可紫外光交联氟代聚芳醚的合成及性能研究

SYNTHESIS AND PROPERTIES OF PHOTO-CROSSLINKABLE FLUORINATED POLY(ARYLENE ETHER)

以丙酮酸、苯甲醚为原料合成了1,1-双(4-甲氧基苯基)(BMPE)乙烯单体,并通过去甲基反应得到了含可交联基团的二酚单体1,1-双(4-羟基苯基)乙烯(BHPE),并且用核磁共振、飞行质谱及元素分析表征了单体的结构,DSC测试了单体的熔点.并将BHPE与全氟联苯(DFBP)在氟化钾和氢化钙的催化作用低温下进行缩聚反应,得到了一种可紫外辐照交联的氟代聚芳醚.通过核磁共振证明了所合成的单体以及聚合物的结构,凝胶渗透色谱(GPC)测定了聚合物的分子量.傅立叶变换红外光谱分析了聚合物紫外辐照下的交联反应.所合成的氟代聚芳醚在室温下可溶于氯仿、四氢呋喃等有机溶剂,紫外交联后不溶于任何有机溶剂.且合成的聚合物具有良好的热稳定性能(玻璃化转变温度为160℃,交联后的5%热失重为465℃).

1,1-Bis（4-methoxyphenyl）ethylene（BMPE） was prepared from α-ketocarboxylic acids and anisole,and with demethylation reaction a kind of biphenol 1,1-bis（4-hydroxyphenyl）ethylene（BHPE） containing crosslinkable moiety was obtained.The structure of the monomers was measured by 1H-NMR,elemental analysis,and the melting point of the monomers was measured by DSC.A kind of photo-crosslinkable fluorinated poly（arylene ether） has been prepared by polycondensation reaction with BHPE and decafluorobiphenyl（DFBP） by using suspending CaH2 with trace amount of KF as catalyst at low temperature.The structures of the obtained polymer were measured by 1H-NMR and 19F-NMR.The molecular weight of polymer was monitored by gel permeation chromatography（GPC）,and the resulting number-average molecular weight is 23400 and the polydispersity index index is 2.94.The obtained polymer exhibits excellent solubility in common organic solvents at room temperature which makes it easy for optical film fabrication.The photo curing of the polymer was monitored by FTIR spectroscopy,and after UV irradiation 10 min the polymer can be completely crosslinked with the present photo initiator.The cured polymer shows good chemical resistance.So the polymer can be used for multi-layer processing.The obtained polymer also shows good thermal stability（the glass transition temperature is 160℃,the temperatures of 5% mass-loss is 465℃ after curing）.