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

Kusumi, Ryosuke; Teramoto, Yoshikuni; Nishio, Yoshiyuki

doi:10.1002/macp.200800332

Cited by 22 publications

(30 citation statements)

References 32 publications

(88 reference statements)

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“…The methods of synthesis and characterization of CA-g-PCLs and CB-g-PCLs have been described in our previous study [5].…”

Section: Ca-g-pcl and Cb-g-pcl Copolymersmentioning

confidence: 99%

“…Recently, the authors' group has synthesized graft copolymers of CA and cellulose butyrate (CB) of acyl DS > 2 with poly(-caprolactone) (PCL), the products being termed CA-g-PCL and CB-g-PCL, respectively [5]; the two trunk CEs (CA and CB) are, respectively, immiscible and miscible with PCL in the corresponding binary polymer blends [5,6]. In that study [5] using copolymer compositions rich in PCL content, it was shown that all the products except copolymers based on CA of DS > 2.9 indicated an obviously single T g in differential scanning calorimetry (DSC) measurements, but the melt-crystallization kinetics of the PCL component and resulting supramolecular morphology were largely different in the manner of the composition dependence between the two graft series. In a subsequent work [7], we investigated enzymatic hydrolysis behavior of PCL for melt-molded films of the above CE-g-PCLs by employing Pseudomonas lipase and demonstrated that the degradation rate and the surface morphology of the films were both subtly changeable by adequate selections of the compositional parameters and intercomponent miscibility of the original copolymer products.…”

Section: Introductionmentioning

confidence: 99%

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Structural characterization of poly(ε-caprolactone)-grafted cellulose acetate and butyrate by solid-state 13C NMR, dynamic mechanical, and dielectric relaxation analyses

Kusumi

Teramoto

Nishio

2011

Polymer

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Investigations were made into the molecular dynamics and intercomponent mixing state in solid films of two series of cellulosic graft copolymers, cellulose acetate-g-poly(-caprolactone) (CA-g-PCL) and cellulose butyrate-g-PCL (CB-g-PCL), both series being prepared over a wide range of compositions with CAs or CBs of acyl DS ≈ 2.1, 2.5, and 2.95. It was shown by T 1 H measurements in solid-state 13 C NMR spectroscopy that all the copolymer samples, except ones using CA of DS = 2.98, formed an amorphous monophase in which the trunk and graft components were mixed homogeneously at least in a scale of a few nanometers. However, those copolymer samples gave, more or less, a response of dynamic heterogeneity, when examined under mechanical oscillation. Through dielectric relaxation measurements, a clear comparison was made between the CA-g-PCL and CB-g-PCL series, regarding the cooperativeness in segmental motions of the trunk and graft chains, directly associated with the extent of the dynamic heterogeneity. The cooperativeness was generally higher in the CB-based copolymer series, probably due to working of the butyryl substituent as an internal compatibilizer.

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“…The methods of synthesis and characterization of CA-g-PCLs and CB-g-PCLs have been described in our previous study [5].…”

Section: Ca-g-pcl and Cb-g-pcl Copolymersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Structural characterization of poly(ε-caprolactone)-grafted cellulose acetate and butyrate by solid-state 13C NMR, dynamic mechanical, and dielectric relaxation analyses

Kusumi

Teramoto

Nishio

2011

Polymer

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“…In recent years, the authors have carried out systematic works for synthesizing biodegradable cellulose estergraft-aliphatic polyesters, through adoption of a homogeneous reaction system and complete removal of a possible oligomeric by-product of the grafting component (Teramoto and Nishio 2003;Teramoto et al 2004;Nishio 2006). Various approaches in this regard have dealt with chemical composition and thermal transition behaviour (Teramoto and Nishio 2003;Teramoto et al 2004), mechanical properties (Teramoto and Nishio 2003), higher-order structure development (Teramoto and Nishio 2004b;Kusumi et al 2008), and enzymatic hydrolysis behaviour (Teramoto and Nishio 2004a;Kusumi et al 2009). …”

Section: Introductionmentioning

confidence: 99%

Molecular orientation and optical anisotropy in drawn films of cellulose diacetate-graft-PLLA: comparative investigation with poly(vinyl acetate-co-vinyl alcohol)-graft-PLLA

