Resins cross-linking

Elastomeric Modified Adhesives. The major characteristic of the resins discussed above is that after cure, or after polymerization, they are extremely brittie. Thus, the utility of unmodified common resins as stmctural adhesives would be very limited. Eor highly cross-linked resin systems to be usehil stmctural adhesives, they have to be modified to ensure fracture resistance. Modification can be effected by the addition of an elastomer which is soluble within the cross-linked resin. Modification of a cross-linked resin in this fashion generally decreases the glass-transition temperature but increases the resin dexibiUty, and thus increases the fracture resistance of the cured adhesive. Recendy, stmctural adhesives have been modified by elastomers which are soluble within the uncured stmctural adhesive, but then phase separate during the cure to form a two-phase system. The matrix properties are mosdy retained the glass-transition temperature is only moderately affected by the presence of the elastomer, yet the fracture resistance is substantially improved. 

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. 

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). 

The cresols occur in cresylic acid, a mixture of the three cresols together with some xylenols and neutral oils, obtained from coal tar distillates. Only the /n-cresol has the three reactive positions necessary to give cross-linked resins and so this is normally the desired material. The o-isomer is easily removed by distillation but separation of the close-boiling m- and p-isomers is difficult and so mixtures of these two isomers are used in practice. 

Hard, intractable, cross-linked resin Figure 23.29... 

Whilst the properties of the cross-linked resins depend very greatly on the curing system used and on the type of resin, the most characteristic properties of commercial materials are their toughness, low shrinkage on cure, high adhesion to many substrates, good alkali resistance and versatility in formulation. 

A variety of silicone polymers has been prepared ranging from low-viscosity fluids to rigid cross-linked resins. The bulk of such materials are based on chloromethysilanes and the gross differences in physical states depend largely on the functionality of the intermediate. 

Epoxy adhesives are cross-linked resins prepared in two steps. The first step involves SN2 reaction of the disodium salt of bisphenol A with epichloro-hydrin to form a low-molecular-weight prepolymer. This prepolymer is then "cured" into a cross-linked resin by treatment with a triamine such as H2NCH2CH2NHCH2CH2NH2-... 

It should be noted that large-size ions may not be absorbed by a medium cross-linked resin so that its effective capacity is seriously reduced. A resin with larger pores should be used for such ions. 

Of course, these conclusions do not rule out completely the occurrence of other reactions such as those listed above, but their contribution to the overall mechanism must be very small in the production of the oligomers. The dark colour of these products was attributed to hydride transfer reactions, similar in nature to those encountered in the cationic polymerization of 2-vinyl furan [see Section III-B-l-c)]. The subsequent process which transforms these oligomers into cross-linked resins was not investigated. 

By replacing insoluble cross-linked resins with soluble polymer supports, the well-estabhshed reaction conditions of classical organic chemistry can be more readily apphed, while still fadhtating product purification. However, soluble supports suffer from the hmitation of low loading capacity. The recently introduced fluorous synthesis methodology overcomes many of the drawbacks of both the insoluble beads and the soluble polymers, but the high cost of perfluoroalkane solvents, hmitation in solvent selection, and the need for specialized reagents may hmit its apphcations. 

The novel concept of synthesizing a molecule while attached to a swollen cross-linked resin bead was introduced and demonstrated by R. B. Merrifield with the solid-phase peptide synthesis method about 20 years ago (1,2). The procedure involves the covalent attachment of an amino-acid residue to the polymer bead followed by the addition of subsequent amino-acid units in a stepwise manner under conditions that do not disrupt the attachment to the support. At the completion of the assembly of the peptide, the product is cleaved from the resin and recovered. The macro-scopically insoluble support provides convenient containment of the desired product so that isolation and purification from soluble co-products in the synthesis can be achieved by simple... 

In the cross-linked resin samples the T s are again not solvent dependent and the n s remain greater for the sample in chloroform. The values for the T and parameters again indicate a lower limit of less than 10 8s for the correlation time. 

Cross-linked Resins It is possible to convert the low Molecular weight urea-formaldehyde resin into the high Molecular weight cross-linked resins by heating the former in acidic conditions. 

Properties The cross-linked resins have been rigid, infusible and insoluble. They show unusual surface hardness, and may be obtained in a wide range of colours. Cross-linked resins have been found to be very resistant to most organic reagents. 

Interestingly however as early as 1971 Sternlicht et al. [196] realized that cross-linked resins sufficiently swollen with solvent were sufficiently mobile to yield much improved NMR spectra, and from this early work gel-phase NMR has emerged. 

Urea will give cross-linked resins with formaldehyde. Methylolureas are formed first under alkaline conditions. 

Unsaturated polyesters have been produced from reaction of ethylene glycol with phthalic anhydride, or maleic anhydride (structure 4.46). These polyesters may be dissolved in organic solvents and used as cross-linking resins for the production of fibrous glass-reinforced composites ... 

In a similar way, Mizota et al. grafted polymer chains functionalized with sulfonic sites over a polystyrene-type polymer. As observed above, the flexibility of the polymer chains allowed better accessibility of the catalytic sites and this solid acid catalyst was ten times more active than the conventionally used cross-linked resin in the hydrolysis of sucrose (Scheme 2) [27]. 

An extension of polymer cross linking to ion exchange resins would make it possible to form heavily cross linked resins after functional groups had been added. Another corollary of this idea would be to use radiation to activate sites along polymer chains, thus permitting the grafting of active groups. 

DVA is heated in absence of air, it.poly- merizes to give liquid low polymers which harden in air to cross-linked resins. Heating of DVA in presence of air usually causes explosions... 

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