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Because of the different chemistry of polyquats and silicones, each of these compounds uses a different method to stay on the hair. On hair, the damaged portions are typically negatively charged. The positive charges on the polyquat allow it to stick to these negative sites on the hair. It is a bit like two magnets being attracted to each other.

Silicones are not usually charged, but stay on the hair because of their incompatibility with water. If you put a drop of silicone in water, it will not dissolve, no matter how much you stir it. When a silicone product is put on your hair, it deposits and resists being washed off.