Thermoset resins Network

Phenolic novolak resins and high styrene SBR resins are used for reinforcing and increasing the hardness and modulus of rubber compounds. Resorcinol novolak resins are used as a part of the adhesion system between rubber and brass plated steel cord or organic fibers. Both phenolic novolak and resorcinol novolak resins require the addition of a methylene donor such as hexamethoxymethylmelamine (HMMM) or hexamethylenetetramine (HMTA) to fully crosslink and become a thermoset. Phenol, alkyl phenols, and resorcinol can be reacted in bulk or in a polymeric formulation with methylene donors. Typical donors are 2-nitro-2methylpropanol (NMP), HMTA, and HMMM, used to produce a thermoset resin network in the... 

If a large number of branches exist that connect all of the backbone molecules into a three-dimensional network, the material will not flow when heated, and it is considered a thermoset resin. Vulcanized rubber is an example where the sulfur linkages create a three-dimensional network, converting the precursor rubber into a solid thermoset material. Crosslinked backbone chains are shown in Fig. 2.8(e). When extruding many thermoplastics, the polymer can undergo chemical reactions to form small amounts of crosslinked material. Partial crosslinking is a problem with some PE resins that contain residual double bonds that are made using... 

The cure of thermoset resins involves the transformation of a liquid resin, first with an increase in viscosity to a gel state (rubber consistency), and finally to a hard solid. In chemical terms, the liquid is a mixture of molecules that reacts and successively forms a solid network polymer. In practice the resin is catalyzed and mixed before it is injected into the mold thus, the curing process will be initialized at this point. The resin cure must therefore proceed in such a way that the curing reaction is slow or inhibited in a time period that is dictated by the mold fill time plus a safety factor otherwise, the increase in viscosity will reduce the resin flow rate and prevent a successful mold fill. On completion of the mold filling the rate of cure should ideally accelerate and reach a complete cure in a short time period. There are limitations, however, on how fast the curing can proceed set by the resin itself, and by heat transfer rates to and from the composite part. 

As long as tn processes of this type only bifunctional monomers are used, the resulting macromolecules are linear and, as a consequence, are of the soluble and fusible type. They can be used as fiber formers, rubbers or thermoplastic resins. If. however, some of the monomers are Ui- or tetra-inethylolnrea, the reaction leads to three-dimensional polymeric networks which are hard and bntde thermosetting resins, such as Bakelite or Glyptal. ... 

Thermosetting space-network polymers can be prepared through the reaction of polybasic acid anhydrides with polyhydric alcohols. A linear polymer is obtained with a bifunctional anhydride and a bifunctional alcohol, but if either reactant has three or more reactive sites, then formation of a three-dimensional polymer is possible. For example, 2 moles of 1,2,3-propane-triol (glycerol) can react with 3 moles of 1,2-benzenedicarboxylic anhydride (phthalic anhydride) to give a highly cross-linked resin, which usually is called a glyptal ... 

IS Plastics are materials that can be heated and then molded or shaped into useful objects. More specifically, thermoplastics can be processed more than once by reheating, while thermoset resins react chemically during initial heating and molding to form a permanent network. The term plastic is often loosely used to describe all polymers, sometimes in an unfavorable way. As we can see in Table 1-2, however, several other categories of polymers exist, each with its own set of properties. 

In contrast to the linear thermoplastic polymers, which are soluble and fusible, the cross-linked network polymers are insoluble and infusible. They are formed from polymerizing systems containing monomers or prepolymers with a functionality of three or more. A good example is the phenol-formaldehyde resin systems. The cross-linking reaction takes place in the bond under applied pressure and heat, and the whole adhesive bond might consist of only one super giant molecule. Such resins are, therefore, called thermosetting resins. 

The cross-link density and the spacing of cross-links along the polymer chain determine the relative flexibility of the rigid network structures, which are naturally more resistant to heat, solvents, and chemical attack than uncross-linked polymers. Flexibilizing polymers or fillers are also added to thermosetting resins to improve toughness and reduce brittleness of the adhesive. 

Thermosetting phenolic resins form a separate class of polymers containing aromatic rings and aliphatic carbon groups in the polymeric network. These resins are formed from the reaction of phenol (or substituted phenols) with formaldehyde. The fully crosslinked macromolecule is insoluble and infusible. Other thermosetting resins are known in practice, some derived from the reaction of melamine or of urea with formaldehyde. Because these have a different chemical structure, containing nitrogen, they are included in a different class (see Section 15.3). 

Much work has been reported on studying the structure of thermoset resins via SAXS, especially focussing on interpenetrating network polymers (IPNs), thermoset nanocomposites, rubber-modified thermosets and thermoset-thermoplastic blends. Most recently Guo et al, (2003) have examined the use of SAXS to monitor the nanostructure and crystalline phase structure of epoxy-poly(ethylene-ethylene oxide) thermoset-thermoplastic blends. This work proposes novel controlled crystallization due to nanoscale confinements. 

A thermosetting plastic is a polymer that can be caused to undergo cross-linking to produce a network polymer, called a thermoset polymer. Quite commonly, thermosetting resins are prepared, by intent, in only partially polymerized states (prepolymers), so that they can be deformed in a heated mold and then hardened by curing (cross-linking). 

Hence a low molecular weight, reactive elastomer is normally used for impact modification of thermosets. The low molecular weight of the mbbery prepolymer aids its easy dissolution or dispersability in the thermosetting resin. The reactive functionality couples the rubber covalentiy to the growing polymer network during the curing reaction. Hence the rubber toughened thermosets may also be considered as co-reacted thermosets and not true blends. 

Polycondensations can be carried out in an aqueous or a solvent medium, or they can be performed while the reactions are in a liquid or in a molten state. In industry, reactions of polyfunctional monomers leading ultimately to the tridimenaonal-network molecules of thermosetting resins are usually interrupted at a stage where the polymers still are soluble and fusible. They then are shipped to the fabricators, who convert them by heat curing processes into the final thermosetting product. 

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