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As per @Airhead,
and,
there may be a couple of wooden wedges, (sometimes recycled from previous wooden window frame), and some expanding foam to quickly fill the irregular void between the uPVC frame and the masonry.
The foam then allows an inadequate thickness bead of sealant to be applied giving the impression of weatherproofness.
You can't 'lock' a uPVC window frame into masonry.
The uPVC will react much more quickly to temperature changes, the frame will expand and contract, as you can see in your picture by 2-3-4mm.
You need to apply an elastomeric sealant, one that can accomodate the movement you can see.
The best elastomeric sealants claim '25% movement accomodation factor', in total.
This means you need for a durable waterproof seal, to apply a bead 16mm wide, and around 8-10mm deep between the masonry and the uPVC frame.
Soudal Fix All High Tack Adhesive & Sealant, (Toolstation 84704) comes in white,
so you save the painting you envisaged.