SURFACE-STRUCTURE OF SEGMENTED POLY(ETHER URETHANES) AND POLY(ETHER URETHANE UREAS) WITH VARIOUS PERFLUORO CHAIN EXTENDERS - AN X-RAY PHOTOELECTRON SPECTROSCOPIC INVESTIGATION
SURFACE-STRUCTURE OF SEGMENTED POLY(ETHER URETHANES) AND POLY(ETHER URETHANE UREAS) WITH VARIOUS PERFLUORO CHAIN EXTENDERS - AN X-RAY PHOTOELECTRON SPECTROSCOPIC INVESTIGATION
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DOI：
10.1021/ma00158a023
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发表时间：
1986-04-01
期刊：
影响因子：
5.5
通讯作者：
RATNER, BD
中科院分区：
文献类型：
--
作者：
YOON, SC;RATNER, BD
以2,2,3,3-四氟-1,4-丁二醇(FB)、2,2,3,3,4,4-六氟-1,5-戊二醇为原料合成了基于4,4'-亚甲基双(亚苯基异氰酸酯)(MDI)的含氟嵌段聚醚型聚氨酯和聚醚型聚氨酯脲。 (FP)、1, 4-二氨基四氟苯 (TFB) 或 4, 4,-二氨基八氟联苯 (OFB) 作为扩链剂。软链段由分子量为1000或2000的聚丁二醇(PTMO)组成。聚合物的表征通过本体元素分析、凝胶渗透色谱、红外光谱和X射线光电子能谱(XPS)进行。对于含 PTMO-2000 的聚合物，XPS 信号的角度依赖性表明，随着样品接近表面，氟含量单调降低，并在最大有效采样深度 (~ 100 Á) 处接近体积值的 80-100%。在相同硬链段含量下，FB扩链聚合物比FP扩链聚合物在表面具有更多的软链段。软链段分子量从2000降低到1000会导致表面区域中氟含量或硬链段浓度在相同水平的硬链段浓度下增加。基于 PTMO-1000 的 FP 扩链聚合物没有表现出角度依赖性，并且具有相同的氟含量，均匀分布在整个表面区域和本体中。所有 XPS 角度相关数据表明，嵌段聚氨酯和聚（聚氨酯脲）的表面形貌很大程度上取决于相分离的程度。
Fluorine-containing segmented poly (ether urethanes) and poly (ether urethane ureas) based on 4, 4'-methylenebis (phenylene isocyanate)(MDI) were synthesized by using 2, 2, 3, 3-tetrafluoro-1, 4-butanediol (FB), 2, 2, 3, 3, 4, 4-hexafluoro-l, 5-pentanediol (FP), 1, 4-diaminotetrafluorobenzene (TFB), or 4, 4,-diaminooctafluorobiphenyl (OFB) as chain extenders. The soft segment consisted of poly (tetramethylene glycol)(PTMO) of molecular weight 1000 or 2000. The characterization of polymers was carried out by bulk elemental analysis, gel permeation chromatography, infrared spectroscopy, and X-ray photoelectron spectroscopy (XPS). For the PTMO-2000-containing polymers, the angular dependence of the XPS signal demonstrated that the fluorine content decreases monotonically as one samples closer to the surface and approaches 80-100% of the bulk value at the maximum effective sampling depth (~ 100 Á). The FB chain-extended polymers have more soft segment at the surface than the FP chain-extended polymers at the same hard-segment content. A decrease in the soft-segment molecular weight from 2000 to 1000 produces an increase of fluorine content or hard-segment concentration in the surface region at the same level of hard-segment concentration. The FP chain-extended polymers based on PTMO-1000 show no angular dependence and have the same fluorine content uniformly distributed throughout thesurface region and in the bulk. Allof the XPS angular-dependent data indicate that thesurface topography of segmented polyurethanes and poly (urethane ureas) strongly depends on the extent of phase separation.