Highly Softened Polyurethane Elastomer Synthesized with Novel 1,2-Bis(isocyanate)ethoxyethane

Kojio, Ken; Fukumaru, Tomoya; Furukawa, Mutsuhisa

doi:10.1021/ma0359988

Cited by 97 publications

(94 citation statements)

References 10 publications

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“…To form the microphaseseparated structure in polymers, they need to possess block structures, which are chemically connected each other. It is well-known that the polyurethane elastomers (PUEs), which possess the multiblock structure, show the microphase-separated structure, [1][2][3][4][5][6] resulting in giving some unique properties, such as mechanical and adhesive properties [6][7][8][9][10][11][12][13][14][15][16] and biocompatibility. 17 To functionalize the PUs with the microphase-separated structure, one needs to control the structures precisely.…”

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The Microphase-separated Structure of Polyurethane Bulk and Thin Films

et al. 2009

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The microphase-separated structure of polyurethane bulk and thin films were investigated using atomic force microscopy (AFM). The polyurethane (PUs) were synthesized with poly(oxytetramethylene) glycol (PTMG), 4,4 0 -diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BD) by a prepolymer method. The hard segment contents were 34 and 45 wt %. Polarized optical microscopy (POM) revealed that the 34 wt % PUE is homogeneous at a macroscopic level, while the 45 wt % one is macrophase-separated into two phases. One phase forms spherulites of ca. 2-5 mm in diameter. AFM observation for the 34 wt % PUE showed the microphase-separated structure, consisting of hard segment domains and a soft segment matrix. In contrast, for the 45 wt % PUE, a lot of the hard segment domains were observed in the spherulite region, indicating that spherulites include much amount of hard segment component, in contrast, outside of spherulite exhibited similar structure to that of 34 wt % one. For the PU bulk, the different microphase-separated structure in the inside and outside of spherulite was successfully observed for the first time. Also, the microphase-separated structure of PU films was investigated as a function of the film thickness. The PU films exhibited similar microphase-separated structure. For the thicker film ($200 nm), the interdomain spacing almost corresponded to bulk one. On the other hand, that for the film thickness below 7 nm dramatically decreased. This seems to be simply related to a decreasing space. We obtained the experimental data, which the phase-separated domain size of multiblock copolymer decreased with decreasing film thickness.KEY WORDS: Polyurethane / Microphase-separated Structure / Atomic Force Microscopy / Thin Film / A microphase-separated structure formed in polymers plays a quite important role for their properties, such as electric, adsorption, mechanical properties. To form the microphaseseparated structure in polymers, they need to possess block structures, which are chemically connected each other. It is well-known that the polyurethane elastomers (PUEs), which possess the multiblock structure, show the microphase-separated structure, 1-6 resulting in giving some unique properties, such as mechanical and adhesive properties [6][7][8][9][10][11][12][13][14][15][16] and biocompatibility.17

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“…There has been reported some factors to control the microphaseseparated structure. A polymerization method, 13 thermal treatment 3,14 and chemical structures of raw materials including molecular weight [6][7][8][9][10][11][12]15,16 can be given as examples. First, by changing the polymerization method, one can control the primary structure of the PUs.…”

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The Microphase-separated Structure of Polyurethane Bulk and Thin Films

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“…The soft segment can be classified as an ether or ester series, including the carbonate ones. 7,8 Studies have been reported with polyamide in the thermoplastic elastomers or rubbers as blends. 9 The PA 6/acrylonitrile-butadiene-styrene blends obtained with an imidized acrylic polymer as a compatabilizer revealed supertough properties over a wide range of component proportions.…”

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High Performance Polyamide 6 Fibers Using Polycarbonate Based Thermoplastic Polyurethane Thin Film Coatings- a Novel Method

