Dynamic Mechanical Behavior of Ordered Off-Stoichiometric Polyurethane Systems at the Gel Point Threshold
作者:
H. VALENTOVÁ,
Z. SEDLÁKOVÁ,
M. ILAVSKÝ,
K. BOUCHAL,
期刊:
Journal of Macromolecular Science, Part B
(Taylor Available online 2000)
卷期:
Volume 39,
issue 5-6
页码: 605-622
ISSN:0022-2348
年代: 2000
DOI:10.1081/MB-100102474
出版商: Taylor & Francis Group
关键词: Dynamic modulus;Frequency-temperature superposition;Gel point;Polyurethanes;Power law behavior;Sol-gel transition
数据来源: Taylor
摘要:
Dynamic mechanical and thermal behavior of ordered off-stoichiometric polyurethane (PU) systems, before and after the gel point, based on the mesogenic diol 6,6′;-[ethylenebis(1,4-phenyleneoxy)]dihexan-1-ol (D),2(4)-methyl-1,3-phenylene diisocyanate (DI), and poly(oxypropylene)triol (T) were studied. Polymer samples were prepared at various initial molar ratios of the reactive groups,r= [OH]T/[NCO]DI/[OH]D, ranging from 1/10/9 to 5/10/9 (the ratio [NCO]DI/[OH]D= 10/9 was constant); the total mole ratio of hydroxy (OH) and isocyanate (NCO) groups, rOH = [OH]/[NCO] = ([OH]D)/[NCO]DI,changed from 1 to 1.4. Dynamic mechanical measurements during the curing reaction showed that the power law parameters that characterize the critical gel state (gel strengthSand relaxation exponentn) are dependent on the initial composition (the ratiorOH). The gel-point critical ratio of reactive groupsrcOH, found during curing in the ordered state of the diol (at low curing temperature), has revealed that the critical gel (CG) structure is determined by a contribution of strong physical interactions as well as chemical junctions and does not correspond to pure chemical gelation (CG structure formed at low temperature exhibits flow at elevated temperatures in the isotropic state). This fact suggests that formation of the mesophase enhances the connectivity of the molecular structure at the gel point. Dynamic mechanical behavior of fully cured chemical networks (rOH<rOHc) and un-cross-linked (rOH>rOHc) samples (and a CG sample) has also been investigated. Decreasing the rOHratio (increasing concentration of chemical cross-links in the systems) inhibits conformational rearrangements required for ordering; at the same time, the intensity of the slow relaxation process in the rubbery region decreases.
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