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Cellulose alkyl ester/vinyl polymer blends: effects of butyryl substitution and intramolecular copolymer composition on the miscibility

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Abstract

The blend miscibility of cellulose alkyl esters, mainly butyrate (CB) and acetate butyrate (CAB), with synthetic homo- and copolymers comprising N-vinyl pyrrolidone (VP) and/or vinyl acetate (VAc) units, i.e., PVP, PVAc, and P(VP-co-VAc), was examined by differential scanning calorimetry. A miscibility map for the CB/vinyl polymer systems was constructed as a function of the degree of substitution (DS) of CB and the VP fraction of the mixing component. CBs were immiscible with PVAc regardless of the DS used (2.11–2.94), but miscible or immiscible with PVP depending on whether the butyryl DS was <2.5 or >2.5. The critical value of DS≈2.5 is lower than the corresponding one (DS≈2.8) evaluated formally for cellulose acetate (CA)/PVP blend series. This lowering is ascribable to an effect of steric hindrance of the bulky butyryl substituents, leading to suppression of the hydrogen-bonding interactions, as a driving factor for miscibility attainment, between residual hydroxyls of CB and carbonyl groups of PVP. The CB/vinyl copolymer system imparted a ‘miscibility window’ in which the VP/VAc composition participated; viz., CBs of DS≈2.54–2.94 were miscible with some P(VP-co-VAc)s of 30–70 mol% VP fractions, in spite of the immiscibility with both PVP and PVAc homopolymers. The result was interpreted in terms of another inter-component attraction derived from repulsion between the monomer ingredients constituting the vinyl copolymer component. For CAB/P(VP-co-VAc) blends, it was observed that the VP/VAc range forming such a miscibility window became further expanded, compared with the corresponding series of CB blends. Fourier transform infrared and solid-state 13C NMR spectroscopy revealed not only the presence or absence of the intermolecular hydrogen-bonding formation, determined according to the lower or higher DS of the cellulose ester component in the blends considered, but also a difference in the mixing scale between the polymer pairs regarded as miscible by the thermal analysis.

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Abbreviations

CA:

cellulose acetate

CAB:

cellulose acetate butyrate

CB:

cellulose butyrate

DS:

degree of substitution

PVAc:

poly(vinyl acetate)

PVP:

poly(N-vinyl pyrrolidone)

P(VP-co-VAc):

poly(N-vinyl pyrrolidone-co-vinyl acetate)

VAc:

vinyl acetate

VP:

N-vinyl pyrrolidone

References

  • Buchanan C.M., Dorschel D., Gardner R.M., Komarek R.J., Matosky A.J., White A.W., Wood M.D. (1996). The influence of degree of substitution on blend miscibility and biodegradation of cellulose acetate blends. J. Environ. Polym. Degrad. 4:179–195

    Article  CAS  Google Scholar 

  • Dulmage W.J. (1957). The molecular and crystal structure of cellulose triacetate. J. Polym. Sci. 26: 277–288

    Article  CAS  Google Scholar 

  • Fowler M.E., Barlow J.W., Paul D.R. (1987). Effect of copolymer composition on the miscibility of blends of styrene-acrylonitrile copolymers with poly(methyl methacrylate). Polymer 28:1177–1184

    Article  CAS  Google Scholar 

  • Fox T.G., Flory P.J. (1954). The glass transition temperature and related properties of polystyrene. Influence of molecular weight. J. Polym. Sci. 14:315–319

    Article  CAS  Google Scholar 

  • Frazier C.E., Glasser W.G. (1995). Intramolecular effects in cellulose mixed ethers blended with poly(ɛ-caprolactone). J. Appl. Polym. Sci. 58:1063–1075

    Article  CAS  Google Scholar 

  • Friebolin H., Keilich G., Siefert E. (1969). Proton magnetic resonance studies on polysaccharide derivatives. Angew. Chem. Int. Ed. Engl. 8:766–767

