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Simply put, yes you can.
But it isn't the ideal stuff. As it is a single pack product, it takes a very long time to cure, and so isn't dimensionally stable. The larger the project scale you are working on, the bigger an issue this is. It also outgasses quite a lot, which can cause other problems. However there's no reason you can't spray it on, shape it as much as you want to, and then cover it with a layer of fibreglass. From there, the spray foam underneath won't have too much affect. Don't be surprised if polyester/vinylester resins attack it a bit and eats out a few holes, some of them are more chemical resistant than others so will depend on the specific product you are using. Would pay to do a small test first before covering your entire sculpted work and watching it melt. If it does react, give it a coat of epoxy first.
Personally, I prefer to use the 2k expanding foam. The spray stuff seems so simple a solution, but for one it actually doesn't expand very much and you need a lot more than you think (and it's ludicrously expensive for what it is). The 2k stuff is a touch harder to use, as it is a pourable foam and hence you need to work out how to put it where you want it. But for jobs like this, I simply let it start to foam for 10 seconds or so, and then use a brush to slather it where I want it. It gets extremely sticky at this point, so it will stay there. Might take a couple of applications, but when it fully cures in 15 minutes and costs about a tenth of the spray on stuff, it is really more economical.
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