【作者】 刘文利；

【导师】 夏宇正；

【作者基本信息】 北京化工大学 ， 材料物理与化学， 2003， 硕士

【摘要】 本论文利用环戊二烯(CPD)衍生物的常温二聚和高温解二聚特性,将双环戊二烯二甲酸钾(DCPD(COOK)2)用于与活性氯型丙烯酸酯橡胶(ACM)侧基上的活性氯进行酯交换反应,将 DCPD引作 ACM的交联键而达到“硫化”目的。在高温时,DCPD 可以发生逆Diels-Alder 反应而解交联成 CPD,交联 ACM 变为线型分子,因而具有了加工流动性,降温后,两个CPD再双取成 DCPD,再度形成交联结构,赋予 ACM良好的力学性能。从而使 ACM 成为一种常温下具有良好性能,同时高温下又具有可热塑性加工的热可逆共价交联的聚合物。 本论文以制备 ACM 的热可逆共价交联的热塑性弹性体为目的,主要以直接共混法和挤出反应法进行了以下工作: (1) 以 DCPD(COOK)2为交联剂、以白炭黑为补强剂,以共混法制得了具有优异力学性能的交联 ACM。研究了交联剂用量、压片温度、相转移催化剂及其用量对 ACM力学性能的影响,得到了最佳加工条件;同时也对重复加工条件、不同交联剂用量下试样的重复加工性能进行了研究,证明了由该交联剂形成的交联 ACM 具有可重复<WP=4>加工性,重复加工后胶样的力学性能基本不变;通过与己二酸钾的对比反应佐证了上述交联 ACM 的可逆加工性是由 DCPD(COOK)2分子上的 DCPD 热解二聚所致。(2)在双螺杆挤出反应法中,以 DCPD(COOK)2为交联剂制得了凝胶含量在 90%以上的交联 ACM,研究了同粘度不同类型的胶料、交联剂用量、相转移催化剂类型及其用量、挤出加工温度、螺杆转速对 ACM 外观、凝胶含量及拉伸强力的影响;通过 IR 谱图证明了DCPD(COOK)2与 ACM 上的活性氯发生了酯化反应;通过 DSC 测试,证明了在交联后的 ACM 中,DCPD 结构在加工过程中没有被破坏,仍可以发生逆 Diels-Alder 反应,在反应溶解性实验中也中验证了交联 ACM 的热可逆转化特性,可逆凝胶含量在 60%以上。更多还原

【Abstract】 It is well known that cyclopentadiene(CPD) can be converted todicyclopentadiene (DCPD) at room temperature and DCPD can beconverted to CPD at high temperature, which is the famous Diels-Alderreaction. Potassium salt of dicyclopentadiene acid(DCPD(COOK)2), aderivative of cyclopertadiene was used as a crosslinking agent for thevulcanization of acrylic rubber(ACM) through esterification between thecrosslinking agent and active chlorine of ACM. Because the crosslinkedstructure is thermally reversible, the “vulcanized ”ACM can become anew type thermoplastic elastomer(TPE). In order to obtain the thermally reversible crosslinked ACM, thefollow studies were focus on the extrude reaction and thermo-modelreaction. Firstly, the crosslinking reaction of ACM filled of white carbon black<WP=6>with DCPC(COOK)2 was conducted by thermo-model methods. Theeffects of dosage of crosslinking agent, model temperature, the kinds anddosage of catalysts on the mechanical properties were studied in detail.All the results showed that the crosslinked ACM’s mechanical propertieshave a good lever and can be reformed for three times. It also be provedthat the crosslinked ACM can be reformed is due to DCPD converted toCPD by contrast to the crosslinking reaction of potassium salt of adipatewith ACM. Secondly, in the extrude reaction of DCPC(COOK)2 with ACM, thegel content of crsslinked ACM can reach to more than 90% and morethan 60% of them were thmally reversible. The effects of dosage ofDCPC(COOK)2, catalysts and its dosage, the temperature and the rotatespeed of screw on the crosslinked ACM were also investigated in detail.The chart of IR can prove that DCPC(COOK)2 do react with the activechlorine of ACM. It also can be proved that the structure of DCPD canbe destroyed at over 180℃.更多还原