early 15c., "action of joining one thing to another," also "agreement, accord," also "state of matrimony," from Anglo-French unioun, Old French union (12c.), from Late Latin unionem (nominative unio) "oneness, unity, a uniting," also in Latin meaning "a single pearl or onion," from unus "one," from PIE root *oi-no- "one, unique."
Sense of "action of uniting into one political body" is attested from 1540s. Meaning "group of people or states" is from 1650s. Short for trade union, it is recorded from 1833. U.S. political sense is attested from 1775; used especially during the Civil War, in reference to the remainder of the United States after the Southern secession.
word-forming element used to make verbs, Middle English -isen, from Old French -iser/-izer, from Late Latin -izare, from Greek -izein, a verb-forming element denoting the doing of the noun or adjective to which it is attached.
The variation of -ize and -ise began in Old French and Middle English, perhaps aided by a few words (such as surprise, see below) where the ending is French or Latin, not Greek. With the classical revival, English partially reverted to the correct Greek -z- spelling from late 16c. But the 1694 edition of the authoritative French Academy dictionary standardized the spellings as -s-, which influenced English.
In Britain, despite the opposition to it (at least formerly) of OED, Encyclopaedia Britannica, the Times of London, and Fowler, -ise remains dominant. Fowler thinks this is to avoid the difficulty of remembering the short list of common words not from Greek which must be spelled with an -s- (such as advertise, devise, surprise). American English has always favored -ize. The spelling variation involves about 200 English verbs.
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Definitions of unionize from WordNet
recruit for a union or organize into a union;
We don't allow people to come into our plant and try to unionize the workers