It's a computed property. Stealing from here, you just need to add a call to RefreshCache
before accessing the property:
Dim domainGroup As New DirectoryEntry("LDAP://our.domain/CN=Domain Users,CN=Users,DC=our,DC=domain")
domainGroup.RefreshCache(New String() {"primaryGroupToken"})
Dim domainGroupGroupToken As String = domainGroup.Properties("primaryGroupToken").Value.ToString()
(Not tested, my VB is a bit rusty)