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Macromolecules, Vol. 36, No. 4, 2003
proceeded homogeneously to afford the polymers with
weight-average molecular weights of ca. 1000. The
active species of the polymerization should be piperidine
as confirmed by the NMR spectroscopic study described
above. Figure 2 depicts the relationships between GPE
conversion and temperature in the polymerization of
GPE with 10 mol % 1a and 1b for 12 h. GPE did not
polymerize below 150 and 100 °C but polymerized
rapidly above the temperatures. It was confirmed that
1b was more active than 1a . The rigid structure of 1b
due to the benzene ring may be preferable to formation
of a lactone ring compared to 1a . Both of the hydroxyl-
amides could cure bisphenol A digylycidyl ether (Epikote
828) quantitatively at 180 °C for 12 h.
In summary, we have demonstrated that the hy-
droxylamides 1a and 1b serve as excellent thermally
latent non-salt-type initiators for polymerization of
epoxide. We believe that our simple and low-cost initia-
tor system is a promising candidate for practical hard-
eners of epoxy resin.
F igu r e 2. Relationships between GPE conversion and tem-
perature in the polymerization of GPE with 10 mol % 1a and
1b for 12 h.
Sch em e 2
Refer en ces a n d Notes
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lactone ring. This enables the hydroxyl group, which is
less nucleophilic than amino group, to attack the amide
carbonyl carbon in a manner similar to the phosphonic
amide esters previously reported.8 On the other hand,
the thermal dissociation of 1a could not be confirmed
at 130 °C by NMR spectroscopy. It is likely that 1a also
dissociates in a manner similar to 1b at higher tem-
perature. In fact, it has been reported that 1a cannot
be distilled without thermal dissociation.10 However, we
could not check it by NMR spectroscopy because of
limitation of the measuring temperature of the NMR
apparatus.
The polymerization of GPE with hydroxylamides 1a
and 1b was carried out in sealed glass ampules. Since
1a and 1b were easily soluble in GPE, the polymerizaion
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