Polymers

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11 pages, 4186 KiB

Open AccessEditor’s ChoiceArticle

The Study of pH Effects on Phase Transition of Multi-Stimuli Responsive P(NiPAAm-co-AAc) Hydrogel Using 2D-COS

by Yeonju Park, Minkyoung Kim, Hae-jin Chung, Ah-hyun Woo, Isao Noda and Young-mee Jung

Polymers 2021, 13(9), 1447; https://doi.org/10.3390/polym13091447 - 29 Apr 2021

Cited by 14 | Viewed by 2585

The temperature and mechanism of phase transition of poly(N-isopropylacrylamide-co-acrylic acid) [P(NiPAAm-co-AAc)], which is one of the multi-stimuli responsive polymers, were investigated at various pHs using infrared (IR) spectroscopy, two-dimensional (2D) gradient mapping, and two-dimensional correlation spectroscopy (2D-COS). [...] Read more.

The temperature and mechanism of phase transition of poly(N-isopropylacrylamide-co-acrylic acid) [P(NiPAAm-co-AAc)], which is one of the multi-stimuli responsive polymers, were investigated at various pHs using infrared (IR) spectroscopy, two-dimensional (2D) gradient mapping, and two-dimensional correlation spectroscopy (2D-COS). The determined phase transition temperature of P(NiPAAm-co-AAc) at pH 4, 3, and 2 based on 2D gradient mapping and principal component analysis (PCA) showed that it decreases with decreasing pH, because COOH group in AAc changes with variation of pH. The results of 2D-COS analysis indicated that the phase transition mechanism of P(NiPAAm-co-AAc) hydrogel at pH4 is different from that at pH2 due to the effect of COOH group of AAc. Full article

(This article belongs to the Special Issue High-Functional Polymeric Materials)

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14 pages, 3849 KiB

Open AccessArticle

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 4 | Viewed by 3478

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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16 pages, 5237 KiB

Open AccessArticle

Fiber Formation and Structural Development of HBA/HNA Thermotropic Liquid Crystalline Polymer in High-Speed Melt Spinning

by Bo Seok Song, Jun Young Lee, Sun Hwa Jang and Wan-Gyu Hahm

Polymers 2021, 13(7), 1134; https://doi.org/10.3390/polym13071134 - 2 Apr 2021

Cited by 4 | Viewed by 3224

Abstract

High-speed melt spinning of thermotropic liquid crystalline polymer (TLCP) resin composed of 4-hydroxybenzoic acid (HBA) and 2-hydroxy-6-napthoic acid (HNA) monomers in a molar ratio of 73/27 was conducted to investigate the characteristic structure development of the fibers under industrial spinning conditions, and the [...] Read more.

High-speed melt spinning of thermotropic liquid crystalline polymer (TLCP) resin composed of 4-hydroxybenzoic acid (HBA) and 2-hydroxy-6-napthoic acid (HNA) monomers in a molar ratio of 73/27 was conducted to investigate the characteristic structure development of the fibers under industrial spinning conditions, and the obtained as-spun TLCP fibers were analyzed in detail. The tensile strength and modulus of the fibers increased with shear rate in nozzle hole, draft in spin-line and spinning temperature and exhibited the high values of approximately 1.1 and 63 GPa, respectively, comparable to those of industrial as-spun TLCP fibers, at a shear rate of 70,000 s⁻¹ and a draft of 25. X-ray diffraction demonstrated that the mechanical properties of the fibers increased with the crystalline orientation factor (f_c) and the fractions of highly oriented crystalline and non-crystalline anisotropic phases. The results of structure analysis indicated that a characteristic skin-core structure developed at high drafts (i.e., spinning velocity) and low spinning temperatures, which contributed to weakening the mechanical properties of the TLCP fibers. It is supposed that this heterogeneous structure in the cross-section of the fibers was induced by differences in the cooling rates of the skin and core of the fiber in the spin-line. Full article

(This article belongs to the Special Issue High-Functional Polymeric Materials)

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12 pages, 3035 KiB

Open AccessEditor’s ChoiceArticle

A Kirigami Approach of Patterning Membrane Actuators

by Harti Kiveste, Rudolf Kiefer, Rain Eric Haamer, Gholamreza Anbarjafari and Tarmo Tamm

Polymers 2021, 13(1), 125; https://doi.org/10.3390/polym13010125 - 30 Dec 2020

Cited by 2 | Viewed by 2727

Abstract

Ionic electroactive polymer actuators are typically implemented as bending trilayer laminates. While showing high displacements, such designs are not straightforward to implement for useful applications. To enable practical uses in actuators with ionic electroactive polymers, membrane-type film designs can be considered. The significantly [...] Read more.

