【作者】 周红欣；

【导师】 蹇锡高；

【作者基本信息】 大连理工大学 ， 高分子材料， 2011， 博士

【摘要】 聚芳醚酮以其优良的物理化学性能在高性能工程塑料领域占有重要的地位,已广泛应用于航空航天、电子电器、分离膜、胶黏剂等领域。本课题组近年来在开发成功具有扭曲非共平面二氮杂萘酮联苯酚新单体(DHPZ)基础上,开发成功了含二氮杂萘酮联苯结构聚芳醚酮类聚合物,与传统商品化聚芳醚酮品种相比,不仅具有更高的耐热等级；而且常温下即可溶解于非质子极性有机溶剂,合成条件温和,成本较低,因而应用领域更为广泛。但是,由于所用的双卤单体仍为传统合成聚芳醚酮采用的价格昂贵的4,4’-二氟二苯甲酮(DFK),与普通工程塑料相比,其成本仍然较高。本论文以价廉易得的4,4’-二氯二苯甲酮(DCK)和DHPZ为原料,通过溶液缩聚法制备了含二氮杂萘酮联苯结构聚芳醚酮PPEK及不同系列含二氮杂萘酮联苯结构共聚芳醚酮PPESKs、PPENKs、PPBESKs和含联苯基结构嵌段共聚物PPESK-b-PEBEK;并系统研究了聚合工艺,以及聚合物结构与性能之间的关系,以期实现含二氮杂萘酮联苯结构聚芳醚酮系列聚合物低成本可控制备。首先,从DHPZ分子结构特点及其反应活性考虑,合成了两种模型化合物2-苯基-4-(4-羟基苯基)-2,3-二氮杂萘-1-酮(PHPZ)和4-(4-甲基苯基)-2,3-二氮杂萘-1-酮(MHPZ),分别含有类似DHPZ活性的-OH和-NH。以两种模型分别与DCK进行反应,证明了DHPZ中-OH和-NH均可与DCK反应：并通过两种模型化合物中-OH和-NH活性比较研究,采用高效液相色谱法计算了-OH和-NH在不同温度下的转化率,结果表明在不同温度下,尤其温度较低时,-NH和-OH活性差异较大,-NH的转化率较低,这为提高聚合反应分子量途径提供了理论基础。论文对DCK和DHPZ的聚合工艺进行了优化,研究了反应条件包括反应溶剂、温度、时间、初始浓度、催化剂种类及用量和加料方式对产物特性黏度、分子量、分子量分布指数以及小分子含量的影响。当采用环丁砜为溶剂,反应温度为210℃,反应时间为7-8h,K2CO3用量摩尔数为DHPZ的1.2倍时,聚合物数均分子量Mn可达22526g/mol,重均分子量Mw可达57434g/mol;当DCK过量0-1.6%时,聚合物的特性黏度可在0.67-0.26dL/g之间调控；当DHPZ过量0-2%时,聚合物的特性黏度可在0.67-0.32dL/g之间调控；所合成的PPEK的热性能和薄膜力学性能与以DFK和DHPZ为原料合成的PPEK相当。采用两步加料法,加入少量KF或DFK(-1.6%)可以提高分子量,聚合物的特性黏度可达1.10dL/g。在上述基础上,分别加入共聚单体4,4’-二氯二苯砜(DCS)、2,6-二氯苯腈(DCBN)、联苯二酚(BP),研究了DCK在杂萘酮联苯结构共聚芳醚酮中的合成。针对不同单体采取了不同的聚合工艺,制备了PPESKs, PPENKs和PPBESKs三个系列共聚物。所合成的聚合物具有较高的玻璃化转变温度和良好的耐热性能,T5%均高于500℃；该类材料呈现良好的成膜性并具有优异的力学性能；PPESKs和PPENKs薄膜的表面电阻和体积电阻在1015数量级以上,表现出良好的电绝缘性能。用哈克流变实验测试了PPBESKs的熔融加工性能,结果表明联苯基的引入有效的降低了聚合物的熔融粘度,从而改善了其熔融加工性能。从分子设计出发,以DHPZ、DCK、DCS、BP以及少量DFK为原料,合成含二氮杂萘酮联苯结构段共聚物PPESK-b-PEBEK,并对其进行了结构和性能研究。测试结果表明：嵌段共聚物主链中含有联苯基结构,PPESK预聚物发生了进一步的聚合反应。PPESK-b-PEBEK嵌段共聚物常温下溶于三氯甲烷、NMP等非质子极性有机溶剂；聚合物具有良好的耐热性能,T5%为510℃,Tmax高于500℃。PPESK-b-PEBEK嵌段共聚物Tg为243℃,Tm为327℃,且PPESK-b-PEBEK的NMP溶液可以制备成乳白色不透明薄膜,其WAXD谱图在2θ=18.8°,23.5°处出现结晶峰,表明共聚物中含有PEBEK有序嵌段结构。哈克流变测试结果表明：与特性黏度相当的PPESK纯树脂相比,PPESK-b-PEBEK的熔融粘度明显降低；将嵌段共聚物在双螺杆挤出机上进行挤出实验,结果表明：在340℃下可顺利挤出,相应的挤出机电流较低(4.9A),挤出样品褐色半透明、光滑无毛刺、韧性良好,造粒后无气孔。更多还原

