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I played around with it too. The silicone mold-making materials are more flexible - so they stretch further on removal but have poorer accuracy. The polyurethane mold materials are preferred because you can get fairly high duro ratings which makes the mold much stiffer and more accurate, but beware that some of them have quite low strength, so they tear easily when stretched.
And yes, vacuum is necessary unless you're using "water thin" materials, and is a benefit even then. You need time for the vacuum to work, which means you need a slower cure (mix, vacuum, mold), and it's all messy and time consuming. I eventually got my process to an acceptable level, then found another way to achieve my desired result.
Clifford Heath