As of January 2019 Google released their own extension for same exact purpose so I recommend switching to it https://chrome.google.com/webstore/detail/picture-in-picture-extens/hkgfoiooedgoejojocmhlaklaeopbecg/
Picture in picture mode can be forced with this extension even if website doesn't support it.
- Click the extension icon whenever any kind of video is present on the current page.
- Right click on the video and click "Force picture in picture mode"
Alt + shift + s
on Windows orCmd+Shift+S
on Mac whenever video is present on the page- Click PiPPY icon which is embedded in supported players(currently only on Twitch.tv)
Extension uses icons which are provided by Icons8