【作者】 阎庆玲；

【导师】 蹇锡高； 王锦艳；

【作者基本信息】 大连理工大学 ， 材料学， 2006， 博士

【摘要】 本论文工作系国家“863”(项目编号2003AA33G030)资助项目和军工配套项目的部分内容。在前期工作的基础上,用聚醚砜酮(PPESK)、聚醚腈酮(PPENK)等不同结构的聚芳醚树脂制备了耐高温绝缘漆和涂料,对影响其性能的诸多因素进行了系统的研究,重点考察了结构和性能的关系,为其生产应用提供一定的理论指导。 本论文工作内容如下: 优化了PPESK绝缘漆的配方和工艺。在测定了聚合物溶解度参数的基础上,依据溶剂化原则、极性相似原则和溶解度参数相近的原则,综合考虑了成本、毒性、沸点等因素,确定了混合溶剂的组成和配比。选择KH-560、KH-550、KH-590三种有机硅烷偶联剂,考察其加入对漆膜性能的影响,结果表明KH-560的引入不但有利于提高漆膜的附着力,还可以降低漆膜的吸水率;聚合物分子量的提高会使分子间的作用力以及聚合物和金属之间的吸引力增强,探讨了聚合物特性粘度对漆膜的机械性能的影响,当特性粘度达到0.50dL/g时,漆膜的附着力、柔韧性和冲击强度分别达到1级、1mm和50cm,漆膜性能优异;研究了聚合物特性粘度和溶液浓度与涂-4粘度的关系,结果表明随着聚合物特性粘度和溶液浓度的提高,漆的涂-4粘度值增加。 研究了结构对绝缘漆膜性能的影响,当PPESK的砜酮比高于8/2(摩尔比)时,漆膜具有优异的机械性能。以二氯苯腈替代二氯砜合成PPENK,以其为主要成膜物制备的绝缘漆具有优异的性能,腈基的引入有利于提高漆膜的附着力。同时研究结果还表明聚合物链中极性砜基、羰基、腈基和醚键的含量的变化对漆膜的性能有很大的影响。 优化了漆包线的制备工艺。适当提高烘炉温度,降低收线速度有利于提高漆包线的厚度、击穿电压以及漆膜的连续性和均匀性。在对绝缘漆研究的基础上,进一步深入考察了聚合物链结构对漆包线性能的影响,结果表明漆包线的柔韧性和附着性与聚合物链段中醚键、羰基以及腈基的含量密切相关。测试结果表明由于扭曲非共平面二氮杂萘酮结构的引入,杂萘联苯型聚芳醚漆包线的机械性能、电性能和热性能远优于220级聚酰亚胺漆包线国家标准,其中PPENK漆包线的热冲击温度高达470℃,是目前耐热等级最高的有机类漆包线品种,能够满足军工产品的要求。 对PPESK防腐涂料的配方和制备工艺进行了系统的研究。考察了分散工艺对涂料储存时间的影响,发现主要成分为不饱和羧酸与聚硅氧烷共聚物的BYK-P104S型润湿分散剂的引入有利于颜料的分散;当研磨时间为3h,研磨转数为2000r/min时,所研磨的颜料粒径适中,涂料的储存稳定性最好;用适量的KH-560偶联剂对颜料进行预处理,更多还原

【Abstract】 This work was financially supported by the national high technology and development program （No.2003AA33G030） and the national army corps program.This work focused on preparing a novel high temperature resistant insulating lacquer and coatings on the basis of poly（phthalazinone ether sulfone ketone） （PPESK） and poly（phthalazinone ether nitrile ketone） （PPENK）, which were deeply exploited by our laboratory. Thus, a variety of effects on properties of poly（phthalazinone ether）s insulating lacquer and coatings were deeply investigated, expecially the ralationship of structure and property, which could be an instruction for the future application.The lacquer’s prescription and procedure were optimized. The optimum solvent component was confirmed in accordance with PPESK’s solubility parameter, solvent boiling point and poison. Three kinds of couplants, KH-560, KH-550, KH-590, were selected to detect their effects on the properties of lacquer film, with the result of KH-560 which could enhance the film’s adhesion to metal and decrease its water absorption. Another crucial factor was polymer’s high weight molecule which could be detected through polymer’s intrinsic viscosity and solution’s flowing viscosity. The results indicated that the lacquer’s mechanical properties were excellent, which showed one grade adhesion to metal, 1mm flexibility and 50cm impact resistance,, when the intrinsic viscosity was more than 0.50 dL/g. T-4 viscosity, used to describe flowing viscosity, increased with the increasing of intrinsic viscosity and concentration of solution.The structure of polymer main chain also had impact on the properties of resulting lacquer film. The result showed that the most excellent mechnical properties of film can be obtained when the ratio of sulfone and ketone of PPESK was more than 8 to 2. The PPENK lacquer embodied the more perfect mechancial properties by virtue of introducing -CN group improving the film’s adhesion.The research also demonstrated that the contain of sulfone, ketone, nitrile and ether group in the polymer chain affacted the properties of the resulting film.The high temperature resistant enamel wires were manufactured with the conventional wire coating process, and the affected factors were discussed. It was proved that if the enamel machine’s baker temperature increased suitably, it can improve the breakdown voltage. If the enamel machine’s drawing speed decreased suitably, it can improve the wire’s continuity.Compared to the properties of PPESK and PPENK and PPENKK wire, the PPENK wire’s properties were excellent. According to the conventional PI enamel round copper wire standard, the properties of Poly（phthalazinone ether ）s wires, which exhibit good thermal, electrical and chemical properties, were superior to those of PI. The PPENK wire which showed the thermal shock of 470℃ has the best heat resistant property up to now.The effects of PPESK anti-corrosion coating’s prescription and fabricating procedure of coating on properties were deeply investigated, too. The effects of dispersant and dispersing process on storing time were discussed. The results showed that BYK-P104S as a dispersant can markedly improve the dispersing properties of the black carbon. The congest paint storing time could be found when dispersing time and rotating speed were 3 hour and 2000r/min, respectively. The anti-heating and anti-corrosion properties of PPESK coatings were tested. The results showed that the PPESK coatings could be used at 250℃, and endure 15% hydrochloric acid and 30% sodium hydroxide solution’s corrosion for more than sixty days.BYK-370 was the excellent additive for the PPESK anti-adhesive coating’s dispersing. CGUF-006 polytetrafluoroethylene was the best stuffing for anti-adhesive coating. The combination of molybdenum disulfide （M0S2） and graphite was observed to best coating’s luster.phthalazinone（DHPZ） and 4,4’-dihydroxy diphenylsulphone（BPS） were selected as monomers to synthesize novel PPESK resin. The intrinsic viscosity of resin and heat resistance of coating decreased with the increasing of BPS percent.Whereas the wire can be used above high glass transition temperature（Tg） for a long time, the crosslinking behaviors of PPENK and PPESK coatings were investigated with Flourier transformed infrared spectroscopy （FTIR） and thermogravimetric analysis （TGA）, initially. The results indicated that the nature of the curing reaction is complex. When the PPENK coating was heated at 290℃ and 330℃, respectively, two weak absorption peaks centered about 1780 cm^-1 and 1730cm^-1 appeared and grew in intensity with the increasing of crosslinking temperature and time. Thermogravimetric analysis （TGA） was performed to do further research. Thermal degradation temperature increased with the increasing of heating time and temperature. The PPESK coating had the samely changes. The catalyst of p-toluenesulfonate acid contributed to the crosslinking of PPENK and PPESK coatings.更多还原