Synthesis and radical ring‐opening polymerization of adamantane‐containing bifunctional vinylcyclopropane undergoing volume expansion on polymerization

Abstract

The synthesis and radical ring‐opening polymerization of an adamantane‐substituted bifunctional vinylcyclopropane monomer is described. The radical polymerization using AIBN as a radical initiator proceeded smoothly at 60 °C along with a large volume expansion (+6.1%) to afford the corresponding networked polymer. The structural analysis with the solid‐state 13C NMR clearly revealed that radical polymerization occurred predominantly by a 1,5 ring‐opened reaction. Furthermore, copolymerization of bifunctional methacrylate monomer with the vinylcyclopropane monomer provided controlled volume shrinkage by varying the feeding ratio.

Photo-polymerizable, low shrinking modular construction kit with high efficiency based on vinylcyclopropanes

“…However, volume expandable resins are known within the literature as well. 28,29 Yet, their applicability is restricted, as the volume expansion is mainly based to the transition of a denser crystalline monomer structure compared to a less compressed, amorphous polymer structure. In fact, this attitude is lost, if the crystalline phase is melted or diluted by any further phase, like it can be observed also for the conetworks of VCP-p-phenyl ( Fig.…”

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

“…According to the reported procedure, 16 VCP 3 was synthesized by the condensation reaction of ethyl 1-cyanoacetate with trans-1,4-dibromo-2-butene under basic conditions, and the other VCP 4 was synthesized similarly from the corresponding 1-cyanoacetate (Scheme S1). The structures of 3 and 4 were confirmed by their 1 H-and 13 C-NMR spectra (Figs.…”

“…Then, the cyclopropane moiety undergoes the ringopening to afford acyclic radical species. The substituents X and Y are often selected from cyano, [11][12][13][14] chloro, 14,15 ester, [12][13][14]16,17 and amide 18,19 groups, which can stabilize the adjacent radical species. In general, cleavage of C1 C2 bond in VCP is favored than that of C1 C3.…”

Synthesis and radical ring‐opening polymerization of vinylcyclopropanes derived from amino acids with hydrophobic moieties

“…The copolymerization with methyl methacrylate afforded the corresponding polymer bearing cycloalkane moieties in the main chain. There have been reports on relatively low volume shrinkage accompanying the RROP of VCPs, which makes VCPs attractive as potential monomers applicable to coating, holographic data storages, and dental materials …”

“…There have been reports on relatively low volume shrinkage accompanying the RROP of VCPs, which makes VCPs attractive as potential monomers applicable to coating, holographic data storages, and dental materials. [13][14][15][16] bonds, are monomers of high interest, because they can be used for synthesis of functionalized polymers with optically active nature [17][18][19][20] and CAC double bonds in the main chain that can be chemically modified by various methods. 21,22 Herein, we report 1,1-disubstituted VCP monomers 1a-1f bearing (L)-amino acid-derived moieties ( Fig.…”