Hi,
For your issue,
1.Is the same net the users using?
2.Is there any gateway deployed?Did the users open the app installed on the session host or the app just published on the web?
3.Have you compare the procmon of the normal users with the issue users?
4.Maybe you could try to view the even log the time the issue happens.note the time the user starts opening the app and the time the app is opened.check the event log in this time period.
you can refer to the following logs:
event viewer>windows logs>Application\system\setup
event viewer>Application and services logs>microsoft>windows>remote app and desktop connections\RemoteDesktopServices-RdpCoreTS\TerminalServices-ClientActiveXCore\TerminalServices-LocalSessionManager\TerminalServices-RemoteConnectionManager
5.If this user use the other office app will the same issue happen?
6.You could create a test account and let the issue user log with this account and then open the app to see if the same issue happen in this way.