【作者】 戴润英；

【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， 2008， 硕士

【摘要】 1.本文采用亲核和亲电两种路线合成了1,4-二(4-苯氧基苯甲酰基)苯(p-EKKE)和1,3-二(4-苯氧基苯甲酰基)苯(m-EKKE)两种PEKK的小分子模型化合物,以p-EKKE和TPC缩聚,合成了全对位聚芳醚酮酮(p-PEKK),并用FT-IR、1H NMR、DSC、WAXD、SEM等技术对p-EKKE和m-EKKE以及PEKK的结构与性能进行分析表征。研究表明:加入适量的Lewis碱以TPC和过量的DPE合成p-EKKE时,没有发现邻位结构及呫吨醇产物生成；WAXD分析显示: p-EKKE的结晶较完整,当其作为PEKK大分子链的结构单元时虽能形成结晶,但结晶不完整,存在缺陷和非晶片。2.以1,4-二(4-苯氧基苯甲酰基)苯(p-EKKE)、1,3-二(4-苯氧基苯甲酰基)苯(m-EKKE)、二苯醚(DPE)为单体分别与对苯二甲酰氯(TPC)、间苯二甲酰氯(IPC)亲电溶液共缩聚,合成全对位、全间位、对间位取代及交替聚芳醚酮酮(p-PEKK、i-PEKK、p/i-PEKK、a-PEKK)。用FT-IR、DSC、WAXD、TG、SEM等技术对p-EKKE和m-EKKE以及PEKKs的结构与性能进行了分析表征。结果表明:随着主链中1,3-苯基含量的增加,共聚物的熔融温度(Tm)和玻璃化转变温度(Tg)逐渐降低;由p-EKKE、m-EKKE与TPC或IPC共聚合成的聚合物比由DPE与TPC或IPC合成的无规共聚物Tg、Tm有所提高,具有较好的链规整性和较高的结晶度;WAXD分析表明,共聚物P-1的结晶衍射峰和小分子模型化合物p-EKKE基本相同,属正交晶系;i-PEKK在熔融冷却过程中很难再次结晶,转变为非晶聚集态,属三斜晶系;交替共聚物a-PEKK的DSC升温曲线出现两个结晶熔融峰,表明有两种晶型存在。3.以1,4-二(4-苯氧基苯甲酰基)苯(p-EKKE)、4,4′-二苯氧基二苯砜(DPODPS)与对苯二甲酰氯(TPC)为单体,无水AlCl3/N,N-二甲基乙酰胺(DMAc)/1,2-二氯乙烷(DCE)为催化剂溶剂体系,通过低温溶液缩聚,合成了一系列p-EKKE /DPODPS/TPC三元无规共聚物,用FT-IR、DSC、WAXD、TG等技术对共聚物进行表征。结果表明:随着DPODPS/p-EKKE比例的增加,共聚物的Tg有所提高,结晶度降低;当DPODPS/p-EKKE大于70/30时,共聚物在DSC曲线中没有出现结晶熔融峰,在WAXD曲线中只出现一个弥散的衍射峰,为无定型聚集态;热失重5%时,分解温度在540℃以上,仍属耐热等级高的聚合物。4.对交替聚合物a-PEKK熔融-淬火,转变为无定形聚合物,进行溶剂、等温和冷牵伸诱导结晶,用DSC、WAXD等技术研究了不同条件处理后的共聚物的结晶性能。结果表明:以CHCl2COOH为溶剂,诱导时间t为48h,S3结晶完全,延长时间对a-PEKK的结晶及热性能几乎没有影响,晶体以晶型Ⅱ为主;等温诱导结晶时,只出现稳定的晶型Ⅰ,DSC中降温速率影响着晶体的结晶完善程度;经牵伸取向的S5在DSC的冷却曲线中没出现冷结晶峰,而在熔融放热峰处等温结晶2h的S6,出现冷结晶峰,WAXD分析表明:样品经冷牵伸后有Ⅰ和Ⅱ两种晶型共存,晶体晶型与分子链的链接结构(酮/醚比例),牵伸温度、牵伸比有关。更多还原

