Phenolics Silicon modification

There are important modifications of alkyds that help in specific applications. Phenolics can be added to improve film hardness and water resistance, but these confer increased yellowing tendencies on the final coating. Silicones impart heat resistance and exterior durability. Styrene increases the drying speed. Methyl methacrylate when added gives faster drying properties and improves the color and durability of the coating. 

Although blending with other coating resins provides a variety of ways to improve the performance of alkyds, or of the other resins, chemically combining the desired modifier into the alkyd structure eliminates compatibility problems and gives a more uniform product. Several such chemical modifications of the alkyd resins have gained commercial importance. They include vinylated alkyds, silicone alkyds, urethane alkyds, phenolic alkyds, and polyamide alkyds. 

The goal of chemical modification of phenolics is the improvement of chemical and physical properties and to tailor the polymer to specific applications. Phenolics can be modified during synthesis by use of substituted monomers or monomer mixtures and after synthesis by electrophilic ring substitution, nucleophilic hydroxyl group capping, and reactions with compounds of boron, phosphorous, silicon, and titanium. 

Alkyd chemistry lends itself to further modification beyond choice of polyol, dibasic acid, and drying oil. Vinyl-modified alkyds, for example, are produced for more durable and quicker drying films, although with some sacrifice in crosslinking rate and consequent development of solvent resistance. Styrene, vinyl toluene, and methyl methacrylate are the most commonly used modifiers. In the presence of a free radical initiator, vinyl polymer will graft onto the alkyd. Tack-free time (i.e. a surface-dry film) may be reduced from 4 to 6 hoius for an unmodified alkyd to 1 hour in styrenated form. Acrylics, silicones, phenolic resins, and natural resins are likewise used to tailor film gloss, flexibility, durability, and drying time for certain applications. 

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