Ionic electroactive polymer actuators are typically implemented as bending trilayer laminates. While showing high displacements, such designs are not straightforward to implement for useful applications. To enable practical uses in actuators with ionic electroactive polymers, membrane-type film designs can be considered. The significantly lower displacement of the membrane actuators due to the lack of freedom of motion has been the main limiting factor for their application, resulting in just a few works considering such devices. However, bioinspired patterning designs have been shown to significantly increase the freedom of motion of such membranes. In this work, we apply computer simulations to design cutting patterns for increasing the performance of membrane actuators based on polypyrrole doped with dodecylbenzenesulfonate (PPy/DBS) in trilayer arrangements with a polyvinylidene fluoride membrane as the separator. A dedicated custom-designed device was built to consistently measure the response of the membrane actuators, demonstrating significant and pattern-specific enhancements of the response in terms of displacement, exchanged charge and force. Full article

(This article belongs to the Special Issue High-Functional Polymeric Materials)

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13 pages, 2286 KiB

Open AccessEditor’s ChoiceArticle

Effects of Poly(ethylene-co-glycidyl methacrylate) on the Microstructure, Thermal, Rheological, and Mechanical Properties of Thermotropic Liquid Crystalline Polyester Blends

by Sang Hoon Lee, Ha-Bin Jeon, Gyu-Hyun Hwang, Young Seung Kwon, Ji-Su Lee, Gyu-Tae Park, Soo-Yeon Kim, Ha-Eun Kang, Eun-Ji Choi, Sun-Hwa Jang, Youn Eung Lee and Young Gyu Jeong

Polymers 2020, 12(9), 2124; https://doi.org/10.3390/polym12092124 - 17 Sep 2020

Cited by 13 | Viewed by 4549

Abstract

In this study, a series of thermotropic liquid crystalline polyester (TLCP)-based blends containing 1–30 wt% poly(ethylene-co-glycidyl methacrylate) (PEGMA) were fabricated by masterbatch-assisted melt-compounding. The scanning electron microscopy (SEM) images showed a uniformly dispersed microfibrillar structure for the TLCP component in cryogenically-fractured [...] Read more.

In this study, a series of thermotropic liquid crystalline polyester (TLCP)-based blends containing 1–30 wt% poly(ethylene-co-glycidyl methacrylate) (PEGMA) were fabricated by masterbatch-assisted melt-compounding. The scanning electron microscopy (SEM) images showed a uniformly dispersed microfibrillar structure for the TLCP component in cryogenically-fractured blends, without any phase-separated domains. The FT-IR spectra showed that the carbonyl stretching bands of TLCP/PEGMA blends shifted to higher wavenumbers, suggesting the presence of specific interactions and/or grafting reactions between carboxyl/hydroxyl groups of TLCP and glycidyl methacrylate groups of PEGMA. Accordingly, the melting and crystallization temperatures of the PEGMA component in the blends were greatly lowered compared to the TLCP component. The thermal decomposition peak temperatures of the PEGMA and TLCP components in the blends were characterized as higher than those of neat PEGMA and neat TLCP, respectively. From the rheological data collected at 300 °C, the shear moduli and complex viscosities for the blend with 30 wt% PEGMA were found to be much higher than those of neat PEGMA, which supports the existence of PEGMA-g-TLCP formed during the melt-compounding. The dynamic mechanical thermal analysis (DMA) analyses demonstrated that the storage moduli of the blends decreased slightly with the PEGMA content up to 3 wt%, increased at the PEGMA content of 5 wt%, and decreased again at PEGMA contents above 7 wt%. The maximum storage moduli for the blend with 5 wt% PEGMA are interpreted to be due to the reinforcing effect of PEGMA-g-TLCP copolymers. Full article

