Old English þan, conjunctive particle used after a comparative adjective or adverb, from þanne, þænne, þonne "then" (see then). Developed from the adverb then, and not distinguished from it by spelling until c. 1700.
The earliest use is in West Germanic comparative forms introducing the second member, i.e. bigger than (compare Dutch dan, German denn), which suggests a semantic development from the demonstrative sense of then: A is bigger than B, evolving from A is bigger, then ("after that") B. Or the word may trace to Old English þonne "when, when as," such as "When as" B is big, A is more (so).