Plasticized polymers

The use of flame retardants came about because of concern over the flammabiUty of synthetic polymers (plastics). A simple method of assessing the potential contribution of polymers to a fire is to examine the heats of combustion, which for common polymers vary by only about a factor of two (1). Heats of combustion correlate with the chemical nature of a polymer whether the polymer is synthetic or natural. Concern over flammabiUty should arise via a proper risk assessment which takes into account not only the flammabiUty of the material, but also the environment in which it is used. 

Raw Materials. PVC is inherently a hard and brittle material and very sensitive to heat it thus must be modified with a variety of plasticizers, stabilizers, and other processing aids to form heat-stable flexible or semiflexible products or with lesser amounts of these processing aids for the manufacture of rigid products (see Vinyl polymers, vinyl chloride polymers). Plasticizer levels used to produce the desired softness and flexibihty in a finished product vary between 25 parts per hundred (pph) parts of PVC for flooring products to about 80—100 pph for apparel products (245). Numerous plasticizers (qv) are commercially available for PVC, although dioctyl phthalate (DOP) is by far the most widely used in industrial appHcations due to its excellent properties and low cost. For example, phosphates provide improved flame resistance, adipate esters enhance low temperature flexibihty, polymeric plasticizers such as glycol adipates and azelates improve the migration resistance, and phthalate esters provide compatibiUty and flexibihty (245). 

Sihcone polymer plasticizers have historically been used in many formulations. These plasticizers (qv) are of the same Si—O backbone as the functional polymers but generally are terrninated with trimethyl groups which are unreactive to the cure system. This nonreactivity means that, if improperly used, the plasticizer can migrate from the sealant and stain certain substrates. Staining has been a widely pubHcized flaw of sihcone sealants, but the potential of a formulation to stain a substrate can be minimized or eliminated with proper formulation work. In general, this is accompHshed by not using plasticizers for formulations developed for stain-sensitive substrates. 

Polymer Plasticizer. Nylon, cellulose, and cellulose esters can be plasticized using sulfolane to improve flexibiUty and to increase elongation of the polymer (130,131). More importantly, sulfolane is a preferred plasticizer for the synthesis of cellulose hoUow fibers, which are used as permeabiUty membranes in reverse osmosis (qv) cells (131—133) (see Hollow-FIBERMEMBRANEs). In the preparation of the hoUow fibers, a molten mixture of sulfolane and cellulose triacetate is extmded through a die to form the hoUow fiber. The sulfolane is subsequently extracted from the fiber with water to give a permeable, plasticizer-free, hoUow fiber. 

Low Temperature Properties. Medium hardness compounds of average methyl acrylate, ie, VAMAC G, without a plasticizer typically survive 180° flex tests at —40° C. Such performance is good for a heat-resistant polymer. Low temperature properties can be greatly enhanced by the use of ester plasticizers (10). Careful selection of the plasticizer is necessary to preserve the heat resistance performance of the polymer. Plasticized high methyl acrylate grades lose only a few °C in flexibiUty, compared to grades with average methyl acrylate levels. 

Fig. 23.12. Shear banding, an alternative form of polymer plasticity which appears in compression.

Polychlorinated biphenyls (PCB) L S A Lubricants and hydraulic fluids Pesticides Plasticizer in paint and polymers Plasticizer (polymers) Transformer oils... 

R. Keshavaraj, R. W. Tock, R. S. Narayan, and R. A. Bartsch, Fluid Property Prediction of Siloxanes with the Aid of Artificial Neural Nets, Polymer-Plastics Technology and Engineering, i5(6) 971-982 ( 996). 

Schmitt, C. R. Polymer-plastics technology and energineering. Vol. 3. New York Marcel Dekker 1974, p. 121... 

Viscoelastic Properties of Highly Filled Polymers Plastic-Bonded Explosives , Univ of Calif, UCRL-70688, AEC (1967) CA 68, 40369 (1968) 49) R.E. Garrison W.R. Kilgore,... 

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