• 폴리머
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• 제32권6호
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• pp.580-586
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• 2008

4,4'-(Hexafluoroisopropylidene) diphthalic anhydride (6FDA) 와 1,3-bis (3-aminophenoxy) benzene(BAPB)의 조성에 2,2-bis [4-(4-aminophenoxy)phenyl] hexafluoropropane (BAPP)를 다양한 몰 비에 따른 폴리이미드(PI) 공중합체를 합성하였다. PI 공중합체 필름들은 여러 열처리 과정을 통하여 용액 캐스팅 (solution casting)된 폴리아믹산(PAA)으로부터 얻었다. 퓨리에 변환 적외선 분광기(FT-IR), 넓은 각 X-선 회절(XRD), 전계 방사형 주사 전자 현미경(FE-SEM) 시차 주사 열량계(DSC)와 열 중량 분석기(TGA), 만능 인장 시험기 (UTM) 그리고 자외선-가시광선 흡광도기 (UV-Vis. spectrometer) 등을 사용하여 PI 공중합체 필름의 열적 기계적 성질, 모폴로지 및 광학 투명도를 측정하였다. PI 공중합체 필름의 유리전이온도 및 최종 강도와 초기 탄성률은 BAPP의 몰 비가 증가할수록 증가하였으나, 초기분해온도는 BAPP의 몰 비 증가에 무관하게 일정하였다. BAPP가 charge transfer complex를 형성하는 이유로 BAPP 농도가 증가함에 따라 PI 공중합체 필름의 투명도는 약간씩 감소하였다.

• 폴리머
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• 제38권4호
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• pp.510-517
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• 2014

이무수물인 4,4'-(hexafluoroisopropylidene)-diphthalic anhydride(6FDA)에 bis(3-aminophenyl) sulfone(APS), bis[4-(3-aminophenoxy)-phenyl] sulfone(BAPS), 2,2-bis(4-aminophenyl)-hexafluoropropane(6FPD), 2,2-bis[4-(4-aminophenoxy)-phenyl]hexafluoropropane(6FBAPP), 2,2'-bis(trifluoromethyl)benzidine(TFDB) 및 1,4-phenylenediamine(PDA) 등 6종류의 디아민 단량체를 이용하여 폴리이미드(PI) 박막을 제조하였다. 이들 박막의 잔류응력 거동은 thin film stress analyzer(TFSA)를 이용하여 전구체의 열적 이미드화에 따라 in-situ로 측정하였으며, 모폴로지 변화를 통해 해석하였다. 박막의 분자 배향성 및 질서도에 따라 잔류응력은 23.1에서 12.5MPa의 값을 보였으며, 사슬이 강직할수록 감소하였다. 열 특성은 시차 주사 열량계(DSC), 열 중량 분석기(TGA) 및 열 기계 분석기(TMA)를 이용하여 측정하였고, 광학 특성은 자외선/가시광선 분광광도계(UV-vis)와 색차계를 이용하였다. 제조된 박막의 특성변화는 그 화학구조와 밀접한 관련이 있으며, 잔류응력과 광학 특성은 트레이드-오프(trade-off)됨을 확인할 수 있었다.

• 폴리머
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• 제32권3호
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• pp.256-262
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• 2008

폴리아믹산(PAA)의 열 이미드화 반응을 이용해서 4,4'-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)와 bis[4-(3-aminophenoxy)phenyl]sulfone(BAFS)의 단량체에 2,2-bis[4-(4-amino-phenoxy)phenyl]hexafluoropropane(BAPP)의 다양한 몰 비에 따른 삼불소메틸($CF_3$) 곁가지를 가지는 공중합체 폴리이미드(PI)를 합성하였다. 이 공중합체 PI는 N,N'-dimethylacetamide(DMAc)와 같은 용매에 잘 녹았으며 용액 캐스팅하여 얻은 필름은 유연하고 질긴 성질을 보였다. 공중합체 PI 필름의 열적-기계적 성질, 모폴로지 및 광학 투명도들을 측정하기 위해 시차 주사 열 분석기(DSC)와 열 중량 분석기(TGA), 넓은 각 X-선 회절도(XRD), 주사 전자현미경(SEM), 만능 인장 시험기(UTM) 그리고 자외선-가시광선 흡광도기(UV-Vis. spectrometer) 등을 사용하였다. 얻은 공중합체 PI 필름은 투명하였으며, 각 필름의 cut-off wavelength(${\lambda}_0$)은 $275{\sim}319\;nm$이었고, 노란색 지수(yellow index: YI)는 $3.65{\sim}10.37$의 값을 보여주었다. 공중합체 PI 필름의 열적-기계적 성질들은 BAPP의 몰비가 증가할수록 증가하였지만, 광학적 특성에서는 반대의 결과를 보여주었다.