    Article  CAS  Google Scholar 

  • Ho. F.F.-L., Kohler R.R., Ward G.A. (1972). Determination of molar substitution and degree of substitution of hydroxypropylcellulose by nuclear magnetic resonance spectrometry. Anal. Chem. 44:178–181

    Article  Google Scholar 

  • Kaplan D.S. (1976). Structure-property relationships in copolymers to composites – molecular interpretation of glass-transition phenomenon. J. Appl. Polym. Sci. 20:2615–2629

    Article  CAS  Google Scholar 

  • Marchessault R.H., Liang C.Y. (1960). Infrared spectra of crystalline polysaccharides. III. Marcerized cellulose. J. Polym. Sci. 43:71–84

    Article  CAS  Google Scholar 

  • Masson J.-F., Manley R.St.J. (1991). Miscible blends of cellulose and poly(vinylpyrrolidone). Macromolecules 24:6670–6679

    Article  CAS  Google Scholar 

  • McBrierty V.J., Douglass D.C. (1981). Recent advances in the NMR of solid polymers. J. Polym. Sci.: Macromol. Rev. 16:295–366

    Article  CAS  Google Scholar 

  • McCormick C.L., Callais P.A. (1987). Derivatization of cellulose in lithium chloride and N-N-dimethylacetamide solution. Polymer 28:2317–2323

    Article  CAS  Google Scholar 

  • McComick C.L., Callais P.A., Hutchinson B.H.Jr. (1985). Solution studies of cellulose in lithium chloride and N,N-dimethylacetamide. Macromolecules 18:2394–2401

    Article  Google Scholar 

  • Min K.E., Paul D.R. (1987). Miscibility of blends of tetramethylbisphenol A polycarbonate and styrene/methyl methacrylate copolymers. Macromolecules 20:2828–2832

    Article  CAS  Google Scholar 

  • Miura K., Kimura N., Suzuki H., Miyashita Y., Nishio Y. (1999). Thermal and viscoelastic properties of alginate/poly(vinyl alcohol) blends cross-linked with calcium tetraborate. Carbohydr. Polym. 39:139–144

    Article  CAS  Google Scholar 

  • Miyashita Y., Kimura N., Suzuki H., Nishio Y. (1998). Cellulose/poly(acryloyl morpholine) composites: synthesis by solution coagulation/bulk polymerization and analysis of phase structure. Cellulose 5:123–134

    Article  CAS  Google Scholar 

  • Miyashita Y., Nishio Y., Kimura N., Suzuki H., Iwata M. (1996). Transition behaviour of cellulose/poly(N-vinylpyrrolidone-co-glycidyl methacrylate) composites synthesized by a solution coagulation/bulk polymerization method. Polymer 37:1949–1957

    Article  CAS  Google Scholar 

  • Miyashita Y., Suzuki T., Nishio Y. (2002). Miscibility of cellulose acetate with vinyl polymers. Cellulose 9:215–223

    Article  CAS  Google Scholar 

  • Miyashita Y., Yamada Y., Kimura N., Suzuki H., Iwata M., Nishio Y. (1997). Phase structure of chitin/poly(glycidyl methacrylate) composites synthesized by a solution coagulation/bulk polymerization method. Polymer 38:6181–6187

    Article  CAS  Google Scholar 

  • Nishio Y. (1994). Hyperfine composites of cellulose with synthetic polymers. In: Gilbert R.D. (eds), Cellulosic Polymers, Blends and Composites. Carl Hanser, Munich, Chapter 5

    Google Scholar 

  • Nishio Y., Koide T., Miyashita Y., Kimura N., Suzuki H. (1999). Water-soluble polymer blends with partially deacetylated chitin: a miscibility characterization. J. Polym. Sci., Part B, Polym. Phys. 37:1533–1538

