Synthesis and properties of phosphinated crosslinkable poly(ether ether ketone)s and polyimides

• Main Authors: Yu-Ru Wang, 王譽儒
• Other Authors: 林慶炫
• Format: Others
• Language: zh-TW
• Published: 2012
• Online Access: http://ndltd.ncl.edu.tw/handle/495ywm

碩士 === 國立中興大學 === 化學工程學系所 === 100 === 1.Linear polyethers are generally prepared from equal molar of bisphenols and aromatic bishalides in the presence of base. Therefore, polyethers with a residual phenol group in the repeating unit are difficult to prepare. In this work, a phosphinated polyether (P1) with a phenol group in the repeating unit was prepared from a one-pot reaction of a BPA-based poly(ether ether ketone), poly(oxy-1,4-phenylenecarboneyl-1,4-phenyleneoxy-1,4-phenylene-isopropylidene-1,4-phenylene (BPA-PEEK), with 9,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and phenol in the presence of H2SO4. The phenol linkages provide reacting cites with epoxy resins. Therefore, flexible and transparent films of epoxy thermosets can be prepared from the curing of P1 with three epoxy resins. The resulting thermosets show high Tg (250 oC), moderate-to-low dielectric constant (3.01), and flame retardancy (UL-94 VTM V-0). The moderate-to-high molecular weight of P1 might be responsible for the flexibility, which is rarely seen in epoxy thermosets. 2.An allyl-containing diphenol (1), was prepared from a one-pot reaction of 9,10-dihydro-oxa-10-phosphaphenanthrene-10-oxide (DOPO), 4-hydroxyacetophenone, and 2-allylphenol in the presence of p-TSA. A allyl-containingdietheramine (3) was nucleophilic substitution of (1) with 4-fluoronitrobenzene, followed by the reduction of the dinitro groups by Fe/HCl. Flexible polyimide (4) with curable characteristic, as supported by the DSC exothermic peak, was prepared from the condensation of (3) and ODPA in m-cresol in the presence of isoqunoline. Thermal properties and solvent resistance of polyimide (4) was significant improved after thermal curing at 300 oC, 1h.