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757
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Thus the kinetic equation in the range of 258–278 K can be rep-
resented as follows:
ꢂ
ꢃ
dCD
dt
ꢂ9:73
¼ 38:5 exp
ðCA ꢂ CDÞðCB ꢂ CDÞ ꢂ 9:07 ꢁ 102
0
0
T
ꢂ
ꢃ
ꢂ22:95
ꢁ exp
CD
ð8Þ
T
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3.5. Mechanism
Strong acid cation-exchange resin is a kind of ion-exchange re-
sin which contains –SO3H groups on the cross-linking polymer ma-
trix. The resin could be represented as R–SO3H, where
R
represented the polymer matrix. The H+ dissociated in solution
and is active. The function of the catalyst is the same as the H+ in
homogeneous catalysis.
It is known that the regio selectivity of a, b- unsaturated alde-
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1,1-diacetates from aldehydes, Synthesis 10 (1981) 824.
hydes tends to direct 1,2-carbonyl addition. The reaction rate of
weak nucleophilic reagents and unsaturated aldehydes would be
very slow if the carbonyl is not activated. The carbonyl of MAL is
activated by the strong acid cation-exchange resin. This makes it
easier for the acetic anhydride carbonyl O to attack the MAL car-
bonyl C. The reaction process is shown in Scheme 2.
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4. Conclusions
DMA was synthesized from MAL and acetic anhydride using a
strong cation-exchange resin as the catalyst. The optimal reaction
conditions were determined to be molar ratio of the reactants (ace-
tic anhydride/MAL) = 1.2:1.0, catalyst loading = 2 g molꢂ1, and stir-
ring speed = 200 rpm. The reaction kinetic equations were
established under conditions that eliminate both internal and
external diffusion. The forward reaction of MAL and acetic anhy-
dride is a second order reaction and the reverse reaction is a first
order reaction. The mechanism of the reaction of MAL and acetic
anhydride proceeds via activation of the MAL C@O by the strong
acid cation-exchange resin followed by the weak nucleophilic re-
agent, acetic anhydride, attacking the activated MAL. The regio
selectivity of the reaction is a 1,2-addition.
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catalyzed by ion-exchange resins, React. Funct. Polym. 67 (2007) 1458–1464.
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Catal., A: Gen. 297 (2006) 182–188.
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(2007) 510–512 (China).
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