【作者】 高华华；

【导师】 宋才生；

【作者基本信息】 江西师范大学 ， 高分子化学与物理， 2009， 硕士

【摘要】 随着高新技术的发展,对高性能特种工程塑料的需求与日俱增,对材料的综合性能特别是耐热性提出了更高的要求。在聚芳醚酮类树脂中由于酮基比醚键更具刚性,所以随着聚合物分子主链中酮基比例的增加,其耐热性也将进一步提高。本文从分子设计出发,合成含多酮基结构单元的芳二酰氯,并以此为单体合成系列主链含多酮基的聚芳醚酮聚合物,研究其结构与性能之间的关系,为开发综合性能优良的耐高温热塑性树脂及其工业化生产提供理论基础和实验依据。主要研究内容包括以下三个方面:1.以甲苯和间苯二甲酰氯(IPC)为原料,经傅-克酰基化反应,制备高纯度的1,3-二(4-甲基苯甲酰基)苯(i-DMBB);以KMnO4/吡啶/水为氧化体系,将1,3-二(4-甲基苯甲酰基)苯(i-DMBB)氧化合成高纯度的1,3-二(4-甲羧基苯甲酰基)苯(i-DMBA);用氯化亚砜将羧基酰化,制得结构新型的芳二酰氯1,3-二(4-氯甲酰基苯甲酰基)苯(i-DMBC)。原料改为甲苯和对苯二甲酰氯(TPC),以同样方法制得1,4-二(4-氯甲酰基苯甲酰基)苯(p-DMBC)。经FT-IR、1H-NMR、元素分析及DSC分析表明:目标产物具有预期的结构和较高的纯度,可作为高性能高分子材料聚芳醚酮(PEK)、聚芳酯(PAR)及聚芳酰胺的单体及改性剂。2.以合成的芳二酰氯1,3/1,4-二(4-氯甲酰基苯甲酰基)苯(i/p-DMBC)为单体,将其分别与4,4’-二苯氧基二苯砜(DPODPS)、1,3-二(4-苯氧基苯甲酰基)苯(i-DPOPKK)、1,4-二(4-苯氧基苯甲酰基)苯(p-DPOPKK)进行低温溶液共缩聚,合成系列主链含多酮基的新型聚芳醚酮。用FT-IR、1H-NMR、DSC、TGA、WAXD等技术对聚合物进行结构和性能表征,研究聚合物的结构与性能的关系。结果表明:增加聚合物主链中酮基的含量可提高其耐热等级,在合成的聚合物中,玻璃化转变温度Tg最高可达189℃、熔融温度Tm最高可达403℃,同时,间位取代苯基及四面体砜基结构的引入可适当降低Tm、改善溶解性,为开发综合性能优良的耐高温聚芳醚酮类树脂提供了依据;此外,聚合物中酮基比例的增大,使得其聚集态晶体结构也产生相应的变化,较易产生多晶型,在合成的聚合物中基本都存在FormⅠ和FormⅡ两种晶型。3.用差示扫描量热法(DSC)及广角X-射线衍射(WAXD)技术较详细地研究了主链含多酮基的新型聚芳醚酮PEKKEKK-i-KK经过不同条件处理后树脂的结晶行为,从微观角度探讨聚芳醚酮类树脂结构与性能之间的关系,为聚芳醚酮类树脂的加工成型和性能的关系提供一定的依据。结果表明:多酮基聚芳醚酮聚合物中存在FormⅠ和FormⅡ两种晶型,FormⅡ较为不稳定,在一定条件下可转化为FormⅠ。通过等温诱导结晶、冷牵伸等方法可以改变聚合物中两种晶型的比例及得到较纯的FormⅠ晶型聚合物。更多还原

【Abstract】 With the development of high-tech, the need for high-performance polymers grows day by day, and higher demand for their integrative property, especially the thermostability have been advanced. As for poly(aryl ether ketone)s(PEKs), the ketonic linkage and the ether linkage are contained, and the rigidity of the ketonic linkage is stronger than the ether linkage’s, so the increasing ratio of the ketonic linkage in the macromolecule chain can make the polymers exhibit more excellent thermostability. In this paper, above all, two monomers have been successfully synthesised. Then PEKs based on them have been synthesised and characterized. Last, the relation between the structure and properties of the polymers have been studied. The main idea of this paper is followed.1. 1,3-Di(4-methyl benzoyl)benzene(i-DMBB) was prepared by Friedel-Crafts electrophilic aromatic substitution reaction from isophthaloyl chloride (IPC) and toluene; i-DMBB was subsequently oxidated into intermediate, 1,3-di(4-carboxyl benzoyl)benzene(i-DMBA) in the presence of KMnO4 in the mixture solvent of pyridine and water; then the reaction of i-DMBA with sulfurous oxychloride yielded polymerization-grade monomer 1,3-di(4-chloro formyl benzoyl)benzene(i-DMBC). 1,4-di(4-chloro formylbenzoyl)benzene(p-DMBC) was obtained on condition that the reaction started with terephthaloyl chloride (TPC) and toluene. The products were characterized by FT-IR, 1H-NMR, elemental analysis and DSC. It was proved that high purified compounds had been obtained, and they can become monomers and remodeling reagents of high-performance polymers, such as poly(aryl ether ketone)(PEK), polyarylates(PAR) and aryl polyamide.2. Novel poly(aryl ether ketone)s(PEKs) containing multi-ketonic linkage were prepared by low temperature solution polycondensation of i/p-DMBC with 4,4’-diphenoxydiphenylsolfone(DPODPS), 1,3-di(4-phenoxybenzoylbenzene (i-DPOPKK) and 1,4-di(4-phenoxybenzoyl)benzene(p-DPOPKK) in 1,2-dichloro -ethane(DCE) with the presence of AlCl3 and DMAc. The resulting polymers were characterized by various analytical techniques, such as FT-IR, 1H-NMR, DSC, TGA and WAXD. The relation between the structure and properties of the polymers had been studied. The results show that high molecular weight polymers have been readily obtained. With the increasing ratio of ketonic linkage in the macromolecule chain, the polymers exhibit excellent thermostability, such as the highest glass transition temperature(Tg) of the polymers is 189℃, the highest melting temperature(Tm) of the polymers is 403℃. At the same time, the introducing of the tetrahedral sulfonyl(-SO2-) and meta-phenyl substitution can make the Tm of the polymers decrease appropriately, and the solubility of the polymers is also improved. Furthermore, with the increasing ratio of ketonic linkage in the macromolecule chain, the structure of the polymers has changed , polymorphism is easily to be found. We have found two crystal types, FormⅠand FormⅡ, in the polymers via the analysis of WAXD and DSC.3. The crystallization of poly(aryl ether ketone) containing multi-ketonic linkage, PEKKEKK-i-KK, was studied by differential scanning calorimetry(DSC) and wide-angle X-ray diffraction(WAXD). The relation between the structure and properties of the polymers has been studied in further from the microcosmic angle, and the evidence of processing and properities has been provided. The results show that there are two crystal types, FormⅠand FormⅡ, in the polymers, and the crystal type of FormⅠis more stable than the crystal type of FormⅡ. The ratio of FormⅠand FormⅡcan be changed by way of different treatment, such as induced crystallization of thermal treatment, elongation and so on. Moreover, the polymer, which just contains the crystal type of FormⅠ, can be obtained via elongation.更多还原