Alkyl thermosets

Unsaturated polyesters refer to the family of polyesters in which the backbone consists of alkyl thermosetting resins having vinyl unsaturation. They are mostly used in reinforced plastics. These are the most widely used as economical family of resins. 

Reactions with Aldehydes and Ketones. An important use for alkylphenols is ia phenol—formaldehyde resias. These resias are classified as resoles or aovolaks (see Phenolic resins). Resoles are produced whea oae or more moles of formaldehyde react with oae mole of pheaol uader basic catalysis. These resias are thermosets. Novolaks are thermoplastic resias formed whea an excess of phenol reacts with formaldehyde under acidic conditions. The acid protonates formaldehyde to generate the alkylating electrophile (17). 

Poly(vinyl chloride) 1838 1931 Thermoplastics (synthetic fiber) Alkyl resins 1847 1915 1926 1928 Thermosets (coatings)... 

Amongst the first studies presenting the use of dendritic polymers for thermoset applications was the work of Hult et al. [62]. They modified hyperbranched hydroxy functional polyesters with various ratios of maleate-allyl ether/alkyl ester end groups. Dependent on this ratio, resins with different vis-... 

By modifying the functional groups they can be used,for example, as crosslinkers in high solid or powder coatings and in thermosets. Because of their good miscibility and low melt viscosity, they find applications as melt modifiers and as blend components. Modified hyperbranched polymers, like alkyl chain substituted poiy(ether)s and po-ly(ester)s sometimes exhibit amphiphilic behavior.They can, therefore, be used as carriers for smaller molecules,for example, dyestuff into polypropylene. 

Bakelite, the first synthetic polymer, is an example of a thermoset polymer. It is prepared by the polymerization of phenol and formaldehyde in the presence of ail acid. Carbocations produced by protonation of formaldehyde bond to the ortho and para positions of the highly reactive phenol molecules in a Friedel-Crafts alkylation reaction. The benzylic alcohols that are produced in this step react to produce carbocations that then alkylate additional phenol molecules. A mechanism for the first few steps of this polymerization process is shown in Figure 24.4. 

Thermosetting acrylics can be produced from a variety of monomers in varying percentage compositions the systems utilize a variety of cross-linking mechanisms (Table IV). A typical thermosetting acrylic can be prepared from 15-80% styrene, 15-18% alkyl acrylate, and 5-10% acrylic acid (27). Acrylic acid provides the functionality for cross-linking with epoxy resins. 

One class of such materials is the fluorinated alkyl esters of acrylic and methacrylic acid, a number of which have been prepared [1]. One of these esters, poly(l,l-dihydropentadecafluoro-octyl methacrylate), has a 11 dynes per cm.—less than Teflon TFE or even FEP [4]. Such materials, and others within the general class of unsaturated, appropriately fluorinated, polyesters warrant investigation for use either as thermoplastic hot-melt adhesives, or for cross linking in situ to form rigid thermoset adhesives. The saturated, appropriately fluorinated polyesters also warrant investigation as thermoplastic hot-melt adhesives. 

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... 

Resins based on para-substituted phenols can be either one-step or two-step, but they cannot cure to a thermoset state. In the manufacture of phenolic resins, smaller quantities of acetaldehyde and furfuraldehyde are used in addition to formaldehyde. Furthermore, resorcinol, bisphenol A, and p-alkylphenols are employed, in addition to phenol, when special properties are desired. Formaldehyde concentrations of 37-50 weight % in aqueous solutions are most commonly employed. The catalysts most frequently used are acids such as oxalic, hydrochloric, sulfuric, p-toluenesul-fonic, and phosphoric and bases such as sodium, calcium, and barium hydroxide. In the weakly acidic range metal carboxylates are employed. Thermoset phenolic resins are employed as structural adhesives for laminating and bonding applications. Para-alkyl-substituted resins are employed as tackifiers in contact adhesives, pressure-sensitive adhesives, and hot-melt adhesives. 

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