• Elastomers and Composites
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• v.58 no.1
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• pp.26-31
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• 2023

Aromatic diamine containing ortho catenation and methyl group was synthesized from 4-methyl catechol and 4-nitrobenzoyl chloride. Subsequently, a poly(amic acid) was prepared by reacting 4-methyl-1,2-phenylene bis(4-aminobenzoate) with 4,4'-hexafluoroisopropylidenediphthalic anhydride (6FDA). The resulting poly(amic acid) was transformed into a polyimide through chemical imidization. The polyimide formed was soluble in N-methyl-2-pyrrolidone (NMP) and could be cast into a flexible, transparent film. Furthermore, the polyimide exhibited a 5% weight loss at 380 ℃ in the nitrogen atmosphere.

• Elastomers and Composites
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• v.59 no.3
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• pp.91-96
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• 2024

A novel aromatic polyimide containing the 4-tert-butyl group was prepared from 4-tert-butyl-1,2-phenylene bis(4-aminobenzoate) and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). 4-tert-Butyl-1,2-phenylene bis(4-aminobenzoate) was synthesized from 4-tert-butyl catechol and 4-nitrobenzoyl chloride. The poly(amic acid) was transformed into a polyimide via chemical imidization. The polyimide was soluble in N-methyl-2-pyrrolidone (NMP) and could be cast into a flexible and transparent film. The thermal stability of the polyimide was decreased slightly due to the pendant tertbutyl group.

• Macromolecular Research
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• v.11 no.3
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• pp.157-162
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• 2003

6FDA-based polyimides were prepared from the thermal imidization reaction of 6FDA with diamines of BAPAF, DAP, and DABA having a polar group of hydroxyL or carboxyl. Properties of the dense polyimide membranes were characterized and their gas permeation properties for H$_2$, $CO_2$, $O_2$, $N_2$, and CH$_4$ were investigated. Permeabilities, diffusion coefficients and diffusivity selectivities of polar group-containing polyimide membranes including 6FDA-BAPAF, 6FDA-DAP, and 6FDA-DABA polymer for the gases did not change largely. The separation properties of 6FDA-TrMPD polyimide membrane used as a reference polymer were compared with those of the polyimide membranes mentioned above. It was found that the polyimides of 6FDA-BAPAF, 6FDA-DAP, and 6FDA-DABA, which were soluble in alcohol or/and 2-methoxyethanol, could be applicable to the preparation of a dense composite membrane by dip-coating method.

• Macromolecular Research
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• v.15 no.4
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• pp.357-362
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• 2007

Polyimide/carbon nanotube (CNT) composite films, for potential use in high performance microelectronics and aerospace applications, were prepared by mixing a polyisoimide (PII) solution and a CNT suspension in NMP, followed by casting, evaporation and thermal imidization. The CNTs were modified by a nitric acid treatment to improve the thermal and electrical properties, as well as to provide good dispersion of the CNTs in a polymer matrix. The formation of functional groups on the modified CNT was confirmed by Raman spectroscopy. Scanning electron microscopy revealed the modified CNTs to be well dispersed in the polyimide matrix, with a uniform diameter of ca. 50 nm. The thermal stability of the films containing the CNTs was improved due to the enhanced interfacial interaction and good dispersion between the polyimide matrix and modified CNTs. In addition, the thermal expansion coefficient of the composites films was slightly decreased, but the dielectric constants increased linearly with increasing CNT content.

• Polymer(Korea)
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• v.38 no.6
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• pp.774-781
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• 2014

Acetylenic or phenylethynyl end-capped polyisoimide oligomers ($M_w$ 2500 g/mol, 5000 g/mol) based upon 4,4'-diamino diphenyl ether (4,4'-ODA)/4,4'-oxydiphthalic anhydride (ODPA) and 4,4'-ODA/3,3',4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA) were synthesized by using 4-ethynylaniline (4-EA) or 4-phenylethynyl phthalic anhydride (4-PEPA) as an end capper. The incorporation of ethynyl groups were confirmed by FTIR spectroscopy. The isomerization temperature was influenced by molecular weight as well as the backbone structure of polyisoimides oligomers. Thus, polyisoimide oligomers with molecular weight of 2500 g/mol was found to be imidized at temperature $10^{\circ}C$ lower than that for the oligomers with molecular weight of 5000 g/mol. The crosslinking reaction of ethynyl groups occurred at a higher temperature than that for the isoimide/imide isomerization reaction. These two reactions were totally or partially overlapped on the DSC thermograms for the polyisoimide oligomer end-capped with 4-EA. Kinetics of thermal imidization and crosslinking reactions for the 4,4'-ODA/ODPA polyisoimide oligomers end-capped with 4-PEPA were investigated by performing dynamic DSC experiments at heating rate of $10^{\circ}C/min$. The activation energy and pre-exponential factors were 141 kJ/mol and $1.45{\times}10^{13}min^{-1}$ for the imidization reaction and 177 kJ/mol and $2.90{\times}10^{13}min^{-1}$ for the crosslinking reaction, respectively.

