含乙二醇低聚体间隔臂的胆酸酯及其甲基丙烯酸衍生物的制备与表征  

PREPARATION AND CHARACTERIZATION OF CHOLIC ACID DERIVATIVES WITH OLIGO(ETHYLENE GLYCOL)S AS SPACER GROUPS

作　　者：许忠海[1] 李涛[1] 宋媛媛[1] 李湛勇[1] 张栩[1] 关英[1] 

机构地区：[1]功能高分子材料教育部重点实验室,南开大学高分子化学研究所,天津300071

出　　处：《离子交换与吸附》2009年第2期97-106,共10页Ion Exchange and Adsorption

基　　金：国家973前期研究专项资助(2002CCA02500)

摘　　要：通过在胆酸羧基端修饰乙二醇低聚体间隔臂,合成了一系列乙二醇低聚体胆酸酯及其甲基丙烯酸衍生物:3′-氧杂-5′-羟基胆酸戊酯,3′,6′-二氧杂-8′-羟基胆酸辛酯,3′,6′,9′-三氧杂-11′-羟基胆酸十一酯,3′-氧杂-5′-甲基丙烯酰氧基戊基-3α,7α,12α–三甲基丙烯酰氧基胆酸酯,3′,6′-二氧杂-8′-甲基丙烯酰氧基辛基-3α,7α,12α–三甲基丙烯酰氧基胆酸酯,3′,6′,9′-三氧杂-11′-甲基丙烯酰氧基十一烷基-3α,7α,12α–三甲基丙烯酰氧基胆酸酯。利用红外光谱研究了含乙二醇低聚体间隔臂胆酸酯分子间的氢键与其物理性质间的关系。结果表明,随着间隔臂链长的增加,胆酸酯中氢键的受体基团由以胆酸24位酯羰基氧和间隔臂上醚键氧为主过渡到以间隔臂上醚键氧为主,醚键氧作为受体形成氢键极大限制了胆酸甾环骨架的运动,影响了其分子骨架的有序排列,使该类胆酸酯的物理形态从固体粉末变为粘稠液体。DSC的测定结果显示,随间隔臂链长的增加,含乙二醇低聚体间隔臂的胆酸酯甲基丙烯酸衍生物功能单体的玻璃化转变温度下降。初步预计该类单体的聚合转化率会随间隔臂链长的增加有所增加。By modification of cholic acid with oligo（ethylene glycol）s, a series of cholic acid esters, including 3＇-oxa-5＇-hydroxypentyl-3α,7α,12α-trihydroxy-5β-cholan-24-ate （CADE）, 3＇,6＇- dioxa-8＇-hydroxyoctyl-3α,7α, 12α-trihydroxy-5β-cholan-24-ate （CATE）, 3＇,6＇,9＇-trioxa- 11 ＇- hydroxyundecyl-3α,7α,12α-trihydroxy-5β-cholan-24-ate（CATrE）, were synthesized with good yield. Each of these compounds have four hydroxyl groups which can be subsequently esterified by reacting with methacryloyal chloride. These tetra-substituted methacrylic monomers include,3＇-oxa-methacryloyloxybutyl-3α,7α, 12α-trimethacryloyloxy-5β-cholan-24-ate （4MACAED）, 3＇,6＇-dioxa-methacryloyloxyoctyl-3α,7α, 12α-trimethacryloyloxy-5β-cholan-24- ate （4MACAET）, 3＇,6＇,9＇-trioxa-methacryloyloxyundecyl-3α,7α,12α-trimethacryloyloxy-5β- cholan-24-ate （4MACAETr）, in which oligo（ethylene glycol）s act as the spacer groups. Melting points of the cholic acid esters decreased with increasing the length of oligo（ethylene glycol）s, which is explained by the hydrogen acceptor change of the hydrogen-bonding and confirmed by FTIR study. Glass transition temperature （Tg） of these monomers were measured by differential scanning calorimetry （DSC） and were found to decrease with increasing length of the spacer. These novel monomers with oligo（ethylene glycol） spacer may serve as interesting crosslinking reagents in the polymerization of other methacrylic monomers.

关 键 词：胆酸 乙二醇低聚体 甲基丙烯酸衍生物 氢键 玻璃化转变温度(Tg) 

分 类 号：O63[理学—高分子化学]