There are some items which will not work if the computer is not domain joined:
PolicyPak Browser Router will work as expected when routing from browser to browser, but Chrome's plug in might need to be activated. See this video for details
PolicyPak Browser Router may or may not work as expected with "External links", say, those from Outlook or Skype or AcroBat. This is because PPBRAgent needs to be expressly specified as the "Default Browser" inside Windows 10; and with a Non-Domain Joined machine, PolicyPak cannot set this value ourselves. You can set it manually on a per-computer basis.
PolicyPak Application Manager will work as expected, except managing CHROME when non-domain joined. Chrome simply has a self-imposed limitation for non-domain joined machines.
PolicyPak File Associations manager will not work unless the machine is domain joined. So if you want to use PolicyPak File Associations manager with PolicyPak Cloud, Group Policy or MDM editions, then the machine must be domain joined first, and then get its directive from the method of your choosing.