• Macromolecular Research
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• v.11 no.3
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• pp.172-177
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• 2003

Biphenyltetracarboximide-phenylene diamine polyimide/silica-titania ternary hybrid composites were Prepared by thermal imidization and sol-gel reaction. Fluorescence spectroscopic, scanning electron microscopy, and atomic force microscopy studies revealed that the addition of small amount of titania showed profound effects on the microstructure and photophysical behaviors of polyimide/silica hybrid composites, when the content of silica-titania mixture was small or when the ratio of silica to titania in the mixture was high.

• Macromolecular Research
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• v.9 no.5
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• pp.247-252
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• 2001

Tricyclic aliphatic dianhydride monomer, tricycle[4.2.2.0]dec-9-ene exo, endo-3,4: 7,8-tetra-carboxylicdianhydride (TCDDA), was synthesized by photochemical reaction and poly(amic acid)s from TCDDA and diamines such as 1,4-bis-(4-aminophenoxy)benzene (BAB), 2,2-bis(4-(4-aminophenoxy) phenyl) propane (BAPP), 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane (BAPHF), bis(4-(4-ami-nophenoxy) phenyl)sulfone (BAPS), and 1,4-bis-(4-aminophenoxy)biphenyl (BABP) were prepared. The inherent viscosities of the poly(amic acid)s were between 0.39 and 0.50 dL/g. The poly(amic acid)s were converted to polyimide films by thermal imidization. The glass transition temperatures (T$\_$g/) of the polyimides were in the range of 201-263$\^{C}$. The thermogravimetric analysis (TGA) thermogram of these polyimides showed the temperatures of 5% weight losses between 375 and 393$\^{C}$ in nitrogen atmosphere. To show their utility for image generation, degradations of these polyimides in UV exposure were investigated by UV spectroscopy.

• Macromolecular Research
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• v.8 no.1
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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.

• Macromolecular Research
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• v.14 no.3
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• pp.300-305
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• 2006

The chemical structure of a semi-aromatic polyimide-I, which was prepared by the chemical imidization of cyclopentanetetracarboxylic dianhydride and 2,2-bis(4-aminophenyl)hexafluoropropane, was characterized by $^{13}C-NMR$ spectroscopy. The chemically imidized polyimide-I was used for the preparation of a photosensitive polyimide (PSPI) through the addition of benzophenone and benzophenone oxime hexamethylene diurethane (BOHD), a photobase generator containing oxime-urethane groups. The polyimide-I film containing benzophenone and BOHD was not soluble in 2.38 wt% tetrabutylammonium hydroxide solution in $H_2O$. However, it became soluble following irradiation with 310 nm UV light. A positive tone image with a resolution of $5{\mu}m$ was obtained with this PSPI, having sensitivity($D_c$) of $1.2J/cm^2$ and contrast(${\gamma}_p$) of 1.08. Thus, a polyimide, which is not intrinsically photosensitive, can become photosensitive through the addition of a photobase generator containing oxime-urethane groups as a photosensitive compound.

• Journal of the Korean Chemical Society
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• v.54 no.6
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• pp.744-748
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• 2010

2,3,4,5-Tetrafluorobenzoic acid, an important intermediates of fluoroquinolone antibiotics, was synthesized from tetrachloride phthalic anhydride through imidation, fluorination, hydrolysis and decarboxylation. The effects of phase transfer catalyst on imidation and fluorination reaction and the effects of surfactants on the hydrolysis reaction were studied, respectively. Experimental results showed that the imidation reaction time was greatly reduced in the presence of a phase transfer catalyst, hexadecyltrimethyl, resulting in imidation yield as high as 98.2%. The fluorination yield reached 81.3% when tetrabutylammonium bromide was chosen as a phase transfer catalyst. The hydrolysis reaction time was also decreased by adding hexadecyltrimethyl while increasing the yield to 88.6%. In the post-processing, the sublimation method was used to purify the product, and ideal effect was obtained. In the decarboxylation reaction, tetrafluoride phthalic acid was obtained by decarboxylation in the solvent of tri-n-butyl amine and decarboxylation yield reached 81.6%. Compared with the literature method, the overall reaction time of the improved method decreased from 53 h to 20.5 h and the total yield increased from 47.3% to 57.4%.