No clue, I've never used Chrome.
Edit: found this, try printing something not from Chrome
When you print through Chrome, it brings up the printer last used. If somebody prints and saves as PDF, the next time they print, Save as PDF will be the options that shows up.
Stole from another forum, something to try
I found a solution. Unfortunately I can't find a PDF to demonstrate. Any way, when you click on Print or use CTRL-P, go to the far left of the screen. If you look at or near the SAVE icon there's a arrow that can be selected. Click on it and you can change the default (cool move, Google!) to print instead of save.
Or try Ctrl Shift P
All Post are Just My Opinion