2009

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Polycarbonate based thermoplastic polyurethanes (CPU2) were prepared and coated onto polyamide 6 (PA 6) fibers. The CPU2 thin film coatings were prepared by dipping the PA 6 fibers into a viscous CPU2 adduct and cured at 100 C for 12 h. Both the tensile strength and the elongation at break of the CPU2 thin film coated PA 6 fibers (CPU2-PA6) increased although both the magnitudes of CPU2 are much lower than for the original PA 6 fibers. FE-SEM observation revealed that there existed an interface interaction region of 10 mm at the interface of PA 6 fiber and the CPU2 thin film coating. Generally speaking, it is considered that the break of PA 6 fibers is due to the formation of the micro-cracks on the fiber surface when it is under a tensile load. The coating of CPU2 onto the PA 6 fibers reduced the formation of micro-cracks during the elongation process, resulted in the improvement of the mechanical properties. Also, the CPU2-PA6 fibers when exposed to weathering tests to check the weathering resistance, showed an increase in the tensile strength for 0-50 h of exposure. This was due to the UV light induced crystalline transformation, i.e., from the crystalline phase to the crystalline phase. The CPU2-PA6 fibers almost retained the strength even after 200 h of exposure in a weatherometer. The crystalline transformations due to the UV irradiations have not been reported yet. Also, the CPU2 showed good adhesion property with the PA 6 films. The blending with various polymers or composites is generally employed for the performance enhancement of PA 6 fibers. On the contrary, the method employed in this study improved the performance of PA 6 fibers without changing its inherent morphological properties.KEY WORDS: Polyamide 6 Fiber / Polyurethane Thin Film / Coating / Micro-cracks / Interface Interaction / Plastic-type Break / Metallic-type Break / Weathering Tests / Polyamide fibers (PAs) are used for a wide variety of applications. They include the textile industry, engineering applications, biomedical and marine applications. The properties of PAs are the high melting point, good mechanical strength, good resistance to hydrocarbons, and the ease of fabrication and processing.1-3 However, the polyamide 6 (PA 6) fibers are prone to break under the mechanical stress due to the formation of micro-cracks on the surface. While, the polyurethanes are widely used in the coatings, adhesives, sealants, foams, elastomers and so on. Thermoplastic polyurethane elastomers are well known for their abrasion resistance, flexibility and high cohesive strength. [4][5][6] They are synthesized from the polymer glycol, diisocyanate and a chain extender. The final structure of polyurethane consists of a soft segment formed from the polymer glycol and a hard segment from the diisocyanate and the chain extender. The soft segment can be classified as an ether or ester series, including the carbonate ones. 7,8 Studies have been reported with polyamide in the thermoplastic elastomers or rubbers as blends. 9 The PA 6/acrylonitrile-butadiene-sty...

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“…Poly(oxytetramethylene) glycol (PTMG: M n ¼ 2000, Asahikasei Chemicals Co., Ltd., Japan), 4,4 0 -diphenylmethane diisocyanate (MDI, Nippon Polyurethane Industry Co., Ltd., Japan) and 1,4-butandiol (BD) and 1,1,1-trimethylol propane (TMP, Wako Chemicals Co., Ltd., Japan) were used. The curing agents used to control the microphase separation were BD, TMP and a mixture of BD plus TMP at weight ratio of 75/25.…”

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confidence: 99%

Microphase Separation of Bulk and Ultrathin Films of Polyurethane Elastomers

Furukawa

Kojio

Kugumiya

et al. 2008

Macromolecular Symposia

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Surmmary: Polyurethane elastomers (PUEs) were synthesized with poly(oxytetramethylene) glycol (PTMG), 4,4 0 -diphenylmethane diisocyanate (MDI) and 1,4-butanediol (BD)/1,1,1-trimethylol propane (TMP) by a prepolymer method. The degree of microphase separation of bulk and ultrathin films for these PUEs was confirmed by Fourier transform infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC) and atomic force microscopy (AFM). In the bulk films, FT-IR and DSC measurements revealed that the degree of micro-phase separation strengthened with increasing BD content. AFM observation of the BD-PUE showed hard segment domains surrounded by a soft segment matrix. The domains ranged in size from 10-20 nm, while BD/TMP-and TMP PUEs did not have clear domains. On the other hand, AFM observation was carried out on thin films (200 mm in thickness) and ultrathin films (approximately 8-5 nm) prepared by spin-coating the different concentrations of PUE solutions. The microphase separated strucuture under 10 nm in thickness showed marked decreases in the size of the microphase-separated domain.

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Highly Softened Polyurethane Elastomer Synthesized with Novel 1,2-Bis(isocyanate)ethoxyethane

Cited by 97 publications

References 10 publications

The Microphase-separated Structure of Polyurethane Bulk and Thin Films

The Microphase-separated Structure of Polyurethane Bulk and Thin Films

High Performance Polyamide 6 Fibers Using Polycarbonate Based Thermoplastic Polyurethane Thin Film Coatings- a Novel Method

Microphase Separation of Bulk and Ultrathin Films of Polyurethane Elastomers

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