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Licensed Unlicensed Requires Authentication Published by De Gruyter June 30, 2014

Enhance Slower Relaxation Process of Poly(ethyl acrylate) through Internal Plasticization

  • X. R. He , H. Yu , R. Zhang and C. H. Yang


In this paper, we report a chemical way to resolve longer motions units in the glass-rubber transition region of poly (ethyl acrylate) (PEA), so called internal plasticization. The ethyl acrylate (EA) monomers were copolymerized with little amount of isoprene (IP) monomers. We propose that the single bonds adjunct to double bonds would have better flexible activity than usual single bonds, so the motion units located between two adjunct double bonds would be enhanced. The dynamic mechanical spectra of internally plasticized PEA (IPPEA) and PEA show that the tan δ of IPPEA is asymmetric, while the tan δ of PEA is symmetric. Furthermore, the results of 2D-DMAS show that the LSM, SRM and RM of IPPEA are located at 7 °C, 12 °C and 36 °C. The shoulder peak of tan δ of IPPEA at higher temperature side was confirmed that it contains sub-rouse mode (SRM) and rouse mode (RM). Thus, internal plasticization is an effective way to resolve modes above Tg.

* Mail address: Rui Zhang, College of Materials Science and Engineering, State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation, Southwest Petroleum University, Chengdu, PRC, E-mail:


Anderson, P. W., “Through the Glass Lightly”, Science, 267, 1610 (1995)10.1126/science.267.5204.1610.bSearch in Google Scholar

Boyer, R. F.; “The High Temperature (T > Tg) Amorphous Transition in Atactic Polystyrene”, J. Polym. Sci. Part C, 14, 267281 (1966)Search in Google Scholar

Boyer, R. F., Miller, R. L.Correlation of Liquid-state Compressibility and Bulk Modulus with Cross-sectional Area Per Polymer Chain”, Macromolecules, 17, 365369 (1984) 10.1021/ma00133a019Search in Google Scholar

Dong, J. H., Zhang, X. and Wang, L.: Polymer Science, Science Press, Beijing (2011)Search in Google Scholar

Donth, E., Beiner, M., Reissig, S., Korus, J., Garwe, F., Vieweg, S., Kahle, S., Hempel, E. and Schroter, K., “Fine Structure of the Main Transition in Amorphous Polymers: Entanglement Spacing and Characteristic Length of the Glass Transition: Discussion of Examples”, Macromolecules, 29, 65896600 (1996)10.1021/ma951881aSearch in Google Scholar

He, X. R., Huang, G. S., Zhou, H., Jiang, L. X., Zhao, X. D., Zhang, J. and Wang, J. H., “Investigation on the Damping Behavior of CIIR/PMAc Blends”, Acta Polym. Sinica, 1, 108112 (2005)Search in Google Scholar

Liao, F. S., Su, A. C., HsuA. C., and Tzu-Chien, J., “Damping Behavior of Dynamically Cured Butyl Rubber/Polypropylene Blends”, Polymer, 35, 25792586 (1994)10.1016/0032-3861(94)90382-4Search in Google Scholar

Ngai, K. L., Plazek, D. J.Identification of Different Modes of Molecular Motion in Polymers That Cause Thermorheological Complexity”, Rubber Chem. Tech., 68, 376434 (1995)10.5254/1.3538749Search in Google Scholar

Ngai, K. L., Plazek, D. J.Resolution of Sub-Rouse Modes of Polystyrene by Dissolution”, Macromolecules, 35, 91369141 (2002)10.1021/ma0209904Search in Google Scholar

Noda, I., “Determination of Two-Dimensional Correlation Spectra Using the Hilbert Transform”, Appl. Spectrosc., 54, 994999 (2000)10.1366/0003702001950472Search in Google Scholar

Noda, I., “Generalized 2-Dimensional Correlation Spectra Method Applicable to Infrared Raman and Other Types of Spectroscopy”, Appl. Spectrosc., 47, 13291336 (1993)10.1366/0003702934067694Search in Google Scholar

Plazek, D. J., Chay, I. C., Ngai, K. L., and Roland, C. M., “Viscoelastic Properties of Polymers. 4. Thermorheological Complexity of The Softening Dispersion in Polyisobutylene”, Macromolecules, 28, 64326436 (1995)10.1021/ma00123a007Search in Google Scholar

Rizos, A. K., Jian, T. and Ngai, K. L., “Determination of the Coupling Parameter of Local Segmental Motion in Poly(isobutylene) by Photon Correlation Spectroscopy”, Macromolecules, 28, 517521 (1995)10.1021/ma00106a015Search in Google Scholar

