Allyl acetate bulk polymerization

Figure 1. Dependence of the percentage of hh linkage on polymerization tempera-ture in bulk polymerizations. Key O, allyl acetate and , methallyl acetate. (Reproduced, with permission, from Ref. 21. Copyright 1981, J. Polym. Sci.

Bulk Polymerization of Allyl Acetate in Sealed Tubes. 298... 

The preceding indicates that in bulk and in benzene solution, the polymerization of allyl acetate leads to polymers of relatively low molecular weight. It had been expected that in emulsion processes, a higher-molecular-weight polymer would be formed. However, with a persulfate initiator, the emulsion polymerization of this monomer led to a product with the same molecular weight as was found upon bulk polymerization [18]. 

The polymerization of allyl acetate has been studied reasonably extensively in the effort to elucidate the mechanisms of the polymerization process. The utility of poly(allyl acetate) as a resin is believed to be negligible. Nevertheless, this compound has been polymerized in bulk, in solution, and in emulsion. There is mention of a cationic polymerization process and of radiation-induced charge-transfer processes. 

The bulk polymerization of allyl acetate using 2,2 -azobisisobutyro-nitrile proceeds in the same manner at 80°C as similar polymerizations involving the... 

In Experiment 1, 9.28 moles of allyl acetate per liter of latex was emulsified with 0.087 mole of sodium lauryl sulfate, buffered with 0.45 mole of sodium pyrophosphate, and initiated with 0.0920 mole/liter of potassium persulfate. In experiment 2, again 9.28 moles of allyl acetate per liter of latex was polymerized in the presence of 0.087 mole of sodium lauryl sulfate, 0.45 mole of sodium pyrophosphate, and 0.366 mole/liter of potassium persulfate. Since the MW of allyl acetate is 100, the above information implies that the basic monomer to water ratio is an unlikely 928 gm of monomer to approximately 70 gm of water. If indeed these are the experimental facts, then the fact that the polymers produced resembled those produced in bulk or in solution is not surprising. A reaction mixture consisting of nearly 93% pure monomer, naturally would be expected to produce a polymer similar to one produced from a pure (i.e., bulk) monomer and not one similar to an emulsion polymer. Compositions of less than 60% monomer in water would ordinarily be expected to produce latices. Perhaps the data in question refer to a ratio of 9.28 moles of monomer to one liter of water. 

Swem and Jordan [60] prepared the allyl esters of caproic, caprylic, pelargonic, capric, lauric, myristic, palmitic, and stearic acids. Attempts to bulk polymerize the compounds with 0.5% of dibenzoyl peroxide resulted in only a slight lowering of the monomers iodine numbers, indicating very limited polymer formation. Copolymers with diallyl o-phthalate seemed to form with 1-20% of allyl esters. These copolymers were insoluble in acetone, amyl acetate, benzene, and acetic acid. 

---