• Macromolecular Research
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• 제8권1호
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• pp.19-25
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• 2000

Aromatic diamine monomers containing allylic ester linkage, 1,5-bis(4-aminobenzoate)-1,2,3,4-tetrahydronaphthalene (4-DABTN) and 1,5-bis(3-amin obenzoate)-1,2,3,4-tetrahydronaphthalene (3-DABTN) were synthesized through the reaction of 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene and 4- or 3-nitrobenzoly chloride. By the reaction of these diamines with pyromellitic dianhydride (PMDA) or 4,4-(hexafluoroisopropylidene)diphthalic anhydride (6FDA), poly(amic acid)s were obtained. The inherent viscosities of the poly(amic acid)s were between 0.55 and 1.31 dL/g. The poly(amic acid)s were converted to polyimides by chemical imidization. The thermogravimetric analysis (TGA) thermograms of these polyimides showed temperatures of 5% weight loss between 323 and 389$^{\circ}C$ in nitrogen atmosphere. The model compound ,1,5-bis (4-nitrobenzoate)-1,2,3,4-tetrahydronaphthalene (4-DNBTN), was decomposed to 4-nitrobenzoic acid and 5-(4-nitrobenzoate)-3,4-dihydronaphthalene upon addition of CF$_3$COOH.

• Bulletin of the Korean Chemical Society
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• 제32권11호
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• pp.4041-4048
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• 2011

High molecular weight tetrasulfonated poly(arylene biphenylsulfone ether) (TsPBPSEH) copolymers containing up to four pendant sulfonate groups per repeat unit were synthesized via aromatic nucleophilic displacement condensation from 4,4'-bis(4-chloro-3-sulfonatophenylsulfonyl)biphenyl-2,2'-disulfonate (SBCSBPD), 4,4'-dichlorodiphenylsulfone (DCDPS) and 4,4'-(hexafluoroisopropylidene)diphenol (6F-BPA). The synthesized copolymers were structurally characterized using $^1H$ NMR and FT-IR techniques. They were analytically pure, amorphous and were readily soluble in a wide range of organic solvents. Electrolyte membranes were successfully cast using the synthesized polymers with various sulfonation levels and N-methyl-2-pyrrolidinone. This new class of polymer membranes exhibited elevated thermal and physical stabilities and reduced swelling at high temperatures. An increase of acidic functional groups in the copolymer yielded high ion exchange capacity and moderate ionic conductivity values even at higher temperatures, which makes them potential ion conducting candidates.

• 한국수소및신에너지학회논문집
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• 제21권4호
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• pp.307-312
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• 2010

Poly (ether sulfone)s with Bisphenol-TP and Bisphenol-AF were prepared with Bisphenol-TP <4,4-dihydroxy tetraphenyl methane>, 4-Fluorophenyl sulfone, and Bisphenol-AF <4,4-(hexafluoroisopropylidene) diphenol> using Potassium carbonate in Sulfolane at $210^{\circ}C$. Sulfonated PBTP-AF were obtained by reaction of Chlorosulfuric acid with copolymers. A series of copolymers were studied by $^1H$-NMR spectroscopy, Differential Scanning Calorimeter (DSC), and Thermo Gravimetric Analysis (TGA). Sorption experiments were conducted to observe the interaction of polymers with water and methanol.

• Bulletin of the Korean Chemical Society
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• 제32권4호
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• pp.1303-1309
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• 2011

Melt copolymerization reactions of bis(diethylamino)tetramethyldisiloxane with several aryldiols were carried out to afford poly(carbotetramethyldisiloxane)s containing fluorescent aromatic chromophore groups in the polymer main chain: poly{oxy(4,4'-biphenylene)oxytetramethyldisiloxane}, poly{oxy(1,4-phenylene)oxytetramethyldisiloxane}, poly[oxy{(4,4'-isopropylidene)diphenylene}oxytetramethyldisiloxane], poly[oxy{(4,4'-hexafluoroisopropylidene)diphenylene}oxytetramethyldisiloxane], poly{oxy(2,6-naphthalene)oxytetramethyldisiloxane}, poly[oxy{4,4'-(9-fluorenylidene)diphenylene}oxytetramethyldisiloxane], poly{oxy(fluorene-9,9-dimethylene)oxytetramethyldisiloxane}, and poly[oxy{4,4'-(9-fluorenylidene)bis(2-phenoxyethylene)}oxytetramethyldisiloxane]. These materials are soluble in common organic solvents such as $CHCl_3$ and THF. The FTIR spectra of all the polymers exhibit the characteristic Si-O-C stretching frequencies at 1021-1082 $cm^{-1}$. In the THF solution, the polymeric materials show strong maximum absorption peaks at 215-311 nm, with strong maximum excitation peaks at 250-310 nm, and strong maximum fluorescence emission bands at 310-360 nm. TGA thermograms indicate that most of the polymers are stable up to $200^{\circ}C$ with a weight loss of less than 10% in nitrogen.

