• Polymer(Korea)
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• v.33 no.4
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• pp.313-318
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• 2009

Copolyimides were synthesized from bis (3-aminophenyl) sulfone (APS) and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) containing a fluorine substituent ($-CF_3$) with different mole ratios of 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride (DSDA) containing a sulfone group (-$SO_2$-). The PI films were obtained from poly (amic acid) (PAA) by solution casting through thermal imidization on a glass plate. Wide-angle X-ray diffraction (XRD), scanning electron microscopy (FE-SEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), universal tensile machine (UTM) measurements, and UV-Vis spectrometry were used to assess thermo-mechanical properties, morphology, and optical transparency. Thermal properties and optical transparency decreased with increasing DSDA mole fraction. In contrast, mechanical properties increased with increasing DSDA mole fraction. As compared to conventional PI films, however, the PI copolymer films in this work were found to exhibit better optical transparency.

• Macromolecular Research
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• v.12 no.6
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• pp.545-552
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• 2004

The long-term stability of sulfonic acid-containing polyimides has been investigated. The hydrolytic degradation of homopolyimide and the block copolyimide comprising $27\;mol\%$ of 2,2'-bis(trifluoromethyl)benzidine and $9\;mol\%$ of m-phenylenediamine (BTFMB27mPl0[7/(3+1)]), was quantified through viscosity measurements and FT-IR spectroscopic analyses. The viscosity decrease with respect to time and the degradation rate were similar. The degrees of degradation with respect to time under ambient conditions and at elevated temperature in water were monitored by FT-IR spectroscopy. A new absorption peak was observed at $1786\;cm^{-1},$ which we corresponds to the presence of anhydride end groups formed by hydrolytic scission of the imide rings.

• 한국정보디스플레이학회:학술대회논문집
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• 2004.08a
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• pp.1188-1192
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• 2004

Polyamic acid precursors were prepared by mixing various main chain dianhydrides, main chain diamines and side chain diamines. Copolyimide films with alkylcyclohexylbenzene as a side chain were prepared by thermal imidization of polyamic acid precursors. Pretilt angles on rubbed polyimides changed according to the side chain and main chain structures of the polyimide. Consequently, we found that LC pretilt angles of polyimide films with a liquid crystal structure as a side chain showed to be approximately 90$^{\circ}$ when a linear and rigid polyimide main chain and a side chain of suitable length were employed.

• Proceedings of the Membrane Society of Korea Conference
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• 1994.04a
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• pp.53-54
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• 1994

Polyimide는 열, 화학적으로 안정하고 기계적성질이 우수하고, 기체분리특성이 비교적 좋다. Polyimide의 화학구조와 기체투과도와의 관계는 화학구조를 체계적으로 변화시키면서 많이 검토되어왔다.[1-2] Polyimide는 강직한 직쇄구조, bulky group에 의한 분자쇄운동성을 제어함과 동시, 약한 분자간 상호작용이 polymer chain의 유효층진을 억제하여 기체투과도를 높여준다. 국부분절운동(local segmental mobility)이 감소된 구조는 기체투과선택도를 향상시켜주는 경향을 보여주었다. [3] kim et al. 과 Stern et al은 6FDA나 fluorine-containing diamines으로 만든 polyimde가 매우높은 투과도를 보여준다고 보고했다. 본 연구에서는 6FDA-2, 4TDA hobopolymer에 BAAF를 가하여 copolyimide Membrane을 제막하여 BAAF 조성에 따라 투과선택도를 측정하는 homopolymer와 copolymer에 따른 변화를 관찰하였다.

• 한국정보디스플레이학회:학술대회논문집
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• 2005.07a
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• pp.389-392
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• 2005

Poly(amic acid) precursors were prepared by mixing various main chain dianhydrides, main chain diamines and side chain diamines. The side chain diamine has an alkylbicyclohexyl group as a side chain. The copolyimide films, produced by casting the poly (amic acids) solution, exhibited the vertical alignment property without the rubbing process in the range of the curing themperature from $90^{\circ}C$ to $240^{\circ}C$ for 1h. The thermal and surface properties of the poly(amic acids) depending on the curing temperature was examined.

