I read your question and realised I was looking for the exact same thing (I think). I have since worked it out. The actual code only ends up being 5 lines, but I have added comments so you can see what each bit does - works like a charm!
'----------------------------------------------------------------
'STEP 1
'DETERMINE THE ACTUAL NAME OF CURRENT DEFAULT PRINTER
'Retrieve name of current default printer and
'Display printer name in a message box
'-----------------------------------------------------------------
'This constant is used to hold the title of the message box
Const Caption As String = "The Default Printer Name Is"
'This variable is used to hold the name of the active printer
Dim DefaultPrinterName As String
'Assign the active printer to the variable
DefaultPrinterName = Application.ActivePrinter
'Display the message box
MsgBox DefaultPrinterName, vbInformation, Caption
'THE RESULT IS A MESSAGE BOX DISPLAYING THE ACTUAL PRINTER NAME
'-----------------------------------------------------------------
'STEP 2
'PRINT TO PRINTER OTHER THAN CURRENT DEFAULT
'-----------------------------------------------------------------
'Retrieve name of current default printer and hold as variable
'-----------------------------------------------------------------
'This variable is used to hold the name of the active printer
Dim DefaultPrinterName As String
'Assign the active printer to the variable
DefaultPrinterName = Application.ActivePrinter
'-----------------------------------------------------------------
'Print to other printer, eg Adobe PDF (becomes default printer)
'-----------------------------------------------------------------
ActivePrinter = "Adobe PDF"
Application.PrintOut Range:=wdPrintAllDocument, _
Item:=wdPrintDocumentContent, Copies:=1
'-----------------------------------------------------------------
'Change default printer back to original default printer
'-----------------------------------------------------------------
Application.ActivePrinter = DefaultPrinterName
