• Polymer(Korea)
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• v.31 no.2
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• pp.130-135
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• 2007

To enhance the thermo-mechanical properties of polyimide films which have potential application for the FCCL, we have synthesized the poly (amic acid) s composed of 4-components PMDA/BTDA and PDA/ODA as monomer system, u4 then they were effectively converted into 4-component polyimide films by thermal imidization process. It has been found that CTE values in the range of $100\sim200^{\circ}C$ decreased with the amount of PDA, which also caused 36% and 59% increases in tensile modulus and strength respectively. And also, peel test results on 3-layered copper clad laminate using 4-component polyimide films showed excellent adhesion strength above 1.8 kgf/cm. On the basis of obtained results it can be concluded that 4-component polyimide films may be applied for the high performance FCCL base films.

• Polymer(Korea)
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• v.38 no.4
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• pp.510-517
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• 2014

A series of polyimide (PI) was prepared by reacting 4,4'-(hexafluoroisopropylidene)-diphthalic anhydride (6FDA) as the anhydride and 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), or 1,4-phenylenediamine (PDA) as the diamine. Residual stress behaviors were detected in-situ during thermal imidization of the polyimide precursors using a thin film stress analyzer (TFSA), and interpreted with respect to their morphology. According to the molecular orientation and packing order, the residual stress varied from 23.1 to 12.5 MPa, decreased with increasing chain rigidity. The thermal properties of the PI films were investigated using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and thermomechanical analysis (TMA). Their optical properties were measured by ultraviolet-visible spectrophotometer (UV-vis), and spectrophotometry. The properties of PI films were found to be strongly dependent upon the morphological structure. However, trade-offs between residual stress and optical properties were identified.

• Membrane Journal
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• v.25 no.3
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• pp.223-230
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• 2015

We synthesized novel polyimides with high gas permeability and selectivity for application of gas separation membrane. 2,2-bis(3,4-carboxylphenyl) hexafluoropropane dianhydride (6FDA) and two kinds of amines with high permeability and solubility were used to prepare the novel polymide. 2,4,6-Trimethyl-1,3-phenylenediamine (DAM) was used to improve gas permeability and 4,4-Methylenedianiline was used to improve the gas selectivity respectively. The polyimide copolymers were synthesized by commercial chemical imidization method using Triethylamine and Acetic anhydride and their average molecular weights were over 100,000 g/mol. The glass temperature (Tg) and the thermal degradation temperature were characterized using differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). The synthesized copolymers showed high Tg over $300^{\circ}C$ and high thermal degradation temperature over $500^{\circ}C$. The gas permeation properties were measured by time-lag equipment. Although general polyimides showed very low gas permeability, synthesized polyimide copolymer showed high $O_2$ permeability of 10.1 barrer with high $O_2/N_2$ selectivity around 5.3. From this result, we confirm that these membranes have possibility to apply to gas separation membrane.

• Membrane Journal
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• v.24 no.4
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• pp.325-331
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• 2014

We synthesized novel polyimides with high gas permeability and selectivity for application of on board inert gas generation system (OBIGGS). 2,2-bis(3,4-carboxylphenyl) hexafluoropropane dianhydride (6FDA) and two kinds of amines with high permeability and solubility were used to prepare the novel polymide. 2,3,5,6-Tetramethyl-1,4-phenylenediamine (TMPD) was used to improve gas permeability and various kinds of diamines were used to improve the gas selectivity respectively. The polyimide copolymers were synthesized by commercial chemical imidization method and their average molecular weights were over 100,000g/mol. The glass temperature ($T_g$) and the thermal degradation temperature were characterized using differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA). The synthesized copolymers showed high $T_g$ over $300^{\circ}C$ and high thermal degradation temperature over $500^{\circ}C$. The gas permeation properties were measured by time-lag equipment. Although general polyimides showed very low gas permeability, synthesized polyimide copolymer showed high $O_2$ permeability of 36.21 barrer with high $O_2/N_2$ selectivity around 4.1. From this result, we confirm that these membranes have possibility to apply to OBIGGS.