    Article  CAS  Google Scholar 

  • Nishio Y., Manley R.St.J. (1988). Cellulose/poly(vinyl alcohol) blends prepared from solutions in N,N-dimethylacetamide-lithium chloride. Macromolecules 21:1270–1277

    Article  Google Scholar 

  • Nishio Y., Matsuda K., Miyashita Y., Kimura N., Suzuki H. (1997). Blends of poly(ɛ-caprolactone) with cellulose alkyl esters: effect of the alkyl side-chain length and degree of substitution on miscibility. Cellulose 4:131–145

    Article  CAS  Google Scholar 

  • Ohno T., Yoshizawa S., Miyashita Y., Nishio Y. (2005). Interaction and scale of mixing in cellulose acetate/poly(vinyl pyrrolidone-co-vinyl acetate) blends. Cellulose 12:281–291

    Article  CAS  Google Scholar 

  • Paul D.R., Barlow J.W. (1984). A binary interaction model for miscibility of copolymers in blends. Polymer 25:487–494

    Article  CAS  Google Scholar 

  • Roche E., Chanzy H., Boudeulle M., Marchessault R.H., Sundararajan P. (1978). Three-dimensional crystalline structure of cellulose triacetate II. Macromolecules 11:86–94

    Article  CAS  Google Scholar 

  • ten Brinke G., Karasz F.E., MacKnight W.J. (1983). Phase behavior in copolymer blends: poly(2,6-dimethyl-1,4-phenylene oxide) and halogen substituted styrene copolymers. Macromolecules 16:1827–1832

    Article  CAS  Google Scholar 

  • Teramoto Y., Ama S., Higeshiro T., Nishio Y. (2004). Cellulose acetate-graft-poly(hydroxyalkanoate)s: synthesis and dependence of the thermal properties on copolymer composition. Macromol. Chem. Phys. 205:1904–1915

    Article  CAS  Google Scholar 

  • Teramoto Y., Nishio Y. (2003). Cellulose diacetate-graft-poly(lactic acid)s: synthesis of wide-ranging compositions and their thermal and mechanical properties. Polymer 44:2701–2709

    Article  CAS  Google Scholar 

  • Teramoto Y., Nishio Y. (2004a). Biodegradable cellulose diacetate-graft-poly(L-lactide)s: thermal treatment effect on the development of supramolecular structures. Biomacromolecules 5:397–406

    Article  CAS  Google Scholar 

  • Teramoto Y., Nishio Y. (2004b). Biodegradable cellulose diacetate-graft-poly(L-lactide)s: enzymatic hydrolysis behavior and surface morphological characterization. Biomacromolecules 5:407–414

    Article  CAS  Google Scholar 

  • Tezuka Y. (1993). 13C NMR determination of the distribution of two ester substituents in cellulose acetate butyrate. Carbohydrate Research 241:285–290

    Article  CAS  Google Scholar 

  • Ultracki L.A. (1990). Polymer Alloys and Blends. Hanser Publishers, Munich

    Google Scholar 

  • Vigo T.L. (1998). Interaction of cellulose with other polymers: retrospective and prospective. Polym. Adv. Technol. 9:539–548

    Article  CAS  Google Scholar 

  • Xiaoqing Z., Takegoshi K., Hikichi K. (1992). High-resolution solid-state 13C nuclear magnetic resonance study on poly(vinyl alcohol)/poly(vinylpyrrolidone) blends. Polymer 33:712–717

    Article  Google Scholar 

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  1. Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University, Kyoto, 606-8502, Japan

    Takahiro Ohno & Yoshiyuki Nishio

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  1. Takahiro Ohno
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  2. Yoshiyuki Nishio
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Correspondence to Yoshiyuki Nishio.

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Ohno, T., Nishio, Y. Cellulose alkyl ester/vinyl polymer blends: effects of butyryl substitution and intramolecular copolymer composition on the miscibility. Cellulose 13, 245–259 (2006). https://doi.org/10.1007/s10570-005-9014-3

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