Kinetics of Ferrocenylmethyl Acrylate and Ferrocenylmethyl Methacrylate Polymerization. Preparation of Polymeric Ferricinium Salts

Abstract

Communications to the Editor 105 Figure 4. Generalized retention curve for polypropylene using hexadecane probe (column C) O, melting curve, first series; , melting curve, second series.those obtained by other procedures is a further corroboration, as is the fact that the values of Tm are not decreased from the expected values for the polymers used. If there were any appreciable solution of the probe molecules in the crystalline regions, some depression of 7", would be anticipated.If further experiments verify this conclusion it would appear possible to use this phenomenon to construct a new definition of "order" in polymers. That is, an "ordered region" would be defined as a region impermeable to probe molecules which can permeate the "amorphous regions" of the polymer. The relation of values obtained using this method to those obtained by more conventional techniques using X-ray diffraction or density measurements must await further study in which all three methods are used on identical polymer samples. However it should be pointed out that this new method should in principle be sensitive to the presence of very small crystallites which cannot be detected by standard X-ray diffraction methods. Unlike the density method, the presence of voids or air bubbles should not affect the results either. However it has the disadvantage that the polymer must be in the form of a thin film in order to be studied. In spite of this, the simplicity of the method has much to commend it, and the additional information on thermodynamic interactions and on structural changes such as glass transitions which may be derived from the same data1,2 represent added features. In view of these considerations we suggest that the "molecular probe" technique will become a standard procedure in the study of melting transitions in macromolecules.

Defined Poly[styrene‐block‐(ferrocenylmethyl methacrylate)] Diblock Copolymers via Living Anionic Polymerization

“…70% yield and very high purity. The applied procedure proved to be superior to the published recipes, [14][15][16][17] which take advantage of methacrylic chloride as the esterification reagent. In the latter case, side products are formed that are hard to remove to the extent needed for anionic polymerization.…”

“…[14][15][16][17] Reduction of ferrocenyl carbaldehyde 1 was achieved using NaBH 4 in methanol solution, to afford hydroxymethylferrocene 2 in essentially quantitative yields. Subsequently, a mixture of 1 equiv.…”

“…Considerable compatibility of PS and PFMMA might be the reason for this observation, but it could also be the consequence of the high T g s of both blocks: while PS has a T g of around 100 8C, we found a T g of 184.5 8C for PFMMA, which is in agreement with data from the literature. [14][15][16][17] As we were quite sure that high T g s are more likely the reason for the disappointingly bad morphology, the pre-treatment of the film samples was varied to give the chains a better chance to complete phase separation. A further increase in annealing temperature to >200 8C did not improve the results.…”

“…Rather surprisingly, however, searching in the literature resulted in the conclusion that the advantage of this option has not been taken so far: certainly, some papers published in the 1970s report both free radical and living anionic polymerization of ferrocene-containing (meth)acrylates, and the first block copolymers were described as well. [14][15][16][17] Success of these attempts was limited, however, as can be concluded from the quite large values of the polydispersity, which ranged from 2.5 to 10 even for the anionic pathway. No further attempts have been documented since then to improve the reaction conditions, although the reactivity of the ferrocene-containing monomers was judged to be similar to what is known for conventional (meth)acrylates.…”

Polymerization studies of isopropenylferrocene

“…* Polymerization studies on vinylferrocene have been reported by various investigators,**4 including a comprehensive study by Baldwin and Johmon. 6 The polymerization studies on other alkenylferrocenes have been very limited;* however, studies have now been extended to include isopropenylferrocene. This paper describes the attempted homopolymerization of isopropenylferrocene and its copolymerization with methyl methacrylate and styrene by freeradical initiation.…”