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Keywords = water-soluble poly(amic acid)

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17 pages, 3575 KB  
Article
Tailoring Properties Through Functionalized Alicyclic Diamine Towards Solution-Processable High-Performance Polyimide Films
by Lei Xiong, Feiyan Ding, Liangrong Li, Xinhai Wei, Jiayao Xu, Guanfa Xiao, Zhenyu Yang and Feng Liu
Polymers 2026, 18(2), 207; https://doi.org/10.3390/polym18020207 - 12 Jan 2026
Cited by 1 | Viewed by 886
Abstract
A novel fluorinated diamine monomer, 4,4′-((bicyclo[2.2.1]hept- 5-ene-2,3-diylbis (methylene)) bis(oxy))bis(3- (trifluoromethyl) aniline) (NFDA), featuring a tailored alicyclic norbornane core, flexible ether linkages, and pendant trifluoromethyl groups, was successfully synthesized. This monomer was polymerized with six commercial dianhydrides to produce a series of poly(amic acid) [...] Read more.
A novel fluorinated diamine monomer, 4,4′-((bicyclo[2.2.1]hept- 5-ene-2,3-diylbis (methylene)) bis(oxy))bis(3- (trifluoromethyl) aniline) (NFDA), featuring a tailored alicyclic norbornane core, flexible ether linkages, and pendant trifluoromethyl groups, was successfully synthesized. This monomer was polymerized with six commercial dianhydrides to produce a series of poly(amic acid) precursors, which were subsequently converted into high-performance polyimide (PI) films via a thermal imidization process. The strategic integration of the alicyclic, ether, and fluorinated motifs within the polymer backbone resulted in materials with an exceptional combination of properties. These PI films display outstanding solubility in a wide range of organic solvents, including low-boiling options like chloroform and tetrahydrofuran, highlighting their superior solution processability. The films are amorphous and exhibit remarkable hydrophobicity, evidenced by high water contact angles (up to 109.4°) and minimal water absorption (as low as 0.26%). Furthermore, they possess excellent optical transparency, with a maximum transmittance of 86.7% in the visible region. The materials also maintain robust thermal stability, with 5% mass loss temperatures exceeding 416 °C, and offer a desirable balance of mechanical strength and flexibility. This unique set of attributes, stemming from a rational molecular design, positions these polyimides as highly promising candidates for next-generation flexible electronics and advanced photovoltaics. Full article
(This article belongs to the Section Polymer Membranes and Films)
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12 pages, 2718 KB  
Article
Eco-Friendly Water-Processable Polyimide Binders with High Adhesion to Silicon Anodes for Lithium-Ion Batteries
by Yujin So, Hyeon-Su Bae, Yi Young Kang, Ji Yun Chung, No Kyun Park, Jinsoo Kim, Hee-Tae Jung, Jong Chan Won, Myung-Hyun Ryou and Yun Ho Kim
Nanomaterials 2021, 11(12), 3164; https://doi.org/10.3390/nano11123164 - 23 Nov 2021
Cited by 32 | Viewed by 7839
Abstract
Silicon is an attractive anode material for lithium-ion batteries (LIBs) because of its natural abundance and excellent theoretical energy density. However, Si-based electrodes are difficult to commercialize because of their significant volume changes during lithiation that can result in mechanical damage. To overcome [...] Read more.
