9,9-二(4-羟基苯基)呫吨、1,4-二(4-氟苯甲酰基)苯和双酚A三元共聚物聚醚醚酮酮的合成与表征

通过亲核取代反应,将9,9-二(4-羟基苯基)呫吨(BHPX)、1,4-二(4-氟苯甲酰基)苯和双酚A(BPA)进行三元共缩聚反应,合成了几种主链含二甲基甲烷和呫吨结构的聚醚醚酮酮无规共聚物(PEEKK-X/PEEKK-A),并以FTIR、DSC、TG、WAXD等对其结构和性能进行了表征.结果表明,共聚物的玻璃化转变温度(Tg)为185～218℃,均为无定形结构,其数均分子量为39500～41600,多分散性指数为1.94～2.05.在氮气、空气气氛中,在430℃之前不分解,5%的热失重温度(Td5)分别为490～511℃、480～505℃,在氮气中700℃时的残炭率均在40%以上;在常温下易溶于非质子极性溶剂(如NMP和DMAc)以及极性较弱的溶剂(如THF和CHCl3)中.共聚物均可通过溶液浇铸成膜,所得到的薄膜韧性好,透明且耐折,其拉伸强度为58～75MPa,杨氏膜量为1.95～2.70GPa,断裂伸长率为8%～13%.当双酚单体BHPX和BPA摩尔比为60/40～50/50时,所得到的PEEKK-X/PEEKK-A共聚物更有潜在的应用前景.

SYNTHESIS AND CHARACTERIZATION OF POLY(ETHER ETHER KETONE KETONE)COPOLYMERS BASED ON 9,9-BIS(4-HYDROXYPHENYL) XANTHENE,1,4-BIS(4-FLUOROBENZOYL)BENZENE AND BISPHENOL A

Four random poly(ether ether ketone ketone) copolymers (PEEKK-X /PEEKK-A)s were prepared via nucleophilic aromatic substitution polycondensation of 9,9-bis(4-hydroxyphenyl) xanthene ( BHPX),1,4- bis(4-fluorobenzoyl) benzene and bisphenol A ( BPA ).The PEEKK-X /PEEKK-A copolymers were characterized by FTIR,DSC,TGA and WAXD,etc.The results showed that the copolymers having number- average molecular weights (Mn’s) in the range of 39500 ～ 41600,the polydispersity index ranging from 1.95 to 2.05 were all amorphous and readily soluble in common organic solvents such as N-methyl-pyrrolidone (NMP),N,N-dimethylacetamide ( DMAc),THF and CHCl3 at room temperature.These polymers showed relatively high glass transition temperatures in the range of 185 ～ 218℃ ,almost no weight loss up to 430℃ in nitrogen or air atmosphere,decomposition temperatures at 5% weight loss ranging from 490℃ to 511℃ ,and 480℃ to 505℃ in nitrogen and air,respectively,and char yields at 700℃ in nitrogen higher than 40% .Transparent,flexible and tough films of these polymers cast from their solutions exhibited tensile strengths ranging from 58 MPa to 75 MPa,Young’s moduli from 1.95 GPa to 2.70 GPa,and elongations at break from 8% to 13% .The novel PEEKK-X /PEEKK-A copolymers derived from the bisphenol monomers of BHPX and BPA with molar ratio in the range of 60 /40 to 50 /50 might serve as new candidates for processable high- performance polymeric materials with potential applications in high technology fields.