Initiation reactivity of anionic polymerization of fluorinated acrylates and methacrylates with diethyl(ethyl cyanoacetato)aluminum

Abstract

Pseudo first-order rate constants of the reaction of diethyl(ethyl cyanoacetato)aluminum [(C 2 H 5) 2 Al(NCCHCOOC 2 H 5)] with 17 fluorinated acrylates and methacrylates and five hydrocarbon analogs for references were investigated to examine the initiation reactivities of the anionic polymerization of fluorinated vinyl monomers to afford the reactivity order: CH 2 ¼ ¼C(CF 3)COOC 2 H 5 [ CH 2 ¼ ¼C(CF 3) COOCH(CH 3) 2 [ CH 2 ¼ ¼CHCOOCH 2 C 6 F 5 [ CH 2 ¼ ¼C(CF 3)COOC(CH 3) 3 [ CH 2 ¼ ¼ C(CF 3)COOCH 2 C 6 F 5 [ CH 2 ¼ ¼C(CF 3)COOCH(CF 3) 2 ! CH 2 ¼ ¼CHCOOCH 3 [ CH 2 ¼ ¼CH COOCH 2 C 6 H 5 ! CH 2 ¼ ¼C(CF 3)COOCH 2 CF 3 [ CH 2 ¼ ¼C(CH 3)COOCH 2 C 6 F 5 [ CH 2 ¼ ¼ CHCOOCH 2 CF 3 [ CH 2 ¼ ¼CHCOOCH 2 C 2 F 5 [ CH 2 ¼ ¼CHCOOCH(CF 3) 2 [ CH 2 ¼ ¼ C(CH 3)COOCH 3 [ CH 2 ¼ ¼C(CH 3)COOCH 2 C 6 H 5 ! CH 2 ¼ ¼C(CH 3)COOCH 2 CH 2 C 8 F 17 [ CH 2 ¼ ¼C(CH 3)COOCH(CH 3) 2 [ CH 2 ¼ ¼C(CH 3)COOCH 2 C 2 F 5 ! CH 2 ¼ ¼C(CH 3)COO CH 2 CF 3. No rate constants for CH 2 ¼ ¼C(CH 3)COOCH(CF 3) 2 , CH 2 ¼ ¼CFCOOC(CH 3) 3 , and CH 2 ¼ ¼CFCOOCH 2 C 2 F 5 were obtained because of too fast polymerization. The incorporation of a trifluoromethyl group into the vinyl group enhanced the reactivity toward the delocalized carbanion. The reactivity of other fluorinated acrylates and methacrylates was concluded to approximately be controlled by the fluorine contents and the bulkiness of substituents of monomers. The reactivity was generally decreased by increasing fluorine contents of fluoroalkyl substituents in ester groups.

Synthesis and polymerization of novel fluoroalkyl 2‐trifluoromethylacrylate possessing tetrahydrofuran moiety

“…Hydrolysis of 2-(1,1,3,3,3-pentafluoro-2-benzoxypropyl)tetrahydrofuran was carried out by adding 30 mmol of 2-(1,1,3,3,3-pentafluoro-2-benzoxypropyl)tetrahydrofuran, 30 mL of methanol with 20 mL of water, and 360 mmol of sodium hydroxide under refluxing for 24 h. After the reaction the product was extracted by diethyl ether followed by washing with saturated water solution of sodium chloride and then distilled under reduced pressure to afford 1,1,3,3,3-pentafluoro-1-tetrahydrofuranyl-2-propanol. 1 2-Trifluoromethylacryloyl chloride was synthesized by the reaction of 2-trifluoromethylacrylic acid (1.0 mol) with phthaloyl dichloride (1.0 mol) at 120 C for 2 h. 6,7 The product was collected by fractional distillation. HFIP (Central Glass Co.) was dried by refluxing over calcium hydride and distilled.…”

“…7 The product was isolated by extracting with diethyl ether and washed with 2 N HCl, saturated aq. sodium hydrogencarbonate, and then saturated sodium chloride solution, and distilled under reduced pressure; bp 85.0 C/1.2 kPa; yield: 45%, purity: >97%.…”

Synthesis of novel fluorinated polymers: facile carbon–carbon bond formation aided by fluorine substituents

“…5,8 Pseudo first-order rate constants, k¢, of the reaction of diethyl(ethyl cyanoacetato)aluminum ((C 2 H 5 ) 2 Al(NCCHCOOC 2 H 5 ; Et 2 AlECA) in the presence of large excess amounts of fluorinated acrylates and methacrylates might allow for quantitative comparisons of reactivity, as Et 2 AlECA showed moderate polymerization reactivity toward these monomers. The reactions should be simple, as the Michael addition would take place without any other side reactions such as carbonyl addition or hydrogen abstraction reactions, which likely take place in typical anionic polymerizations of hydrocarbon analogs initiated by organolithiums and organomagnesiums.…”

Synthesis and polymerization of novel bis(2‐trifluoromethylacrylate)

“…1 7,8 by the reaction of 2-trifluoromethylacrylic acid (1.0 mol) with phthaloyl dichloride (1.0 mol) at 120 C for 2 h. The product was collected by fractional distillation; bp: 82 C; yield: 68%. 2-Trifluoromethylacrylic acid supplied by Tosoh F-Tech and phthaloyl dichloride from Iharanikkei were used as received.…”