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Nishio, Yoshiyuki; Matsuda, Kensuke; Miyashita, Yoshiharu; Kimura, Naoki; Suzuki, Hidematsu

doi:10.1023/a:1018475520600

Cited by 57 publications

(43 citation statements)

References 21 publications

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“…A similar explanation has been proposed to interpret a miscibility map conducted for the binary system of the alkyl-esterified cellulose/PCL mixture, where the carbon atoms C-1 to C-6 in a glucopyranose unit were considered to attain a structural unit similar to that of PCL. [37][38][39] In the present system too, conceivably, the experimental results suggest that such a structural effect of the substituents is contributive to the attainment of miscibility, even though almost half the hydroxyl groups of the original OSL are aromatic ones (Table I).…”

Section: Driving Force For Attainment Of Miscibilitymentioning

confidence: 55%

Phase Structure and Mechanical Property of Blends of Organosolv Lignin Alkyl Esters with Poly(ε-caprolactone)

2009

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Organosolv lignin (OSL) alkyl esters (carbon number n, 2-5) were synthesized by homogeneous reaction with different acyl anhydrides/4-dimethylamino pyridine in pyridine solution. Miscibility of the esterified OSL with poly("-caprolactone) (PCL) was investigated through DSC, morphological observation, and spectroscopy. DSC revealed a composition-dependent shift in T g for blends of OSL esters (n ¼ 3{5) with PCL; thus these three systems can be regarded as miscible on a T g -detection scale. AFM indicated that no remarkable phase separation occurred in these blends. In observations of crystallization behavior of the PCL component, the OSL derivatives of n ¼ 4 and 5, the alkyl ester substituents of which make a higher similarity in chemical structure with a repeating unit of PCL, exhibited a higher level of miscibility with the aliphatic polyester, compared to the other OSL derivative of n ¼ 3. Thermal-molded blend sheets of OSL esters of n ¼ 3{5 with PCL attained !500% of elongation at rupture at 20 C even when the blends contained 50 wt % of the respective esterified lignin components, reflecting the good miscibility of these OSL esters with PCL.KEY WORDS: Organosolv Lignin / Alkyl Ester / Poly("-caprolactone) / Blends / Miscibility / Glass Transition / Isothermal Crystallization / Currently, studies on bioethanol production from lignocellulosics are being actively pursued.1-4 Irrespective of the bioethanol manufacturing process, lignin is inevitably produced as a consequence of the saccharification of the cellulosic components of lignocellulosics. Although the lignin by-product is considered merely as a heat resource for the process in the present circumstances, its effective application will contribute to cost reduction of the total system for biofuel production.Generally, however, the utilization of lignin as a solid material is constrained by poor film formability and less thermal moldability due to its molecular architecture and intermolecular interactions in itself. Upon heating, lignin molecules decompose rather than soften and flow. In order to alter lignin's viscoelastic properties, considerable efforts have been conducted to employ lignin components either as extenders in polyurethanes, phenol-formaldehyde resins, epoxies, and acrylics, or as grafting backbones for the attachment of other synthetic polymer chains. 5Meanwhile, the importance of polymer blends is now well established as an alternative method of developing completely novel polymers. Furthermore, polymer blending can offer opportunities to modify the thermal and other physical properties of the target polymers. However, it is generally difficult to prepare miscible blends due to the small contribution of the mixing entropy and therefore, in most cases, certain attractive intermolecular interactions between the component polymers should be adopted in order to attain the miscibility or practically good compatibility. Lignin blends or other combinations with synthetic polymers have been investigated many times over the last three decades 6-8 f...

