Dual-Functional Bis-phenyl Intermediates with Hydroxyl and Amino Functional Groups – Their Syntheses from BPA and Some Applications

• Main Authors: Yi-Ting Shen, 沈怡廷
• Other Authors: Shenghong A. Dai
• Format: Others
• Language: zh-TW
• Published: 2014
• Online Access: http://ndltd.ncl.edu.tw/handle/26145591415067830415

碩士 === 國立中興大學 === 化學工程學系所 === 102 === This study has been a portion of the recent effort of our research group to develop new dual-function polymer intermediates from isopropenyl phenol (IPP), which is originated from the cracking of bisphenol-A (BPA). One of our goals has been to functionalize IPP followed by oxidation of isopropenyl group into hydroquinone derivatives. On the other hand, my effort in this study has focused on the alkylation of anilines by IPP derivatives into dual function hydroxyl ,amino bis-phenyl (Bis-Ph-H-A) intermediates. IPP could be readily obtained from BPA through a base-catalyzed thermolysis. In my process development, IPP was alkoxylated first with ethylene carbonate or propylene carbonate into alkoxylated IPP possessing either ethoxylated primary ether alcohol or propoxylated secondary ether alcohol of IPP. These IPP derivatives were used to alkylate anilines to bis-phenyl (Bis-Ph-H-A) compounds with hydroxyl and amino functionalized groups. All of the alkylation reactions were catalyzed by aniline-hydrochloride in formation of the final products in the yields in excess of 80% isolated yields. Since the synthesized new intermediates have a high-reactive amino group on one-side of the molecule and a less-reactive OH on the other, they were selectively added to diisocyanates on the amine side and leave the other side mostly un-touched. This selective methodology has resulted in making four PU hard-segment extenders (HSEH、HSPH、HSEM、 HSPM) of narrow molecular weight distribution with PD of ≦1.3 for future PU formulation study. The prepared DP-E-A and DP-P-A intermediates have also been utilized in preparation of PU Engineering Thermoplastics(ETPs) by direct mixing them with aliphatic and aromatic diisocyanates. Except for those from H12-MDI and IPDI, PU plastics with molecular weights of greater than 80,000s with good film properties were prepared using MDI and HDI with DP-E-A or DP-H-A. In the case of MDI derived product, high Tg films with flexable films were obtained. In yet another synthetic effort, cyclic polybezozaxines oligomers with functional groups of 3,4, and 5 have been prepared and characterized from DP-H-A intermediates. This is perhaps in the first known case of poly-benzoxzines prepared with ring structures. Through these new intermediates, many new themoset polymer materials could be opened up for study and possibly brought about the high value polymeric materials.