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tetraiodide
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[*] posted on 30-6-2018 at 15:19
Diamond based polymer.


Recently I've been reading about adamantane, which is the smallest carbon compound that bears the diamond lattice structure. I have been toying with the idea of trying to use it to polymer units, now of course the lattice would have to be part of the actual chain and not just a side branch to actuly take advantage of it, most of the ideas that I have revolve around using the gingard reaction, which isn't very practical for a polymer but its a thought, in the synthesis of adamantane there is a diketone generated that has the structure were after at it's core, there are still two carboxylic acid groups on the sides but they should have no affect on the strength of the core, I was thinking using that and reacting it with the gingard reagent form bromonated adamantane. Trouble with that is in order to put bromine in useful places you have to add more than two (it would seem), most likely tetrabromo adamantane,( the bromine attaches to the carbons that are attached to 3 other carbons not to the ones attached to two carbons) there's also the idea of pairing that either the tetraketo-, or tetraaldehyde derivative, (the ketones have to be attached to the carbons that are only attachex to two other carbons) and creating the 3d carbon lattice from. it wouldn't be diamond but I'd venture to guess if you could minimize inclusions of your reaction mixture it could be quite strong. Not practical at all it's somthing interesting to think about, anyone have any other ideas for an adamantane containing polymer?
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clearly_not_atara
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[*] posted on 30-6-2018 at 15:37


https://onlinelibrary.wiley.com/doi/abs/10.1002/pol.1964.110...



[Edited on 04-20-1969 by clearly_not_atara]
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tetraiodide
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[*] posted on 30-6-2018 at 21:10


Quote: Originally posted by clearly_not_atara  
https://onlinelibrary.wiley.com/doi/abs/10.1002/pol.1964.110...:)

How does everyone on this site seem to have access to this stuff ?every time I try to read these articles it's behind a paywall. (This one is actually glitching out on me and every time I try to open the article it just reloads the landing page.) But still is there somthing I'm missing?
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Sulaiman
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[*] posted on 30-6-2018 at 21:17


Many members have access to pay-walled documents due to their careers,
for complete amateurs such as me:
if a document seems REALLY useful to whatever I'm currently interested in,
then I can ask here https://www.sciencemadness.org/whisper/viewthread.php?tid=62...




CAUTION : Hobby Chemist, not Professional or even Amateur
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tetraiodide
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[*] posted on 30-6-2018 at 21:30


I have a friend who has a good bit of access to some things, but I'd say it's less than half of what I bother him for and it would be nice not to have to rouse him from half the planet away just to pirate a pdf. But this getting a bit off topic, is anyone here able to.... make it possible to view the above article?
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wg48
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[*] posted on 30-6-2018 at 22:30


Quote: Originally posted by clearly_not_atara  
https://onlinelibrary.wiley.com/doi/abs/10.1002/pol.1964.110...

Attachment: polyad.pdf (65kB)
This file has been downloaded 64 times
and an other general paper on Diamondoids
Attachment: Diamondoids402.pdf (1.9MB)
This file has been downloaded 94 times




Borosilicate glass:
Good temperature resistance and good thermal shock resistance but finite.
For normal, standard service typically 200-230°C, for short-term (minutes) service max 400°C
Maximum thermal shock resistance is 160°C
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tetraiodide
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[*] posted on 30-6-2018 at 22:34


Thank you wg48
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wg48
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[*] posted on 30-6-2018 at 23:45


Your welcome.

You should check out the sci hub thread it may be very usefull for you.




Borosilicate glass:
Good temperature resistance and good thermal shock resistance but finite.
For normal, standard service typically 200-230°C, for short-term (minutes) service max 400°C
Maximum thermal shock resistance is 160°C
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CobaltChloride
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[*] posted on 30-6-2018 at 23:47


You could always use sci-hub to access these documents tetraiodide : https://sci-hub.tw/https://onlinelibrary.wiley.com/doi/abs/1...
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[*] posted on 1-7-2018 at 11:16


the idea of diamantoid polymers kept me thinking the whole day. For 3d ones you could create the tetrabromo variant and do as suggested in the paper a wurtz reaction with alkaline metal.
Here something about making the bromo variants: http://www.chem.msu.su/rus/teaching/oil/spezprakt-adam.htm
Inclusions of salts might be problematic.
However linear polymers make me even more interested. Diamantane seems to be a better base structure for chains since it has two isolated orthogonal h's as endpoints. https://en.wikipedia.org/wiki/Diamantane
It is very hard to make though. The end to end dicarboxylic acid of diamantane might be worth a try, any idea of a synthesis?





