Radical Ring‐Opening Polymerization Behavior of 1,1‐Dicyano‐2‐Vinylcyclopropane and Its Copolymerization with 1‐Cyano‐1‐Ester‐2‐Vinylcyclopropane

Abstract

Radical ring‐opening polymerization of 1,1‐dicyano‐2‐vinylcyclopropane 1 was performed in benzonitrile to find the corresponding homopolymer 2 soluble in organic solvents was successfully obtained while that in other solvents gave crosslinked and thus insoluble homopolymer. In addition, 1 underwent radical copolymerization with 1‐cyano‐1‐ester‐2‐vinylcyclopropanes 3 and 4 to afford the corresponding copolymers 7 and 8. By increasing the content of the 1‐derived unit in the resulting copolymers, the solubility of the copolymers in organic solvents became lower and the residual weights at 600 °C and their glass transition temperatures became higher. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1723–1729

Synthesis of reactive polyureas bearing vinylcyclopropane moiety in main chain and their radical cross‐linking with multifunctional thiols

“…The obtained filtrate was evaporated under reduced pressure and the residue was isolated by using kulgholor (90 C; 3.37 mbar) to obtain 2 as a colorless liquid (1.62 g; 12.8 mmol; 64%). 1…”

“…The resulting reaction solution was poured into toluene (60 ml) to precipitate a white solid. The obtained solid was dried under reduced pressure at 100 C to obtain 5b (309 mg; 83% of the theoretical weight): 1 3,350, 3,302, 2,972, 2,966, 2,871, 1,639, 1,557, 1,264, 1,144, 904, 704. M n = 67,200, M w = 136,000, M w /M n = 2.0 (DMF including 10 mM LiBr).…”

“…The resulting reaction solution was poured into methanol (60 ml) to precipitate a white solid. The obtained solid was dried under reduced pressure at 100 C to obtain 5c (330 mg; 88% of the theoretical weight): 1 2.9 | Synthesis of networked polymer 9 2.9.1 | Typical procedure A solution of 5b (111 mg; 0.300 mmol), diethylpropane bis(3-mercaptopropionate) 6 (46 mg; 0.15 mmol) and AIBN (1.5 mg; 0.0091 mmol) was heated at 65 C under a nitrogen atmosphere. After 4 hr, the reaction solution was transformed into a gel.…”

“…Vinylcyclopropanes (VCPs) with two radical-stabilizing groups (cyano, [1][2][3][4] ester, [2][3][4][5][6][7] and amide [8,9] ) undergo radical ring-opening polymerization (RROP) to yield polymers with C C bonds in main chains. [1][2][3][4][5][6][7][8][9][10][11][12][13][14] As shown in Scheme 1a, the vinyl group of VCP derivative reacts with radical species. After that, the resulting radical will be transformed into an acyclic radical species via the preferential cleavage of C1-C2 bond on VCP moiety.…”

“…2,2-Diethyl-1,3-propanediol (99%) was purchased from Sigma-Aldrich Co. 2-Vinylcyclopropane-1,1-dicarbonitrile 1 was synthesized according to the previously reported method. [1] The procedure for the synthesis of 2,2-diethylpropane-1,3-diyl bis(3-mercaptopropionate) 6 is described in the Supporting Information.…”