• Applied Chemistry for Engineering
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• v.10 no.7
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• pp.1014-1019
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• 1999

Copolyamic acid PMDA/6FDA-PDA(PAA) and homopolyamic acids PMDA-PDA(PAA) and 6FDA-PDA(PAA) were synthesized from 1,2,4,5-benzenetetracarboxylic dianhydride(PMDA) and 2,2'-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride(6FDA) as the dianhydride and 1,4-phenylenediamine (PDA) as the diamine. Residual stresses were detected in-situ during thermal imidization of the co- and homopolyimide precursors as a function of processing temperature over the range of $25{\sim}400^{\circ}C$ using thin film stress analyzer(TFSA), and morphological structures were investigated by WAXD. In comparison, the resultant residual stress of polyimide films composed of different compositions decreased with the increasing content of PMDA unit in the chain and was about 5 Mpa in compression mode for PMDA-PDA. In this study, the synthesis of random PMDA/6FDA-PDA copolyimide could be completed and compensate for the difficulty of process due to high $T_g$ of PMDA-PDA and relatively higher stress of 6FDA-PDA. It showed that we can make a low level stress copolyimied having excellent mechanical properties by incorporating appropriate rod-like rigid structure PMDA-PDA unit into 6FDA-PDA polyimide backbone which generally shows higher stress due to rotational hinges such as bulky di(trifluoromethyl). Specially, PMDA/6FDA-PDA(0.9:0.1:1.0) satisfied excellent mechanical property and low level stress as an inter layer showing low dielectric constant.

• Korean Chemical Engineering Research
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• v.48 no.1
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• pp.45-52
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• 2010

Two different imide oligomers(6FDA-ODA/APA and 6FDA-MDA/MA) having crosslinkable end groups were prepared by using a solution imidization method and their properties were investigated. Also, semi-interpenetrating polymer networks(semi-IPN) were prepared using the blends of imide oligomers with polyetherimide $Ultem^{(R)}$, which is used in dual-ovenable packaging materials. The characteristic properties of semi-IPN films were interpreted by using TGA, Thin Film Diffusion Analyzer, and WAXD. Molecular weights of imide oligomers were successfully controlled utilizing 2-aminophenylacetylene(APA) and maleic anhydride(MA) as an endcapping agent. Exotherm reactions by crosslinking appeared and the amount of exthotherm heat was linearly increased as the content of imide oligomers was increased. For semi-IPNs of $Ultem^{(R)}$ and imide oligomers, 5% and 10% weight loss temperatures increased as the contents of imide oligomers were increased. Diffusion coefficient and water uptake of semi-IPNs decreased as the content of imide oligomers was increased, which might be resulted from hydrophobic fluorine group and high packing density. It was concluded that relatively low thermal stability and hydrolytic stability of polyetherimide $Ultem^{(R)}$ were improved by incorporating new developed imide oligomers.

• Polymer(Korea)
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• v.36 no.4
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• pp.478-485
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• 2012

A series of transparent polyimide (PI) nanocomposite films was synthesized from bicyclo(2,2,2)oct-7-ene-2,3,5,6-tetracarboxylic dianhydride (BTDA) and 1,3-bis(3-aminophenoxy)benzene (BAPB) with various organoclay contents via solution intercalation polymerization to poly(amic acid)s, followed by thermal imidization. Varying organoclay loading in a range of 0 to 1.5 wt% produced variations in the optical transparency, morphology, and oxygen barrier property of the hybrids. An optimum oxygen barrier property was observed for the hybrids containing 1.0 wt% Cloisite 30B; these properties were degraded gradually by further increases in the clay content. The PI hybrid films were found to exhibit excellent optical transparency and almost no color. However, the transparency of the hybrid films decreased slightly with increasing organoclay content. Transparent PI hybrid films containing 1.0 wt% Cloisite 30B were stretched equi-biaxially with various stretching ratios in a range of 100-140% to investigate their optical transparency and oxygen permeability in detail; the variations of clay dispersion and morphology were also determined as a function of equi-biaxial stretching ratio. PI hybrid films with ${\geq}120%$ stretching were found to contain homogeneously dispersed clay in the polymer matrix and exfoliated nanocomposites. The highest barrier to oxygen permeation was found at an equi-biaxial stretching ratio of 130%.

• Polymer(Korea)
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• v.32 no.3
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• pp.256-262
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• 2008

Copolyimides containing pendant trifluoromethyl ($CF_3$) groups were synthesized from 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and bis[4-(3-aminophenoxy)phenyl]sulfone (BAPS) with various concentrations of 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane(BAPP) to poly(amic acid)(PAA), followed by thermal imidization. These copolyimides were readily soluble in N,N'-dimethylacetamide (DMAc) and could be solution-cast into a flexible and tough film. The thermomechanical properties, morphology and an optical transparency of the copolyimide films were determined using differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), wide angle X-ray diffraction (XRD), scanning electron microscopy (SEM), universal tensile machine (UTM), and a UV-Vis spectrometer. The cast copolyimide films exhibited high optical transparency with a cut-off wavelength (${\lambda}_0$) of $275{\sim}319\;nm$ in UV-vis absorption and a low yellow index(YI) value of $3.65{\sim}10.37$. The thermo-mechanical properties of copolyimide films were enhanced linearly with increasing a BAPP content. In contrast, the optical transparency of the copolyimide films was found to get worse with increasing a BAPP content.