Gel formation with multiple interunit junctions. II—mixture of different functional molecules

Number‐ and weight‐average molecular weight of condensation polymers formed in the mixture of primary molecules carrying different species of functional groups A and B are derived by the cascade theory. These functional groups are allowed to form multiple junctions of arbitrary multiplicity k. From the weight average, the gel point condition is found to be given by 1 ? (f_w ? 1)(μ_A,A ? 1) ? (g_w ? 1)(μ _B,B ? 1) + (f_w ? 1)(g_w ? 1)D_μ = 0, where f_w and g_w are average functionality of the primary molecules, μ _αβ the average multiplicity of β groups in the junctions where a path of an α‐group enters, and D_μ ≡ (μ_A,A ? 1)(μ _B,B ? 1) ? μ _A,Bμ _B,A the multiplicity determinant. Possible applications to thermoreversible gelation are suggested. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2413–2421, 2003     

Crosslinking polymerization leading to interpenetrating polymer network formation. II. Polyaddition crosslinking reactions of poly(methyl methacrylate‐co‐2‐methacryloyloxyethyl isocyanate) with various diols

As part of our continuing studies concerned with the elucidation of the crosslinking polymerization mechanism leading to interpenetrating polymer network (IPN) formation, in which IPNs consist of both polymethacrylates and polyurethane (PU) networks, this article explores the polyaddition crosslinking reactions of multifunctional poly(methyl methacrylate‐co‐2‐methacryloyloxyethyl isocyanate) [poly(MMA‐co‐MOI)] [MMA/MOI = 90/10] with various diols leading to PU network formation. Thus, the equimolar polyaddition crosslinking reactions of poly(MMA‐co‐MOI) with ethylene glycol (EG), 1,6‐hexane diol, and 1,10‐decane diol (DD) were carried out in N‐methyl pyrrolidone at a 0.25 mol/L isocyanate group concentration at 80 °C. The second‐order rate constants decreased from EG to DD. The deviation of the actual gel point from the theoretical one was smaller from EG to DD. The intrinsic viscosity of resulting prepolymer demonstrated almost no variation with progressing polymerization for the EG system, whereas it gradually increased with conversion for the DD system. Close to the gel point conversion it increased rather drastically for both systems. The swelling ratio of resulting gel was higher from EG to DD. These are discussed mechanistically in terms of the significant occurrence of intramolecular cyclization and intramolecular crosslinking reactions leading to shrinkage of the molecular size. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3243–3248, 2003     

Photoinitiators with functional groups. VII. Covalently bonded camphorquinone—amines

Camphorquinone (CQ), a widely used photoinitiator (PI) in dental applications, was covalently bonded to aromatic amines to enhance the rate of electron and proton transfer effect due to the close vicinity of the diketone and the amine group. 10‐bromocamphorquinone and 10‐bromomethylcamphorquinone were selected as suitable precursors for esterification with the carboxyl group containing aromatic amines based on 4‐dimethylaminobenzoic acid. Properties of the new photoinitiating systems were investigated by UV spectroscopy and differential scanning photocalorimetry in lauryl acrylate. Compared to physical mixtures, in all cases similar or even better performance was obtained. Surprisingly, 10‐acetyl derivatives 7 – 9 and 18 especially, were found to be highly reactive. Compared to CQ/ethyl 4‐dimethylaminobenzoate, the rate of photopolymerization was increased by a factor of up to 2. Intramolecular reaction was confirmed by photo‐differential scanning calorimetry experiments with varying PI concentrations. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4948–4963, 2004     

Designing new donor materials based on functionalized DCCnT with different electron-donating groups: A density functional theory (DFT) and time dependent density functional theory (TDDFT)-based study

Finding a promising donor/acceptor material of organic solar cells is one of the most important ways to improve their power conversion efficiency. Extensive studies have focused on designing and synthesizing new and suitable materials. Small organic molecule materials, different from polymers, have many merits, such as easy synthesis and modification, less by-products, and crystallinity. In the present work, we theoretically design a series of new donor materials based on 1-(1,1-dicyanomethylene)-cyclohex-2-ene-substituted oligothiophenes, that is, DCCnT (n = 1-4) series. Furthermore, we model and predict photoelectric properties of functionalized DCCnT with different electron-donating groups (─CH₃/─CHCH₂/─OCH₃/─NH₂/─OH). The calculated results, based on density functional theory and time-dependent functional theory, show that DCCnT-X (X = OH, NH₂, and OCH₃) series show odd-even effect of dipole moments when n varies from 1 to 4, whereas DCCnT-CH₃ and DCCnT-CHCH₂ do not. Finally, we find that DCC3T-X (X = OH, OCH₃, and NH₂) may be better candidates of donor materials because of their larger dipole moments, stronger electron donating ability, and smaller exciton binding energy with respect to prototype DCCnT molecules.