Former teacher Sinnott, 56, became general secretary of the union in 2004. He previously served as the union's deputy general secretary, president and a member of its national executive.
The union described his loss as "grievous for the teaching profession, catastrophic for its members and desperately sad for his colleagues and friends". Acting general secretary Christine Blower said: "Our hearts go out to Steve's family. He would have wanted the union to go ahead with its campaigns because he believed in all of them."
Mary Bousted, general secretary of the Association of Teachers and Lecturers, said: "Steve Sinnott was a committed teacher and a passionate and effective trade unionist."
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