An octa-functional acrylate of C-tetramethyl calix[4]resorcinarene(CMC-4-RA) was facilely synthesized and characterized with 1H NMR, 13C NMR and FTIR spectroscopy. The CMC-4-RA was added to a thiol-acrylate system with different mass ratios, and exposed to a middle pressure mercury lamp. The maximum photopolymerization rate and final vinyl group conversion in the cured film increased greatly along with CMC-4-RA addition that was monitored with Photo-DSC. The tensile strength and pendulum hardness were improved significantly after the addition of CMC-4-RA. With increasing the content of CMC-4-RA to 60%(mass fraction), the glass transition temperature increased from 34.2 °C to 84.1 °C; the cross-link density was calculated to be increased from 23.83 mmol/cm3 to 82.40 mmol/cm3 according to dynamic mechanical thermal analysis; the thermostability was greatly improved.
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