• Bulletin of the Korean Chemical Society
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• 제24권3호
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• pp.357-362
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• 2003

The pathway producing imide ring closure during the thermal imidization of poly(amic acid) (PAA) was investigated in detail using a new analytical method, two-dimensional (2D) Raman correlation spectroscopy. The signs of the cross peaks in synchronous spectra provided evidence of the thermal imidization of PAA into PI as the heating temperature increased. The signs of the cross peaks in asynchronous spectra suggested that the imide-related modes changed prior to the amide or carboxylic mode, which indicates that cyclization occurred before the amide proton was abstracted.

• 폴리머
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• 제36권4호
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• pp.448-454
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• 2012

폴리아믹산(poly(amic acid), PAA)은 불소치환 단량체인 4,4'-(hexafluoroisopropylidene)diphthalic anhydride(6FDA)와 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluropropane(BAPP)의 조성으로 N,N'-dimethylacetamide(DMAc) 용매에서 반응을 하여 얻어졌으며, 폴리이미드(polyimide, PI) 필름은 PAA을 각각 다른 온도에서 열처리하여 얻었다. 제조된 필름을 얻기 위해 $80-230^{\circ}C$까지 열처리를 하였으며, 용제 증발에 따른 이미드화도 변화를 알아보기 위해서 폴리아믹산 용액을 얻은 후 열중량 분석기(thermogravimetric analysis, TGA)를 통하여 시간과 온도에 따른 용제 증발 정도를 측정하였다. 이에 따른 이미드화 지수는 적외선 분광분석기(fourier transform infrared spectroscopy, FTIR) 스펙트럼을 통해 확인하였다. 시간과 온도에 따른 이미드화도를 통해 용매가 빠르게 증발하지만 용매가 잔류하고 있는 반응의 초기에 이미드화가 빠르게 일어나는 것을 확인하였고, 시간이 흘러 용매의 증발 정도가 줄어들고, 잔류용매가 사라지는 시점에서의 이미드화 지수는 일정하게 나타나는 것을 확인하였다. 이미드화는 온도가 증가함에 따라 진행되나 반응 온도가 $200^{\circ}C$ 이상으로 과도하게 높은 경우에는 용매가 남아 있지 않아 반응시간을 증가시켜도 이미드화 지수가 오히려 감소하는 현상을 보였다.

• Macromolecular Research
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• 제9권6호
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• pp.303-312
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• 2001

The fabrication of liquid crystal display (LCD) panels involves several thermal processes such as imidization of the alignment layer (AL) and annealing of the rubbed polyimide AL. The nature of these processes on the LC alignment, especially on the pretilt angle (Θ$\_$p/) has been systematically studied, employing various types of polyimide structures. The imidization effect depends on the nature of polyimid precursors; Θ$\^$p/ increases with the degree of the imidization for the main-chain type of ALs, due to the decrease in the surface polarity, but this relation is not applicable to the alkylated ones in which the steric effect at the AL surface by the aliphatic side chains is dominant. Annealing of the rubbed polyimide AL deteriorates its rubbing-induced molecular orientation and subsequently the overlying LC alignment, resulting in the decrease in Θ$\_$p/. Especially, annealing of the LC cell affects the LC-AL interaction as well as the AL orientation and thus its effect on LC alignment depends sensitively on the nature of LC-polyimide interface; aromatic moiety in the polyimide structure gives better thermal stability of LC alignment while fluorinated polyimide ALs induce the less stable alignment.

• Macromolecular Research
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• 제11권5호
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• pp.297-302
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• 2003

The imidization and cure reaction of a thermosetting phenylethynyl-terminated amic acid (LaRC PETI-5) in film form have been monitored as a function of temperature by means of a steady-state fluorescence technique using a front-face illumination method. The variation of the fluorescence emission spectra of LaRC PETI-5 can be divided into four temperature regions; Region I: below 15$0^{\circ}C$, Region II: 150-25$0^{\circ}C$, Region III: 250-35$0^{\circ}C$, and Region IV: above 35$0^{\circ}C$. The fluorescence spectra in Region I are largely influenced by residual N-methyl-2pyrrolidinone in the polymer and also slightly by partial imidization of the polymer. There is a combined effect of imidization and solvent removal on the fluorescence behavior in Region II. The spectra in Regions III and IV are due significantly to the cure reaction of LaRC PETI-5 and to a post-cure effect of the polyimide, respectively. This spectroscopic evidence indicating the transformation of the amic acid imide oligomer into the corresponding polyimide via imidization and cure, agrees well with thermal analysis results obtained previously. The intermediate stage of cure in the range of 250-30$0^{\circ}C$ predominantly influences the change of the fluorescence intensity. The later stage above 30$0^{\circ}C$ significantly influences the position of the spectrum. This fluorescence study also supports the mechanism proposed in earlier work that the crosslinking reaction takes place at the reaction sites in the conjugated polyene and the phenylethynyl end group in the polyimide chain.

