Try this link:
http://www.darkcoding.net/software/printing-word-and-pdf-files-from-python/
from win32com import client
import time
word = client.Dispatch("Word.Application")
def printWordDocument(filename):
word.Documents.Open(filename)
word.ActiveDocument.PrintOut()
time.sleep(2)
word.ActiveDocument.Close()
word.Quit()