Linear viscoelastic behavior was investigated during a gelation process of two poly(dimethyl siloxane) prepolymers A and B of molecular weight
Mw,pre = 3.5×10
4. The gelation occurred mainly through a reaction of monomethylsilyl groups (0.7 mol% in the backbone of the prepolymer B) and vinyl groups at the chain ends of A and B, giving a scarcely crosslinked gel having a large sol fraction (
wsol = 0.58 on completion of gelation) and exhibiting the equilibrium modulus much smaller than a nominal modulus calculated from
Mn,pre, (1-
wsol)ρ
RT/Mn,pre with ρ = density. The reaction was conducted at a relatively low temperature, 50 °C, so that this reaction proceeded slowly and the viscoelastic changes during the gelation process were well resolved. The terminal flow behavior was observed at a reaction time
tr ≤ 54 min (pre-gel stage), while the elasticity at low angular frequencies ω became prominent at
tr ≥ 60 min (post-gel stage). The critical gelation behavior characterized with a power-law relationship between the storage/loss moduli and ω ,
G' ∝
G" ∝ ω
n (0 <
n < 1), was
not observed at
tr between these stages, suggesting that the gelation did not occur through formation of a huge, self-similarly hyper-branched critical gel network. For further examination of this gelation process, the prepolymer mixture was collected at several reaction times
tr and the molecular characteristics of toluene-soluble sol component therein and a number fraction of the remaining (unreacted) monomethylsilyl group
nMeSi were examined. It turned out that the high-
M tail of the sol became enriched with densely branched chains of
M reaching 1×10
7 (≅ 300
Mw,pre) and
nMeSi rapidly decreased to ∼ 0.3 with increasing
tr up to 65 min while the branch content/molecular weight of the sol decreased and
nMeSi gradually approached 0 on a further increase of
tr. These results suggested a gelation mechanism that densely branched pre-gel chains involving up to 300 prepolymer chains were first formed on consumption of the majority of the monomethylsilyl groups at
tr ≤ 65 min and then these pre-gel chains were scarcely linked through a small amount of remaining monomethylsilyl groups to form the 3-dimensional gel at
tr > 65 min. The lack of critical gelation behavior as well as the small equilibrium modulus (<<(1 -
wsol)ρ
RT/Mn,pre) on completion of gelation are consistent with this mechanism.
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