Stir or shake the paint so it is well blended. Pour 6 to 8 ounces of paint into a small container that is easy to hold. Dampen a sash brush and gently flex the bristles back and forth.
Cut the silicone mat with scissors to make a barrier, about 5 by 10 inches. Hold the sash brush in one hand and the silicone barrier in the other. Press the edge of the silicone mat into the crack between the window frame and the jamb. Bend the mat away from the window frame.
Paint the window frame, with the silicone mat in place. When you have completed one section, remove the mat and reposition it further along the edge of the window. Paint the next section, always painting on the same side of the mat. Wipe away drips with a cleaning rag before they dry.
Allow the paint to dry, according to the manufacturer's directions. Once the paint on the window frame has dried, paint the jamb. Insert the silicone mat into the crack between the window frame and the jamb. Bend the mat toward the frame. Paint the first section of the jamb. Reposition the mat and paint the next section. Continue until you have painted the entire window jamb. If additional paint coats are needed, allow the paint to dry, then repeat this process.