Estimation of Miscibility and Interaction for Cellulose Acetate and Butyrate Blends with <i>N</i>‐Vinylpyrrolidone Copolymers

Ohno, Takahiro; Nishio, Yoshiyuki

doi:10.1002/macp.200600510

Cited by 24 publications

(37 citation statements)

References 30 publications

(55 reference statements)

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“…Thus we could not detect any appreciable interaction between the cellulose alkyl ester and PCL components in the blends by the solidstate NMR and FT-IR spectra measurements. The above result forms a striking contrast to that obtained for blends composed of cellulose alkyl ester and N-vinyl pyrrolidone (VP)-containing vinyl polymer (Ohno et al 2005;Ohno and Nishio 2007). In the latter case, it has been clearly demonstrated by FT-IR and 13 C NMR spectroscopy that the hydrogenbonding interaction between the residual hydroxyls of the cellulose ester component and the carbonyl groups of VP units of the vinyl polymer component plays an important role in the miscibility attainment.…”

Section: Insight Into Factors For Miscibility Attainmentcontrasting

confidence: 64%

Cellulose alkyl ester/poly(ε-caprolactone) blends: characterization of miscibility and crystallization behaviour

et al. 2007

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Cellulose valerate (CV)/poly(e-caprolactone) (PCL) blends were investigated to clarify the effect of the degree of substitution (DS) of the cellulose ester component on the miscibility. CVs of DS > 2.15 were miscible with PCL in their amorphous states, as judged from the detection of a single T g by differential scanning calorimetry (DSC). This result and other complementary data for cellulose acetate (CA), propionate (CP), and butyrate (CB) blends with PCL made up a miscibility map as a function of the number N of carbons in the normal acyl substituent as well as of DS. CB of N = 4 and CV of N = 5, the ester side-chains of which make a higher similarity in chemical structure with a repeating unit of PCL, were found to be miscible with the aliphatic polyester at a comparatively lower DS; the critical butyryl DS of *1.85 being still lower than 2.15. For PCL-rich compositions of CB(DS > 2.0)/PCL and CV(DS > 2.2)/PCL blends, isothermal melt-crystallization behaviour was characterized by calorimetry and polarized optical microscopy. The CB and CV components gave rise to a marked diminution of the crystallization rate of PCL, as a result of the diluent action of the cellulose esters in the respective miscible, molten mixtures. Through a quantitative analysis of the kinetics, it is suggested regarding the supramolecular morphology that the bulky cellulose esters would be trapped not only on the fold surfaces but also on the growth faces of PCL lamellar crystals, to form a non-crystalline mixed polymer phase in the crystal boundary regions. Keywords Cellulose alkyl ester Á Poly(e-caprolactone) Á Polymer blends Á Miscibility Á Crystallization behaviour Abbreviations CA Cellulose acetate CAV Cellulose acetate valerate CB Cellulose butyrate CBV Cellulose butyrate valerate CC Cellulose caproate CE Cellulose enanthate CP Cellulose propionate CPV Cellulose propionate valerate CV Cellulose valerate DS

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Section: Insight Into Factors For Miscibility Attainmentcontrasting

confidence: 64%

Cellulose alkyl ester/poly(ε-caprolactone) blends: characterization of miscibility and crystallization behaviour

et al. 2007

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“…3 for two systems in which P(VP-co-MMA) was combined with either CA (Ohno and Nishio 2007b) or CP (Sugimura et al 2013b); however, the mapping for CB/P(VP-co-MMA) blends is not made in this figure (see later discussion). Again interestingly, the miscible pairing region for the CP/ P(VP-co-MMA) system is much larger than that for the CA/P(VP-co-MMA) system, with spreading to the upper right side of higher DS of CP and lower VP fraction of P(VP-co-MMA) in the map.…”

Section: Introductionmentioning

confidence: 89%

“…In a previous (a) 3 (Miyashita et al 2002), b CP/P(VP-coVAc) (Sugimura et al 2013a), and c CB/P(VP-coVAc) (Ohno and Nishio 2006) (Ohno and Nishio 2007b), we preliminarily estimated the attractive or repulsive action between chain segments of the polymer ingredients participating in the three systems, CA/P(VP-co-VAc), CA/ P(VP-co-MMA), and CB/P(VP-co-VAc), in terms of Krigbaum-Wall polymer-polymer interaction parameters (Db and l) determinable by dilute solution viscometry. Particularly l data gave a satisfactory account of the difference in the miscibility behaviour between the three blend systems (see later discussion).…”

