Conclusions
From an overall analysis of the above results it appears that the rheological properties of plasticized PVC are governed, below about 200 °C, not only by the usual parameters (composition, temperature, molecular weight) but also by the crystallinity of the polymer. Recent estimations of the crystallinity degree in commercial PVC samples vary from 3% (45) to about 10% (46), the actual value depending on the thermal history of the sample.
Apparently even small values of the crystallinity degree can affect rather strongly the rheological behaviour of plasticized PVC in the rubbery and flow regions.
For the fractions here investigated, the fractional precipitation procedure used to carry out the separation (1) leads probably to a fractionation based not only on molecular weight but also on stereoregularity (47), the result being that the fractions precipitated firstly are more polydisperse and more crystallizable. In dilute solution, they give easily aggregates (1), stable up to relatively high temperatures (2).
The dynamic-mechanical data discussed above (fig. 1) as well as the anomalies presented by the rheological results (fig. 7 to 12) can be therefore explained on the basis of a model in which supermolecular structures linked together by crystalline bonds are present in the samples.
The marked dependence of PVC mechanical properties on the annealing temperature described recently byAndrews andKazama (48) seems to give considerable support to such a model.
Similar content being viewed by others
References
Pezzin, G. andP. Sanmartin, F. Zilio-Grandi, J. Appl. Polymer Sci.11, 1539 (1967).
Pezzin, G. andG. Zinelli, J. Appl. Polymer Sci. 12, 1119 (1968).
Convalle, G., XV International Congress on Plastics, Torino 1963.
Merz, E. H. andR. E. Colwell, ASTM Bull. No.232, 63 (1958).
Bagley, E. B., J. Appl. Phys.28, 624 (1957).
Rabinowitsch, B., Z. phys. Chem. A145, 1 (1929).
Képès, A., J. Polymer Sci.22, 409 (1956).
Ajroldi, G., C. Garbuglio andG. Pezzin, J. Polymer Sci. A2/5, 289 (1967).
Leaderman, H., Ind. Eng. Chem.35, 374 (1943).
Walter, A. T., J. Polymer Sci.13, 207 (1954).
Sabia, R. andF. R. Eirich, J. Polymer Sci. A1, 2497, 2511 (1963).
Shen, M. C. andA. V. Tobolsky, Advan. Chem. Ser.48, 118 (1965).
Schmieder, K. andK. Wolf, Kolloid-Z.127, 65 (1952).
Marvin, R. S., “Viscoelasticity, Phenomenological Aspects”,J. T. Bergen, Ed. (New York 1960).
Oyanagi, Y. andJ. D. Ferry, IV Intern. Congress on Rheology, Providence 1963.
Pezzin, G., J. Appl. Polymer Sci.10, 21 (1966).
Ferry, J. D., “Viscoelastic Properties of Polymers” (New York 1961). p. 280.
Tobolsky, A. V. andK. Murakami, J. Polymer Sei.40, 433 (1959).
Andrews, R. D. andA. V. Tobolsky, J. Polymer Sci.7, 221 (1951).
Ninomiya, K., J. Colloid Sci.14, 49 (1959).
Tobolsky, A. V. andA. Murakami, J. Colloid Sci.15, 282 (1960).
Tobolsky, A. V., J. J. Aklonis andG. Akovali, J. Chem. Phys.42, 723 (1965).
Sobue, H., K. Murakami andH. Hoshino, J. Polymer Sci. A 2, 1523 (1964).
Ferry, J. D., R. F. Landel andM. L. Williams, J. Appl. Phys.26, 359 (1955).
Peticolas, W., J. Chem. Phys.39, 3392 (1963).
Fox, T. G. andP. J. Flory, J. Phys. Chem.55, 221 (1951).
Fox, T. G. andV. R. Allen, J. Chem. Phys.41, 344 (1964).
Taylor, R. B. andA. V. Tobolsky, J. Appl. Polymer Sci.8, 1563 (1964).
Kockott, D., Kolloid-Z. u. Z. Polymere198, 17 (1964).
Pezzin, G., paper presented at the Symposium on Polymer Gels and Concentrated Solutions, Prague 1967.
Van der Vegt, A. K., Plastics Inst. Trans.32, 165 (1964).
Ram, A. andN. Narkis, J. Appl. Polymer Sci.10, 481 (1966).
Gruver, J. T. andG. Kraus, J. Polymer Sci. A2, 797 (1964).
Stratton, R. A., J. Colloid Sci.22, 517 (1966).
Krishnamurthy, S., J. Polymer Sci. B5, 69 (1967).
Berens, A. R. andV. L. Folt, Trans. Soc. Rheol.11, 95 (1967).
Strella, S., J. Appl. Polymer Sci.12, 218 (1968).
Rouse, P. E. J. Chem. Phys.21, 1272 (1953).
Bueche, F., J. Chem. Phys.22, 1570 (1954).
Pao, Y. H., J. Polymer Sci.61, 413 (1962).
Graessley, W. W., J. Chem. Phys.43, 2696 (1965).
Middleman, S., J. Appl. Polymer Sci.11, 417 (1967).
Pezzin, G. andG. B. Gechele, J. Appl. Polymer Sci.8, 2195 (1964).
Dunleavy Jr. J. E. andS. Middleman, Trans. Soc. Rheol.10, 157 (1966).
Wilski, H., Kolloid-Z. u. Z. Polymere210, 37 (1966).
Lebedev, V. P., N. A. Okladnov andM. N. Shlykova, Vysokomol. soyed. A9, 495 (1967).
Kratochvil, P., M. Bohdanecky, K. Solc, M. Kolinsky, M, Ryska, andD. Lim, „Intern. Symp. on Macromolecular Chem.“ Tokyo 1966.
Andrews, R. D. andY. Kazama, J. Appl. Phys.38, 4118 (1967).
Author information
Authors and Affiliations
Additional information
The authors are indebted to Mr.Sangiovanni and Mr.Zinelli for most of the experimental results.
Rights and permissions
About this article
Cite this article
Pezzin, G., Ajroldi, G. & Garbuglio, C. Influence of molecular weight on some rheological properties of plasticized polyvinylchloride. Rheol Acta 8, 304–311 (1969). https://doi.org/10.1007/BF01973958
Received:
Issue Date:
DOI: https://doi.org/10.1007/BF01973958