Unsaponifiable material?

OKay, I know this is getting really nerdy... but I have not found a specific chemical explanation of what "unsaponifiable" material actually is... only explanations that continue to echo the fact that it is the portion/fraction/leftover remains that cannot be saponified into soap (using alkali substances, namely alkalki hydroxides).  So they cannot be fatty acids, fatty alcohols, wax esters (acid+alcohol), but they are soluble in ether and some organic solvents.  If someone can determine all of that, why couldn't they just identify WHAT IT IS then.  I'm thinking it can't just be long-chain hydrocarbons.  And even though beeswax is a complex mix of longer chains waxes, it is still saponifiable.  This is developed from a plant (olive trees), so there can't be that many possibilities, right?

So where I'm getting this from is the increasingly popular olive plant products that are making their way into the natural skincare market.  It used to be produced by B&T of Italy, but was bought up by Hallstar (which I think is now the 2nd largest natural ingredient making business).  They are making olive based emollients and emulsifiers; for example "Olivem" (consisting of cetearyl olivate and sorbitan olivate); and they have an "olive wax" product that is some unspecified blend of hydrogenated olive oil and "olive oil unsaponifiables".

Even though I always obtain Certificates of Analysis and Technical Data sheets with all of my ingredients purchased from different suppliers, this information is not available from HallStar, so it cannot be passed along to suppliers.

In any case, finding out the chemical composition of "unsaponifiables" isn't propriety because they are not "synthesizing" or creating it in a laboratory; so since this is a natural "leftover" substance, it shouldn't be that difficult to get to the core of it.  I can't be the only one that's ever had that question.

Anyone knowledgeable on this one?


Comments

  • johnbjohnb Member, Professional Chemist
    The term "saponifiable" should only be applied to materials capable of forming a soap when hydrolysed by appropriate treatment with an alkali. This being so, the only materials capable of saponification are fats ( which are defined as the fatty acid esters of glycerol). Naturally occurring fats are seldom 100% glyceride and contain minor amounts of other materials which may not be reactive under the conditions imposed by the saponification process - these are the unsaponifiables.



  • johnbjohnb Member, Professional Chemist
    Rereading the above I notice part of a sentence has been lost somewhere. What it should read is:

    The term "saponifiable" should only be applied to materials capable of forming a soap and glycerol when hydrolysed by appropriate treatment with an alkali. This being so, the only materials capable of saponification are fats ( which are defined as the fatty acid esters of glycerol). Naturally occurring fats are seldom 100% glyceride and contain minor amounts of other materials which may not be reactive under the conditions imposed by the saponification process - these are the unsaponifiables.
  • BobzchemistBobzchemist Member, PCF student
    edited May 2017
    I've always suspected that "unsaponifiable" actually means in practice "all the stuff that's left behind after we turn the oil into soap". 

    Turning reaction byproducts into cosmetic materials isn't a new idea - it's been done for decades, at the very least. I don't think that the lack of information has to do with trade secrets, etc. - it's just that no one has the time or the money to run a full-scale chemical analysis on this raw material. (Or any sort of analysis, for that matter).

    From a supplier standpoint, why would you bother to analyze this for a CoA if it sells perfectly well without one?
    Robert Zonis, Sr. Formulation Chemist, Beaumont Products "All opinions and comments expressed are my own, have no relation to Beaumont Products, are fully copyrighted, and may not be used without written permission."
  • Oh, I didn't think that it was some kind of a trade "secret", but rather just not important for most people to care about exploring.... that's why I said it's kinda nerdy to be wondering.  So I agree with your layman's explanation of "all the stuff that's left behind" after turning fatty acids into soap... but I guess another way to ask my question is, by putting fatty acids through the saponification process (and I know that separates out the glycerin), there is something about that "stuff" that leaves it UNABLE to be saponified... so WHAT is that stuff that cannot be saponified (I'm wondering in terms of the chemical structure)... it would have to have a different chemical structure that the original fatty acids, otherwise you could just take the "leftovers" and put it through the process of saponification again... I'm sure there's a reason why it cannot be "saponified" and I'd like to know what those substances are comprised of... I think this is still in the realm of chemistry... if we were dealing with energy, I'd ask a physicist.

    I can't be only the one that's ever had this question, so I'll to find the people that got to the bottom of the answer... know where they are? LOL!

  • BobzchemistBobzchemist Member, PCF student
    Brenda,

    It is certainly within the realm of chemistry, but...I'm not sure that anyone has ever quantified precisely what's in the different varieties of olive oil, so that the only descriptions I can find are rather vague: glycerol, phosphatides, pigments, flavor compounds, sterols, and microscopic bits of olive.

    But - the question of how these are altered by going through the saponification process will most likely remain unknown. As I said before, no one has the time or money to actually find out.
    Robert Zonis, Sr. Formulation Chemist, Beaumont Products "All opinions and comments expressed are my own, have no relation to Beaumont Products, are fully copyrighted, and may not be used without written permission."
  • What I have been told by one chemist now, and his colleague concurred, is that since there is a significant fraction of "squalene" in olive oil, this will be the majority of what makes up the "unsaponifiables" portion.  Because it's an unsaturated hydrocarbon, it cannot go through the saponification process the way fatty acids do, but still remains well in tact at the end.  Once you hydrogenate natural squalene, it becomes "squalane", but still provides the same texturing, moisturizing, and other aesthetic properties of it's unadulterated counterpart "squalene"; it just has a much longer shelf life after that.  He commented that there could be small remnants of other phytosterols, polyphenols, and vitamin or antioxidant compounds, but those will have little impact because it would be such a small fraction.  So I will just accept that the unsaponifiable portion of the olive oil is squalene (or squalane once it's been hydrogenated).  I really like the results it provides in the emulsions I've put together.
  • If it is squalene which is a triterpinoid with mucho double bonds--it could be comedogenic,Hope it is squalane.
  • johnbjohnb Member, Professional Chemist
    Olive oil derived squalene/ane is a marketed product and far from being a mysterious "unsaponifiable". Available from eBay and Amazon (and many other places) quite easily.

    You might like this https://www.ncbi.nlm.nih.gov/pubmed/10908812

  • Yes, the olive squalene and squalane is a separate product by itself, that is ONLY that substance; when you buy olive squalene/ane it should not have any other substances in it.   With the "unsaponifiables" it can include a list of other things, that are mentioned above.  Even though a significant portion of it includes both squalene and squalane, they can only estimate a general proportionate range, and no one's going to guarantee any specific amounts.  If someone really wanted to just have squalane/ene they could buy that pure substance on its own.  And "BobzChemist" makes a good point that it's a triterpinoid, so lots of double bonds, and could be comedogenic for some face formulas.  I think it's very complimentary to body lotions, and I find it ideal for use in a luxurious hand cream.
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