RESOLVED by removing PortableApps version and installing WinPenPack.
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Office won’t let me change the temporary files path
I go to Tools —> Options —> LibreOffice —> Paths —> Temporary files
The default location is: C:\Users{username}\AppData\Local\Temp\LibreOfficePortableTemp\temp
I change it to a new location, then I close Office, then when I run it again the path is back to the default location.
The same happens in both OpenOffice and LibreOffice.
Windows 10, Office v. 5.4.5.1