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Keywords = CpODA

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69 pages, 46804 KB  
Article
Colorless Polyimides Derived from Novel Role-Dividing Spiro-Type Monomers: Strategies to Overcome the Trade-Off Between Low Linear Coefficients of Thermal Expansion and Low Thickness-Direction Birefringence Without Fillers
by Masatoshi Hasegawa, Yoshihiko Terada, Ko Nagahaba, Soichi Tsukuda, Toya Ikuma, Hikaru Sugihara, Ryosuke Masaka, Shinya Takahashi, Junichi Ishii and Takao Miwa
Polymers 2026, 18(9), 1108; https://doi.org/10.3390/polym18091108 - 30 Apr 2026
Viewed by 823
Abstract
This study presents unique polymeric materials applicable to plastic substrates for use in flexible-display devices that overcome the trade-off between low linear coefficients of thermal expansion (CTE) and low thickness-direction birefringence (Δnth) while combining a very high Tg, [...] Read more.
This study presents unique polymeric materials applicable to plastic substrates for use in flexible-display devices that overcome the trade-off between low linear coefficients of thermal expansion (CTE) and low thickness-direction birefringence (Δnth) while combining a very high Tg, sufficiently high thermal stability, excellent optical transparency, good solubility, and minimum-required ductility. Polyimide (PI) films obtained from 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) with 2,2′-bis(trifluoromethyl)benzidine (TFMB) under different conditions resulted in widely varying CTE values and provided a clear CTE–Δnth correlation, which can be regarded as a virtual lower boundary in the CTE–Δnth relationship for various PI systems. The pristine CBDA/TFMB and CpODA/TFMB (CpODA = norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride) systems were modified using numerous specifically designed monomers, i.e., a vertical-alignment-type liquid-crystalline diamine and cardo-type and spiro-type monomers. However, it was very challenging to overcome the trade-off between low CTE and low Δnth, that is, to significantly exceed this lower boundary by modifying the pristine systems, while ensuring other target properties. One of the keys to achieving the present goal was compatibility with chemical imidization or one-pot polymerization processes (i.e., high solubility of the PIs), because these processes were more advantageous in reducing CTE and enhancing film transparency than the conventional two-step process. The modifications using phenyl-substituted xanthene-pendant 2,7-diaminofluorene and fluorene-pendant 2,3,6,7-xanthenetetracarboxylic dianhydride exhibited a prominent effect on overcoming the trade-off without the help of any fillers, while combining other excellent target properties. Polarized FT-IR difference spectra measured at varying incidence angles suggested that these side groups, which are connected perpendicularly to the PI main chains, align in the Z-direction, rationalizing the observed prominent effect. Thus, unique high-temperature transparent materials applicable to plastic substrates were successfully obtained in this study. Full article
(This article belongs to the Section Polymer Chemistry)
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47 pages, 13613 KB  
Article
Colorless Polyimides with Low Linear Coefficients of Thermal Expansion and Their Controlled Soft Adhesion/Easy Removability on Glass Substrates: Role of Modified One-Pot Polymerization Method
by Masatoshi Hasegawa, Takehiro Shinoda, Kanata Nakadai, Junichi Ishii, Tetsuo Okuyama, Kaya Tokuda, Hiroyuki Wakui, Naoki Watanabe and Kota Kitamura
Polymers 2025, 17(13), 1887; https://doi.org/10.3390/polym17131887 - 7 Jul 2025
Cited by 2 | Viewed by 2004
Abstract
This study presents colorless polyimides (PIs) suitable for use as plastic substrates in flexible displays, designed to be compatible with controlled soft adhesion and easy delamination (temporary adhesion) processes. For this purpose, we focused on a PI system derived from norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride (CpODA) [...] Read more.