Rizos, A. K., “Local segmental and Sub-rouse Modes in Polyisobutylene by Photon Correlation Spectroscopy”, Polymer, 38, 61036107 (1997)10.1016/S0032-3861(97)00188-2Search in Google Scholar

Strobl, G.: The Physics of Polymers: Concepts for Understanding Their Structure and Behavior, Springer, Berlin, Heidelberg (2007)Search in Google Scholar

Wang, X. A., He, X. J., Huang, G. S. and Wu, J. R., “Correlations between Alkyl Side Chain Length and Dynamic Mechanical Properties of Poly(n-alkyl acrylates) and Poly(n-alkyl methacrylates)”, Polymer, 53, 665672 (2012)10.1016/j.polymer.2011.11.059Search in Google Scholar

Wang, X. A., Huang, G. S., Wu, J. R., Nie, Y. J., He, X. J. and Xiang, K. W., “Molecular Motions in Glass-rubber Transition Region in Polyisobutylene Investigated by Two-dimensional Correlation Dielectric Relaxation Spectroscopy”, Appl. Phys. Lett., 99, 121902121902 (2011)10.1063/1.3640479Search in Google Scholar

Wang, X. A., Huang, G. S., Wu, J. R., Nie, Y. J. and He, X. J., “Using Two-Dimensional Correlation Dynamic Mechanical Spectroscopy to Detect Different Modes of Molecular Motions in the Glass-Rubber Transition Region in Polyisobutylene”, J. Phys. Chem., 115, 17751179 (2011)10.1021/jp110890nSearch in Google Scholar PubMed

Wu, J. R. et al, “Study on Liquid-Liquid Transition of Chlorinated Butyl Rubber by Positron Annihilation Lifetime Spectroscopy”, Appl. Phys. Lett., 89, 121904121904-3 (2006)10.1063/1.2335376Search in Google Scholar

Wu, J. R., Huang, G. S., Pan, Q. Y., Zheng, J., Zhu, Y. C. and Wang, B., “An Investigation on the Molecular Mobility through the Glass Transition of Chlorinated Butyl Rubber”, Polymer, 48, 76537659 (2007)10.1016/j.polymer.2007.11.006Search in Google Scholar

Wu, J. R., Huang, G. S., Wang, X. A., He, X. J. and Xu, B., “Changes in the Viscoelastic Mechanisms of Polyisobutylene by Plasticization”, Macromolecules, 45, 80518057 (2012)10.1021/ma3001274Search in Google Scholar

Wu, X. B., Xu, Q. L., Shui, J. P. and Zhu, Z. G., “Low Frequency Mechanical Spectroscopy Study of Conformational Transition of Polymer Chains in Concentrated Solution”, Rev. Sci. Instrum., 79, 126105 (2008); in Google Scholar PubMed

Wu, X. B., Liu, C. S., Zhu, Z. G., Ngai, K. L. and Wang, L. M., “Nature of the Sub-Rouse Modes in the GlassRubber Transition Zone of Amorphous Polymers”, Macromolecules, 44, 36053610 (2011)10.1021/ma102897eSearch in Google Scholar

Wu, X. B., Zhu, Z. G.Effects of Polyethylene Oxide on The Dynamics of The α and α′ Relaxations Observed in Polystyrene by Low Frequency Anelastic Spectroscopy”, Appl. Phys. Lett., 90, 251908251908 (2007)10.1063/1.2749842Search in Google Scholar

Zhang, J., Tsuji, H., Noda, I. and Ozaki, Y., “Structural Changes and Crystallization Dynamics of Poly(L-lactide) during the Cold-Crystallization Process Investigated by Infrared and Two-Dimensional Infrared Correlation Spectroscopy”, Macromolecules, 37, 64336439 (2004)10.1021/ma049288tSearch in Google Scholar

Zhang, J., Tsuji, H., Noda, I. and Ozaki, Y., “Weak Intermolecular Interactions during the Melt Crystallization of Poly(L-lactide) Investigated by Two-Dimensional Infrared Correlation Spectroscopy”, J. Phys. Chem. B, 108, 1151411520 (2004)10.1021/jp048308qSearch in Google Scholar

Zhu, Y. C. et al, “Study on Damping Mechanics Based on the Free Volume for CIIR by PALS”, J. Phys. Chem. B, 111, 1138811392 (2007)10.1021/jp071670vSearch in Google Scholar PubMed

Received: 2013-11-02
Accepted: 2014-02-15
Published Online: 2014-06-30
Published in Print: 2014-07-30

© 2014, Carl Hanser Verlag, Munich

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