• Macromolecular Research
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• 제12권3호
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• pp.263-268
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• 2004

We have synthesized a water-soluble polyimide precursor, poly(amic acid) amine salt (PAD), from pyromellitic dianhydride (PMDA), 4,4'-oxydianiline, and N,N -dimethylethanolamine (DMEA) and have investigated in detail its properties with respect to the degree of salt formation (D$\_$sf/). The maximum value of D$\_$sf/ we obtained upon precipitation of the precursor solution into acetone was 79%. We synthesized a PAD having a D$\_$sf/ of 100% (PAD100) by the solid state drying of an organic solution. The precursors showed different solubility depending on the D$\_$sf/ to make up to 4 wt% solutions in water containing a small amount of DMEA. PAD100 is completely soluble in pure water. We investigated the imidization behavior of PAD in aqueous solution using various spectroscopic methods, which revealed that PAD 100 has faster imidization kinetics relative to that of the poly(amic acid)-type precursors. The resulting polyimide films prepared from an aqueous precursor solution possess almost similar physical and thermal properties as those prepared from N-methyl-2-pyrrolidone(NMP) solution. Therefore, we have demonstrated that PAD can be used as a water-based precursor of polyimide; this procedure avoids the use of toxic organic solvents, such as NMP.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 1995년도 춘계학술대회 논문집
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• pp.111-114
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• 1995

This paper describes the imidization of PAAS(polyamic acid alkylamine salts) Langmuir-Blodgett (LB) films and the electrical properties of PAAS and polyimide(PI) LB films, The imidization conditons were investigated by TGA(Thermal Gravi-tational Analysis). FT-IR and UV/ visible absorption spectra. A thermal imidiczation was peformed at 300$^{\circ}C$ for 1 hour. The electrical properties of the PAAS and polymide LB films were measured by current-voltate(L-V) characteristics It shows that the electrical condcutivity of PL LB films is about 10 $\^$-15/S/cm which is two orders of magnetiude lower than that of the PAAS LB films A Schottky effect was also observed in both films.

• 한국인쇄학회지
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• 제15권2호
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• pp.117-130
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• 1997

Studies have been conducted to explore thermal imidization of polyamic acid. Aromatic polyimides are well recognized as high temperature linear polymers, and polyimide are used as structural materials, fibers, and adhesive. Two different kinds of polyimide were prepared by theimidization of polyamic acid which were synthesized from 2,2-bis[4-(4-aminophenoxy)phenyl]- hexafluoropropane, 2,2-bis [4-(4-aminophenxy)phenyl] - hexamethylpropane and caprolactam and pyromelliti dianhydride under N-Methly-pyrrolidinone solvent. Polyamic acids were converted to polyimides containing imide bond by thermal imidization. The weight 50% loss temperatures of polyimide by TGA thermogram were recorded in the range of 700 ~ 720$^{\circ}$C in nitrogen gas. According, as a results, we conclued polyamic acid were cycliation after H2O molecule separationed, and this polyimide film could be used for Printed Circuit Boand.

• 한국재료학회:학술대회논문집
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• 한국재료학회 2001년도 춘계학술발표강연 및 논문개요집
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• pp.125-125
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• 2001

• 한국섬유공학회:학술대회논문집
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• 한국섬유공학회 2001년도 학술발표회 논문집(Proceedings of the Korean Textile Conference)
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• pp.43-46
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• 2001

• 접착 및 계면
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• 제5권1호
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• pp.29-35
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• 2004

친유기 합성 층상실리케이트(STN)의 함량(1~9 wt%)을 변화하며 폴리아믹산/STN 나노복합재용액을 DMAc 및 THF/MeOH 혼합용매에서 각각 제조하였고, 이를 폴리에스테르 필름에 코팅하여 열적 이미드화 및 화학적 이미드화 반응을 통하여 폴리에스테르/폴리이미드 나노복합필름을 제조하였다. XRD 및 TEM을 이용하여 제조된 폴리에스테르/폴리이미드 나노복합필름의 미세 구조를 조사한 결과 박리형 폴리이미드 나노복합재가 제조되었음을 확인하였다. 표면의 모폴로지 변화는 AFM을 통하여 확인하였으며, 열적 및 기계적 특성은 TGA, DMA와 UTM을 통하여 측정하였다. 또한 STN이 첨가됨에 따라 폴리에스테르/폴리이미드 나노복합필름의 수분투과도는 감소하였고, 화학적 이미드화에 의해 제조된 필름이 열적 이미드화에 의한 필름에 비해 좀더 우수한 수분 차단성을 보였다. 또한 상대적으로 비점이 낮은 THF/MeOH 혼합용매 시스템의 경우가 DMAc를 용매로 사용한 경우보다 더 향상된 수분 차단성을 보였다.