Approach to Ideal Simultaneous Interpenetrating Network Formation via Topological Cross-Links between Polyurethane and Polymethacrylate Network Polymer Precursors

Abstract

The equimolar polyaddition cross-linking reaction of poly(methyl methacrylate-co-2-methacryloyloxyethyl isocyanate) with tri(oxytetramethylene) glycol leading to polyurethane (PU) networks was carried out in methyl benzoate at a 0.1 mol/L concentration of functional groups at 80 °C. Simultaneously, the free-radical cross-linking copolymerization of methyl methacrylate with tri(oxytetramethylene) dimethacrylate leading to polymethacrylate (PM) networks was progressed at a dilution of 1/10 in the presence of CBr4 as a chain transfer agent. The simultaneous interpenetrating networks (SINs) were formed via the topological cross-links between PU and PM network structures introduced by the respective intramolecular cross-linking reactions. Under the same polymerization conditions, no gelation was observed for respective cross-linking homopolymerizations leading to PU and PM homo-networks because respective intramolecular cross-linking reactions would be enhanced at a diluted solution. The topological cross-link formation between PU and PM network polymer precursors was pursued by SEC monitored with a multichannel UV−vis spectrometer device. The enhanced occurrence of intermolecular cross-linking via the topological cross-link formation was reflected on the variations of both the UV−vis monitored SEC curves and the molecular weights of the resulting PU and PM network polymer precursors with conversion. In addition, the respective actual gel points were compared with the corresponding theories for PU and PM networks formation or gelation. The swelling ratio of the resulting gel was quite high, suggesting a rather low cross-link density of PU/PM SIN produced through the topological cross-link formation between PU and PM network polymer precursors.

Photomechanical Switching Behavior of Semi‐Interpenetrating Polymer Network Consisting of Azobenzene‐Carrying Crosslinked Poly(vinyl ether) and Polycarbonate

“…[1][2][3] Such IPN structures can be prepared by several methods involving the polymerization of monomers in a matrix of a crosslinked polymer. [4,5] In the process of IPN formation, the monomer diffuses into the matrix polymer and polymerizes to form the corresponding new polymer network, which is topologically interlocked with the matrix.…”

Construction of Crosslink‐System‐Materials Utilizing Designed Network‐Polymer‐Precursor Modules

“…Thus, we could construct novel CSMs utilizing designed NPPs as modules, providing semi-interpenetrating polymer network (IPN) involving DAT networks and linear poly(BzMA), [46] and simultaneous-IPN between polymethacrylate and polyurethane networks, [47][48][49] novel amphiphilic CSMs [37][38][39]50,51] and patchwork-type CSMs, [52] and so on. Another example is concerned with the emulsion crosslinking (co)polymerization of multivinyl monomers, [53] especially focusing on the formation of reactive crosslinked polymer nanoparticles (CPNs) as models of microgels, with the intention of clarifying the correlation of the network structure with the reactivity of resulting CPNs which would be useful as functionalized polymeric materials.…”

Molecular architecture effect on reactivity of polynorbornenes with pendant α,β-unsaturated amide or ester bridged chains via ring-opening metathesis polymerization

“…Recently, active polymers have found increased and wide demand such as in photoresists, coatings, and printing inks; however, there are a few example of functional metathesis polymeric materials that have been synthesized with polar active side chains such as cross-linkable (meth)acryloyl group [2,[4][5][6][7][8]. Furthermore, the reactivity of the active side chain plays an important role in the preparation of polymeric network materials [2,[4][5][6][7][8]. Crosslinkable polymers have found a wide demand in the domain of interpenetrating polymer networks, non-linear optical materials, macro-and microlithography, and the formation of more thermally and chemically resistant materials [9].…”

“…poly(NB-co-5c) ROMP of 5b with [monomer]/[catalyst] ratio, [M]/[C]Z103 was successfully carried out and poly(5b) with high molecular weight of 3.1!10 4 was obtained (P9)[4][5][6][7][8]. The poly(5b) was soluble in dimethylsulfoxide (DMSO), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidinone (NMP), CH 2 Cl 2 , CHCl 3 and THF.…”