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Investigation of the structure and properties of polyisobutylene-based telechelic ionomers of narrow molecular weight distribution. II. mechanical

✍ Scribed by Don Loveday; Garth L. Wilkes; Youngkwan Lee; Robson F. Storey


Publisher
John Wiley and Sons
Year
1997
Tongue
English
Weight
251 KB
Volume
63
Category
Article
ISSN
0021-8995

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✦ Synopsis


Sulfonated polyisobutylene (PIB) telechelic ionomers with narrow molecular weight distribution (MWD) have been recently developed, providing additional control over the structure and properties of these novel polymers. A small angle X-ray scattering (SAXS) peak often associated with the aggregation of the ionic species in the bulk, and a secondary peak, were recently observed in the narrow MWD sulfonated PIB telechelics for the first time. SAXS evidence, given earlier as part I of this two-part series, suggests that compression-molded sulfonated PIB telechelic ionomers with a narrow MWD (M V w /M V n Γ‰ 1.15) may have a local secondary structure of ionic lamellae or cylin- ders, and no such structure is found in similar broad MWD ( M V w /M V n Γ‰ 1.8) telechelics. It is shown that narrowing the MWD, which acts to promote locally continuous structure in the tri-arms, alters the character of the network, in that the modulus of the tri-arm telechelic systems increases and the elongation at break is lowered by narrowing the MWD or decreasing the M V n . The tri-arms of the highest M V n (49.5 kg/mol) exhibit strain hardening and the lowest modulus, highest-breaking stress, and highest elongation at break in the ionomers studied. The presence of local ionic structure is also indicated by stress relaxation experiments in which the long-term or near-equilibrium stress is seen to decrease when the MWD is broadened or M V n increases. It is believed that the difunctional materials do not form extensive ionic networks at all, but principally chainextend, as has also been found before. It is observed that the properties of a solution ''blend'' of narrow MWD ionomers that has the same counterion, M V n , and polydispersity as a broad MWD system exhibits lower elongation to break, lower breaking stress, and modulus of narrow MWD systems relative to the broader MWD material. Dynamic mechanical data indicate that narrowing the MWD or decreasing M V n increases the flow transition temperature and rubbery plateau modulus. The ''blend'' exhibits dynamic mechanical properties between the narrow and broad, having a higher flow transition temperature than the broad MWD, but lower than the narrow MWD, and a rubbery plateau modulus between the other two. α­§ 1997


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