Thermally Reversible Covalent Linking of Halide-containing Polymers

热可逆共价（TRC）连接卤化物的基于碘烯形成的交联聚合物可能特别适合于制造可回收材料，并在不损失热塑性的情况下改善传统热塑性材料的机械和物理性能。这些交联聚合物也可用作热传感器材料。两种热可逆反应，即二烯的热可逆Diels-Alder环加成反应和热可逆Menschutkin反应，将被用来生成TRC链。双环戊二烯二羧酸盐（SDCPDCA）将用作含卤化物聚合物的TRC交联剂。含有苯氯、伯氯、仲氯、三级氯或烯丙基氯的含氯聚合物将与SDCPDCA发生酯化交联。后一种化合物是由双环戊二甲酸（DCPDCA）与乙氧化物或氢氧化物反应制备的。由于- dcpd -桥的热可逆脱二聚/二聚作用，交联聚合物将表现出TRC交联。上述含cl的聚合物也将与二食胺交联，形成基于Menschutkin反应的离子烯网络。由于离子烯桥在加热时的脱季和冷却时的再渗，所生成的离子烯网络预计会表现出TRC交联。

ABSTRACTPI: Eli Ruckenstein Institution: SUNY BuffaloProposal Number: 0086491Thermally reversible covalently (TRC) linked halide containing crosslinked polymers based on ionene formation may be particularly suitable for manufacturing recyclable materials and for improving the mechanical and physical properties of traditional thermoplastic materials without loss of thermoplasticity. These crosslinked polymers can also be employed as thermal sensor materials.Two kinds of thermally reversible reactions, namely the thermally reversible Diels-Alder cycloaddition of a diene and the thermally reversible Menschutkin reaction, will be employed to generate TRC links. Salts of dicyclopentadiene dicarboxylic acid (SDCPDCA) will be used as TRC crosslinkers of halide-containing polymers. CL-containing polymers possessing benzyl chlorine, primary Cl, secondary Cl, tertialy Cl or allyl Cl moieties, will be subjected to esterification crosslinking with SDCPDCA. The latter compounds are prepared by reacting dicyclopentadience dicarboxylic acid (DCPDCA) with ethoxide or hydroxide. The crosslinked polymers will exhibit TRC crosslinking due to the thermally reversible dedimerization/dimerization of -DCPD- bridges. The above CL-containing polymers will also be crosslinked with ditertiary amines vial the formation of ionene networks based on the Menschutkin reaction. The generated ionene networks are expected to exhibit TRC crosslinking due to the dequarternization on heating and requarternization on cooling of the ionene bridges.