• Applied Chemistry for Engineering
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• v.9 no.1
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• pp.13-19
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• 1998

Copolyimide membranes of different chemical structure based on pyromellitic dianhydride (PMDA)/methylendianiline(MDA) were prepared by varying their chemical compositions with adding meta-phenylendiamine (MPD), para- phenylendiamine (PPD), 2,4,6- trimethyl-1,3-phenylenediamine(TriMeMPD) as a co-monomer. The $N_2$ and $O_2$ permeation properties are qualitatively correlated to specific free volume and intersegmental distance of membrane. The partial replacement of MDA with MPD or PPD caused in the PMDA/MDA based membranes increase in density, and decrease in free volume, d-spacing, consequently resulted in decreased permeability coefficient. In the case of TriMeMPD, opposite results were observed. In all membranes, the permeability coefficients were pressure independent, and membranes which have high permeability coefficient showed low $N_2/O_2$ ideal separation factor as an usual manner. The permeability coefficient also increased with temperature and $N_2/O_2$ ideal separation factor decreased. The increase ratio of the $N_2$ permeability coefficient was larger than that of $O_2$.

• Applied Chemistry for Engineering
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• v.2 no.4
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• pp.340-347
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• 1991

Siloxane containing copolyimide (SPI) was synthesized from 3, 3', 4, 4'-benzophenonetetracarboxylic dianhydride(BTDA), 4, 4'-methylene dianiline(MDA), 4, 4'-oxydianiline(ODA) and amine-terminated polydimethyl-siloxane(PDMS). Homopolyamic acid(HPAA) in tetrahydrofuran(THF) was reacted with PDMS to obtain siloxane containing polyamic acid(SPAA) followed by the thermal curing to manufacture SPI. SPAA and HPAA exhibited inherent viscosity value of 0.35~0.48dl/g. Glass transition temperature of SPI ranged in $258^{\circ}C{\sim}264^{\circ}C$. SPI had a lower $T_g$ than that of HPI. ODA based HPI and SPI showed slightly higher $T_g$ values, thermal stability, and water content.

• Membrane Journal
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• v.24 no.1
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• pp.1-9
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• 2014

In this study, four soluble homo- and co-polyimides using 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride (DOCDA) and 4,4'-diaminodiphenyl ether (ODA) monomers were synthesized to develop the gas separation membrane with good $CO_2/CH_4$ separation properties. To prepare the copolyimides, 20 mol% of three dianhydrides - (4,4'-(hexafluoroisoproplidene)diphthalic anhydride (6FDA), 4,4'-biphthalic anhydride (BPDA), 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA) - were added in DOCDA-ODA monomer mixture, respectively. All the synthesized homo- and co-polyimides were characterized by FT-IR. Their thermal properties were analyzed with differential scanning calorimeter (DSC). Dense membranes were prepared from these copolyimides to check their gas permeation properties for $CO_2$ and $CH_4$ gases using a time-lag method. The permeation testing results are as follows; DOCDA/ODA homopolymer showed 1.71 barrer of $CO_2$ permeability and 74.35 of $CO_2/CH_4$ selectivity. The three polyimide copolymers (DOCDA/6FDA-ODA, DOCDA/BPDA-ODA, DOCDA/BTDA-ODA) showed lower $CO_2/CH_4$ selectivities and higher $CO_2$ permeabilities than the homopolymer (DOCDA-ODA). DOCDA/6FDA-ODA showed twice times higher $CO_2$ permeabilities without severe $CO_2/CH_4$ selectivity loss than the DOCDA-ODA.

• Membrane Journal
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• v.25 no.3
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• pp.231-238
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• 2015

Co-polyimide membranes were prepared by two-step polymerization using semi-alicyclic 5-(2,5-dioxotetrahydrofuryl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride (DOCDA) with five diamines such as 2,5-dimethyl-1,4-phenylene diamine (2M), 2,4,6-trimethyl-1,3-phenylene diamine (3M), 1,5-naphthalene diamine (NDA), 4,4-diaminodiphenyl methane (MDA), 4,4'-diaminodiphenyl ether (ODA). Synthesized co-polyimides were characterized by FT-IR, viscosity, solubility, DSC, TGA and gas permeation properties, compared with 6FDA-based co-polyimides. All co-polyimides had the intrinsic viscosity of 0.32~0.58 and excellent solubility in various solvents. DOCDA-based co-polyimides had thermal stability over $400^{\circ}C$ although those were lower than 6FDA-based co-polyimides. Gas permeabilities of the copolyimide membranes were measured for $CO_2$ and $CH_4$ at room temperature and presented the trade-off relationship.