If your goal ends up being to merge a bunch of polygons you already have (regions, city blocks, whatever) into a single polygon any GIS tool will allow you to do this (ESRI ArcGIS offers a trial). I also looks like http://www.gadm.org/ might have you data in the detail you are requesting: Click on:
- Download by Country
- Select United Kingdom and KMZ then hit ok
- Choose level 2 data in the bottom right of the map