than that of PNIPAM (32 ${^{\circ}C}$), depending on their molecular weights. The copolymers were soluble in water below the LCSTs but formed micelles above the LCSTs. The thermosensitive micellization behaviors of the polymers were investigated by fluorescence spectroscopy. With increasing the temperature of an aqueous solution of P2 and pyrene above the LCST, the peak of 333 nm red-shifted to appear around 339 nm and its intensity increased significantly, indicating the micelle formation. The transfer of pyrene into the micelles was also confirmed by a confocal laser scanning microscope. The fluorescence image obtained from P2 in an aqueous pyrene solution exhibited a green emission resulting from the pyrene transferred into the micelles. Salt effects on the solubility of the copolymers in an aqueous solution were investigated. The LCST of P2 decreased sharply as the concentration of sodium chloride increased, while decreased slowly with potassium chloride.

• KSBB Journal
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• 제14권1호
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• pp.58-65
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• 1999

온도 및 pH에 동시에 민감한 하이드로젤 Poly(N-isopropy-lacrylamide-co-N,N'-dmerhylaminopropyl methacrylamide)을 합성하고, 그 팽윤 특성을 연구하였다. pH 민감성분인 N,N'-dmerhylaminopropyl methacrylamide (DMAPMAAn)의 물분율이 5%인 하이드로젤이 팽윤정도는 lower critucal solution temperature(LCST) 이상의 온도($37^{\circ}C$ 및 $40^{\circ}C$)에서 pH가 낮은 범위(pH 1-8)일 때 크게 증가하였다. 이는 온도민감성 하이드로젤이 같은 pH범위에서 전혀 팽윤이 일어나지 않는 것과 대조되었다. DMAPMAAm의 물분울이 20%인 경우에는 높은 pH(pH 12)에서도 젤이 상당히 팽창하였다. $40^{\circ}C$에서 pH가 12에서 2로 감소할 때 젤의 수분함량은 5mol%젤의 경우 38.8 wt%에서 84.7wt%로 증가하였고, 20mol%젤의 경우 60.6 wt%에서 90.8wt%로 증가하였다. 온도 및 pH에 동시에 민감한 하이드로젤의 부피 변화에 대해 이와 같이 pH는 온도 및 젤 조성의 영향을 받아 $37^{\circ}C$에서 pH 8보다 $40^\circC$에서 (pH 7) 더 낮아졌고, 5 mol%에서 (pH 7)보다 20 mol%일때 (pH 9) 증가하였다 LCST 이하의 온도 ($25^{\circ}C$)에서는 젤의 팽윤정도가 pH에 의해 크게 영향받지 않았다. 젤의 투명도와 LCST는 DMAPMAAm의 물분율에 따라 증가하였다.

• 대한화학회지
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• 제42권1호
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• pp.84-91
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• 1998

고분자 전해질 복합체 형성이 poly(N-isopropyl acrylamide)(PNIPAAm) 공중합체의 저임계 용해온도 (lower critical solution temperature, LCST)에 미치는 영향을 조사하기 위하여 N-isopropyl acrylamide (NIPAAm)와 acrylic acid (AAc)를 선택하여 온도 감응성과 pH 감응성을 동시에 지니는 pH/온도감응성 고분자를 합성하였다.합성된 고분자들을 FT-IR과 적정실험을 통해 확인하였다. 고분자전해질로서 poly(allylamine) (PAA)과 poly(L-lysine)(PLL)을 사용하여 pH 2로부터 12에 이르는 넓은 범위의 pH 영역에서 고분자전해질 복합체 형성이 pH/온도감응성 고분자의 LCST에 미치는 영향을 조사하였다. 수용액상에서 poly(NIPAAm-co-AAc)중 PNIPAAm의 LCST는 cloud-point 측정 방법으로 결정하였다. 또한 역적정 실험을 통해 공중합체 중의 AAc 함량을 결정하고 AAc의 이온화 정도가 LCST에 미치는 영향을 조사하였다. 수용액상에서 poly(NIPAAm-co-AAc) 중 PNIPAAm의 LCST는 pH, 고분자전해질의 존재 유무, AAc의 함량, 그리고 고분자 사슬에 존재하는 전하밀도 등에 큰 영향을 받았다. 고분자전해질 복합체는 PAAc의 pKa와 PAA또는 PLL의 pKb 사이인 중성영역에서 형성됐으며 PNIPAAm의 LCST에 미치는 PLL의 영향은 PAA에 비해 크게 나타났다.

• 한국섬유공학회:학술대회논문집
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• 한국섬유공학회 2003년도 가을 학술발표회 논문집
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• pp.193-194
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• 2003

전기활성 고분자인 poly(vinylidene fluoride)(PVDF)를 전기 비활성 고분자와 블렌드시키는 경우 어떤 블렌드계에서는 용융 온도 이상에서 LCST(lower critical solution temperature) 상분리 거동을 나타내는데[1,2], 이때 외부 전장을 가해주면 이들의 상분리 거동에 영향을 미칠 수 있다[3]. PVDF와 블렌딩시켰을 때 LCST 상분리 거동을 나타내는 고분자로는 poly(methyl methacrylate), poly(ethyl methacrylate), poly(1,4-butylene adipate) (PBA) 등이 있다[l,3]. (중략)