• Polymer(Korea)
• /
• v.36 no.4
• /
• pp.448-454
• /
• 2012

A poly(amic acid) (PAA) was prepared by reaction of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluropropane (BAPP) in N,N-dimethylacetamide (DMAc). The cast films of the synthesized PAA were thermally treated at different temperatures to create polyimide (PI) films. The heat treatment temperature varied between 80 and $230^{\circ}C$ to investigate the imidization index in relation with the solvent evaporation rates. The progress of PAA imidization was examined using a thermogravimetric analyzer (TGA) and a Fourier transform infrared spectroscope (FTIR) at various time and temperature. The experimental results showed that the imidization index was fast at the initial stage in the presence of solvent, DMAc, reaching the final imidization. When the imidization temperature is high over $200^{\circ}C$, the imidization index decreased because the solvent was evaporated too fast.

• Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
• /
• 1998.11a
• /
• pp.61-64
• /
• 1998

We have investigated the effects of ultraviolet (UV) light irradiation condition and imidization temperature for the generation of pretilt angle in nematic liquid crystal (NLC) on the two kinds of the polyimide (PI) surfaces. High pretilt angle of NLC is generated with oblique p-polarized UV light irradiation of 30$^{\circ}$ on PI surface for 20 min. Also, the high pretilt angle of NLC is generated with oblique p-polarized UV light irradiation of 10-30$^{\circ}$ on PI surface at 20min. The pretilt angle of NLC decreases with increasing the imidization temperature on all rubbed PI surfaces ; the pretilt angle of NLC with oblique p-polarized UV light irradiation of 30$^{\circ}$on PI surface decreases with increasing the imidization temperature. The high pretilt angle of NLC is observed due to high photo-depolymerization reaction by low surface energy at low imidization temperature. We suggest that the pretilt angle of NLC is strongly attributed to the photo-depolymerization reaction with the UV light irradiation condition and imidization temperature.

• Bulletin of the Korean Chemical Society
• /
• v.24 no.3
• /
• pp.357-362
• /
• 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.

• Korea-Australia Rheology Journal
• /
• v.12 no.1
• /
• pp.69-76
• /
• 2000

We have derived the translation diffusion coefficient and the intrinsic viscosity formula adopting the Kholodenko's theory using 3＋1 dimensional Dirac propagator in the Kirkwood and Riseman scheme. We also performed static light scattering experiments and intrinsic viscosity measurement of dilute solutions of polyimides with different rigidities. In the framework of Kholodenko's theory, we can easily measure the persistence length of polyimide. We prepared five different polyamic acids and polyimides with different degree of imidization by controlling imidization temperatures. From experimental results, we obtained molecular weights and persistence lengths according to the Kholodenko's plot. The molecular weight and the intrinsic viscosity decreased and then increased with the imidization temperature but the persistence length increased monotonically and then leveled off. The persistence lengths calculated from intrinsic viscosities showed very good agreement with those from light scattering experiments.

• Proceedings of the Korean Institute of Surface Engineering Conference
• /
• 1998.05a
• /
• pp.61-62
• /
• 1998

• Macromolecular Research
• /
• v.11 no.5
• /
• pp.297-302
• /
• 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
• /
• v.9 no.6
• /
• pp.303-312
• /
• 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.

• Proceedings of the Membrane Society of Korea Conference
• /
• 1999.07a
• /
• pp.83-86
• /
• 1999

The imidization effect of a poly (amic acid) dope solution on membrane formation has been investigated. Poly (amic acid) solution in S-methyl-2-pyrrolidione hs been thermally imidized at $120^{\circ}C$ with different curing time and its degree of imidization was determined by infrared spectroscopy. The solution properties have been studied as a function of concentration and curing time by dynamic light scattering. The quality of a solvent was changed from good to poor with increasing imidization of poly(amic acid).The reduced polymer-solvent interaction diminishes the membrane formation time. The morphology of a membrane was able to be controlled by the characteristics of dope solution.

• Macromolecular Research
• /
• v.14 no.1
• /
• pp.1-33
• /
• 2006

Polyimides (PIs) exhibit excellent thermal stability, mechanical, dielectric, and chemical resistance properties due to their heterocyclic imide rings and aromatic rings on the backbone. Due to these advantageous properties, PIs have found diverse applications in industry. Most PIs are insoluble because of the nature of the high chemical resistance. Thus, they are generally used as a soluble precursor polymer, which forms complexes with solvent molecules, and then finally converts to the corresponding polyimides via imidization reaction. This complexation with solvent has caused severe difficulty in the characterization of the precursor polymers. However, significant progress has recently been made on the detailed characterization of PI precursors and their imidization reaction. On the other hand, much research effort has been exerted to reduce the dielectric constant of PIs, as demanded in the microelectronics industry, through chemical modifications, as well as to develop high performance, light-emitting PIs and liquid crystal (LC) alignment layer PIs with both rubbing and rubbing-free processibility, which are desired in the flat-panel display industry. This article reviews this recent research progresses in characterizing PIs and their precursors and in developing low dielectric constant, light-emitting, and LC alignment layer PIs.

• Macromolecular Research
• /
• v.12 no.3
• /
• pp.263-268
• /
• 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.