含羧酸酯侧基的聚芳醚酮酮醚酮酮的合成与表征

SYNTHESIS AND PROPERIES OF POLY(AROMATIC ETHER KETONE KETONE ETHER KETONE KETONE)CONTAINING CARBOXYLIC ESTER SIDE GROUPS

以含羧基侧基的聚芳醚酮酮醚酮酮(PEKKEKK-A)树脂为原料,二氯亚砜(SOCl2)、二氯乙烷(DCE)、吡啶为催化溶剂体系,合成带甲酰氯侧基的聚芳醚酮酮醚酮酮(PEKKEKK-C)树脂.PEKKEKK-C与甲醇、乙醇、丁醇、辛醇、苯酚等发生酯化反应,得到5种含羧酸酯侧基的聚芳醚酮酮醚酮酮(PEKKEKK-E)s.用红外光谱(FTIR)、氢核磁谱(1H-NMR)、广角X射线衍射(WAXD)、热失重(TGA)、示差扫描量热(DSC)等技术对其结构与性能进行了分析表征.结果表明,聚合物为非晶聚集态;玻璃化转变温度(Tg)在175.7～236.8℃之间,较PEKK有较大幅度提高;出现两次热失重平台,分别在335～365℃,460～505℃之间,第一次失重可能由于酯分解所致,第二次失重可能是分子主链开始分解;树脂能溶解于DMAc、NMP、二氯甲烷等普通有机溶剂中,溶剂挥发后成膜性良好,可制成透明薄膜;断裂伸长率在6.34%～15.43%之间,拉伸强度在74.68～85.35MPa之间。

Five novel poly（aryl ether ketone ketone ether ketone ketone） with carboxylic ester side groups（PEKKEKK-E）s were synthesized from poly（aryl ether ketone ketone ether ketone ketone） having pendent carboxyl groups（PEKKEKK-A） and alcohols,in the presence of 1,2-dichoroethane and thionyl chloride as acylchlorination reagent,pyridine as a catalyst.While PEKKEKK-A was prepared from trimellitic anhydride chloride（TMAC） and 1,4-bis（4-phenoxybenzoyl） benzene（p-EKKE） by low temperature solution polycondensation.PEKKEKK-Es were characterized by FTIR,1H-NMR,WAXD,TGA,DSC,the solubility and mechanical properties of the polymers were investigated.Results show that the glass transition of the polymers is in the range of 175℃ to 237℃.The structure of the polymers is amorphous as expected.The esterified polymers have better solubility than the corresponding polymer.Flexible and colorless films were easily obtained by solution casting taking DMAc as solvent.It shows that the polymers have good mechanical properties.Tensile strength,elongation at break and Young＇s module of polymers are in the range of 74.7 MPa to 85.4 MPa,6.34% to 15.43%,and 1.74 GPa to 3.08 GPa,respectively.