Oxirane/cyclic acid anhydride

The tendency towards alternation in the oxirane/cyclic acid anhydride system with the zinc-based coordination catalyst is connected, according to literature data [193], with the stronger nucleophilic properties of the oxygen atom of the zinc alcoholate species and the weaker electrophilic properties of the zinc atom in such species compared with the respective properties of zinc carboxylate species. Studies of the copolymerisation of propylene oxide and maleic anhydride in the presence of catalysts such as diethylzinc-monoprotic compound (1 1) showed an increasing tendency towards alternation in systems with catalysts of decreasing electrophilicity of the zinc atom [186], which may corroborate the coordination mechanism proposed scheme (24). 

Oxirane/cyclic acid anhydride alternating copolymers of controlled molecular weight with a narrow molecular weight distribution were found by Aida et al. [188,189] to be formed under mild conditions when copolymerising ethylene oxide and phthalic anhydride in the presence of the (tpp)AlCl-quater-nary phosphonium salt catalyst system. The copolymerisation carried out with (tpp)AlCl alone proceeded very slowly, and the product was not polyethylene terephthalate) but contained ether linkages in considerable amount. The development of the living character and the tendency towards alternation of the copolymerisation when using the aluminium porphyrin catalyst, coupled with a quaternary salt, have been postulated [188,189] to be due to the formation of... 

Taking the above into account, the oxirane/cyclic acid anhydride/tetrahydrofuran terpolymerisations should rather be considered to involve active sites of a cationic nature, such as those, shown in scheme (26), that are responsible for the formation of oxyalkylene sequences [82] ... 

Block copolymers characterised by different backbone structures of well-defined block lengths have been obtained from oxiranes and other heterocyclic monomers in the presence of catalysts that are effective at bringing about living polymerisations. Aida et al. [127,188,189,195,196] applied aluminium porphyrins and Teyssie et al. [125,197,198] applied bimetallic /i-oxoalkoxidcs for block copolymerisations in systems involving oxirane lactone, oxirane oxirane/cyclic acid anhydride, and oxirane/cyclic acid anhydride lactone as block forming units and obtained respective polyether polyester and polyester polyester block copolymers. Such copolymers seem to be of exceptionally wide potential utility [53]. 

Block Copolymerisation of Oxiranes and Lactones or Cyclic Acid Anhydrides... 

Since oxiranes are representative heterocyclic monomers containing an endo-cyclic heteroatom, and the most commonly polymerised of such monomers, they have been subjected to copolymerisations with heterocyclic monomers containing both an endocyclic and an exocyclic heteroatom. Coordination copolymerisations of heterocyclic monomers with different functions are focused on oxirane copolymerisation with cyclic dicarboxylic acid anhydride and cyclic carbonate. However, the statistical copolymerisation of heterocyclic monomers with an endocyclic heteroatom and monomers with both endocyclic and exocyclic heteroatoms have only a limited importance. Also, the block copolymerisation of oxirane with lactone or cyclic dicarboxylic acid anhydride is of interest both from the synthetic and from the mechanistic point of view. Block copolymerisation deserves special interest in terms of the exceptionally wide potential utility of block copolymers obtained from comonomers with various functions. It should be noted, however, that the variety of comonomers that might be subjected to a random, alternating and block polymerisation involving a nucleophilic attack on the coordinating monomer is rather small. 

Lipase-catalyzed synthesis of polyesters from cyclic anhydrides and oxi-ranes was reported. The polymerization took place by PPL catalyst and the molecular weight reached 1 x 10" under the selected reaction conditions. During the polymerizahon, the enzymatically formed acid group from the anhydride may open the oxirane ring to give a glycol, which is then reacted with the anhydride or acid by lipase catalysis, yielding the polyesters. 

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