【Abstract】 1.1,4-Bis(4-Phenoxybenzoyl)benzene was synthesized by nucleophilic and electrophilic substitution: (1)1,4-bis(4-chlorobenzoyl)benzene was obtained from chlorobenzene and terephthaloyl chloride (TPC). Then, the resulting compound p-EKKE was synthesized by 1,4-Bis(4-chlorobenzoyl)benzene with Natrium phenate, taking N-methyl-2-pyrrolidone (NMP) as solvent. (2) p-EKKE was synthesized by Friedel-Crafts acylation of terephthaloyl chloride (TPC) and excessive diphenylether (DPE) in 1,2-dichloroethane with aluminium trichloride (AlCl3) as catalyst. Its structure was characterized by FT-IR, 1H NMR, Micromelting point apparatus, WAXD, SEM and DSC etc. The results show that the compound was anticipated and has high purity. EKKE has the same crystalline diffraction characterization as PEKK which is the unqiue crystallinaion habits of PEKK.2.Poly(Aryl Ether Ketone Ketone)s have excellent thermal stability, resistance to corrosion, creep and other properties, considered as outstanding engineering thermo- plastics. It is very difficult to investigate their micro-structure and properties, for their high melting points and poor solubility in common organic solvents. One of efficient strategies studied the compositions and crystal properties of the macromolecule, attributed to comparing the model compounds which are similar to their segment. In this paper, a series of high molecular weight of alternative and random Poly(Aryl Ether Ketone Ketone) copolymers were prepared by low-temperature solution poly-condensation, with 1,4-Bis(4-Phenoxybenzoyl)benzene (p-EKKE), 1,3-Bis(4- Phenoxybenzoyl)benzene (m-EKKE), diphenyl ether (DPE) and terephthaloyl chloride (TPC) or isophthaloyl chloride (IPC) respectively. The inherent viscosities (ηinh) of resulting copolymers were in the range of 0.63~1.08 dL/g. The chemical structure of p-EKKE, m-EKKE and PEKKs were confirmed by FT-IR. Thermal properties of copolymers obtained by DSC and TG, DSC results indicated that the melt temperature (Tm) and the glass transition temperature (Tg) decreased with increasing of the amount of meso- phenylene substituted in the main chain. TG results show that copolymers had excellent thermo-oxidative stability, and their thermally stable were above 530℃, which affected slightly by the amount of meso- phenylene substituted in the main chain. The alternative copolymer a-PEKK has better order and higher crystallinity than random copolymers. WAXD show that copolymer a-PEKK and the model compound has the same crystallization diffraction spectra, which belong to rhombic system. While the morphology of copolymer i-PEKK and the corresponding model compound attribute to needle crystals, and their type of crystallization belong to anorthic system. i-PEKK is difficult to crystallize again in the course of melting, and it converts into amorphous.3.Poly(aryl ether ketone ketone ether ketone ketone/ether sulfone ether ketone ketone) (PEKKEKK/ESEKK) copolymers of high molecular weight were synthesized by low temperature solution polycondensation of 1,4-bis(4-chlorobenzoyl)-benzene (p-EKKE), 4,4′-diphenoxydiphenylsulfone (DPODPS) and terephthaloyl chloride (TPC) in a catalyst/solvent of AlCl3/ClCH2CH2Cl/DMAc. The copolymers characterized by FT-IR, DSC, TG and WAXD. The results show that copolymers exhibited excellent thermal stability. With increasing the content of DPODPS in the copolymer the glass transition temperature (Tg) of the copolymer improved greatly, while Tm and the degree of crystallinity decreased. When the ratio of DPODPS/p-EKKE is above 70 to 30, copolymers turn into amorphous.4.The alternative polymer a-PEKK which is changed to amorphism by quenching, crystallized by solvant, fusion and elongation at above melting temperature treatment. The crystal morphology of alternative copolymers was examed by DSC and WAXD. The results show that the sample of S3 is crystallized completely treated in dichloroacetic acid about forty-eight hours. Prolonged the time has not been effected to the crystallination. WAXD results showed two crystal types co-exist, but typeⅡdominated in the crystalline. Provided that the thermal treatment of the induced crystallization sample is done at ambient conditions, typeⅡconverted into the most stable crystal typeⅠ. The sample of S4 induced crystallization by fusion in the same temperature only exist crystal typeⅠ. The density of crystalline was affected by the speed of cooling down in DSC. There is no cold crystallization peak in DSC curve by fusion wire drawing orientation treatment. While the sample of S5 processed at fusion temperature for two hours, there is a cold crystallization peak in DSC curve. This strategy indicated that crystal has two types of crystallization. The ratio of crystallinity typeⅠand typeⅡis determined by the the ratio of ketone to ether in the macromolecular chain, wire drawing temperature, the ratio of drawing.更多还原