Polypeptidic Macromonomers

The monoadduct of p-DVB and N,N -diethylethylenediamine (I) is itself a new monomer. Several other monomers have been prepared by reaction of p-DVB with various amines or diamines 82,86). p-Vinylbenzyl derivatives carrying a primary amine function (instead of a secondary amine moiety) have also been obtained in high yields 87 

It is well known that primary amines are efficient initiators for the polymerization of Leuch s anhydrides (oxazolidinediones) and that initiation proceeds by the addition of the amine to the monomer. This pathway has been utilized recently to synthesize polypeptide macromonomers bearing a terminal p-vinylbenzyl group 88). Copolymerization of these macromonomers with a vinylic or acrylic comonomer yields graft copolymers with polypeptide grafts. Alternately, the monomer adduct (IV) was copolymerized with styrene, and the primary amine functions of this polymer were used to initiate the polymerization of an oxazolidinedione whereby polypeptide grafts are formed 89). Such graft copolymers may be of interest for biomedical applications. 

The same kind of addition reaction as described in Section IV 1) and 2) can be performed with substituted bisacryl amides such as bisacryloylpiperidide and N,N -dimethylethylenediamine. However, the difference in the reactivity between the two acrylic double bonds is much less pronounced than in the case of p-divinylbenzene, so that a mere polycondensation occurs. Upon using a calculated excess of 1,4-bis-acryloylpiperidine bifunctional macromonomers of a known average molecular weight have been obtained by Ferruti et al. 90)  

This reaction proceeds at room temperature in two days in aqueous solution. 

The macromonomer obtained was copolymerized with styrene in the presence of AIBN and is apparently not cross-linked. The copolymers obtained seem to exhibit 

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Fig. 19 (a) Synthesis of polypeptide macromonomers for grafting through and (b) grafting from for the synthesis of polymer brushes with polypeptide side chains [125]... 

Macromonomers of poly(crown ether)s (543) and polypeptides (544) have also been prepared by this method. 

The catalytic polyaddition reaction of divinylbenzene and disecondary amines in the presence of a lithium amide yields polyamines with a p-vinylbenzyl (VB) substituent as in equation (21) using iV,iV -diethylethylenediamine. Macromonomers of poly(crown ethers) were also prepared by this method. Macromonomers of polypeptides were synthesized by the ring-opening polymerization of y-benzyl-L-glutamate-N-carboxyanhydride initiated by N-methyl-N-(4-vinylphenethyl) ethylenediamine, and of DL-phenylalanine-N-carboxyanhydride initiated by m, p-vinylbenzyl-... 

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