[Claymore]

Is it possible to take an amino-functional chemical (R-NH2) and bind it to a hydrocarbon (polypropylene or aromatics) by using a peroxide as a catalyst? Resulting in something along the lines of R-N-R'

I know that peroxides will open up bond sites on hydrocarbons by stripping off hydrogen atoms, leaving unsaturated carbons behind.

I also know that sulfonylazides can be used to functionalize hydrocarbon polymers, since at high temperature the azide will partially decompose to form reactive nitrenes that are capable of insertion into carbon-hydrogen bonds.

However, sulfonylazides are expensive, whereas the amino chemicals and peroxide catalysts are relatively cheap.

My thought is that the peroxide could potentially strip the hydrogen molecules from the amino (R-NH2 into R-N-...I think), which is then capable of insertion into the hydrocarbon. The N-H bond energies are lower than C-H energies so I assume the amine stripping would occur first...but the reaction could be taken in such a way to introduce the polymer later.

Is this a reasonable route or am I way off base and should be going about with another catalyst? A quick look on wikipedia yields some interesting paths...but involving chemicals I don't have on hand. http://en.wikipedia.org/wiki/Nitrene

[discodermolide]

Is it possible to take an amino-functional chemical (R-NH2) and bind it to a hydrocarbon (polypropylene or aromatics) by using a peroxide as a catalyst? Resulting in something along the lines of R-N-R'

I know that peroxides will open up bond sites on hydrocarbons by stripping off hydrogen atoms, leaving unsaturated carbons behind.

I also know that sulfonylazides can be used to functionalize hydrocarbon polymers, since at high temperature the azide will partially decompose to form reactive nitrenes that are capable of insertion into carbon-hydrogen bonds.

However, sulfonylazides are expensive, whereas the amino chemicals and peroxide catalysts are relatively cheap.

My thought is that the peroxide could potentially strip the hydrogen molecules from the amino (R-NH2 into R-N-...I think), which is then capable of insertion into the hydrocarbon. The N-H bond energies are lower than C-H energies so I assume the amine stripping would occur first...but the reaction could be taken in such a way to introduce the polymer later.

Is this a reasonable route or am I way off base and should be going about with another catalyst? A quick look on wikipedia yields some interesting paths...but involving chemicals I don't have on hand. http://en.wikipedia.org/wiki/Nitrene

This is not a method for the generation of nitrenes, see the Wiki page you quote. Amines and peroxides will give N-oxides.

[Claymore]

Is there a method then for binding amines to hydrocarbons?  I've been researching and checking my text book but most seem to just rely on starting with alkylhalides, which is not an option here...unless I was to pretreat it somehow, but might not be a reliable method in the future.

[discodermolide]

Is there a method then for binding amines to hydrocarbons?  I've been researching and checking my text book but most seem to just rely on starting with alkylhalides, which is not an option here...unless I was to pretreat it somehow, but might not be a reliable method in the future.

Yes you can insert nitrenes into C-H bonds or add them across C=C to give aziridenes which you can then open to give the amines.

[Claymore]

Sorry, I don't think I'm being clear.  That would be a method for functionalizing hydrocarbons with NH2 groups, but I instead need to use the R-NH2 group as a linker to the polymer.  

Edit - unless you're saying that the aziridenes can be used for R'-NH-NH-R cross-linking, which could be useful, but then I need to find some nitrenes to add into the polymer as well as figure out the amine-amine bridge reaction.

I guess what I'm trying to get at is that I need to convert my current amine functional compounds (R-NH2) into nitrenes (R-N:) which then enable me to bond the compound into alkyl compounds.

It looks like the first half of the question was asked back in 2006 on here but was never fully answered (of course, haha) - http://www.chemicalforums.com/index.php?topic=6919.0

Seems that I am in need of a compound (oxidizer is suggested in the previous thread) to strip the hydrogen groups from the amine without contaminating the resulting nitrene.

Alternatively, if its possible to convert the amine group into a sulfonylazide, that would enable the reaction as well.

[discodermolide]

Sorry, I don't think I'm being clear.  That would be a method for functionalizing hydrocarbons with NH2 groups, but I instead need to use the R-NH2 group as a linker to the polymer.  

Edit - unless you're saying that the aziridenes can be used for R'-NH-NH-R cross-linking, which could be useful, but then I need to find some nitrenes to add into the polymer as well as figure out the amine-amine bridge reaction.

I guess what I'm trying to get at is that I need to convert my current amine functional compounds (R-NH2) into nitrenes (R-N:) which then enable me to bond the compound into alkyl compounds.

It looks like the first half of the question was asked back in 2006 on here but was never fully answered (of course, haha) - http://www.chemicalforums.com/index.php?topic=6919.0

Seems that I am in need of a compound (oxidizer is suggested in the previous thread) to strip the hydrogen groups from the amine without contaminating the resulting nitrene.

Alternatively, if its possible to convert the amine group into a sulfonylazide, that would enable the reaction as well.

Sorry I mis-understood you, perhaps someone with more experience in polymer chemistry could jump in here. Not being a polymer chemist makes it difficult to see what you are getting at. I spent my entire career avoiding the formation of polymeric material.