非异氰酸酯法合成脂肪族热塑性聚氨酯及其性能研究

Studies on the Synthesis and Properties of Aliphatic Thermoplastic Polyurethanes via Non-isocyanate Route

利用二氨酯二醇氨酯交换的非异氰酸酯法合成高分子量的脂肪族热塑性聚氨酯.以己二氨酯二醇（BHCH）的自缩聚,合成了Mn为29200的聚己二氨酯（PBHCH）,其熔点为154.31℃,拉伸强度为28.41MPa,断裂伸长率为3.91%;利用己内酰胺与乙醇胺的共聚合成了同时带有端氨基及端羟基的尼龙-6低聚物,并与己内酯反应转化为端羟基尼龙-6低聚体,经与BHCH在170℃常压反应4 h及180℃减压反应6.5 h,获得了数种带有短尼龙-6段的酰胺型聚氨酯（s-PAUs）,红外、核磁、GPC、广角X-射线衍射、DSC、TGA和力学性能表征表明,此类s-PAUs的Mn在26000以上、熔点在123.85-170.89℃之间、拉伸强度达28.53 MPa、断裂伸长率达299.0%.

A non-isocyanate route to synthesize high molecular weight aliphatic thermoplastic polyurethanes through transurethane polymerization from a diurethanediol was provided. A homopolymer of 1, 6-bis （ hydroxyethyloxy carbonyl amino） hexane （BHCH） , i. e. PBHCH, was synthesized via melt polycondensation of BHCH. The PBHCH had M of 29200,Mw of 39700,tensile strength of 28.41 MPa and elongation at break of 3.91%. Meanwhile, a nylon-6 oligomer having H2N- and HO- terminal groups （H2N-PA-OH） was prepared via ring-opening polymerization from eaprolactam with ethanolamine,and was transformed into HO- terminated nylon-6 oligomer （HO-PA-OH） through reaction with excessive eaprolactone. Co-polycondensation of BHCH with HO-PA-OH was carried out at 170℃ under normal pressure for 4 h and at 180℃ under reduced pressure of 399 Pa for 6.5 h. Several aliphatic thermoplastic poly （amide-urethane） s having short nylon-6 segments （s-PAUs） were prepared. They were characterized by viseometry, gel permeation chromatography, FTIR, 1H-NMR, differential scanning calorimetry, thermogravimetrie analysis, wide angle X- ray scattering and tensile test. The s-PAUs had Mn above 26000, MW above 33900, Tm between 123.85 and 170.89℃ ,and initial decomposition temperature over 267.86℃. Their tensile strength reached 28.53 MPa with elongation at break up to 299.0%. These s-PAUs were constituted with short nylon-6 segments and PBHCH sequences or merely dicarbamate units. The s-PAUs were crystallizable thermoplastic polyurethanes. Introducing about 10 tool% short nylon-6 segments having polymerization degree of 2.55 increased the crystallinity of the PBHCH sequences,and improved the toughness of the s-PAUs obviously.