<?php


$times = array('Time 01','Time 02','Time 03','Time 04','Time 05','Time 06','Time 07','Time 08','Time 09','Time 10','Time 11','Time 12','Time 13','Time 14','Time 15','Time 16','Time 17','Time 18','Time 19','Time 20');

function gera_jogos($times) {
    shuffle($times);
    return call_user_func_array('array_combine', array_chunk($times, sizeof($times) / 2));
}

for ($i = 0; $i < count($times); $i += 1) {
  echo "<pre>";
    print_r(gera_jogos($times));
}