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Epoxy Cure Chemistry Part 4: Nucleophiles in Action

The document discusses nucleophilic addition reactions of epoxides. Specifically: - Epoxides react with nucleophiles through an SN2 mechanism where the nucleophile attacks the electrophilic carbon of the epoxide, opening the ring. This relieves ring strain and forms a substituted alcohol product. - Amines act as nucleophiles that react with epoxy groups, crosslinking the chains. The reaction proceeds by the amine attacking the epoxy carbon, forming an intermediate that then breaks the epoxy ring and forms an alcohol and regenerated amine group. - Diamines can react at both ends, crosslinking two epoxy chains and

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92 views4 pages

Epoxy Cure Chemistry Part 4: Nucleophiles in Action

The document discusses nucleophilic addition reactions of epoxides. Specifically: - Epoxides react with nucleophiles through an SN2 mechanism where the nucleophile attacks the electrophilic carbon of the epoxide, opening the ring. This relieves ring strain and forms a substituted alcohol product. - Amines act as nucleophiles that react with epoxy groups, crosslinking the chains. The reaction proceeds by the amine attacking the epoxy carbon, forming an intermediate that then breaks the epoxy ring and forms an alcohol and regenerated amine group. - Diamines can react at both ends, crosslinking two epoxy chains and

Uploaded by

siska pebriani
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Epoxy Cure Chemistry Part 4:

Nucleophiles in Action
The image below shows an SN2 nucleophilic addition to an epoxy group

As I wrote this post, it harkens to the days when Morrison and Boyd was a constant companion
in my backpack! For those of you who might not be familiar, Organic Chemistry by Morrison
and Boyd is a 1250 page classic textbook used extensively in “Orgo” classes when I was an
undergrad in the 1970’s
In the last three posts we provided the basics for understanding the curing of epoxy resins with
amine hardeners. In this post we will take a deep dive onto the chemistry of the epoxy amine
crosslinking reaction as an example of how chemical reactions cause crosslinking in thermoset
networks.

Summary of nucleophilic addition to epoxies:

 Epoxides are much more reactive than simple ethers due to ring strain.
 Nucleophiles attack the electrophilic C of the C-O bond causing it to break,
resulting in ring opening.
 Opening the ring relieves the ring strain.
 The products are typically 2-substituted alcohols.
 Epoxides can react with a large range of nucleophiles

Reactive nucleophiles attach the least hindered end of the epoxide in an S N2 type
reaction resulting in the formation of the more substituted alcohol. Another way to think
about this is that a nucleophile is a “hot tamale” at the dance looking for a “lonely
carbon.” The amine nucleophile has high electron density from the lone electron pair on
the nitrogen, and the unhindered carbon on the epoxy ring has low electron density
(remember oxygen has two electron pairs that withdraw electrons making the carbon
electrophilic). Let’s take a closer look on how epoxy is crosslinked by a diamine.
The diamine’s electrons attack the electrophilic carbon next to the epoxide oxygen, resulting in a
negative charge on the oxygen and a positive charge on the nitrogen.

oxygen’s extra pair of electrons abstracts a hydrogen from the ammonium nitrogen, making an
alcohol group and an amine group (reforms the nucleophile which can react with another epoxy
group).

Another amine (nucleophile) adds to another epoxy group forming a tertiary amine (no longer
reactive, since it doesn’t have an active hydrogen).
epoxide groups add to the amine at the other end of the diamine, tying together two growing
epoxy chains and forming a crosslink (red oval).

Diamines can form four bonds (f = 4 for most diamines) so they can build a network
quickly. With continued reaction of amines and epoxies, the molecular weight increases
dramatically along with the crosslinking reactions results in a highly crosslinked network as can
be seen in the following:
In the above schematic, the R in the diamine can be a variety of chemical structures
from aliphatic chains ( for example the Jeffamines from Huntsman) to highly aromatic
chains like 4,4’ diaminodiphenyl sulfone (DDS) used in structural composites. As
discussed previously, there are also a wide range of epoxies (aliphatic and aromatic)
which can also be used to tailor the network structure and properties.

Now that we have established the basics of how chemical crosslinks are formed, the
next post will give examples of how to “put it all together” to develop useful thermoset
networks.

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