One-Component Adhesives

The 150 kilotons of ammoninm chloride that are prodnced per year are mostly nsed as fertilizer and, in order of importance, for solid electrolytes in dry cell batteries, a component of quarrying explosives, hardeners for formaldehyde-based adhesives, one component of etching solutions in the manufacture of printed circuit boards, and a component, along with zinc chloride, of fluxes in tin and zinc plating. 

Acralane. [PPG Industries/Adhesives] One-component structural adhesive for plastics. 

EN 15425 2008, Adhesives, one-component polyurethane, for load bearing timber structures — Classification and performance requirements. 

Adhesive, one-component—An adhesive material incorporating a latent hardener or catalyst activated by heat. Usually refers to thermosetting materials, but also describes anaerobic, hot-melt adhesive, or those dependent on solvent loss for adherence. Thermosetting one-component adhesives require heat to cure. 

Polyurethane engineering adhesives can be formulated as one- or two-component systems that cure to very tough flexible adhesives. One-component systems are cured using heat or atmospheric moisture (or can be misted with sprayed water), whereas two-component systems must be mixed thoroughly before use. 

Sealants reacting with ambient humidity Some sealants and adhesives (one component PU, MS polymers) cure by a chemical reaction with ambient humidity. 

Polyurethane sealant formulations use TDI or MDI prepolymers made from polyether polyols. The sealants contain 30—50% of the prepolymer the remainder consists of pigments, fiUers, plastici2ers, adhesion promoters, and other additives. The curing of the sealant is conducted with atmospheric moisture. One-component windshield sealants utili2e diethyl malonate-blocked MDI prepolymers (46). Several polyurethane hybrid systems, containing epoxies, siUcones, or polysulfide, are also used. 

In seeking to minimize the contact angle or to promote wetting of the adherend by the adhesive, one must consider the effects both of the chemistry of the components and of the morphology of the adherend surface on the observed contact angle. Finally, comment must be made on the dynamics of the wetting process and the factors upon which it depends. 

Urethane adhesives are classified as one-component or two-component adhesives. Each category includes several different types of adhesives. 

The reaction of water with isocyanate is shown in the third item of Fig. 1 [5]. The water/isocyanate reaction is the major curing mechanism for the one-component urethane adhesives. Most one-component urethanes are based on an isocyanate-terminated prepolymer (I). Usually, the moisture in the air is used to cure the adhesive, but in some instances, a fine mist of water may be introduced on top of the adhesive before the bond is closed, in order to facilitate cure ... 

For all its benefits, the water/isocyanate reaction can be troublesome as well. All raw materials that go into a one-component moisture-cured adhesive must have very low moisture content, usually less than 0.05% water. If higher water levels are present, the adhesive can start curing in the reactor, causing an increase in viscosity, or, in extreme cases, gelation. 

The amorphous polyesters are becoming increasingly important for one-component 100% solid moisture-curing adhesives. These materials are usually viscous, amorphous liquids. Poly(2-methylpropane adipate), an example of an amorphous polyester, is a liquid even at a molecular weight of 2000. The amorphous polyesters are usually asymmetrical in structure. In the poly(2-methylpropane adipate) example, the pendant methyl group would be expected to interfere with chain packing, thereby preventing crystallization [27]. 

The soft segments made from asymmetrical (amorphous) polyols are important for two-component structural adhesives and one-component moisture-curing adhesives. These materials are applied and usually cured at room temperature. 

Several large applications for one-component moisture-cure urethane adhesives are available. Polymeric MDI is an exceptional binder for wood products, such as oriented strand board and particleboard. One-component urethane windshield adhesives are used almost exclusively in both the OEM and automotive aftermarket. One-part urethane adhesives are used to assemble the sidewalls for recreational vehicles (RV s), manufactured housing, and mobile homes. In construction applications, one-part urethanes are used to bond metal doors, hardwood flooring, panels, and partitions. 

Catalysts serve a dual purpose in one-component moisture-curing urethanes. The first purpose is to accelerate the prepolymer synthesis. The second purpose is to catalyze the curing reaction of the adhesive with moisture. The most common catalysts used to promote both prepolymer formation (NCO/OH) and later the adhesive curing reaction (NCO/H2O) are dibutyltin dilaurate and DMDEE ((tertiary amine. A stabilizer such as 2,5-pentanedione is sometimes added when tin is used, but this specific stabilizer has fallen from favor in recent years, due to toxicity concerns. DMDEE is commonly used in many one-component moisture-curing urethanes. DMDEE is one of the few tertiary amines with a low alkalinity and a low vapor pressure. The latter... 

