Preparation of allylic copolymers of broad molecular weight distributions

#1. Field of the Invention

#The invention relates to the preparation of allylic copolymers. More particularly, the invention relates to the preparation of allylic copolymers that have broad molecular weight distributions. The copolymers are particularly useful, for example, as toner resins.

#2. Background Art

#Synthesis of Toner Resin (With Water)

#A 1-liter glass reactor equipped with an agitator, a temperature controller, a monomer addition funnel, a condenser, and a nitrogen inlet, is charged with allyl monopropoxylate (40 g, product of Lyondell Chemical Company) and distilled water (42.5 grams). The reactor contents are purged with nitrogen for 30 minutes. Styrene (256 g), n-butyl methacrylate (64 g), divinylbenzene (1.5 g, 80%, product of Aldrich) and di-tert-butyl peroxide (20 g) are mixed and charged into the addition funnel. The reactor is initially charged with 39.5 grams of the mixture, and is heated to 145° C. under the protection of nitrogen. The remaining mixture is added into the reactor over a period of 6 hours as follows: first hour, 78 g; second hour, 66 g; third hour, 54 g; fourth hour, 44 g; fifth hour, 34 g; and sixth hour, 26 g. The reaction is allowed to continue for an additional 30 minutes at 145° C. after the completion of addition. During the course of reaction, no stirring problem was encountered. The water and unreacted monomers is removed by vacuum distillation at 155° C. with nitrogen purging. The product (362.5 g) is collected (85.5% yield). The resulting copolymer is colorless and has good clarity. GPC shows two main peaks at 104 and 106. The product has Mn: 6,010, Mw: 104,600, glass transition temperature (Tg, by DSC): 65° C., and toluene insoluble portion: 1% by weight.

#Synthesis of Toner Resin (With Water)