This study presents colorless polyimides (PIs) suitable for use as plastic substrates in flexible displays, designed to be compatible with controlled soft adhesion and easy delamination (temporary adhesion) processes. For this purpose, we focused on a PI system derived from norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride (CpODA) and 2,2′-bis(trifluoromethyl)benzidine (TFMB). This system was selected with the aim of exhibiting excellent optical transparency and low linear coefficient of thermal expansion (CTE) properties. However, fabricating this PI film via the conventional two-step process was challenging because of crack formation. In contrast, modified one-pot polymerization at 200 °C using a combined catalyst resulted in a homogeneous solution of PI with an exceptionally high molecular weight, yielding a flexible cast film. The solubility of PI plays a crucial role in its success. This study delves into the mechanism behind the significant catalytic effect on enhancing molecular weight. The CpODA/TFMB PI cast film simultaneously achieved very high optical transparency, an extremely high glass transition temperature (Tg = 411 °C), a significantly low linear coefficient of thermal expansion (CTE = 16.7 ppm/K), and sufficient film toughness, despite the trade-off between low CTE and high film toughness. The CpODA/TFMB system was modified by copolymerization with minor contents of another cycloaliphatic tetracarboxylic dianhydride, 5,5′-(1,4-phenylene)-exo-bis(hexahydro-4,7-methanoisobenzofuran-cis-exo-1,3-dione) (BzDAxx). This approach was effective in improving the film toughness without sacrificing the low CTE and other target properties. The peel strengths (σpeel) of laminates comprising surface-modified glass substrates and various colorless PI films were measured to evaluate the compatibility with the temporary adhesion process. Most colorless PI films studied were found to be incompatible. Additionally, no correlation between σpeel and PI structure was observed, making it challenging to identify the structural factors influencing σpeel control. Surprisingly, a strong correlation was observed between σpeel and CTE of the PI films, suggesting that the observed solid–solid lamination is closely linked to the unexpectedly high surface mobility of the PI films. The laminate using CpODA(90);BzDAxx(10)/TFMB copolymer exhibited suitable adhesion strength for the temporary adhesion process, while meeting other target properties. The modified one-pot polymerization method significantly contributed to the development of colorless PIs suitable for plastic substrates. Full article
(This article belongs to the Section Polymer Applications)
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11 pages, 2979 KB  
Article
Colorless Polyimides Derived from an Alicyclic Tetracarboxylic Dianhydride, CpODA
by Hiroki Ozawa, Eriko Ishiguro, Yuri Kyoya, Yasuaki Kikuchi and Toshihiko Matsumoto
Polymers 2021, 13(16), 2824; https://doi.org/10.3390/polym13162824 - 22 Aug 2021
Cited by 51 | Viewed by 6414
Abstract
An alicyclic tetracarboxylic dianhydride having cyclopentanone bis-spironorbornane structure (CpODA) was polycondensated with aromatic dianhydrides to form the corresponding poly(amic acid)s which possessed logarithmic viscosities in the range 1.47–0.54 dL/g. The poly(amic acid) was imidized by three methods: a chemical, a thermal, and a [...] Read more.
An alicyclic tetracarboxylic dianhydride having cyclopentanone bis-spironorbornane structure (CpODA) was polycondensated with aromatic dianhydrides to form the corresponding poly(amic acid)s which possessed logarithmic viscosities in the range 1.47–0.54 dL/g. The poly(amic acid) was imidized by three methods: a chemical, a thermal, and a combined chemical and thermal process. In a thermal method, imidization temperature markedly influenced the film quality and molecular weight of the polyimide. When the poly(amic acid) was cured over the Tg of the corresponding polyimide, the flexible polyimide films were obtained and the molecular weights increased several times, which means that the post-polymerization took place. In spite of low-temperature cure below Tg flexible films with the imidization ratio of 100% were fabricated by a combined chemical and thermal imidization technique. The films possessed the decomposition temperatures in a range of 475–501 °C and Tgs over 330 °C. The high Tg results from a dipole–dipole interaction between the keto groups of the polymer chains as well as development of the rigid polyalicyclic unit. The polyimide films exhibited CTE between 17 and 57 ppm/K. All the films fabricated were entirely colorless and possessed the λcut-offs shorter than 337 nm. Notably, the films prepared by a chemical method exhibited outstanding optical properties. Full article
(This article belongs to the Special Issue Advanced Polyimides and Other High Performance Polymers)
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13 pages, 2208 KB  
Article
An Efficient Bioemulsifier-Producing Bacillus subtilis UCP 0146 Isolated from Mangrove Sediments
by Patrícia C. V. S. Maia, Vanessa P. Santos, Adriana S. Fereira, Marcos A. C. Luna, Thayse A. L. Silva, Rosileide F. S. Andrade and Galba M. Campos-Takaki
Colloids Interfaces 2018, 2(4), 58; https://doi.org/10.3390/colloids2040058 - 13 Nov 2018
Cited by 17 | Viewed by 4616
Abstract
In this work, we investigated the potential of Bacillus subtilis UCP 0146 in the bioconversion of a medium containing 100% cassava flour wastewater to obtain a bioemulsifier. The evaluation of the production was carried out by the emulsification index (IE24) and [...] Read more.
In this work, we investigated the potential of Bacillus subtilis UCP 0146 in the bioconversion of a medium containing 100% cassava flour wastewater to obtain a bioemulsifier. The evaluation of the production was carried out by the emulsification index (IE24) and the surface tension (ST). The ionic charge, stability (temperature, salinity, and pH measured by IE24 and viscosity), and ability to remove and disperse oil and textile dye were investigated. B. subtilis produced an anionic bioemulsifier in the medium containing 100% cassava wastewater under Condition 4 of the factorial design (inoculum 9% at a temperature of 35 °C and shaken at 100 rpm), and showed a surface tension of 39 mN/m, an IE24 of 95.2%, and a yield of 2.69 g·L−1. The bioemulsifier showed stability at different pH (2–8), temperatures (0–120 °C), and NaCl concentrations, a dispersion oil displacement area (ODA) test of 55.83 cm2, and a reduction of the viscosity of the burned engine oil (90.5 Cp). The bioemulsifier was able to remove petroleum (94.4%) and methylene blue azo dye (62.2%). The bioemulsifier and its synthesis from bacteria also emphasizes the role of surfactants in oil remediation. Full article
(This article belongs to the Special Issue Biosurfactants: Trends and Applications)
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