Phosphonated methacrylate polymerization

Spontaneous polymerization of 4-vinyl pyridine in the presence of polyacids was one of the earliest cases of template polymerization studied. Vinyl pyridine polymerizes without an additional initiator in the presence of both low molecular weight acids and polyacids such as poly(acrylic acid), poly(methacrylic acid), polyCvinyl phosphonic acid), or poly(styrene sulfonic acid). The polyacids, in comparison with low molecular weight acids, support much higher initial rates of polymerization and lead to different kinetic equations. The authors suggested that the reaction was initiated by zwitterions. The chain reaction mechanism includes anion addition to activated double bonds of quaternary salt molecules of 4-vinylpyridine, then propagation in the activated center, and termination of the growing center by protonization. The proposed structure of the product, obtained in the case of poly(acrylic acid), used as a template is ... 

A similar concept was used in the development of artificial chymotrypsin mimics [54]. The esterase-site was modeled by using the phosphonate template 75 as a stable transition state analogue (Scheme 13.19). The catalytic triad of the active site of chymotrypsin - that is, serine, histidine and aspartic acid (carboxy-late anion) - was mimicked by imidazole, phenolic hydroxy and carboxyl groups, respectively. The catalytically active MIP catalyst 76 was prepared using free radical polymerization, in the presence of the phosphonate template 75, methacrylic acid, ethylene glycol dimethacrylate and AIBN. The template removal conditions had a decisive influence on the efficiency of the polymer-mediated catalysis, and best results were obtained with aqueous Na2CC>3. 

Dausend J, Musyanovych A, Dass M, et al. (2008) Uptake mechanism of oppositely charged fluorescent nanoparticles in HeLa cells. Macromol Biosci 8 1135-1143 Ziegler A, Landfester K, Musyanovych A (2009) Synthesis of phosphonate-functionalized polystyrene and poly(methyl methacrylate) particles and their kinetic behavior in miniemulsion polymerization. Colloid Polym Sci. http //dx.doi.Org/10.1007/s00396-009-2087-z Lorenz MR, Kohnle MV, Dass M, et al. (2008) Synthesis of fluorescent polyisoprene nanoparticles and their uptake into various cells. Macromol Biosci 8 711-727... 

Ziegler A, Landfester K, Musyanovych A (2009) Synthesis of phosphonate-functionalized polystyrene and poly(methyl methacrylate) particles and their kinetic behavior in miniemulsion polymerization. Colloid Polym Sci 287 1261-1271... 

Figure 2.3 Kinetic plot for the RAFT polymerization of both diethyl 2-(methacryl-amido)ethylphosphonate (DMAAmEP) and diethyl 2-(acrylamido)ethyl-phosphonate (DAAmEP), at 70 and 80 °C, respectively. The theoretical molecular weight was equal to 5000 g moP, at 60 and 80% conversion for DMAAmEP and DAAmEP, respectively.

Recently, Garska et al. took an interest in the preparation of methacrylated calix[4]arene PAs (Scheme 8.5). Moszner et al. had previously demonstrated that the incorporation of modified calix[4]arenes into dental materials results in a significant decrease of the polymerization shrinkage. As an extension of this work, the phosphonic acid PA-7 and the diphosphonic acid PA-8 were prepared in three steps, starting from j-tert-butylcalix[4]arene. To evaluate their adhesive properties, those two monomers were... 

Commercial anticorrosion phosphonated polymer compounds are generally formed from Sipomer or Phosmer monomers, which are phosphate-type (meth)actylates and can be readily polymerized via emulsion or solution. Polymers with some phosphonate functionality have long been established as excellent adhesives and anticorrosion compounds however, there has been very little investigation into the use of phosphonate-type methacrylates for the same purpose. 

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