2011

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Cellulose diacetate-graft-poly(L-lactide) (CDA-g-PLLA) and poly(vinyl acetate-co-vinyl alcohol)-graft-PLLA (P(VAc-co-VOH)-g-PLLA) were synthesized over a range of compositions, by ringopening copolymerization of L-lactide at the original hydroxyl positions of the respective trunk polymers, CDA (acetyl DS = 2.15) and P(VAc-co-VOH)-g-PLLA (VAc = 64.2 mol%). All the products of both graft copolymer series were non-crystallizable and their solution-cast films showed no domain segregation of the two components that constituted the trunk and side-chains. A comparative study on the molecular orientation and optical anisotropy induced by uniaxial stretching of film samples was undertaken for the two copolymer series with various side-chain lengths. Overall behaviour of the orientation was estimated from the statistical second (\cos 2 x[) and fourth (\cos 4 x[) moments obtained by a fluorescence polarization method using a rod-like probe of *2.5 nm. Upon stretching, any film of both series imparted a positive orientation function, i.e., f = (3 \cos 2 x[ -1)/2 [ 0, which increased with the extent of deformation. The degree of molecular orientation was higher in the CDA-graft series with a semi-rigid trunk, and, in both series, it declined monotonically with increasing content of the PLLA side-chain. With regard to the optical anisotropy, CDA-g-PLLA films always exhibited a positive birefringence (Dn [ 0) upon stretching, while drawn films of P(VAc-co-VOH)-g-PLLA displayed a negative one. This contrast in polarity reflects a difference in the intrinsic birefringence between the two trunk polymers. Of interest was the finding of a discontinuous change in Dn value with copolymer composition (PLLA content) for the respective graft series, when compared at a given stage of elongation of the films. Discussion took into consideration the locally different orientation manners of the attached PLLA chain segments.

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“…Chemical modification of cellulosics makes it easier for processing, but attention should be paid to the respect that their original biodegradability is lost in some cases. A remedy for overcoming such problems could be improvement of thermal moldability of cellulosics by grafting1–5 or blending1, 6–12 with biodegradable aliphatic polyeters.…”

Section: Introductionmentioning

confidence: 99%

“…It was revealed that cellulose butyrate of n = 4 and cellulose valerate of n = 5 exhibit the highest miscibility on blending with PCL. However, biodegradable13, 14 and commodity‐type cellulose acetate (CA) of n = 2 was judged to be immiscible with PCL over the entire composition range, although a certain material modification using the CA‐PCL combination could be achieved by graft copolymerization 2, 4, 5…”

Section: Introductionmentioning

confidence: 99%

Poly(vinyl pyrrolidone‐co‐vinyl acetate)‐graft‐poly(ε‐caprolactone) as a compatibilizer for cellulose acetate/poly(ε‐caprolactone) blends

Higeshiro

Teramoto

Nishio

2009

J of Applied Polymer Sci

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Poly(vinyl pyrrolidone‐co‐vinyl acetate)‐graft‐poly(ε‐caprolactone) (PVPVAc‐g‐PCL) was synthesized by radical copolymerization of N‐vinyl‐2‐pyrrolidone (VP)/vinyl acetate (VAc) comonomer and PCL macromonomer containing a reactive 2‐hydroxyethyl methacrylate terminal. The graft copolymer was designed in order to improve the interfacial adhesiveness of an immiscible blend system composed of cellulose acetate/poly(ε‐caprolactone) (CA/PCL). Adequate selections of preparation conditions led to successful acquisition of a series of graft copolymer samples with different values of molecular weight ( $M_{n}^{{\rm PVPVA} {{\rm c} - g - {\rm PCL}}}$), number of grafts (n), and segmental molecular weight of PVPVAc between adjacent grafts (Mn (between grafts)). Differential scanning calorimetry measurements gave a still immiscible indication for all of the ternary blends of CA/PCL/PVPVAc‐g‐PCL (72 : 18 : 10 in weight) that were prepared by using any of the copolymer samples as a compatibilizer. However, the incorporation enabled the CA/PCL (4 : 1) blend to be easily melt‐molded to give a visually homogeneous film sheet. This compatibilizing effect was found to be drastically enhanced when PVPVAc‐g‐PCLs of higher $M_{ n}^{{\rm PVPVA}{\rm c} - g - {\rm PCL}}$ and Mn (between grafts) and lower n were employed. Scanning electron microscopy revealed that a uniform dispersion of the respective ingredients in the ternary blends was attainable with an assurance of the mixing scale of several hundreds of nanometers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

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

Cited by 22 publications

References 32 publications

Structural characterization of poly(ε-caprolactone)-grafted cellulose acetate and butyrate by solid-state 13C NMR, dynamic mechanical, and dielectric relaxation analyses

Structural characterization of poly(ε-caprolactone)-grafted cellulose acetate and butyrate by solid-state 13C NMR, dynamic mechanical, and dielectric relaxation analyses

Molecular orientation and optical anisotropy in drawn films of cellulose diacetate-graft-PLLA: comparative investigation with poly(vinyl acetate-co-vinyl alcohol)-graft-PLLA

Poly(vinyl pyrrolidone‐co‐vinyl acetate)‐graft‐poly(ε‐caprolactone) as a compatibilizer for cellulose acetate/poly(ε‐caprolactone) blends

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