【Abstract】 Poly(aryl ether ketone)s (PAEKs) are an important category of high-performance materials for their excellent thermal and mechanical properties, which have been used in aerospace, electronics, separation film and adhesive etc. Poly(phthalazinone ether ketone)s, a type of novel PAEK materials, have been developed in our group in the last decade. Compared with traditional poly(aryl ether ketone)s, this kind of materials is possessed of better thermal properties with improved solubility, which not only facilitates the synthetic conditions but also improves the solution processibility. From a raw materials cost point view, however,4,4’-difluorobenzophenone (DFK) is used as traditional industry, which results in high cost.In this thesis, poly(phthalazinone ether ketone) (PPEK) and its copolymers of PPESKs, PPENKs, PPBESKs and blockcopolymer PPESK-b-PEBEK containing biphenyl groups were synthesized from 4-(4-hydroxyphenyl)(2H)-phthlazin-l-one (DHPZ) and 4,4’-dichlorobenzo phenone (DCK). And the polymerization conditions and relationships between properties and structures of the polymers were also elaborated in details.First, considering the structure character of DHPZ,2-phenyl-4-(hydroxylphenyl)(2H)-phthalazin-1-one (PHPZ) and 4-(4-methlyphenyl)(2H)-phthalazin-l-one (MHPZ) were synthesized. The products of the reactions of MHPZ and DCK, PHPZ and DCK indicated that it was feasible for the reaction of DHPZ and DCK. High performance liquid chromatogram (HPLC) was used to monitor the reaction of MHPZ, PHPZ and DCK, which implied that the reactivity of-OH and-NH was different, and the conversation of-NH was lower.The influence of polymerzaition conditions of DCK and DHPZ, including the solvents, temperature, reaction time etc. on the product was investigated. When sulfolane was chosen as the solvent, high molecular weight polymer could be obtained in 7-8h at 210℃. Moreover, the molecular weight was controlled and molecular weight could increase with the addition of a third comonomer. When the excessive DCK was 0-1.6% and the excessive DHPZ was 0-2%, the intrinsic viscosities of the polymer could be controlled between 0.67-0.26dL/g and 0.67-0.32dL/g, respectively. And the thermal and mechanical properties of the obtained polymer were identified with those of PPEK synthesized from DHPZ and DFK. By a two-step procedure with addition of a little DFK, the intrinsic viscosity of the polymer could be up to 1.10dL/g. On the basis of statements above, the comonomer such as 4,4’-dichloro diphenyl sulfone (DCS),2,6-dichlorobenzonitrile (DCBN) and 4,4’-biphenol (BP) had been used to synthesize copoly(phthalazinone ether ketone)s. These series of copolymer of PPESKs, PPENKs and PPEBSKs were successfully prepared. The copolymers were possessed with high glass transition and excellent thermal stability. T5%s were above 500℃. Tough, flexible and transparent thin film can be readily prepared from their N-methyl-2-pyrrolidone solution. And the films exhibited good mechanical properties. The melt viscosity of PPBESKs was effectively decreased by the introduction of the biphenyl groups according to the HAAKE tests. And the more biphenyl groups led to lower melt viscosity.Block polymer of PPESK-b-PEBEK containing phthalzinone and biphenyl groups was successfully synthesized from DHPZ, DCK, DCS BP and DFK. The biphenyl groups were introduced to the polymer’s main chain indicated by FT-IR and 1H-NMR. The block copolymer could be soluble in CHCl3, N-methyl-pyrollidione (NMP) etc. at room temperature. The block polymer was possessed with excellent thermal properties, T5% was 510℃. The glass transition temperature of PPESK-b-PEBEK was 243℃, and the melting temperature was 327℃, which indicated the crystalline segments. And the PEBEK crystalline segments also could be evidenced by the peaks at 2θ=18.8°,23.5°on the WAXD curve and the white and opaque film of the polymer’s NMP solution. Compared with pure PPESK, the melt viscosity of PPESK-b-PEBEK was increased according to the HAAKE tests. The blockcoplymer could be easily extruded at about 340℃, and the extrusion sample was translucent brown, smooth and tough.更多还原