含二氮杂萘酮联苯结构耐高温、可溶解嵌段聚芳醚酮的合成  

Synthesis of Phthalazinone-containing Poly(aryl-ether-ketone) Block Copolymers with Good Solubility and High Thermal Stability

作　　者：鲍锋 刘程[1,2] 宋媛媛 邬祚强 王锦艳 蹇锡高[1,2] Feng Bao;Cheng Liu;Yuan-yuan Song;Zuo-qiang Wu;Jin-yan Wang;Xi-gao Jian(Department of Polymer Science ＆ Materials, Dalian University of Technology;Liaoning Province Engineering Technology Center of High Performance Resins, Dalian 116024)

机构地区：[1]大连理工大学高分子材料系 [2]辽宁省高性能树脂工程技术研究中心,大连116024

出　　处：《高分子学报》2018年第6期692-699,共8页Acta Polymerica Sinica

基　　金：国家重点基础研究发展计划(863计划;项目号2015AA033802);国家重点研发计划(项目号2017YFB0307600);科技部重点领域创新团队(项目号2016RA4053)资助

摘　　要：从分子设计的角度出发,设计、合成了3种不同嵌段长度的耐高温、可溶解的嵌段共聚物PPENK-b-PEEKK,成功地将含二氮杂萘酮联苯结构聚芳醚酮PPENK链段与结构规整PEEKK链段进行结合.首先采用溶液聚合方法合成了羟基封端聚醚醚酮酮(PEEKK-OH)低聚物,并通过正交实验对聚合工艺进行了优化,获得了最优的合成条件.然后,采用一锅分步加料的方法,合成了PPENK-b-PEEKK嵌段共聚物.红外测试结果表明了共聚物的成功合成,广角X射线衍射(WXRD)测试结果表明3种共聚物均存在结晶结构.示差扫描量热仪(DSC)测试结果显示3种共聚物均只有一个玻璃化转变温度(Tg)(较PEEKK的Tg有较大的提升),且存在熔点,具有潜在的热成型加工性能.热重分析仪(TGA)测试结果表明,3种共聚物的Td5%、Td10%分别为491~510、523~530°C,800°C残炭为63%~65%,共聚物具有优异的热稳定性.溶解性测试结果显示,共聚物常温即可溶解在N-甲基吡咯烷酮(NMP)中,加热可以促进其溶解,可作为基体树脂用于制备纤维增强复合材料.Through molecular design, three different block copolymers PPENK-b-PEEKK with phthalazinone moiety were synthesized via modest polycondensation reaction from the two macromers PEEKK-OH and PPENK-F. Hydroxy terminated PEEKK-OH macromer was obtained by solution polymerization from HQ and BFBB with sulfolane as the solvent. And the molecular weight of PEEKK-OH was successfully controlled by adjusting the monomer ratio, and the polymerized conditions were optimized by orthogonal experiments. While different molecular weight PPENK-F macromer, endcapped with ―F groups, was prepared from DHPZ, DFK and DFBN. Chemical structures and properties of these block copolymers were inverstigated by Fourier transforming infrared spectrum（FTIR）, wide X-ray diffraction（WXRD）, differantial scanning calorimetry（DSC） and thermogravimetric analyses（TGA）. The FTIR spectra confirmed the formation of the block copolymers.Furthermore, WXRD measurement showed that all the block copolymers presented crystalline structure, and the crystallinity of the coplolymers decreased with increasing molecular weight of PPENK-F chain segments. All the block copolymers showed only one glass transition temperature（Tg）, above that of PEEKK-OH. The Tg of the block copolymers increased with the molecular weight of PPENK-F, due to the introduction of PPENK chain segments into the block copolymers. Moreover, for the reason of of PEEKK incorporation, all these copolymers have a same melting point（Tm） of about 340 °C, which would facilitate their thermal processing. Besides, all the three copolymers also exhibited remarkable thermal stability in nitrogen atmosphere with the Td5% weight loss temperature ranging from 491 °C to 510 °C, and Td10% from 523 °C to 530 °C, respectively. The char yields of the three copolymers at 800 °C were higher than 63%. Finally, all the copolymers showed improved solubility in selectively tested organic solvents, such as NMP and sulfolane, due to the introduction of twisted and noncoplanar DHPZ structur

关 键 词：二氮杂萘联苯结构 嵌段共聚物 聚芳醚 耐高温 溶解性 

分 类 号：TQ322.3[化学工程—合成树脂塑料工业]