To do a bulk mailboxexport on exchange 2010 for all mailboxes, it mus tbe to a share and the share needs appropriate permissions.
Filter the get-mailbox to get a subset of the mailboxes.
$a=get-mailbox
foreach ($u in $a) {
$u.alias
$ua=$u.alias
new-mailboxexportrequest $ua -filepath \\mailserver\exportedemail\$ua.pst
}