用三氯化铝催化六氯三聚膦腈开环聚合制得线性聚二氯膦腈(PDCP),通过PDCP磷原子上的亲核取代反应,合成了新的水溶性高分子聚[(甲氧基乙氧基乙氧基)。(乙氧基吡咯烷酮)1.0]膦腈(P3),用^31PNMR,^1H NMR,^13C NMR和IR对其结构进行了确证,用DSC测定了其玻璃化转变温度Tg和熔融温度Tm,用蒸汽压渗透法(VPO)测定了其数均分子量.改进了聚二(乙氧基吡咯烷酮)膦腈(P2)的合成方法.体外降解实验表明,P3具有和P2类似的pH响应性降解行为,降解速率在pH=5.0时最快,而在pH=7.4和8.0时较慢.P3在所测试的3个pH缓冲溶液中均比P2降解慢.用^31P NMR、薄层色谱(TLC)和滴定法对降解产物进行了检测,初步推断了P3在不同pH介质中的水解机理,其在pH=5.0的缓冲溶液中的降解,除侧链断裂外,聚膦腈的骨架也裂解;而在pH=7.4和8.0时的降解仅为侧链的断裂.用噻唑蓝(MTT)比色法进行的体外细胞毒性评价实验表明,P3及其在pH=5.0的缓冲溶液中降解49d后的产物均对细胞表现出了很好的生物相容性,而且其降解产物在浓度为800μg/mL时还表现出一定的促进细胞增殖作用.
Polydichlophosphazene (PDCP) was prepared by the ring-opening polymerization of hexachlorocyclotriphosphazene in the presence of 2%AlCl3. A new mixed substituent poly (organophosphazene) bearing 2-(2-oxy-l-pyrrolidiny) ethoxy and methoxyethoxyethoxy side groups was synthesized via the macromolecular substitution reactions of poly (dichlorophosphazene) with the sodium salt of 1 - (2-hydroxyethyl) -2-pyrrolidone and sodium methoxyethoxyethoxide. Its structure was verified by ^31p NMR, ^1H NMR, ^13C NMR, IR and DSC. Its molecular weight was determined by vapor pressure osmometry(VPO). 18-Crown-6 was used in the synthesis of poly[ di (2-oxy-l-pyrrolidiny)ethoxyphophazene ] (PYRP) as phase transfer catalysis in order to improve its synthetic method. The new polymer and PYRP were water-soluble and their in vitro degradation behavior was studied at varied pH conditions. The results indicate that the degradation of poly ( organophosphazenes) with (2-oxy-l-pyrrolidiny)ethoxy side groups is dependent on pH of the buffer solution. The rate of hydrolysis was more rapid at pH = 5.0 than at pH = 7.4 and pH = 8.0. It was shown that addition of methoxyethoxyethoxy side group to PYRP structure resulted in a decrease in the rate of hydrolysis. The hydrolysis products of the poly(organophosphazenes) were analyzed by ^31P NMR, thin layer chromatography(TLC ) and titration methods. A hydrolysis pathway of the new polymer in buffer solutions with pH = 5.0, 7.4 and 8. 0 was proposed. The degradation of the polymers at pH =5.0 involved a hydrolytic cleavage of (2-oxy-l-pyrrolidiny) ethoxy from the chain followed by the degradation of the phosphorus-nitrogen backbone to form phosphate and ammonium. However, the degradation of the polymers at pH = 7.4 and pH = 8.0 was only cleavage of the side group. The MTT test for the new polymer and its hydrolysis products at pH = 5.0 in HepG2 cell revealed that an increase in polymer concentration from 1.3 to 800 μg,/mL was not harmful for the cell