Curing speed

The routine compositional and functional testing done on the adhesives includes gas chromatographic testing for purity, potentiometric titrations for acid stabilizer concentrations, accelerated thermal stabiUty tests for shelf life, fixture time cure speed tests, and assorted ASTM tests for tensile shear strengths, peel and impact strengths, and hot strengths. 

Epoxidized phenol novolak and cresol novolak are the most common curing agents. The composition of the resin and hardener system is optimized for each specific appHcation eg, incorporating phenol novolaks in the matrix resin can iacrease cure speed. 

Typical substrates for siUcone release coatings are supercalendered kraft paper, glassines, and thermally sensitive films such as polyethylene and polypropylene. Ideal curing conditions are 150°C or lower, and line speeds are as fast as 460 m /min. Key properties for release coatings are cure speed, integrity of cure, and stable release values. 

This low viscosity resin permits cure at low (70°C) temperatures and rapidly develops excellent elevated temperature properties. Used to increase heat resistance and cure speed of bisphenol A epoxy resins, it has utihty in such diverse appHcations as adhesives, tooling compounds, and laminating systems. A moleculady distilled version is used as a binder for soHd propellants (see Explosives and propellants) and for military flares (see Pyrotechnics). Its chief uses depend on properties of low viscosity and low temperature reactivity, particularly with carboxy-terminated mbbers. 

Advantages of the hydrosilation system (Fig. 3) include the elimination of solvent, improved cure speed, and potential for UV or thermal cure. Drawbacks to the system include more expensive multiroll coating methods, potential poisoning of the Pt catalyst (with Sn, S, Cr, amines, etc.), poor anchorage to some films, and a need to carefully balance the hydride to vinyl ratio employed for cure to avoid detrimental interactions with acid containing adhesives [23,53]. 

Advantages of the epoxy systems are the absence of solvent, UV initiated cure that does not require inerting, a wide range of release levels possible and excellent anchorage to film. Disadvantages include cure inhibition on basic substrates and the need to carefully balance formulation cure speed and completeness with release properties. 

Silicone acrylates (Fig. 5) are again lower molecular weight base polymers that contain multiple functional groups. As in epoxy systems, the ratio of PDMS to functional material governs properties of release, anchorage, transfer, cure speed, etc. Radiation induced radical cure can be initiated with either exposure of photo initiators and sensitizers to UV light [22,46,71 ] or by electron beam irradiation of the sample. 

Ethyl cyanoacrylate is the monomer which is most widely used in both consumer and industrial applications, because of its combination of fast cure speed and ease of manufacture. 

It is probably obvious at this point that the molecular weight distribution of a resole is an extremely important characteristic. It has major influence on such important performance capabilities as cure speed, viscosity, green strength development (or prepress), assembly time tolerance, required application rates. 

Typical features of a plywood resole formulation are a formaldehyde-to-phenol molar ratio in the 2.0 1 to 2.5 1 range, programmed formaldehyde, an alkali content from 4 to 8 wt% (calculated as sodium hydroxide), and pan solids of 40-50%. Resins used for laminated veneer lumber (LVL) tend to be similar to plywood resins in composition and molecular weight, though they are often designed for high-end cure speed. 

All of the observations above relate well to our own with respect to the effects of molecular weight on the available cure speed in manufacturing, both in plywood and OSB. They also correlate with our experience on the effects of molecular weight and dry-out on bond quality. 

Resorcinol will react rapidly with hydroxymethyl as well as free formaldehyde thus only a resin with low-to-nonexistent methylol will be stable in its presence. Such a resin is not likely to show good cure speed unless some sort of latent, protected methylene donor is present. This approach may be viable in a user s mill where the storage time after resorcinol addition is relatively short. If the resorcinol is dissolved, in-line mixing with the PF would be a reasonable approach. 

