一锅法合成含磺酸基超支化聚氨酯

ONE-POT SYNTHESIS OF SULFONIC ACID GROUP-CONTAINING HYPERBRANCHED POLYURETHANE

N-三羟甲基甲基氨基乙磺酸(TES)的胺基与异佛尔酮二异氰酸酯(IPDI)环上活性较高的NCO在低温15℃下发生选择性反应,生成AB3型单体.随后提高反应温度(70～90℃),使AB3型单体原位聚合,一锅法合成出含磺酸基超支化聚氨酯.随着聚合温度的提高,超支化聚氨酯的支化度、分子量及分子量分布系数变大.90℃时,聚合产物的Mn为22410,支化度达到0.87.以此含磺酸基超支化聚氨酯为基础制得的聚合物电解质膜具有良好的耐热性、机械强度,其锂盐室温(约25℃)的离子电导率为3.1×10-5S/cm,100℃达到1.4×10-3 S/cm.

A novel sulfonic acid group-containing hyperbranched polyurethane was synthesized by the reaction of N-tris （hydroxymethyl） methyl-2-aminoethanesulfonic acid （TES） and isophorone diisocyanate （IPDI） with a one-pot method. The amino group of TES added selectively to the secondary isocyanate group of IPDI at low temperature （ 15℃ ） to afford an AB3 type monomer. The resultant AB3 monomer could be polymerized in situ at high temperature （70 -90℃ ） to give hyperbranehed polyurethanes. The degree of branching （DB）, molecular weight and molecular weight distribution （MWD） of the hyperbranched polyurethane increased with increasing polymerization temperature. The number average molecular weight （Mn ） , MWD and DB of the polymer obtained at 90℃ were 22410,3.36 and 0.87, respectively. The polymer electrolytes based on the obtained hyperbranched polyurethane sulphonate had good heat stability and high tensile strength. The temperature for 1% weight loss was more than 220℃ ,and the tensile strength was up to 17 MPa. The ionic conductivity of the polymer electrolyte （lithium salt） was 3.1 × 10^-5 S/cm at room temperature （ca. 25℃ ） , 1.4 ×10^-3 S/cm at 100℃.