Methacrylic anhydride cyclopolymerization

Thus, we investigated in detail the factors influencing intramolecular addition modes in the radical cyclopolymerization of some unconjugated dienes, including diallyl and dimethallyl dicarboxy-lates, acrylic and methacrylic anhydrides, and allyl -substituted acrylates and discussed the selectivity of reaction mode of intramolecular hh or ht addition in terms of the thermodynamical standpoint. The present article gives a summary of our recent work including published papers(18-23). 

In the cyclopolymerization of methacrylic anhydride(MA) as a typical 1,6-diene, five- and six-membered ring anhydride structures can be formed, respectively corresponding to intramolecular hh and ht addition of uncyclized radical. The IR spectrum of poly-MA has been tentatively compared earlier with that of poly-MA prepared by dehydration of poly(methacrylic acid)(37) no five-membered cyclized anhydrides were detected, any absorption at higher frequency due to the strain of a five-membered ring being absent. 

Figure 6. Dependence of the absorbance ratio DmS/D, cc on monomer concentration in the cyclopolymerization of methacrylic anhydride in benzonitrile. Key ...

Cyclopolymerizations also occur with methacrylic anhydride, divinyl formal, o-divinyl benzene, o-diallyl phthalate, and even 1,4-dimethylene cyclohexane ... 

Attempts to prepare H-H poly(methyl methacrylate) by radical cyclopolymerization of methacrylic anhydride and methacrylimides have given promising results (42). The cyclopolymerization must be directed to the exclusive formation of the unfavorable five membered ring intermediate. Cyclopolymers which consist of mixtures of five and six membered rings were obtained with five membered ring intermediates predominating (23,42,59). 

The polymerization of acrylic and methacrylic anhydride is interesting because linear polymers can be obtained in contrast to the cross-linked networks usually formed from difunctional vinyl monomers [588-590]. In a cyclopolymerization reaction, alternating... 

Supemucleophilic polymers containing the 4-(pyrro-lidino)pyridine group were synthesized from the corresponding maleic anhydride copolymers and also by cyclopolymerization of N-4-pyridyl bis(methacryl-imide). The resulting polymers were examined for their kinetics of quaternization with benzyl chloride and hydrolysis of pj-nitrophenylacetate. In both instances, the polymer bound 4-(dialkylamino)pyridine was found to be a superior catalyst than the corresponding low molecular weight analog. 

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