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Section: Driving Force For Attainment Of Miscibilitymentioning

confidence: 55%

Phase Structure and Mechanical Property of Blends of Organosolv Lignin Alkyl Esters with Poly(ε-caprolactone)

2009

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“…CB was synthesized with acid chloride/base catalyst from the cellulose solution in a way similar to that used in previous studies. [6,10] The typical procedure can be summarized as follows.…”

Section: Synthesis Of Cellulose Butyratementioning

confidence: 99%

Crystallization Behavior of Poly(ε‐caprolactone) Grafted onto Cellulose Alkyl Esters: Effects of Copolymer Composition and Intercomponent Miscibility

Kusumi

Teramoto

Nishio

2008

Macro Chemistry & Physics

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Graft copolymers of CA and CB with PCL were prepared at compositions rich in PCL. Kinetic DSC data were analyzed in terms of a folded‐chain crystallization formula expanded for a binary mixing system of amorphous/crystalline polymers. The order of crystallization rates was plain PCL > CA‐g‐PCL (DS = 2.98) > CB‐g‐PCL (DS = 2.1–2.95) > CA‐g‐PCL (DS = 2.1–2.5), and the fold‐surface free energy of the PCL crystals obeyed the reverse order. POM revealed a generally tardy growth of spherulites for all the graft copolymers. The slower crystallization process may be ascribed primarily to the compulsory effect of anchoring PCL chains onto the semi‐rigid cellulose backbone. Intercomponent miscibility of the CA/PCL and CB/PCL pairs was also taken into consideration.

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“…In order to remedy the drawback, the authors' attention has been paid to two potential methods; one is graft copolymerization of CA with biodegradable aliphatic polyesters, [5][6][7][8] and the other is compatibly blending CA with flexible polymers as a polymeric plasticizer. [9][10][11][12] Polymer/polymer blending is a well-established, useful method to improve the original physical properties of one or both of the components, or to design new polymeric materials exhibiting wide-ranging properties and/or synergistic functions without parallel in single polymers and in the gross mechanical mixture. [13] This should also hold for blending cellulosics as one component.…”

Section: Full Papermentioning

confidence: 99%

Estimation of Miscibility and Interaction for Cellulose Acetate and Butyrate Blends with N‐Vinylpyrrolidone Copolymers

Ohno

Nishio

2007

Macro Chemistry & Physics

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The miscibility of CA/P(VP‐co‐MMA) blends was examined as a function of DS of CA and the VP fraction in the copolymer composition, in an extension of the previous studies on cellulose ester blends using P(VP‐co‐VAc) as a counter component. It was observed by DSC thermal analysis that when CA of DS ≤ 2.5 and P(VP‐co‐MMA) of VP > 30 mol‐% were two blending components, most of the binary polymer systems were miscible, whereas the other combinations of DS and VP values led to an immiscible series of blends, a possible exception being the miscible pair of DS = 2.70 and VP = 100 mol‐%. Results of FT‐IR and solid‐state 13C CP/MAS NMR spectra measurements suggested the miscibility to be driven by the hydrogen‐bonding interaction between the residual hydroxyls of CA and the carbonyls of VP units in P(VP‐co‐MMA), as in the case of CA/P(VP‐co‐VAc) blends where the range of miscible pairing of acetyl DS and VP fraction was rather wide. From evaluations of proton spin‐lattice relaxation times in the NMR study, it was confirmed that the homogeneity of the miscible blends of CA/P(VP‐co‐MMA) was substantially on a scale within a few nanometers. To interpret the difference in the DS‐ and copolymer composition‐dependence of the miscibility behavior between three blend systems, CA/P(VP‐co‐MMA), CA/P(VP‐co‐VAc), and CB/P(VP‐co‐VAc), Krigbaum‐Wall intermolecular interaction parameters were estimated by solution viscometry for different polymer pairs pertinent to those blends. In particular, discussion took into consideration the effectiveness of an intramolecular repulsive action between the two units (VP and VAc, or VP and MMA) constituting the vinyl copolymers.magnified image

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Untitled

Cited by 57 publications

References 21 publications

Phase Structure and Mechanical Property of Blends of Organosolv Lignin Alkyl Esters with Poly(ε-caprolactone)

Phase Structure and Mechanical Property of Blends of Organosolv Lignin Alkyl Esters with Poly(ε-caprolactone)

Crystallization Behavior of Poly(ε‐caprolactone) Grafted onto Cellulose Alkyl Esters: Effects of Copolymer Composition and Intercomponent Miscibility

Estimation of Miscibility and Interaction for Cellulose Acetate and Butyrate Blends with N‐Vinylpyrrolidone Copolymers

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