Thermoset polymerisation

The final stage of thermoset polymerisation occurs in the moulding press. Under pressure, the partially reacted compound undergoes crosslinking reactions between the molecular chains. Thermoset monomers with three or more reactive ends lead its molecular chains to crosslink in three dimensions. Flexible thermosets have longer chains with fewer crosslinks. 

The thermoplastic or thermoset nature of the resin in the colorant—resin matrix is also important. For thermoplastics, the polymerisation reaction is completed, the materials are processed at or close to their melting points, and scrap may be reground and remolded, eg, polyethylene, propjiene, poly(vinyl chloride), acetal resins (qv), acryhcs, ABS, nylons, ceUulosics, and polystyrene (see Olefin polymers Vinyl polymers Acrylic ester polymers Polyamides Cellulose ESTERS Styrene polymers). In the case of thermoset resins, the chemical reaction is only partially complete when the colorants are added and is concluded when the resin is molded. The result is a nonmeltable cross-linked resin that caimot be reworked, eg, epoxy resins (qv), urea—formaldehyde, melamine—formaldehyde, phenoHcs, and thermoset polyesters (qv) (see Amino resins and plastics Phenolic resins). 

If the bismaleimide-amine reaction is carried out with a deficiency of amine the polymer will have terminal double bonds which allows a cure site to give a thermosetting polymer via a double bond polymerisation mechanism. This approach was developed by Ciba-Geigy with their product P13N (Figure 18.42). 

Such reactions allow chain extension and/or cross-linking to occur without the elimination of small molecules such as water, i.e. they react by a rearrangement polymerisation type of reaction. In consequence these materials exhibit a lower curing shrinkage than many other types of thermosetting plastics. 

Compression moulding is one of the most common methods used to produce articles from thermosetting plastics. The process can also be used for thermoplastics but this is less conunon - the most familiar example is the production of LP records. The moulding operation as used for thermosets is illustrated in Fig. 4.62. A pre-weighed charge of partially polymerised thermoset is placed in the lower half of a heated mould and the upper half is then forced down. This causes the material to be squeezed out to take the shape of the mould. The application of the heat and pressure accelerates the polymerisation of the... 

Can be further polymerised and processed into thermoset plastic products having higher impact properties than do phenolics... 

PP-g-MA) silicate nanocomposites and intercalated thermoset silicate nanocomposites for flame-retardant applications were characterised by XRD and TEM [333], XRD, TEM and FTIR were also used in the study of ID CdS nanoparticle-poly(vinyl acetate) nanorod composites prepared by hydrothermal polymerisation and simultaneous sulfidation [334], The CdS nanoparticles were well dispersed in the polymer nanorods. The intercalation of polyaniline (PANI)-DDBSA (dodecylbenzene-sulfonate) into the galleries of organo-montmorillonite (MMT) was confirmed by XRD, and significantly large 4-spacing expansions (13.3-29.6A) were observed for the nanocomposites [335],... 

The polymers can be categorised as formaldehyde containing and formaldehyde free and as thermoset or thermoplastic resins. Typical formaldehyde containing resins are melamine formaldehyde sulfonamide resins, where the sulfonamide is ortho and para toluenesulfonamide. The sulfonamide, which is a solvent for the dye, undergoes a condensation polymerisation with formaldehyde and melamine, the latter acting as a cross-linking agent. Non-formaldehyde, thermoplastic resins are usually polyamides and polyesters. 

If the monomers are bifunctional, as in the above example, then a linear polymer is formed. Terminating monofunctional groups will reduce the average degree of polymerisation. Polyfunctional monomers, such as glycerol and phthalic acid, are able to form branching points, which readily leads to irreversible network formation (see Chapter 9). Bakelite, a condensation product of phenol and formaldehyde, is an example of such a space-network polymer. Linear polymers are usually soluble in suitable solvents and are thermoplastic - i.e. they can be softened by heat without decomposition. In contrast, highly condensed network polymers are usually hard, are almost completely insoluble and thermoset - i.e. they cannot be softened by heat without decomposition. 

In some cases the raw material is already in a fluid state with thermosets as a resin for casting or impregnating, with thermoplasts, as an exception, sometimes as a monomer which is able to polymerise in the mould. In these cases the forming processes are relatively simple, since they can be carried out on low-viscous fluids which do not require high pressures to be transported. 

The metathesis polymerisation of dicyclopentadiene, an inexpensive monomer (commercially available cyclopentadiene dimer produced by a Diels-Alder addition reaction containing ca 95 % endo and ca 5 % exo form), leads to a polymer that may be transformed into a technically useful elastomer [144-146, 179] and thermosetting resin [180,181]. The polymerisation has characteristics that make it readily adaptable to the reaction injection moulding ( rim ) process [182], The main feature of this process comes from the fact that the polymerisation is carried out directly in the mould of the desired final product. The active metathesis catalyst is formed when two separate reactants, a precatalyst (tungsten-based) component and an activator (aluminium-based) component, are combined. Monomer streams containing one respective component are mixed directly just before entering the mould, and the polymerisation into a partly crosslinked material takes place directly in this mould (Figure 6.5) [147,168,183-186],... 

Catalysts are currently not covered specifically by EU directives on food contact plastics. They tend to decompose during the polymerisation process. Again, the degradation products are often predictable and may sometimes be found in the finished food contact material. However, catalysts are usually present at low levels and the degradation products are often volatile. For example, the common catalyst t-butyl perbenzoate may decompose to give benzene when used in some thermoset polymers.Tert-butyl peroxide is used as a catalyst in certain polymers and will decompose to give tert-butanol. 

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