摘要
聚芳醚腈以其优良的耐热性能和机械性能在高性能高分子材料领域占有重要的地位，具有广泛的应用前景。然而，已商品化聚芳醚腈是结晶型聚合物，导致其溶解性能较差，只能溶解于浓硫酸，限制了其在一些领域的应用，例如：绝缘漆、涂料及分离膜等领域。本文将扭曲、非共平面的二氮杂萘酮联苯结构引入到聚芳醚腈的主链中，合成了一系列含二氮杂萘酮联苯结构的新型聚芳醚腈高性能聚合物，系统研究其结构与性能关系，优化合成条件，以期优选出综合性能优异，制备成本较低的新型聚芳醚腈树脂，为其进一步放大产业化提供依据。
本文首先从分子设计出发，以含二氮杂萘酮联苯结构类双酚单体4-(4-羟基苯基)-2，3-二氮杂萘-1-酮(简称二氮杂萘酮联苯酚单体DHPZ)，和2，6-二氟苯腈(DFBN)为主要原料，通过亲核取代逐步聚合反应，将扭曲非共平面的二氮杂萘酮联苯结构引入到聚芳醚腈主链中，成功地合成了含二氮杂萘酮联苯结构聚芳醚腈新品种(PPEN)。并系统研究了影响聚合反应的各种因素，对聚合反应工艺进行了优化，聚合物的特性粘度达到1.02 dL／g。聚合物的玻璃化转变温度为295℃，N_2气氛下10％的热失重温度为527℃，可溶解于NMP、DMAc和氯仿等溶剂中。PPEN既耐高温又可溶解，综合性能优于传统聚芳醚腈品种。
为降低制备成本，在上述聚合体系中采用价廉易得的2，6-二氯苯腈(DCBN)直接代替DFBN，结果发现，由于前者的反应活性较低，得不到高分子量的聚合物。
本文通过在DHPZ苯环上引入供电性的取代基，提高其与DCBN的反应活性，从而实现DCBN替代DFBN，成功地合成了三种具有不同取代侧基的聚芳醚腈类高分子量聚合物。室温下可溶解于NMP、DMAc和氯仿等极性非质子溶剂中，并具有良好的成膜性。FT-IR、~1H NMR证明聚合物的结构与设计结构一致。采用差示扫描量热(DSC)、热重分析(TGA)、广角X衍射(WAXD)等分析手段对聚合物的主要性能进行了研究，结果表明取代基的存在降低了聚合物的耐热性能，其中苯基取代的聚合物具有最低的玻璃化转变温度T_g为277℃，两个甲基取代的聚合物具有最低的热失重温度，N_2气氛下10％的热失重温度为451℃之间。
采用氟化钾(KF)作为聚合反应体系的共催化剂，在DHPZ和DCBN聚合反应体系中同时加入K_2CO_3和KF。DCBN在KF的作用下转化为DFBN，此新生态的DFBN在K_2CO_3的催化作用下与DHPZ发生亲核取代逐步聚合反应。通过对聚合过程中的影响因素进行研究，成功地制得了高分子量的聚芳醚腈聚合物PPEN，其特性粘度达到0.90dL／g，大幅降低了含二氮杂萘酮联苯结构聚芳醚腈的原料成本。
本文研究开发了含二氮杂萘酮联苯结构新型聚芳醚腈共聚物。一方面，引入4，4’-二氟二苯酮(DFK)、4，4’-二氯二苯砜(DCS)和1，4-二(4-氟代苯甲酰基)苯(DFKK)三种双卤单体作为第三单体，制备得到聚芳醚腈酮(PPENK)、聚芳醚腈砜(PPENS)和聚芳醚腈酮酮(PPENKK)三个系列的聚芳醚腈类共聚物。对聚合物的热性能、电性能和结晶性能等方面进行了测试。研究了聚合物的结构与性能的关系。该类聚芳醚腈共聚物同时具有优异的耐热性能和良好的溶解性能。其玻璃化转变温度T_g在252～323℃之间，N_2气氛下10％的热失重温度在449～541℃之间，可溶解于NMP、DMAc和氯仿等极性非质子溶剂中。通过聚合物结构的调整实现了对聚合物性能的调控。
另一方面，采用对苯二酚(HQ)和双酚A(BPA)两种双酚单体作为第三单体，部分代替DHPZ，与DCBN进行共聚合，制备得到了两个系列的共聚型聚芳醚腈(PPEN-HQ、PPEN-BPA)。对聚合物的热性能、溶解性能、电性能、结晶性能等方面进行了测试。研究了聚合物的结构与性能的关系。结果表明，高活性的双酚单体HQ和BPA的引入在适当降低了聚合物的耐热性能的同时，提高了聚合物的特性粘度，聚合物的玻璃化转变温度T_g在200～277℃之间，N_2气氛下10％的热失重温度在449～517℃之间，并且可溶解于NMP、DMAc和氯仿等极性非质子溶剂中。通过共聚降低了聚芳醚腈的原料成本，实现了对聚合物性能的调控。
将二氮杂萘酮联苯结构聚芳醚腈酮应用于绝缘漆领域，制备了新型的绝缘漆和漆包线。绝缘漆的附着力等级为1级，铅笔硬度为6H，表面电阻为10~(13)Ω，体积电阻为10~(16)Ω·cm；漆包线的最小刮破力大于9.1 N，25℃时的击穿电压大于6800 V，耐热冲击温度最低为400℃。绝缘漆和漆包线在耐酸、耐碱和耐盐腐蚀性方面表现出良好的稳定性。
Poly(arylene ether nitrile)s has been noted as a kind of important polymeric material which present a combination of outstanding properties such as high thermal stability, good chemical resistance and excellent mechanical properties. However, the commercial poly(arylene ether nitrile)s was crystalline polymer with poor solubility in most organic solvents at room temperature, which resulted in difficulty for application in the insulating coating and separative membrane etc. In this work, our efforts had been focused on synthesis of poly(arylene ether nitrile)s with good solubility and high thermal properties by the introduction of twisted, noncoplanar phthalazinone moieties into poly(arylene ether nitrile)s backbone.
