ZHENG Shunxing, LIN Yuanjie, Lü Zhaoping. FTIR STUDIES ON THE CHANGE OF FUNCTIONAL GROUPS OF SILICA/PHENOLIC RESIN HYBRID MATERIALS WITH DIFFERENT DEGREES OF CURE. [J]. Acta Polymerica Sinica (10):979-984(2008)
DOI:
ZHENG Shunxing, LIN Yuanjie, Lü Zhaoping. FTIR STUDIES ON THE CHANGE OF FUNCTIONAL GROUPS OF SILICA/PHENOLIC RESIN HYBRID MATERIALS WITH DIFFERENT DEGREES OF CURE. [J]. Acta Polymerica Sinica (10):979-984(2008) DOI: 10.3724/SP.J.1105.2008.00979.
FTIR STUDIES ON THE CHANGE OF FUNCTIONAL GROUPS OF SILICA/PHENOLIC RESIN HYBRID MATERIALS WITH DIFFERENT DEGREES OF CURE
Silica/phenol resin hybrid material was prepared by a sol-gel process.Resole
tetraethoxysilare (TEOS)
ethanol and water were mixed to form the precursor
the ratio being resole∶TEOS∶ethanol∶water = 4.1 g∶1.5 g∶20 mL∶2 mL.The precursor was hydrolysed for 24 h to obtain a hybrid material (organic/inorganic weight ratio 9∶1).Resole and the precursor was cured at 120℃
2 h concurrently
then
part of the hybrid material was postcured at 160℃
1 h.The three samples (phenol resole
hybrid material and post-cured hybrid material) were analysed by FTIR and evaluated in view of application as organic coatings.Because phenol resin is liable to change its color in service
the hybrid material is only applied as undercoat.The wavenumber shift of O—H stretch vibration
the ratio of peak width at half hight Δ1/2(O—H)/Δ1/2(C=C) and absorbance ratios were used to characterize the structure changes of the hibrid material.Under the same curing conditions (120℃
2 h)
the O—H peak of the hybrid material shifts 49 cm-1 downward from that of resole
Hbond of the hybrid material (half hight 4.25) is stronger than that of resole (half hight 7.76)
and there is more hydroxyl concentration in the hybrid material.As an undercoat
the hybrid material can have enough functional groups to react with those of the topcoat in order that the multiple coatings can cure without interface between undercoat and topcoat.Post cure (160℃
1 h) can greatly reduce the hydroxyl concentration of the hybrid material.Phenol resole has a weak absorbance peak at 1070 cm-1 (A1070/A1612=0.81)
the hybrid materials (A1067/A1612=1.87; postcured A1069/A1612=2.99) have two very strong absorbance peaks in the range of 1100~1065 cm-1
therefore
the hybrid materials have more ether bonds than resole
and post-cure can form more ether bonds.The absorbance ratio [A]754/[A]1612 that expresses the substitution reaction of o-positions of the phenol rings increases from 4.25 of resole to 7.76 of the hybrid material
which means the substitution reaction of o-positions in the hybrid material is much more remarkabe than that in resole.The [A]818/[A]1612 that expresses the substitution reaction of p-positions increases from 0.32 of the hybrid material to 0.51 of postcured hybrid material
but [A]754/[A]1612 increases unremarkably
which means the substitution reaction of p-positions in the hybrid material during postcure is predominant
and the substitution reaction of o-positions is negligible.The ratio A1646/A1612 of phenol resin is 0.53
and that of the post-cured hybrid material is 0.54
which means the postcured hybrid material gets the same oxidation degree as the phenol resin.The post-cured hybrid material does not have free phenols
consequently
the post-cured hybrid material is more environment-friendly than resole.