含萘环聚芳醚酮类聚合物的分子设计与性质研究  

Molecular Design and Characterization of Poly(aryl ether ketone)s Containing Naphthalene

作　　者：牛亚明[1] 姜振华[1] 

机构地区：[1]教育部吉林大学特种工程塑料研究中心,吉林长春130023

出　　处：《波谱学杂志》2006年第4期552-556,共5页Chinese Journal of Magnetic Resonance

摘　　要：聚芳醚酮类聚合物由于具有优良的韧性、刚性、耐热等级高、电性能、耐辐射、耐疲劳、耐冲击、抗蠕变、耐磨、耐热水性好、阻燃性好等特点,在热塑性聚合物领域占有极其重要的位置.其在航空、航天、核能、信息、通讯、电子电信、石油化工、机械制造、交通运输等高技术领域得到了成功的应用,使许多行业的传统产品实现了更新换代.但是,随着世界新科技革命的蓬勃发展,对高性能结构材料提出了日益广泛而迫切的需求.为进一步提高聚芳醚酮类聚合物的性能,满足某些特殊情况下的使用要求(例如高温、高辐照强度),可考虑对它们进行交联.使之可用热塑性材料的加工方法加工,然后通过热处理使其交联,成为热固性材料.这就要求在聚合物链上引入可交联基团.常用的脂肪族交联基团的引入,会导致聚芳醚酮耐热性降低,而只能寻找芳香族可交联集团的聚合物材料.本论文的目的是从分子结构设计的角度出发,从合成新型单体入手,采用芳香族亲核取代路线,将萘环引入聚合物主链,合成出一系列的新型含萘环聚芳醚酮类聚合物,并在不同条件下对它们进行了热处理.主要利用电子自旋共振(ESR)这一手段对热处理前后的聚合物进行了表征,研究了聚合物的热交联行为,讨论了萘环的化学环境、键连位置及热处理条件对交联反应的影响,建议了交联机理.我们首先通过1,5-萘二酚(1,5-DHN)、对苯二酚(HQ)和4,4′-二氟二苯酮(DFB)合成了新型高分子量的含1,5-萘二醚型聚醚醚酮无规共聚物(1,5-PENEK),发现随着萘环含量的增加,聚合物的玻璃化转变温度升高,熔点和结晶能力逐步下降直至消失,力学性能略有下降但基本保持了聚芳醚酮的优良性能.这些性质的改变是由于萘环的引入在增加了聚合物的刚性同时也降低了聚合物的有序排列能力所致.通过DSC、WAXR检测发现,1,5-萘�In recent years aromatic polyether ketones have achieved remarkable positions among other thermoplastic polymers because of their unique combination of toughness, stiffness, thermooxidative stability, electrical performance, flame retardancy and retention of physical properties at high temperatures. So they have been successfully applied to many fields such as aviation, spaceflight, nuclear energy, communication, telecom, petroleum, machine manufacturing and traffic. But following the booming development of new science and technology revolution in world, the high performance materials have been required extensive and urgent. In order to improve the characterization of poly（aryl ether keonte）s further, and fulfill the requirement of some extreme environment like the high temperature and irradiation environment, it is made them to take place crosslinking reaction. It is thermoplastic material before process that can be molded or casted, and then becomes thermoset through crosslinking reaction after process, so it has advantage of both kinds of materials. It＇s required to introduce crosslinking group. It can not be used the generally aliphatic crosslinking group over the polymer material because it can decease thermal stability of poly（aryl ether keonte）s, but only to look for the material which has aromatic crosslinking group. The aim of the dissertation is from the design of molecular structure to synthesize new monomers and then to synthesize new poly（aryl ether ketone）s containing naphthalene with different chemical environment and linking position through the nucleophilic displacement condensation reaction. Electric Spin Resonance （ESR） as the major method was used to investigate the thermal crossliniking behavior, discussed the affection of naphthalene with different chemical environment and linking position, and made up the mechanism of crosslinking reaction. We used 1, 5-dihydroxynaphthalene（1, 5-DHN）, hydroquinone（HQ）and 4, 4＇-Difluorobenzophenone （DFB） to synthesize the new

关 键 词：电子自旋共振 含萘环聚芳醚酮类聚合物 分子设计 交联反应机理 自由基 

分 类 号：TQ463.24[化学工程—制药化工]