Polyamine macromonomers

This reaction was applied to the synthesis of macromonomers81 83). If p-DVB is reacted with N,N -diethylethylenediamine in the presence of a lithiated diamine the 

If the diadduct is desired, a large excess of the diamine is required, and the reaction mixture has to be kept at —17 °C for a long period to attain high conversion. 

The monoadduct (I) contains a terminal vinyl group and a secondary amine function. Thus, self-condensation appears to be possible. Lithium diisopropylamide was used to create the amide function, instead of butyllithium which could possibly attack the double bond. Thus, the metalation of the secondary amine function is straightforward, and the occurring self-condensation can be monitored by 13C-NMR and by GPC. No side reaction has been detected. This process can be illustrated by the following scheme  

However, each step of the reaction can also be considered as an anionic polymerization that does not propagate. The stabilized lithiated site (III), resulting 

An adequate control of the average molecular weight of the macromonomers formed can be achieved. Macromonomers of the type (II) covering a wide range of molecular weights have been obtained and characterized. 

---

HA copolymers were prepared by radical copolymerization of HEMA with polyamine macromonomer which had been synthesized by a self-polyaddition reaction of N, N -diethyl-AT-(vinylphenethyI)ethyIenediamine (EDAS) in the presence of lithium diisopropylamide [98-100]... 

It had been found previously [106] that cell adhesion on the surface of HA copolymers decreased with increasing ambient pH. With polyHEMA, on the other hand, no pH-dependency was observed. We considered the adhesion to be caused primarily by ionic interaction between the lymphocytes and the HA surfaces. The degree of protonation (a) of amino groups in HA copolymer was estimated by acid-base titration of an HCI solution of polyamine macromonomer with NaOH solution. In physiological conditions (pH 7.2-7.4) about 50% of the amino groups of the macromonomer are protonated. In this pH range, the polyamine macromonomer was found to be insoluble. 

Nabeshima, Y., A. Maruyama, T. Tsuruta, and K. Kataoka. 1987. A polyamine macromonomer having controlled molecular weight-synthesis and mechanisRolym. J.19 593-601. 

The polyamine macromonomers developed by Tsuruta and his coworkers81,84, 135> were also copolymerized with styrene, using AIBN as the free-radical initiator. 

Polyamine macromonomers with ferf-amino groups were prepared by selfpolyaddition of the 1 1 adduct of 1,4-divinylbenzene and N,N -diethylethylene diamine using lithium acrylamide as a catalyst [191] according to the reaction (Scheme 60). 

Polyaddition of non-conjugated dienes and diamines, under stoichiometric conditions, leads to the formation of polyamine macromonomers. For example, polyaddition of divinylbenzene and a secondary diamine gives a polyamine... 

The p-DVB-piperazine adducts can also undergo self condensation whereby the macromonomers formed exhibit rather low molecular weights, and are insoluble in the reaction mixture (benzene or THF). They dissolve only upon the addition of an acid or in hot chloroform. Free-radical copolymerization of this macromonomer with styrene was carried out in benzene in the presence of some acetic acid (to obtain a homogeneous reaction mixture) to yields of about 20% M). Here again separation of the unreacted macromonomer is possible, and the polyamine content of the graft copolymer is very close to the amount contained in the reaction mixture. 

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-... 

---