Thermoset resin cross-link structure

The novolak resins themselves contain no reactive methylol groups and do not form cross-linked structures on heating. If, however, they are mixed with compounds capable of forming methylene bridges, e.g. hexamethylenetetramine or paraformaldehyde, they cross-link on heating to form infusible, thermoset structures. 

Thermosetting materials, which have a rigid, cross-linked structure for example, the polyester and epoxy resins. 

However, the most important furan resins are those produced with 2-furfuryl alcohol, for example, the 2-furfuryl alcohol-formaldehyde-based resins, which are normally synthesized by a condensation reaction catalyzed by acidic sites and promoted by heat [224] or the poly(furfuryl alcohol) thermosetting resin that is usually synthesized by the cationic condensation of its monomer 2-furfuryl alcohol, which polymerizes exothermically in the presence of a catalyst such as acid and iodine in methylene chloride, producing black, amorphous, and branched and/or cross-linked structures [225],... 

Polymers in the category of engineering resins and plastics may be classified in several ways. They may be thermoplastic or thermoset. They may be crystalline or amorphous and they may be single phase or multiphase systems. This would allow for eight types of materials except that thermosets, because of their irregular cross-linked structure, are never crystalline. Single phase polymers do not have discemable second phase structures of different chemical composition. Thus homopolymers and random copolymers are single phase polymers, even if they are semicrystalline and so contain amorphous and... 

The less simple polymers (like the epoxies, the polyesters and the formaldehyde-based resins) are networks each chain is cross-linked in many places to other chains, so that, if stretched out, the array would look like a piece of Belgian lace, somehow woven in three dimensions. These are the thermosets if heated, the structure softens but it does not melt the cross-links prevent viscous flow. Thermosets are usually a bit stiffer than amorphous thermoplastics because of the cross-links, but they cannot easily be crystallised or oriented, so there is less scope for changing their properties by processing. 

A thermosetting resin converts to an infusible, cross-linked plastic which is insoluble in any solvent after curing. Because of this irreversible cross-linking reaction, excellent physical properties such as heat resistance, creep resistance, mechanical strength, etc., are obtainable through design of the polymer structure. 

In the previous chapter we talked about linear polymers and have mentioned the concept of cross-linking only in passing. Linear polymers are usually thermoplastic they soften or melt when heated and will dissolve in suitable solvents. They can be remelted and shaped into their finished product with no further chemical reactions. Thermoset resins, those having elaborately cross-linked three-dimensional structures, set or harden by undergoing a chemical reaction during the manufacture of finished products. They decompose on heating and are infusible and insoluble. Their chemistry and physical properties are quite different from thermoplastic polymers. The important ones are now discussed. 

The chemistry of synthetic polymers is similar to the chemistry of small molecules wnth the same functional groups, but the physical properties of polymers are greatly affected by size. Polymers can be classified by physical property into four groups thermoplastics, fibers, elastomers, and thermosetting resins. The properties of each group can be accounted for by the structure, the degree of crystallinity, and the amount of cross-linking they contain. 

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