In this thesis, the twist and noncoplanar phthalazinone moieties had been successfully introduced into poly(arylene ether nitrile)s by the nucelophilic reaction of the bisphenol-like monomer, 4-(4-hydroxyphenyl)-phthlazin-1(2H)-one (DHPZ) and 2,6-difluorobenzonitrile (DFBN) firstly. The synthesis process was optimized. After the optimization of the polymerization, the inherent viscosity of this polymer could reach 1.02 dL/g. The poly(phthalazinone ether nitrile)s (PPEN) showed amorphous nature as determined by wide angle X-ray diffraction (WAXD) and was soluble in a variety of aprotic polar solvents, such as N-methyl-2-pyrrolidinone (NMP), N, N-dimethylacetamide (DMAc), chloroform etc. The PPEN exhibited outstanding thermal properties with glass transition temperature (T_g) of 295℃and 10% loss temperature (T_(10%)) of 527℃in nitrogen atmosphere.
In order to reduce the cost, 2,6-dichlorobenzonitrile(DCBN) had been used to replace DFBN. But we couldn't obtain high molecular weight because of DCBN's lower reactivity.
With the help of the molecular design, the bisphenol-like monomer DHPZ's reactivity was increased by the incorporation of electron-donating group. Three substituted PPENs were synthesized by the substituted bisphenol-like monomer and DCBN. All polymers showed good solubility in polar solvents such as NMP, DMAc, chloroform etc. The structures of these PPENs were confirmed by FT-IR and ~1H NMR techniques. The thermal properties, crystalline properties were characterized through differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and WAXD. All polymers exhibited lower thermal properties compared with the unsubstituted PPEN, and the lowest Tg of these copolymers was 277℃, the lowest T_(10%) was 451℃in N_2 atmosphere.
Aim to prepare high molecular weight PPEN from DHPZ and DCBN, utilized potassium fluoride (KF) as the cocatalyst of the polymerization system. K_2CO_3 and KF were added in the polymerization system of DHPZ and DCBN together. The fluoridation and nucleophilic replacement polymerization had carried in the same reaction system. The high molecular weight PPEN was obtained by the optimization of the reaction conditions. The inherent viscosity of this polymer could reach 0.90dL/g. The utilization of KF as cocatalyst could obviously reduce the cost.
The high reactivity third monomer such as 4,4'-difluoro benzophenone(DFK)、4,4'-dichloro diphenyl sulfone(DCS) and bis(4-fluorobenzoyl)-benzene (DFKK) had been used to synthesize the PPEN copolymers. PPENK, PPENS, and PPENKK had been successfully prepared. The thermal properties, solubilities, electronical properties and crystalline properties of copolymers were characterized. New copoly(arylene ether nitrile)s had good thermal properties and solubility. T_g of these copolymers ranged from 252 to 323℃, T_(10%) ranged from 449 to 541℃in nitrogen atmosphere. All polymers showed good solubility in polar solvents. The polymers' properties could be controlled by the structure adjustment.
The high reactivity and cheap third monomer such as hydroquinone (HQ) and 2, 2-bis (4-hydroxyphenyl)-propane (BPA) had been used to partilly replaced DHPZ to synthesize the PPEN copolymers. Two series of PPENs copolymers including PPEN-HQ and PPEN-BPA had been synthesized. The polymers' thermal properties, solubilities, electronical properties and crystalline properties had been studied. The results showed that the introduction of HQ and BPA could increase the polymers' inherent viscosities with the little decrease of the thermal properties. T_g of these copolymers ranged from 200 to 277℃, T_(10%) ranged from 449 to 517℃in nitrogen atmosphere. All polymers showed good solubility in polar solvents. We could reduce the cost by the copolymerization.
The application of poly(phthalazinone ether nitrile ketone)s in insulating varnish was reported. The insulating varnish prepared from PPENKs had excellent mechanical properties electro-insulating properties and thermal properties. The adhesion of the coatings was 1 grade and pencil hardness was 6H. The surface resistance coefficients and volume resistance coefficients were 10~(13)Ωand 10~(16)Ω·cm respectively. The minimum scrape forces were larger than 9.1 N. The breakdown voltages was larger than 6800 V (25℃). The thermal shock temperatures was larger than 400℃. Both insulting coatings and enamel wires showed good stability in strong acid, strong base and salt solutions.
引文
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