• Macromolecular Research
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• 제9권6호
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• pp.327-331
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• 2001

A new soluble photosensitive poly(amide-co-imide) containing p-phenylenediacryloyl moiety was synthesized and its photoreactivity was characterized. The copolymer was synthesized fromp-phenylenediacryloyl chloride, 4,4-(hexafluoroisopropylidene)diphthalic anhydride and two equivalents of bis(4-aminophenyl) ether in NMP with a subsequent chemical imidization of the resulting poly[amide$\xi$ο-(amic acid)] by acetic anhydride and pyridine. The structure and thermal properties of the polymer were characterized by spectroscopic methods and thermal analyses. The polymer was stable up to 350$\^{C}$, showed good solubility in polar aprotic solvents, and became insoluble after UV irradiation due to the[2+2] cycloaddition of phenylenediacryloyl moiety. Photoreactivity of the polymer was investigated in solution or as a film with respect to the various exposure conditions by UV/Vis spectroscopy. The photosensitivity was noticeably increased with the irradiation temperature, especially in the presense of photosensitizer. The reason for the increased sensitivity was speculated based on the flexibilization of main chain at elevated temperature. Exposure characteristic curves were obtained from the gel fraction experiments after UV irradiation. The sensitivity and contrast at 160$\^{C}$ were measured to be 293 mJ/㎠ and 1.64, respectively.

• Macromolecular Research
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• 제15권3호
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• pp.234-237
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• 2007

3,4-Bis-(3,4-dicarboxyphenylcarboxyethoxy)-4'-nitrostilbene dianhydride was prepared and reacted with 4,4'-(hexafluoroisopropylidene)dianiline to yield a novel Y-type polyimide containing the 3,4-dioxynitrostilbenyl group as an NLO-chromophore, which constituted part of the polymer backbone. The resulting polyimide was soluble in polar solvents such as acetone and N,N-dimethylformamide. The polymer exhibited good thermal stability up to $370^{\circ}C$ in the thermogravimetric analysis. The glass-transition temperature ($T_g$) obtained from the differential scanning calorimetry thermogram was near to $153^{\circ}C$. The second harmonic generation (SHG) coefficient ($d_{33}$) of the poled polymer film at the fundamental wavelength of $1064\;cm^{-1}$ was around $2.15\;{\times}\;10^{-8}\;esu$ (9.01 pm/V). The dipole alignment exhibited exceptionally high thermal stability even at a temperature $30^{\circ}C$ above the $T_g$, and there was no SHG decay below $180^{\circ}C$ because of the partial main chain character of the polymer structure.

• 폴리머
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• 제34권6호
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• pp.495-500
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• 2010

4,4'-(Hexafluoroisopropylidene)diphthalic anhydride(6FDA)와 bis[4-(3-amino phenoxy)phenyl] sulfone(BAPS)의 조성에 cis-4-cyclohexene-1,2-dicarboxylic anhydride(CDBA)를 다양한 몰%로 사용하여 사슬 말단에 가교 반응이 된 폴리이미드(PI)를 얻었다. Grubbs 촉매 0.1 wt%를 사용하여 가교된 폴리아믹산(poly(amic acid), PAA)을 합성한 후에 PAA를 다양한 온도에서 열처리를 통해 가교된 PI 필름을 합성하였다. 제조된 필름의 열적-기계적 성질은 퓨리에 변환 적외선 분광기(FTIR), 시차주사 열량계(DSC), 열중량 분석기(TGA), 열기계 분석기(TMA), 만능인장 시험기(UTM) 등을 사용하여 측정하였고, 색차계(spectrophotometer)와 자외선-가시광선 흡광도기(UV-Vis. spectrometer)를 이용하여 광학적 특성을 확인하였다. CDBA의 몰%가 증가함에 따라 열적 기계적 성질은 증가하였지만 광학적 투명도는 이와는 반대로 감소하였다.