Windshield sealants comprise some of the most significant applications of one-component urethane adhesives. Several years ago, the requirements for these sealants were increased. In an accidental rollover, in certain automobiles, the windshield becomes a structural part of the car. Therefore, the windshield adhesive, which holds the windshield in place, must have structural strength. An example of a one-component windshield sealant is shown below [48] ... 

One-component waterborne urethanes are used as packaging adhesives and tie coats and for automotive bonding of PVC. 

Internal surfactants, i.e., surfactants that are incorporated into the backbone of the polymer, are commonly used in PUD s. These surfactants can be augmented by external surfactants, especially anionic and nonionic surfactants, which are commonly used in emulsion polymerization. Great attention should be paid to the amount and type of surfactant used to stabilize urethane dispersions. Internal or external surfactants for one-component PUD s are usually added at the minimum levels needed to get good stability of the dispersion. Additional amounts beyond this minimum can cause problems with the end use of the PUD adhesive. At best, additional surfactant can cause moisture sensitivity problems with the PUD adhesive, due to the hydrophilic nature of the surfactant. Problems can be caused by excess (or the wrong type of) surfactants in the interphase region of the adhesive, affecting the ability to bond. 

One interesting advantage of the one-component waterborne adhesives is that many are re-positionable. For example, if, for some reason, the two substrates are poorly aligned when the bonding occurs, this problem can be corrected by heating the bonded substrates above the bond activation temperature. The two substrates... 

The concept of utilizing a blocked isocyanate in a one-component adhesive system is shown below ... 

The two-component waterborne urethanes are similar in nature to the one-component waterborne urethanes. In fact, many one-component PUD s may benefit from the addition of a crosslinker. The two-component urethanes may have higher levels of carboxylic acid salt stabilizer built into the backbone than is actually needed to stabilize the urethane in water. As a result, if these two-component urethane dispersions were to be used as one-component adhesives by themselves (without crosslinker), they would show very poor moisture resistance. When these two-component urethane dispersions are used in conjunction with the crosslinkers listed in Fig. 8, the crosslinkers will react with the carboxylic pendant groups built into the urethane, as previously shown in the one-component waterborne urethane section. This accomplishes two tasks at the same time (1) when the crosslinker reacts with the carboxylic acid salt, it eliminates much of the hydrophilicity associated with urethane dispersion, and (2) it crosslinks the dispersion, which imparts solvent and moisture resistance to the urethane adhesive (see phase V in Fig. 5). As a result of crosslinking, the physical properties may be modified. For example, the results may be an increase in tensile properties and a decrease in elongation. Depending upon the level of crosslinking, the dispersion may lose the ability to be repositionable. (Many of the one-component PUD s may... 

Thus far, the discussion has dealt with the versatility of urethane adhesives, the wide variety of substrates urethanes can bond, and the infinite variations of one-component and two-component urethanes. Some substrates have posed particular challenges for urethanes. Many adhesion problems have been discussed, but not all can be covered in this brief synopsis. However, two of the more common problems, with possible solutions, will be mentioned. 

Few non.chemists know exactly what an epoxide is. but practically everyone has used an "epoxy glue for household repairs or an epoxy resin for a protective coating. Epoxy resins and adhesives generally consist of two components that are mixed just prior to use. One component is a liquid "prepolymer/ and the second is a "curing agent" that reacts with the prepolymer and causes it to solidify. 

Example 11. One-Component, Moisture-Cure Polyurethane Sealant. This example is of a low-hardness, high-elongation, moisture-curable polyurethane sealant. The material is based on a low-%NCO prepolymer made from 4,4 -MDI and a low-unsaturation (low-monol-content) Acclaim polyol from Bayer. It is adapted from (a) J. Lear et al., Adhesives Age, February 1999, pp. 18-23 and (b) B. Lawrey, et al., presented at UTECH 2000, The Hague, The Netherlands, March 30, 2000, Crain Communications London, 2000. 

Other problems in adhesion may be tackled by studying the surface of the material after fracture. Mass spectroscopic methods like SIMS may reveal transfer of molecular fragments from the one component towards the other one. 

One component of a terpolymer of butadiene, styrene and vinyl pyridine used in latex form to promote good adhesion between rubber and textiles, particularly rayon and nylon. Viscoelasticity... 

These subgel prepolymers have been manufactured by industry for some time and used in two-component adhesives or coating materials. For one-component materials, storage below the actual Tg, whenever applicable, is the most efficient method for blocking the reactivities. This kind of blocking is used in powder coatings. 

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