Silicon is an attractive anode material for lithium-ion batteries (LIBs) because of its natural abundance and excellent theoretical energy density. However, Si-based electrodes are difficult to commercialize because of their significant volume changes during lithiation that can result in mechanical damage. To overcome this limitation, we synthesized an eco-friendly water-soluble polyimide (W-PI) precursor, poly(amic acid) salt (W-PAmAS), as a binder for Si anodes via a simple one-step process using water as a solvent. Using the W-PAmAS binder, a composite Si electrode was achieved by low-temperature processing at 150 °C. The adhesion between the electrode components was further enhanced by introducing 3,5-diaminobenzoic acid, which contains free carboxylic acid (–COOH) groups in the W-PAmAS backbone. The –COOH of the W-PI binder chemically interacts with the surface of Si nanoparticles (SiNPs) by forming ester bonds, which efficiently bond the SiNPs, even during severe volume changes. The Si anode with W-PI binder showed improved electrochemical performance with a high capacity of 2061 mAh g−1 and excellent cyclability of 1883 mAh g−1 after 200 cycles at 1200 mA g−1. Therefore, W-PI can be used as a highly effective polymeric binder in Si-based high-capacity LIBs. Full article
(This article belongs to the Special Issue Emerging Nanomaterials for Lithium-Sulfur Batteries and Beyond II)
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14 pages, 3849 KB  
Article
Colorless and Transparent Polyimide Microporous Film with Excellent Physicochemical Property
by Jong Won Kim, Seon Ju Lee, Moon Young Choi and Jin-Hae Chang
Polymers 2021, 13(8), 1298; https://doi.org/10.3390/polym13081298 - 15 Apr 2021
Cited by 7 | Viewed by 4923
Abstract
4,4′-(4,4′-isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA) as a dianhydride and bis(3-aminophenyl) sulfone (APS) and bis(3-amino-4-hydroxyphenyl) sulfone (APS-OH) as diamines were used to synthesize two types of poly(amic acid) (PAA). Varying amounts (0–5.0 wt%) of water-soluble poly(vinyl alcohol) (PVA) were mixed with PAA, and the resulting blend [...] Read more.
4,4′-(4,4′-isopropylidenediphenoxy)bis(phthalic anhydride) (BPADA) as a dianhydride and bis(3-aminophenyl) sulfone (APS) and bis(3-amino-4-hydroxyphenyl) sulfone (APS-OH) as diamines were used to synthesize two types of poly(amic acid) (PAA). Varying amounts (0–5.0 wt%) of water-soluble poly(vinyl alcohol) (PVA) were mixed with PAA, and the resulting blend was heat-treated at different stages to obtain the colorless and transparent polyimide (CPI) blend films. The synthesized blended film completely removed water-soluble PVA in water. The possibility as a porous membrane according to the pore size varied according to the amount of PVA was investigated. The dispersibility and compatibility of CPI containing APS-OH monomer were higher than those of the APS monomer. This could be attributed to the hydrogen-bonding interactions between the CPI main chains and PVA. Scanning electron microscopy was conducted to characterize the material. The results revealed that the pore size of the CPI blend film increased as the PVA concentration increased. It was confirmed that uniform pores of μm-size were observed in CPI. The thermal stabilities, morphologies, optical properties, and solubilities of two CPIs obtained using APS and APS-OH monomers were investigated and their properties were compared with each other. Full article
(This article belongs to the Special Issue High-Functional Polymeric Materials)
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17 pages, 3418 KB  
Article
Highly Stable Porous Polyimide Sponge as a Separator for Lithium-Metal Secondary Batteries
by Junyoung Choi, Kwansoo Yang, Hyeon-Su Bae, Isheunesu Phiri, Hyun Jeong Ahn, Jong Chan Won, Yong Min Lee, Yun Ho Kim and Myung-Hyun Ryou
Nanomaterials 2020, 10(10), 1976; https://doi.org/10.3390/nano10101976 - 6 Oct 2020
Cited by 14 | Viewed by 6351
Abstract
To inhibit Li-dendrite growth on lithium (Li)-metal electrodes, which causes capacity deterioration and safety issues in Li-ion batteries, we prepared a porous polyimide (PI) sponge using a solution-processable high internal-phase emulsion technique with a water-soluble PI precursor solution; the process is not only [...] Read more.
