Structurally-Controlled Synthesis of Amphiphilic Polymers Having Tetrahydropyrans in their Main Chains by Ring-Opening Polymerization Meghod and Appearance of their Functions

1.新型双环氧杂内酰胺的合成及开环聚合研究合成了2-氧杂-5-氮杂双环[2.2.2]辛-6-酮（2，5-BOL）和2-氧杂-6-氮杂双环[2.2.2]辛-5-酮（2，6-BOL）两种新型双环氧杂内酰胺，并考察了它们的开环聚合性能。以吡咯烷酮钾和N-苯甲酰基BOL为催化剂和活化剂，使2，5-BOL聚合，得到主链含顺式-2，5-四氢吡喃环的聚酰胺，再以三苯基膦和六氯乙烷为活化剂，由反式-5-氨基-四氢吡喃-2-羧酸直接缩聚，得到相应的主链含反式-2，5-四氢吡喃环的聚酰胺。与顺式聚酰胺相比，反式聚酰胺在常见的有机溶剂中的溶解度低得多，并且其溶解于三氟乙醇、六氟-2-丙醇和间甲酚中。2，6-BOL不进行阴离子聚合，只生成二聚体加合物，产率低。在康特拉 ...更多信息 St，2，6-BOL在阳离子引发剂如三氟甲磺酸的作用下较容易聚合，得到主链含六元内酰胺环的低聚醚.主链含四氢吡喃环聚酯的合成以三苯膦和六氯乙烷为活化剂，通过直接缩聚法制备了由反式-2，5-四氢吡喃环组成的聚酯。聚酯在高温下退火后变得高度结晶，并且在有机溶剂中显示出有限的溶解度。新合成了3个4位上带有酯基的2，6-二氧杂双环[2.2.2]辛-3-酮衍生物，其醇部分为低聚氧杂双环链或苄基。这些单体容易进行阳离子聚合以产生在主链中具有2，5-连接的四氢吡喃环和相应的酯基作为侧链的聚酯。与不含酯侧链的母体聚酯相比，聚酯显示出大大改善的溶解性。当将这些聚酯的薄膜浸入pH7.2的boffer溶液中时，它们在30 ℃下非常缓慢地水解。少

1. Synthesis and Ring-Opening Polymerization of Novel Bicyclic OxalactamsTwo new bicyclic oxalactams, 2-oxa-5-azabicyclo[2.2.2]octan-6-one (2,5-BOL) and 2-oxa-6-azacicyclo[2.2.2]octan-5-one (2,6-BOL) were synthesized and their ring-opening polymerizabilities were examined. 2,5-BOL was polymerized in the presence of potassium pyrrolidonate and N-benzoyl BOL as catalyst and activator respectively to give a polyamide having cis-2,5-linked tetrahydropyran rings in the main chain.The corresponding polyamide consisting of trans-2,5-linked tetrahydropyran rings was prepared by direct polycondensation of trans-5-amino-tetrahydropyran-2-carboxylic acid using triphenyl phosphine and hexachloroethane as activators. The trans-polyamide was much less soluble in comon organic solvents compared with the cis polyamide, and it dissolves in trifluoroethanol, hexafluoro-2-propanol, and m-cresol. 2,6-BOL did not undergo-anionic polymeri- zation, and afforded only a dimeric adduct in a low yield. In contra … More st, 2,6-BOL was polymerized relatively easily with cationic initiators such as trifluoro- methanesulfonic acid to give oligoethers containing 6-membered lactam rings in the main chains.2. Synthesis of Polyesters Having Tetrahydropyran Rings in their Main ChainsChains A polyester composed of trans-2,5-linked tetrahydropyran rings was prepared by direct polycondensation using triphenyl phosphine and hexachloroethane as activators. The polyester became highly crystalline after annealing at elevated temperature, and showed limited solubility in organic solvents. Three 2,6- dioxabicyclo[2.2.2]octan-3-one derivatives having at 4-position an ester group of which alcohol moiety was oligooxyethylene chains or a benzyl group were newly prepared. These monomers readily underwent cationic polymerization to produce polyesters having 2,5-linked tetrahydropyran rings in the backbones and the corresponding ester groups as the side chains. The polyesters showed much improved solubilities compared with the parent polyester without ester side chains. These polyesters were very slowly hydrolyzed at 30ﾟC when their films were immersed in a boffer solution adjusted at pH7.2. Less