Does anyone know if it is possible to publish directly from MS word to a published site with workflow in SharePoint 2010? The articles will have images and ideally I would like to get the images from the asset library, type my content and submit the page for approval.
I believe what you are trying to do is akin to posting to blog, basically transferring your content to SharePoint for display.
In this case, no, Word cannot perform this action. You can use an editor and get the content in with just a few more steps, but Word isn't the best choice because it's difficult to get at HTML conversion.
I would use the MS Live Writer tool, which is a free download.
With live writer you can format your text and pictures (see below about pictures), change the view to HTML and copy out the code. Now on your publishing page, edit the content block and from the toolbar select the view HTML button (lookl like a two brackets and a pencil) and past in your HTML.
Incidentally you don't require a publishing site to do this, you can use this with any rich text box inside SharePoint as well as the Content Editor Web Part.
If you want to include pictures, you need to upload those pics to a SharePoint library first. You can then grab the URL for those pics as the source and use them in Live Writer as you compose, and when you past the code in, it will still work.
You could do this from word, but you would need to save your document as an HTML document, then grab the code from there, using Live Writer or similar will at least cut out that step for you.