To inhibit Li-dendrite growth on lithium (Li)-metal electrodes, which causes capacity deterioration and safety issues in Li-ion batteries, we prepared a porous polyimide (PI) sponge using a solution-processable high internal-phase emulsion technique with a water-soluble PI precursor solution; the process is not only simple but also environmentally friendly. The prepared PI sponge was processed into porous PI separators and used for Li-metal electrodes. The physical properties (e.g., thermal stability, liquid electrolyte uptake, and ionic conductivity) of the porous PI separators and their effect on the Li-metal anodes (e.g., self-discharge and open-circuit voltage properties after storage, cycle performance, rate capability, and morphological changes) were investigated. Owing to the thermally stable properties of the PI polymer, the porous PI separators demonstrated no dimensional changes up to 180 °C. In comparison with commercialized polyethylene (PE) separators, the porous PI separators exhibited improved wetting ability for liquid electrolytes; thus, the latter improved not only the physical properties (e.g., improved the electrolyte uptake and ionic conductivity) but also the electrochemical properties of Li-metal electrodes (e.g., maintained stable self-discharge capacity and open-circuit voltage features after storage and improved the cycle performance and rate capability) in comparison with PE separators. Full article
(This article belongs to the Special Issue Emerging Nanomaterials for Lithium-Sulfur Batteries and Beyond)
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14 pages, 4635 KB  
Article
Syntheses of Colorless and Transparent Polyimide Membranes for Microfiltration
by Jong Won Kim and Jin-Hae Chang
Polymers 2020, 12(7), 1610; https://doi.org/10.3390/polym12071610 - 20 Jul 2020
Cited by 16 | Viewed by 4786
Abstract
Herein, poly(amic acid) (PAA) was synthesized using 4,4’-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) as a dianhydride and 2,2-bis(3-aminophenyl)hexafluoropropane (6FAm) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAm-OH) as diamines. Poly(vinyl alcohol) (PVA) at various contents (0–5.0 wt%) was blended with PAA to prepare a composite material. Then, colorless and transparent [...] Read more.
Herein, poly(amic acid) (PAA) was synthesized using 4,4’-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) as a dianhydride and 2,2-bis(3-aminophenyl)hexafluoropropane (6FAm) and 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (6FAm-OH) as diamines. Poly(vinyl alcohol) (PVA) at various contents (0–5.0 wt%) was blended with PAA to prepare a composite material. Then, colorless and transparent polyimide (CPI) composite films were prepared by applying various stages of heat treatment using the PAA/PVA blend film as a precursor. These film-type composites were immersed in water to completely dissolve PVA, a water-soluble polymer, and their pore sizes were investigated to determine their potential as a porous membrane. According to the results of scanning electronic microscopy (SEM), as the concentration of PVA increased from 0 to 5.0 wt% in the CPI/PVA composite films, the size of the pores resulting from the dissolution of water-soluble PVA increased. Further, the micrometer-sized pores were uniformly dispersed in the CPI films. The thermal properties, morphology, and optical transparency of the two types of CPI membranes synthesized using 6FAm and 6FAm-OH monomers were examined and compared. Full article
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24 pages, 4045 KB  
Article
Poly(ester imide)s Possessing Low Coefficients of Thermal Expansion and Low Water Absorption (V). Effects of Ester-linked Diamines with Different Lengths and Substituents
by Masatoshi Hasegawa and Tomoaki Hishiki
Polymers 2020, 12(4), 859; https://doi.org/10.3390/polym12040859 - 8 Apr 2020
Cited by 38 | Viewed by 6223
Abstract
A series of ester-linked diamines, with different lengths and substituents, was synthesized to obtain poly(ester imide)s (PEsIs) having improved properties. A substituent-free ester-linked diamine (AB-HQ) was poorly soluble in N-methyl-2-pyrrolidone at room temperature, which forced the need for polyaddition by adding tetracarboxylic [...] Read more.