Recently, a two-part cross-catalyzed system has been developed that takes advantage of both the acceleration abilities of resorcinol resin and ester [179], The term cross-catalyzed is applied because the phenolic resin contains an accelerator-crosslinker for the resorcinol resin while the resorcinol resin carries an accelerator for the PF, in addition to itself being capable of improving PF cure speed. In each part, the resin carrier for the accelerator is not susceptible to acceleration by the material contained. It is only when the systems are mixed that the accelerators are activated. This system is faster and lower in cost than most of the resorcinol accelerators and gives better bonds (in wood products) than the ester cure alone [179], Another variant of the resorcinol approach utilizes resorcinol-glutaraldehyde resins [180-182],... 

While phenol is the most common monomer for novolac manufacture, it is far more common to see incorporation of other phenolic materials with novolacs than with resoles. Cresols, xylenols, resorcinol, catechols, bisphenols, and a variety of phenols with longer alkyl side chains are often used. While most resoles are made with a single phenolic monomer, two or more phenolic materials are often seen in novolac formulae. These additional monomers may be needed to impart special flow characteristics under heat, change a glass transition temperature, modify cure speed, or to adjust solubility in the application process among others. 

One way to obtain enhanced heat and solvent resistance in SBR-based PSA is sulfur addition. It is difficult to obtain sufficient cure with sulfur during normal drying cycles (2-5 min at 150-180°C). Furthermore, cure via sulfur may continue after leaving the oven, thus degrading adhesion. When used in contact with copper, the sulfur may promote corrosion. The use of phenolic overcomes all of these problems despite the fact that its natural cure speed is also insufficient for the time frame available. This is overcome through addition of one of the accelerators... 

Oligomer and Film Characterization. Brookfield viscosity measurements were taken on a Model RVTD digital readout viscometer. Samples for Instron testing were prepared on glass plates using 25 or 75 pm (1.0 or 3.0 mil) Byrd film applicator. Coatings for cure speed and MEK double rub (MEKDR) studies were prepared on aluminum Q-Panels using a 40 wire wound rod (100 pm or 4.0 mil). 

Variation of Maleate to Vinyl Ether Ratio. Variation of the stoichiometric ratio of vinyl ether double bond to maleate double bond should produce more flexible films due to plasticization by dangling end groups but also may reduce cure speed and mechanical properties. The curing of unsaturated polyester F with DVE-3 using 4% Darocur 1173... 

The results for the formulations containing isobutyl vinyl ether are shown in Figure 2. Due to the vinyl ether double bond to maleate double bond ratio constraint, the compositions used for this study are located in one comer of the triangular graph. It was unfortunate that compositions containing little or no DVE-3 were incompatible and could not be evaluated. Viscosities were not measured on these formulations. Cure dose increases as the amount of monofunctional diluent increases. Pencil hardness increased as the vinyl ether double bond to maleate double bond ratio increased. These results indicate that substitution of a monofunctional maleate or vinyl ether diluent results in reduced cure speed and pencil hardness. 

Maleate/vinyl ether formulations based on a model unsaturated polyester prepared from maleic anhydride and 1,5-pentane diol and triethylene glycol divinyl ether were studied. At molecular weights of less than about 10,000 the cured films were extremely brittle. When the equivalent weight of the unsaturated polyester was increased by replacing some of the maleic anhydride with succinic anhydride, measurable values for film elongation could be obtained but the cure speed was definitely slower. When either diethyl maleate or isobutyl vinyl ether were added as monofunctional diluents the cure dose needed to obtain 200 MEKDR was increased and the flexibility measured by pencil hardness increased as the amount of diluent was increased. A urethane vinyl ether was synthesized and used to replace DVE-3 and films with increased elongation were obtained at equivalent at dosages as low as 1 J/cm2. 

The most important attribute of the thiol-ene system is its insensitivity to oxygen thus, it is not inhibited by it. Another attractive feature is its very high cure speed. The disadvantage of the thiol-ene system is an unpleasant odor of the volatiles emitted from some polythiol compounds. ... 

Oxman et al. (3) determined that cure speed and enthalpy were improved in photopolymerizable compositions when using anthracene derivatives containing electron donors as photoinitators for cationic curing. Dimethoxy-, diethoxy-, and diphenoxyanthracene were especially preferred. 

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