Section: Introductionmentioning

confidence: 94%

Insight into miscibility behaviour of cellulose ester blends with N-vinyl pyrrolidone copolymers in terms of viscometric interaction parameters

2015

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We previously offered miscibility maps for blend systems of cellulose esters (CEs) including cellulose acetate (CA), propionate (CP), and butyrate (CB) with vinyl copolymers containing an N-vinyl pyrrolidone (VP) unit, i.e., poly(N-vinyl pyrrolidoneco-vinyl acetate) [P(VP-co-VAc)] and poly(N-vinyl pyrrolidone-co-methyl methacrylate) [P(VP-co-MMA)]; the maps were constructed based on data of thermal analysis as a function of the degree of ester substitution (DS) of the CE component and the VP fraction in the copolymer component. The blend system using CP among the three CEs imparted the largest region of miscible pairings with the vinyl copolymers, and both of the maps for the CP/P(VP-coVAc) and CP/P(VP-co-MMA) systems comprised a ''miscibility window'' associated with the respective copolymer compositions at high DSs of [2.65. The present work was made to interpret the expansion of the miscible markings for the CP/copolymer systems in comparison with the cases using CA and CB, in terms of a Krigbaum-Wall interaction parameter (l) obtained by solution viscometry for selective polymer pairs involved in the respective CE/copolymer blends. The results of l measurements were in good accordance with the earlier miscibility estimations. The assessment of very small negative l values (i.e., extremely weak repulsion) for CP/PVAc and CP/ PMMA combinations and that of considerably larger negative l values for PVP/PVAc and PVP/PMMA combinations enabled us to give a rational explanation for the CP systems. The strongly repellent character of the two different monomer units constituting the copolymers permits accession of the CP component (DS [ 2.65) to them, which would be responsible for the advent of the miscibility window. Further expansion of the window observed when cellulose acetate propionate (CAP) was adopted instead of CP as the CE component was also well explained on the basis of a l data indicative of additional intramolecular repulsion in the CAP side.

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“…In contrast, both CTA and CDA show a broad peak, located at almost 40 °C higher temperature than that of CAP. According to Ohno et al [23], T g of cellulose ester derivatives becomes lower with increasing the side-chain length, and with increasing degree of substitution (DS). However, the T g which can be defined by the peak temperature of ' ' E , of CTA in this study is found to be located almost at the same temperature with that of CDA.…”

Section: Dynamic Mechanical Propertiesmentioning

confidence: 99%

“…For all ATR-FTIR measurements, the peak intensity for 50% humidity is almost at an intermediate value between those of 0% and 100% humidity. In cellulose esters, water molecules could form hydrogen bonds with the hydroxyl and the carbonyl groups [20,23]. Considering that CAP and CTA contain only a small amount of the hydroxyl group, hydrogen bonding between carbonyl groups and water molecules would mainly be responsible for the decrease in orientation birefringence upon hydration.…”

Section: Atr Spectramentioning

confidence: 99%

Effect of Moisture on the Orientation Birefringence of Cellulose Esters

et al. 2011

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Orientation birefringence and its wavelength dispersion are studied for hot-drawn films of cellulose esters such as cellulose triacetate (CTA), cellulose diacetate (CDA), and cellulose acetate propionate (CAP) exposed to three different humidities of environments. Hot-drawn CTA films show negative birefringence that decreases with increasing wavelength. On the other hand, CDA and CAP films show positive birefringence that increases with increasing wavelength, i.e., the so-called extraordinary wavelength dispersion of birefringence. Upon exposure to high humidity environment, the orientation birefringence of CDA and CAP decreases. The decrease is prominent for the samples containing a large amount of water. CTA, however, shows an increase in magnitude of its negative orientation birefringence with increasing moisture content. The results can be explained by the increase of the polarizability anisotropy perpendicular to the stretching direction in the cellulose esters. It is found from ATR-FTIR measurements that hydrogen bonds are formed between carbonyl groups of cellulose esters and water molecules. Considering that orientation birefringence of cellulose esters is determined mainly by ester groups, the formation of hydrogen bonds contributes to the polarizability anisotropy, thus affecting the orientation birefringence.

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

Cited by 24 publications

References 30 publications

Cellulose alkyl ester/poly(ε-caprolactone) blends: characterization of miscibility and crystallization behaviour

Cellulose alkyl ester/poly(ε-caprolactone) blends: characterization of miscibility and crystallization behaviour

Insight into miscibility behaviour of cellulose ester blends with N-vinyl pyrrolidone copolymers in terms of viscometric interaction parameters

Effect of Moisture on the Orientation Birefringence of Cellulose Esters

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