(This article belongs to the Special Issue High-Functional Polymeric Materials)

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12 pages, 3915 KiB

Open AccessEditor’s ChoiceArticle

Novel Conjugated Polymers Containing 3-(2-Octyldodecyl)thieno[3,2-b]thiophene as a π-Bridge for Organic Photovoltaic Applications

by Jong-Woon Ha, Jong Baek Park, Hea Jung Park and Do-Hoon Hwang

Polymers 2020, 12(9), 2121; https://doi.org/10.3390/polym12092121 - 17 Sep 2020

Cited by 6 | Viewed by 3229

Abstract

3-(2-Octyldodecyl)thieno[3,2-b]thiophen was successfully synthesized as a new π-bridge with a long branched side alkyl chain. Two donor-π-bridge-acceptor type copolymers were designed and synthesized by combining this π-bridge structure, a fluorinated benzothiadiazole acceptor unit, and a thiophene or thienothiophene donor unit, ( [...] Read more.

3-(2-Octyldodecyl)thieno[3,2-b]thiophen was successfully synthesized as a new π-bridge with a long branched side alkyl chain. Two donor-π-bridge-acceptor type copolymers were designed and synthesized by combining this π-bridge structure, a fluorinated benzothiadiazole acceptor unit, and a thiophene or thienothiophene donor unit, (PT-ODTTBT or PTT-ODTTBT respectively) through Stille polymerization. Inverted OPV devices with a structure of ITO/ZnO/polymer:PC₇₁BM/MoO₃/Ag were fabricated by spin-coating in ambient atmosphere or N₂ within a glovebox to evaluate the photovoltaic performance of the synthesized polymers (effective active area: 0.09 cm²). The PTT-ODTTBT:PC₇₁BM-based structure exhibited the highest organic photovoltaic (OPV) device performance, with a maximum power conversion efficiency (PCE) of 7.05 (6.88 ± 0.12)%, a high short-circuit current (J_sc) of 13.96 mA/cm², and a fill factor (FF) of 66.94 (66.47 ± 0.63)%; whereas the PT-ODTTBT:PC₇₁BM-based device achieved overall lower device performance. According to GIWAXS analysis, both neat and blend films of PTT-ODTTBT exhibited well-organized lamellar stacking, leading to a higher charge carrier mobility than that of PT-ODTTBT. Compared to PT-ODTTBT containing a thiophene donor unit, PTT-ODTTBT containing a thienothiophene donor unit exhibited higher crystallinity, preferential face-on orientation, and a bicontinuous interpenetrating network in the film, which are responsible for the improved OPV performance in terms of high J_sc, FF, and PCE. Full article

(This article belongs to the Special Issue High-Functional Polymeric Materials)

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13 pages, 2456 KiB

Open AccessArticle

Heteroaromatic Polyamides with Improved Thermal and Mechanical Properties

by Miriam Trigo-López, Ana M. Sanjuán, Aranzazu Mendía, Asunción Muñoz, Félix C. García and José M. García

Polymers 2020, 12(8), 1793; https://doi.org/10.3390/polym12081793 - 10 Aug 2020

Cited by 12 | Viewed by 3446

Abstract

We prepared high-performance aromatic copolyamides, containing bithiazole and thiazolo-thiazole groups in their main chain, from aromatic diamines and isophthaloyl chloride, to further improve the prominent thermal behavior and exceptional mechanical properties of commercial aramid fibers. The introduction of these groups leads to aramids [...] Read more.

We prepared high-performance aromatic copolyamides, containing bithiazole and thiazolo-thiazole groups in their main chain, from aromatic diamines and isophthaloyl chloride, to further improve the prominent thermal behavior and exceptional mechanical properties of commercial aramid fibers. The introduction of these groups leads to aramids with improved strength and moduli compared to commercial meta-oriented aromatic polyamides, together with an increase of their thermal performance. Moreover, their solubility, water uptake, and optical properties were evaluated in this work. Full article

(This article belongs to the Special Issue High-Functional Polymeric Materials)

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24 pages, 4045 KiB

Open AccessArticle

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 27 | Viewed by 4945

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 (W_A) 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 T_g (424 °C), a very low CTE (5.6 ppm K⁻¹), a low W_A (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 ε_r (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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