Thermally Reversible Covalent Linking of Halide-containing Polymers

摘要：Eli Ruckenstein机构：SUNY Buffalo提案编号：基于紫罗烯形成的热可逆共价（TRC）连接的含卤化物的交联聚合物可特别适用于制造可回收材料和改进传统热塑性材料的机械和物理性能而不损失热塑性。 这些交联聚合物也可以用作热传感器材料。两种热可逆反应，即热可逆的Diels-Alder环加成反应和热可逆的Menschutkin反应，将被用来生成TRC链接。 双环戊二烯二羧酸（SDCPDCA）的盐将用作含卤素聚合物的TRC交联剂。 含有苄基氯、伯氯、仲氯、叔氯或烯丙基氯的含氯聚合物将与SDCPDCA进行酯化交联。 后一种化合物是通过使二环戊二烯二羧酸（DCPDCA）与乙醇盐或氢氧化物反应来制备的。 由于-DCPD-桥的热可逆去二聚/二聚，交联聚合物将表现出TRC交联。 上述含CL的聚合物也将与二叔胺交联，从而基于Menschutkin反应形成紫罗烯网络。 由于紫罗烯桥在加热时的脱季铵化和在冷却时的再季铵化，预期所产生的紫罗烯网络表现出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.