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tetraiodide
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[*] posted on 1-7-2018 at 14:24


You have a point subskune,
I found this article that deals with synthesis of many diamondoids, including diadamantane substuted with halogens, hydroxyls, or carboxylic acids, specifically at those to apical points.
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[*] posted on 1-7-2018 at 15:03


Unsubstituted versions of such polymers with any significant molecular weight are going to have very poor solubility, if any at all. Processing from things like refluxing tetralin is usually distasteful.
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[*] posted on 2-7-2018 at 01:44


Quote:

Unsubstituted versions of such polymers with any significant molecular weight are going to have very poor solubility, if any at all. Processing from things like refluxing tetralin is usually distasteful.


It is more about the monomers, thex dissolve quite well in organics, page 26 is a nice start, their synthesis doesn't hit my spots at the end but the fact that the triple bonded carbons will brominate first is very useful. They provide a goog way from the bromo-diamantoid to acyl chloride, which would be the polymerisation starting point, combinded with an alcohol or an amine. That compund seems to be worth a try.

Now its up on making diamantane and finding a route to the right bromination. As an amateur I need larger quantity to perform tests. Buying does not seem to be an option, checked the web, nothing for privates and nothing in price range for eg. 50g.

The synthesis is hell for an amateur lab, lots of catalytic action, probably sensitive to contamination, finding a convenient, good yielded amateur suitable path will be worse than a needle in the haystack.




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[*] posted on 2-7-2018 at 05:04


Sci-hub.tw you only need the doi
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wildfyr
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[*] posted on 2-7-2018 at 08:42


Quote: Originally posted by subskune  


It is more about the monomers, they dissolve quite well in organics


What happens in this type of situation is that the oligomer will crash out of solution before high molecular weight can occur. Decently high molecular weight is typically desirable in polymers.

More generally if you want to actually DO anything with a polymer (even just get its properties) it usually either needs to be soluble in something reasonable or melt-processable. This issue is why there is a lot of research on processing or creating soluble P3MT (poly-3-methylthiophene). Its a very useful monomer for organic solar cell concepts, but its not soluble in useful solvents and degrades before melting.

The answer to preventing this is probably to use adamatyl monomers with long solubilizing alkyl chains attached. That will help get it into hydrocarbon solvents and even (hopefully) keep the polymer soluble in the monomer during polymerization.

[Edited on 2-7-2018 by wildfyr]
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tetraiodide
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[*] posted on 2-7-2018 at 12:50


Hmmm, solubility could be an issue, but there a number of workarounds, like, as wildfyr said using long side chains, down side to that is that I think it may make the end product low density (strands wouldn't pack as well) an idea of a friend of mine was to make it a copolymer with somthing more easily prossesed, which is sacrifice some strength in theory but make it more useful, make the linkages more suseptable, like by using amide bonds instead of carbon, or connect them with a substituted methyl or ethyl group, or use a solventless polymerization scheme and then "polymerize in place" like in the shape of the final product, or a preform to me machined later.

[Edited on 3-7-2018 by tetraiodide]
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[*] posted on 3-7-2018 at 02:13


if it has something like an mp or softening temperature, something comparable to the (salt based) nylon synthesis could be approached. If this is not the case, my first plan was to make a polyamide, as they are usually soluble in polar solvents, some under extreme conditions, but soluble.

Befor we can guess around, I think we should make it first, maybe its a surprise.
The synthesis is not doable for me, I dont't access the catalysts.
This paper seems to offer an alternative route:
https://link.springer.com/article/10.1134/S0965544108060029




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