There are typically two types of glue on an envelope: one on the upper flap that the consumer uses to seal the envelope, and another that is used to hold the entire envolope together. The first of the two glues, the one used to seal the letter, is usually a gum, such as the natural gum arabic which comes from acacia trees or a synthetic gum made from dextrans, a product of sugar fermentation. A more permanent, starch-based glue is used to hold the rest of the envelope together. It is commonly made from corn, wheat, potatoes, and rice.
If the glue used to seal envolopes does not sound appealing to you, recipes to make your own are quite popular. Check a few out here.
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