Novel Polymer Syntheses by Anionic Polymerization of Fluoroalkyl Alpha-Fluoroacrylates

研究了α-氟代丙烯酸甲酯（CH_2=CFCOOCH_3）（MFA）和α-氟代丙烯酸2，2，2-三氟乙酯（CH_2=CFCOOCH_2CF_3）（TFEFA）等α-氟代丙烯酸氟烷基酯的阴离子聚合活性。在自由基聚合中，对MFA和α-氟丙烯酸乙酯（EFA）进行了一些详细的研究，并报道了Q，e值：MFA分别为0.47和0.73，EFA分别为0.49和0.68。这些高e值可能表明α-氟代丙烯酸酯应显示高阴离子聚合反应性。虽然n-C_4 H_9 Li和C_2H_5MgBr生成聚（MFA）的产率很低，但LiZnC_4H_9（C_2H_5）_2和LiAlC_4H_9（C_2H_5）_3等配合物生成聚（MFA）的产率较高。与有机锌引发剂相比，有机铝化合物通常显示出更高的活性。（C_2H_5）_2Al（NCCHCOOC_2H_5）（Et_2AlECA）和Et_2Al（CH_3OCOCHCOOCH_3）的聚合反应活性最高。结果表明，由于在4小时内消耗了约35%的Et_2AlECA，引发反应相当缓慢。推测MFA与Et_2AlECA的聚合反应是以阴离子方式进行的。在MFA和TFEFA聚合体系中，由于分子量分布为单峰，且在~ 1H NMR中没有观察到乙烯基质子峰或其它附加信号，乙烯基的简单加成聚合反应主要发生在聚合物中，而聚合物的微观结构分析主要是通过~ 1H NMR谱进行的，~ 1H NMR谱的测量结果<13><19>表明，用~ 1H NMR谱分析含氟聚合物的微观结构<19><13>是可行的。

The anionic polymerization reactivity of fluoroalkyl alpha-fluoroacylates such as methyl alpha-fluoroacrylate (CH_2=CFCOOCH_3)(MFA) and 2, 2, 2-trifluoroethyl alpha-fluoroacrylate (CH_2=CFCOOCH_2CF_3) (TFEFA) was investigated. In the radical polymerization some detailed studies were carried out on MFA and ethyl alpha-fluoroacrylate (EFA), and Q, e-values were reported to be : 0.47 and 0.73 for MFA, and 0.49 and 0.68 for EFA, respectively. It was probable these high e-values suggested that alpha-fluorbacrylates should show high anionic polymerization reactivity. Although n-C_4H_9Li and C_2H_5MgBr produced poly (MFA) in very low yields, ate complexes such as LiZnC_4H_9(C_2H_5)_2 and LiAIC_4H_9(C_2H_5)_3 produced poly (MFA) with appreciable yields. Organoaluminum compoun ds showed generally higher activity compared to organozinc initiators. (C_2H_5)_2Al(NCCHCOOC_2H_5)(Et_2AlECA) and Et_2Al(CH_3OCOCHCOOCH_3) showed the highest polymerization reactivity.In order to get some information on the polymerization mechanism, initiation reaction of MFA with Et_2AlECA was carried out. According to the results the initiation reaction was found to be rather slow since about 35% of Et_2AIECA was consumed in 4 hours. The initiation reaction of the polymerization of MFA with Et_2AlECA was inferred to take place in anionic fashion. The simple addition polymerization of the vinyl group took place predominantly without any remarkable side reactions in the systems of MFA and TFEFA polymerizations since the molecular weight distributions were unimodal and no peaks assignable to vinyl protons or other additional signals were observed in ^1H NMR.The results of ^<13>C- and ^<19>F-NMR measurements of poly (MFA) suggested the possibility that the microstructure of fluorinated polymers could be analyzed by ^<19>F-NMR spectra though the analyses of the microstructures of the polymer have mainly been carried out by ^<13>C-NMR spectra.