Cross-linking of epoxides

Barton JM, Monitoring the cross-linking of epoxide resins by thermoanalytical techniques, 25-32,... 

Fig ure 7.9 Cross-linking of epoxidized mcl-PHA using hexamethylene diamine (HMDA) as a cross-linker. 

When the epoxide is to be used, a basic curing agent such as a tertiary amine, R3N, is added to cause the individual prepolymer chains to link together. This "cross-linking" of chains is simply a base-catalyzed epoxide... 

In conclusion, we would like to mention that, in addition to this new direction, a large consumer of metal alkoxides (initially aluminium and titanium) is by tradition the technology of materials, where the alkoxides are used for hy-drophobization and for cross-linking of the polyhydroxocompounds, epoxides and polyester resins, and organosilicon polymers. The products of the partial hydrolysis and pyrolysis of alkoxides — polyorganometalloxanes — are applied as components of the thermally stable coatings [48J. 

Unsaturated resins are usually mixtures of vinyl monomers and prepolymers, such as unsaturated polyesters, polyurethane acrylates, and ac-rylated epoxides of the bisphenol A type. Polymerization of styrene-based resins involves the formation of a three-dimensional network via the cross-linking of prepolymer chains by styrene radicals. These standard thermoset resins are therefore characterized by great hardness (Shore D over 80, DIN 53505, arbitrary scale 0-100 based on the penetration of a needle point in the tested material), do not melt, and are not soluble in organic solvents. 

Photogenerated acids can also catalyze various other reactions, e.g. the cross-linking of polymers containing epoxide groups (see Chart 9.4), or Claisen and pinacol rearrangements in polymers as shown in Scheme 9.5. Resist systems operating on the basis of these reactions have been proposed [12, 13]. 

Lipoxygenase (LOX) converts polyunsaturated fatty acids, such as linoleic and linolenic acids, to lipid hydroperoxides (Figure 2)(52,73,74). The lipid hydroperoxides then form hydroperoxide radicals, epoxides, and/or are degraded to form malondialdehyde. These products are also strongly electrophilic, and can destroy individual amino acids by decarboxylative deamination (e.g., lysine, cysteine, histidine, tyrosine, and tryptophan) cause free radical mediated cross-linking of protein at thiol, histidinyl, and tyrosinyl groups and cause Schiff base formation (e.g., malondialdehyde and lysine aldehyde) (39,49,50,74-78). 

The cross-linking of these polymers is further discussed in Epoxide adhesives curatives. 

Epoxide resins comprise a broad and important class of adhesives. In the article Epoxide adhesives, an introduction was given to some of the molecules to which the epoxy groups in these materials may be attached. The cure (cross-linking) of epoxies may be achieved... 

Notably, the Dimroth rearrangement has been shown to occur in nature with the purine and pyrimidine bases of nucleosides and nucleotides upon exposure to certain chemical entities. For example, 3,4-epoxybutene, styrene oxide and other aromatic hydrocarbon based epoxides, butadiene and butadiene monoxide, chloroethylene oxirane, chlorambucil, and acrolein, " among others, have been shown to facilitate Dimroth rearrangement, and in some cases subsequent cross-linking of DNA. While interesting from a mechanistic and biological perspective, these reactions will not be reviewed here. 

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