Polymerisation cross-linking

Theoretically the polymerisation (cross-linking) process should not result in a random network of dextran chains but in a heterogeneous gel with crosslink-dense, matrix-rich, water-poor domains intermingled with cross-link-sparse, matrix-poor, water-rich regions (2,20). 

Organic peroxides are used in the polymer industry as thermal sources of free radicals. They are used primarily to initiate the polymerisation and copolymerisation of vinyl and diene monomers, eg, ethylene, vinyl chloride, styrene, acryUc acid and esters, methacrylic acid and esters, vinyl acetate, acrylonitrile, and butadiene (see Initiators). They ate also used to cute or cross-link resins, eg, unsaturated polyester—styrene blends, thermoplastics such as polyethylene, elastomers such as ethylene—propylene copolymers and terpolymers and ethylene—vinyl acetate copolymer, and mbbets such as siUcone mbbet and styrene-butadiene mbbet. 

As the length and frequency of branches increase, they may ultimately reach from chain to chain. If all the chains are coimected together, a cross-linked or network polymer is formed. Cross-links may be built in during the polymerisation reaction by incorporation of sufficient tri- or higher functional monomers, or may be created chemically or by radiation between previously formed linear or branched molecules (curing or vulcanisation). Eor example, a Hquid epoxy (Table 1) oligomer (low molecular weight polymer) with a 6-8 is cured to a cross-linked soHd by reaction of the hydroxyl and... 

Additional hydrolysis to promote polymerisation and cross-linking leading to a three-dimensional matrix and gel formation. 

For all three diallyl phthalate isomers, gelation occurs at nearly the same conversion DAP prepolymer contains fewer reactive allyl groups than the other isomeric prepolymers (36). More double bonds are lost by cyclisation in DAP polymerisation, but this does not affect gelation. The heat-distortion temperature of cross-linked DAP polymer is influenced by the initiator chosen and its concentration (37). Heat resistance is increased by electron beam irradiation. 

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). 

An alternative route to cross-linking is to start with a linear polymer and then cross-link the molecules by tying the molecule through some reactive group. For example, it is possible to cross-link unsaturated polyesters by an addition polymerisation across the double bond as shown schematically in Figure 2.12. 

Chemical reactions of polymer intermediate during polymerisation and/or cross-linking. This is important with polyurethanes. 

Acrylic and methacrylic acids and their esters are highly versatile materials in that the acid and ester side groups can partake in a variety of reactions to produce a very large number of polymerisable monomers. One particularly interesting approach is that in which two methacrylic groupings are linked together so that there are two, somewhat distant, double bonds in the molecule. In these cases it is possible to polymerise through each of these double bonds separately and this will lead eventually to a cross-linked network structure. 

By introducing branch points into the polymer chains, for example by incorporating about 2% of 1,2,3,-trichloropropane into the polymerisation recipe, chain extension may proceed in more than two directions and this leads to the formation of networks by chemical cross-links. However, with these structures interchange reactions occur at elevated temperatures and these cause stress relief of stressed parts and in turn a high compression set. 

On heating with a peroxide, diallyl phthalate will polymerise and eventually cross-link because of the presence of two double bonds (Figure 25.13). 

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. 

Loss of unsaturation during cross-linking indicates that this reaction is essentially a form of double bond polymerisation, viz Figure 28.3. 

Many polymers containing boron in the main chain have been prepared but most of them have either been of low molecular weight or intractable cross-linked structures. Some interest has been shown in the tri-3-aminoborazoles, which polymerise on heating (Figure 29.15f. ... 

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