There are some bugs that seem to reappear again after some time in Libreoffice. One of these bugs is the handling of connections to remote cupsd servers and their printer queues. See:
In my present installation of Libreoffice 184.108.40.206 on an Opensuse 13.1 system with KDE 4.13 this bug reappeared. (The libreoffice packages are from the standard Opensuse 13.1 update repository). Currently the connection to our remote cups printer queues is lost after 5 minutes. This is the standard timeout for idle connections on the cups server (see the settings for the cupsd daemon). LibreOffice obviously does not reactivate the connection - at least not on my systems in their present status.
Deinstalled "libreoffice-kde4" as a cause ?
I did not check all and every LibreOffice setting that may influence this behavior. Furthermore, due to other problems with a previous LibreOffice release I had uninstalled the KDE extension package "libreoffice-kde4" on my machine - although I use KDE4. Instead I used the "libreoffice-gnome" package which worked more reliable for some aspects. So, I cannot exclude at the moment that the printing problem had to do with my deinstallation of "libreoffice-kde4".
The Kamppeter workaround may help
I had and have no intention to change my cupsd settings on the print server, because LibreOffice has a problem with reopening connections. What still helped in my situation and despite the deinstalled "libreoffice-kde4" was to change the print dialog from "LibreOffice dialog" to the standard system dialog. This workaround was described some time ago by Till Kamppeter; see "https://bugs.launchpad.net/ubuntu/+source/libreoffice/+bug/1020048/comments/33". It requires that one activates advanced options under
Tools >> Options >> LibreOffice >> Advanced >> Set Checkbox "Enable experimental features".
Then go to the "general" settings and deactivate "Use LibreOffice dialogs" under "print dialogs:
Tools >> Options >> LibreOffice >> General >> section "Print dialogs" >> Unset Checkbox "Use LibreOffice dialogs".
This worked in my case and maybe it helps others, too. If it does not I would also try to reinstall "libreoffice-kde4" again in case you use KDE4 (and see if it works better again than in some previous versions).