Monomer diallylamine

Hydrophobic polymers with some hydrophilic groups can be obtained with an emulsion polymerization technique. Suitable monomers are nitrogen-containing acrylics and methacrylics allyl monomers such as dimethylamino-ethyl methacrylate, dimethylaminopropyl methacrylamide, diethylamino-ethyl methacrylate, dimethylaminoethyl acrylate, diethylaminoethyl acrylate and nitrogen-containing allyl monomers (e.g., diallylamine and N,N-diallyl-cyclohexylamine) [225,226]. 

Figure 22-5. Acrylic monomers for demulsifiers dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylamide, diethylaminoethyl acrylate, N,N-diallylcyclohexylamine, diallylamine.

In contrast, diallylamino-substituted dyes copolymerized poorly with MMA, despite the reported polymerizability of other aliphatic (24-25) and aromatic (26) diallylamines. The concentration of dye-bearing repeat units m the polymer was far below the monomer feed concentrations. The possibility that these diallyl dye-monomers (or some unidentified impurity in them) acted as inhibitors of polymerization can be ruled out because the dye was found to be present uniformly in all molecular weight fractions and the molecular weights of the copolymers were again nearly identical to control samples of PMMA. Therefore, only a small amount of the diallyl amino substituted chromophores can be covalently incorporated into the crosslinked matrix because of the apparently unfavorable reactivity ratio. The balance of the chromophore remains simply dissolved in the mixture. 

This type of polymerization method has the potential to give more complex polymer structures with less defects than the normal practice of carrying out reactions on preformed polymers. Therefore we have continued with the synthesis and cyclopolymerization of new complex monomers. Most of the previously synthesized monomers were made by a one-step Mannich reaction using a diallylamine and either a phenol or an aromatic amine. This chapter describes the synthesis and attempted polymerization of a much wider variety of monomer structures. 

The monomers generally were obtained in high yield with none of the problems of multiple substitution evident in the preparation of phenolic Mannich monomers (2). The reaction of acetone with excess diallylamine and formaldehyde could be made to yield a disubstituted product, but this was difficult to isolate in a highly purified form. Monomers such as VII could be obtained from a-picoline by a Mannich reaction but the yields were much lower than those obtained with the 2-vinylpyridine/ diallylamine reaction. 

In general, the 13C NMR peak positions in Figure 4 and the IR spectra in Table III were very similar to those of the equivalent monomers except for those groups directly associated with, or very closely connected to the pyrrolidine ring. This confirmed that the functional groups attached to the diallylamine unit have not taken part in the polymerization. 

Materials and Instrumentation. Diallylamine and the various starting materials for monomer synthesis were readily available commercial materials of the highest available purity and were used without further treatment. The formaldehyde used was either BDH analytical reagent solution with 37-40% w/v formaldehyde and 11-14% w/v methanol or BDH analytical reagent paraformaldehyde. 

Kawaguchi and coworkers at Teijin have prepared a series of polymers based on poly(diallyl amine), its copolymer with sulfur dioxide, and various terpolymers.39 The chemistry of this polymer synthesis is shown below. The patent description shows the diallylamine polymers to be polypiperidine (six-membered ring) derivatives, but there are a number of publications that show this monomer to produce preferably polypyrrolidine (five-membered ring) structures ... 

Polyamine sulfone n. A water-soluble copolymer of diallylamine monomer and sulfur dioxide, used as a paint additive, antistatic agent, synthetic-fiber modifier, and polishing agent for metal platings. 

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