Metallic cure promoters

Catalyst Selection. The low resin viscosity and ambient temperature cure systems developed from peroxides have faciUtated the expansion of polyester resins on a commercial scale, using relatively simple fabrication techniques in open molds at ambient temperatures. The dominant catalyst systems used for ambient fabrication processes are based on metal (redox) promoters used in combination with hydroperoxides and peroxides commonly found in commercial MEKP and related perketones (13). Promoters such as styrene-soluble cobalt octoate undergo controlled reduction—oxidation (redox) reactions with MEKP that generate peroxy free radicals to initiate a controlled cross-linking reaction. 

Cure promoters include metal compounds, for optimal cure hot press moulding acetylacetone, with ketone peroxides and cobalt accelerator for a short geltime, giving a fast cure at room temperature and at elevated temperature and tertiary dodecyl mercaptane, for a gradual cure and moderate peak exotherm, in filament winding. 

Ketone Peroxides. These materials are mixtures of compounds with hydroperoxy groups and are composed primarily of the two stmctures shown in Table 2. Ketone peroxides are marketed as solutions in inert solvents such as dimethyl phthalate. They are primarily employed in room-temperature-initiated curing of unsaturated polyester resin compositions (usually containing styrene monomer) using transition-metal promoters such as cobalt naphthenate. Ketone peroxides contain the hydroperoxy (—OOH) group and thus are susceptible to the same ha2ards as hydroperoxides. 

Commercially available MEKP formulations are mixtures of the dihydroperoxide (1), where X = OOH R = H, R = methyl, and R = ethyl (2,2-dihydroperoxybutane [2625-67 ]) and dialkyl peroxide (2), where X = OOH, Y = OOH, R = methyl, and R = ethyl (di(2-hydroperoxy-2-butyl) peroxide [126-76-1J). These formulations are widely used as free-radical initiators in the metal-promoted cure of unsaturated polyester resins at about 20°C. 

The action of redox metal promoters with MEKP appears to be highly specific. Cobalt salts appear to be a unique component of commercial redox systems, although vanadium appears to provide similar activity with MEKP. Cobalt activity can be supplemented by potassium and 2inc naphthenates in systems requiring low cured resin color lithium and lead naphthenates also act in a similar role. Quaternary ammonium salts (14) and tertiary amines accelerate the reaction rate of redox catalyst systems. The tertiary amines form beneficial complexes with the cobalt promoters, faciUtating the transition to the lower oxidation state. Copper naphthenate exerts a unique influence over cure rate in redox systems and is used widely to delay cure and reduce exotherm development during the cross-linking reaction. 

The reluctance of acrylic monomers to polymerise in the presence of air has been made a virtue with the anaerobic acrylic adhesives. These are usually dimethacrylates such as tetramethylene glycol dimethacrylate. The monomers are supplied with a curing system comprising a peroxide and an amine as part of a one-part pack. When the adhesive is placed between mild steel surfaces air is excluded, which prevents air inhibition, and the iron present acts as a polymerisation promoter. The effectiveness as a promoter varies from one metal to another and it may be necessary to use a primer such as cobalt naphthenate. The anaerobic adhesives have been widely used for sealing nuts and bolts and for a variety of engineering purposes. Small tube containers are also available for domestic use. 

Metal oxides. Zinc oxide is the most effective metal oxide. The zinc oxide should have a low lead content. Zinc oxide has three main functions (a) promote cure (b) improves ageing, heat and weathering resistance (c) acid acceptor. In general, 2-5 phr zinc oxide is added in latex formulations. 

There are other initiator systems of lesser commercial importance. Cumene hydroperoxide is reported to cure acrylic adhesives in the presence of alkyl or pyridyl thioureas [105]. These initiators have been combined with a phosphated acrylate to promote adhesion to metal [106]. Thiourea-based initiators can be applied as a one-part on galvanized metal, where the metal surface provides the second part of the redox initiator [107]. 

Whiskers can be incorporated into the metallic matrix using a number of compositeprocessing techniques. Melt infiltration is a common technique used for the production of SiC whisker-aluminum matrix MMCs. In one version of the infiltration technique, the whiskers are blended with binders to form a thick slurry, which is poured into a cavity and vacuum-molded to form a pre-impregnation body, or pre-preg, of the desired shape. The cured slurry is then fired at elevated temperature to remove moisture and binders. After firing, the preform consists of a partially bonded collection of interlocked whiskers that have a very open structure that is ideal for molten metal penetration. The whisker preform is heated to promote easy metal flow, or infiltration, which is usually performed at low pressures. The infiltration process can be done in air, but is usually performed in vacuum. 

Zinc soaps, which are complexes of long chain fatty acids, find similar applications in the curing and hardening of coatings to other transition metal soaps. A summary is available.123 The more important anions are 2-ethylhexanoate, naphthenate and stearate. Mixtures of zinc and calcium soaps are also effective stabilizers for poly(vinyl chloride).124 The complexes [Zn 0P(0)-(OBun)2 2] and [Zn SP(S)(OBun)2 2] both promote antiwear properties of lubricating oils.125... 

Titanates are valuable in other paint applications. Corrosion-resistant coatings have been described for tinplate, steel, and aluminum (440—444). Incorporation of phosphoric acid or polyphosphates enhances the corrosion resistance. Because titanates promote hardening of epoxy resins, they are often used in epoxy-based paint (445). Silicones (polysiloxanes) are often cured by titanates. Pigments, eg, Ti02, Si02, Al O and Zr02, are frequently pretreated with titanates before incorporation into paints (441,446). In these applications, the Ti(OR)4 compounds are often mixed with Si(OR)4, Al(OR)3, Zr(OR)4, and other metal alkoxides (12). 

These aminohydroxy compounds in the form of their salts are extremely useful as catalysts for permanent press resins. The utilization of these compounds alone or in combination with metal salts such as magnesium chloride or zinc nitrate promotes balanced curing action with a wide range of textile resins. These catalysts provide ... 

In BPDA-PDA, the only hydrolysis observed was of anhydride. If the samples are cured to at least 400 °C to minimize the residual anhydride, the bulk polymer should be quite stable to hydrolysis. In this material, then, the major remaining concerns about hydrolytic stability center on the polymer-substrate interfaces whether possible polymer-metal interactions could result in the formation of hydrolytically unstable products and whether or not agents used to promote adhesion will retain their efficacy under humid aging. 

---