CHEN Yangfei, CHEN Zhiqin, LIU Hongbo. Effect of Methylene Substituents on the Thermal Degradation of Phenolic Resin. [J]. Acta Polymerica Sinica (5):399-404(2008)
DOI:
CHEN Yangfei, CHEN Zhiqin, LIU Hongbo. Effect of Methylene Substituents on the Thermal Degradation of Phenolic Resin. [J]. Acta Polymerica Sinica (5):399-404(2008) DOI: 10.3724/SP.J.1105.2008.00399.
Effect of Methylene Substituents on the Thermal Degradation of Phenolic Resin
The phenolic resin was synthesized by condensation of formaldehyde and phenol
with a molar ratio of 1.2
in aqueous solutions containing ammonia at 90℃ for 1.5 h under vacuum dehydration.The synthesized resin was cured at 170℃ for 3 h and then characterized by using TG under nitrogen.The cured resin was heat_treated at 300
350
400
450
500
550 and 600℃
respectively and then characterized with FTIR. In the FTIR spectra of the cured samples
the absorption bands of the methylene groups for orth-orth (o-o′)
orth-para (o-p) and para-para (p-p′) substituents were at 1437~1440 cm-1,1452~1456 cm-1 and 1473~1477 cm-1
respectively. The variations of the individual absorbance with heat-treatment temperature were compared in terms of the relative absorbance
i.e. Ix/I1610
where I1610is the absorbance of aromatic ring backbone stretching at 1610 cm-1. The experimental results show that the thermal degradation of the phenolic resin is significantly related to the substitution position of the methylene groups.The para-substitution of methylene groups was suddenly transferred to the orth-one in some content during the condensation.Otherwise
in the cured process
para-substitution was prior formed because its activity is higher than that of the ortho-one.According to the TG and FTIR spectra
the decomposition process of methylene groups could be divided into two stages.The bond cleavages of o-o′ and p-p′ substituents occurred at 350~450℃ and 400~620℃
respectively.It means the o-o′ substituent is thermally unstable and then partially cyclized to form xanthene by intramolecular etherification.Also
the benzylic-bonded keto-intermediates could be formed through ketoenol tautomerism.The benzylic bond energy in the keto-form is at least 168 kJ/mol less than that of the original aromatic structure.Therefore
at higher temperatures
the o-o′ substituent of the methylene groups was prior decomposed. For the p-p′ substituents
the hydroxyl groups are distant form each other
and the benzylic bonded ketointermediate formation is hindered.Finally
the decomposition temperature is higher than that of the o-o′ substituents.