The Formation of Linear Polymers from Diene Monomers by a Cyclic Polymerization Mechanism. II. Polyacrylic Anhydride and the Derived Polyacrylic Acid^1,2

Abstract

Acrylic anhydride has been polymerized in solution to afford a series of saturated, linear polymers. Values of molecular weight from a few thousand up to 95,000 were recorded for the various products. The properties of the polymers showed that polymerization had occurred by the alternating intramolecular-intermolecular mechanism, in this case leading to a poly-3(5)-methyleneglutaric anhydride structure.The polyacrylic acid obtained by hydrolysis of a polyacrylic anhydride has been shown to have a much more regular structure than normal polyacrylic acid, as reflected in their relative degrees of crystallinity.Certain monomers containing a 1,6-diene system can, on polymerization, undergo an alternating intramolecular-intermolecular chain propagation or cyclization, leading to the formation of saturated, linear polymers.8-6 Such polymers have a structure consisting of a linear chain of six-membered rings alternating with methylene groups along the chain. In the first paper of this series,6 the proof of the structure in the case of the poly-(diallylammonium halides) ivas given.

Complex polymer architectures through free-radical polymerization of multivinyl monomers

“…As per the "5 Å rule [G] ", 90 smaller DVMs with a short intervinyl distance, such as unconjugated 1,5-and 1,6 dienes, are inherently desirable. Following Butler's initial study on FRP of diallyldimethylammonium salts, 87,88 various 1,5-and 1,6 dienes such as (meth)acrylic anhydride, 91 divinyl acetals, 92 o-divinylbenzene 93 and diallylsilanes 94 weresubjected to FRP and the structures obtained were demonstrated to have five-and six-membered rings (Figure 5a) distributed along the C-C chains. The rapid expansion of RDRP techniques in the last two decades have greatly facilitated the synthesis of cyclopolymers with well-defined MW, low dispersity and high chain end functionalities.…”

Cyclocopolymer of N-cyclohexyldimethacrylamide and Application to a Photoresist with Photo-Acid Generator.

“…Yield was 1.01 g. The cyclized polymerization has been studied since A. Crawshaw and G. B. Butler reported. [ 13 ] The copolymerization proceeded to form the cyclic structure in the main chain. This polymerization was high reactivity to radical initiator and the cyclized polymer was easily obtained.…”

Cyclopolymerization

“…It is indeed unfortunate that the initial work in this field, which so admirably demonstrated the presence of cyclic structures, has been interpreted as demonstrating that the cyclic structures contained 6-membered rings. In the polymer derived from the quaternary ammonium derivative of diallylamine, Butler et al [27,28] clearly demonstrated the presence of cyclic structures by chemical degradation of the polymer as shown in Figures 5 and 6. However, it should be clear from the reactions shown that no conclusion should have been drawn regarding the ring size.…”

“…Attempts to degrade polydiallylamines using the methods of Butler [27,28] and other methods, did not proceed in a manner that permitted the identification of ring size. These methods were not pursued because of the promising results obtained with 13C nuclear magnetic resonance (NMR) spectroscopy.…”