A series of ester-linked diamines, with different lengths and substituents, was synthesized to obtain poly(ester imide)s (PEsIs) having improved properties. A substituent-free ester-linked diamine (AB-HQ) was poorly soluble in N-methyl-2-pyrrolidone at room temperature, which forced the need for polyaddition by adding tetracarboxylic dianhydride solid into a hot diamine solution. This procedure enabled the smooth progress of polymerization, however, accompanied by a significant decrease in the molecular weights of poly(amic acid)s (PAAs), particularly when using hydrolytically less stable pyromellitic dianhydride. On the other hand, the incorporation of various substituents (–CH3, –OCH3, and phenyl groups) to AB-HQ was highly effective in improving diamine solubility, which enabled the application of the simple polymerization process without the initial heating of the diamine solutions, and led to PAAs with sufficiently high molecular weights. The introduction of bulkier phenyl substituent tends to increase the coefficients of thermal expansion (CTE) of the PEsI films, in contrast to that of the small substituents (–CH3, –OCH3). The effects of ester-linked diamines, consisting of longitudinally further extended structures, were also investigated. However, this approach was unsuccessful due to the solubility problems of these diamines. Consequently, the CTE values of the PEsIs, obtained using longitudinally further extended diamines, were not as low as we had expected initially. The effects of substituent bulkiness on the target properties, and the dominant factors for water uptake (WA) and the coefficients of hygroscopic expansion (CHE), are also discussed in this study. The PEsI derived from methoxy-sustituted AB-HQ analog and 3,3′,4,4′-biphenyltetracarboxylic dianhydride achieved well-balanced properties, i.e., a very high Tg (424 °C), a very low CTE (5.6 ppm K−1), a low WA (0.41%), a very low CHE value (3.1 ppm/RH%), and sufficient ductility, although the 26 μm-thick film narrowly missed certification of the V-0 standard in the UL-94V test. This PEsI film also displayed a moderate εr (3.18) and a low tan δ (3.14 × 10−3) at 10 GHz under 50% RH and at 23 °C. Thus, this PEsI system is a promising candidate as a novel dielectric substrate material for use in the next generation of high-performance flexible printed circuit boards operating at higher frequencies (≥10 GHz). Full article
(This article belongs to the Special Issue High-Functional Polymeric Materials)
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14 pages, 3579 KB  
Article
Polyimide-Coated Glass Microfiber as Polysulfide Perm-Selective Separator for High-Performance Lithium-Sulphur Batteries
by Mi-Jin Kim, Kwansoo Yang, Hui-Ju Kang, Hyun Jin Hwang, Jong Chan Won, Yun Ho Kim and Young-Si Jun
Nanomaterials 2019, 9(11), 1612; https://doi.org/10.3390/nano9111612 - 13 Nov 2019
Cited by 7 | Viewed by 5036
Abstract
Although numerous research efforts have been made for the last two decades, the chronic problems of lithium-sulphur batteries (LSBs), i.e., polysulfide shuttling of active sulphur material and surface passivation of the lithium metal anode, still impede their practical application. In order to mitigate [...] Read more.
Although numerous research efforts have been made for the last two decades, the chronic problems of lithium-sulphur batteries (LSBs), i.e., polysulfide shuttling of active sulphur material and surface passivation of the lithium metal anode, still impede their practical application. In order to mitigate these issues, we utilized polyimide functionalized glass microfibers (PI-GF) as a functional separator. The water-soluble precursor enabled the formation of a homogenous thin coating on the surface of the glass microfiber (GF) membrane with the potential to scale and fine-tune: the PI-GF was prepared by simple dipping of commercial GF into an aqueous solution of poly(amic acid), (PAA), followed by thermal imidization. We found that a tiny amount of polyimide (PI) of 0.5 wt.% is more than enough to endow the GF separator with useful capabilities, both retarding polysulfide migration. Combined with a free-standing microporous carbon cloth-sulphur composite cathode, the PI-GF-based LSB cell exhibits a stable cycling over 120 cycles at a current density of 1 mA/cm2 and an areal sulphur loading of 2 mgS/cm2 with only a marginal capacity loss of 0.099%/cycle. This corresponds to an improvement in cycle stability by 200%, specific capacity by 16.4%, and capacity loss per cycle by 45% as compared to those of the cell without PI coating. Our study revealed that a simple but synergistic combination of porous carbon supporting material and functional separator enabled us to achieve high-performance LSBs, but could also pave the way for the development of practical LSBs using the commercially viable method without using complicated synthesis or harmful and expensive chemicals. Full article
(This article belongs to the Special Issue Emerging Nanomaterials for Lithium-Sulfur Batteries and Beyond)
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