Purification and Storage of Monomers

In all polymerizations, the purity of the starting materials is of prime importance. Impurities present at concentrations of 10 -10 wt.% often have a considerable influence on the course of the reaction. With unsaturated mmiomers the impurities mentioned below may be encountered  

By-products formed during their preparation (e.g., ethylbenzene and divin-ylbenzenes in styrene acetaldehyde in vinyl acetate) added stabilizers (inhibitors) autoxidation and decomposition products of the monomers (e.g., peroxides in dienes, benzaldehyde in styrene, hydrogen cyanide in acrylonitrile) impurities that derive from the method of storage of the monomer (e.g., traces of metal or alkali from the vessels, tap grease etc.) dimers, trimers, and polymers that are generally soluble in the monomer, but sometimes precipitate, for example, polyac-rylOTiitrile from acrylonitrile. Likewise, in polycondensation reactions it is important to remove reactive impurities because they can cause considerable interference during the polyreaction. 

The purification procedures to be applied depend on the monomer, the expected impurities, and especially on the purpose for which the monomer is to be employed, e.g., whether it is to be used for radical polymerization in aqueous emulsion or for ionic polymerization initiated with sodium naphthalene. It is not possible to devise a general purification scheme instead the most suitable method must be chosen in each case from those given below. A prerequisite for successful purification is extreme cleanliness of all apparatus (if necessary, treating with hot nitrating acid and repeatedly thorough washing with distilled water). 

The usual procedures of fractional, azeotropic, or extractive distillation under inert gases, crystallization, sublimation, and column chromatography, must be 

So-called prepolymerization is frequently used to achieve a very high purification a monomer that has already been purified by the normal methods is polymerized to about 10-20% conversion by heating or irradiation, or if necessary by addition of initiator. It is then separated from the polymer by fractional distillation under nitrogen. Impurities that affect the initiation (e.g., by reaction with the initiator or its fragments) or react with the growing macromolecules (causing chain termination or chain transfer) are thereby removed. 

By-products formed during their preparation (e.g., ethylbenzene and divinyl-benzenes in styrene acetaldehyde in vinyl acetate) added stabilizers (inhibitors) autoxidation and decomposition products of the monomers (e.g., perox- 

The usual procedures of fractional, azeotropic, or extractive distillation under inert gases, crystallization, sublimation, and column chromatography, must be carried out very carefully. For liquid, water-insoluble monomers (e.g., styrene, Example 3-1), it is recommended that phenols or amines which may be present as stabilizers, should first be removed by shaking with dilute alkali or acid, respectively the relatively high volatility of many of these kinds of stabilizers often makes it difficult to achieve their complete removal by distillation. Gaseous monomers (e.g., lower olefins, butadiene, ethylene oxide) can be purified and stored over molecular sieves in order to remove, for example, water or CO2. 

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