Halogen-Bearing Polymers

The volume of commercial fluorine containing polymers is not large when compared with other polymers, such as poly(vinyl chloride). Fluoropolymers, however, are required in many important applications. The main monomers are tetrafluoroethylene, trifluorochloroethylene, vinyl fluoride, vinylidine fluoride, and hexafluoropropylene. 

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Lithiated polystyrene reacts readily with halogen-bearing polymers like polychlorotri-fluoroethylene. This can be utilized in the formation of graft copolymers. The reactions can be conducted in solutions as well as in preparations of surface grafts on films." ... 

Exceptional heat resistance and low compression set can be obtained by curing butyl rubbers with dimethylol phenol resins. The curing reaction is very slow even at high temperatures and when activated by halogens. Stannous chloride, and combinations of a halogenated polymer (such as neoprene, halobutyl or brominated resin) with zinc oxide, are the most commonly used halogen-bearing activators. The systems shown in Table 5 are typical. 

PPS is used at an annual rate of about 2,000 tons but is anticipated that this rate will Increase to 25 thousand tons in the late 1980 s. This polymer is being used for pumps, sleeve bearings, cookware, quartz halogen lamp parts and electrical appliances.(23)... 

Lithiation Reactions. One of the earliest reactions of this type made use of metal-halogen exchange reactions carried out on poly[bis(p-bromophenoxy)phosphazene]. Polyphosphazenes that bear p-bromophenoxy side oups are normally unreactive. However, they can be lithiated, as shown in Scheme III, and the lithio derivatives react with a wide variety of electrophiles that range from chlorophosphines (19) to organometallic halides (42-45), This provides an access route to polymer-bound transition metal catalysts and other metallated or silylated polymers. 

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