Polyurethane adhesives applications

Certain fillers are commonly added to protect the urethane backbone from oxidative degradation. Carbon black and titanium dioxide are commonly used in conjunction with antioxidants to protect polyether polyurethanes in exterior adhesive applications that may be exposed to oxygen and light (Fig. 12). 

Solvent wiping. Rubbers tend to swell by application of solvents and the mechanical interlocking of the adhesive is favored. Although chlorinated hydrocarbon solvents are the most effective, they are toxic and cannot be used toluene and ketones are currently the most common solvents. The treatment with solvents is effective in the removal of processing oils and plasticizers in vulcanized mbbers, but zinc stearate is not completely removed and antiozonant wax gradually migrates to the mbber/polyurethane adhesive interface. Table 27.1 shows the moderate increase in adhesion produced in SBR by MEK wiping. 

One of the more advanced technical offerings from castor oil is a line of polyester diols, triols, and higher functional polyols derived from 100% castor oil as products for the preparation of polyurethane prepolymers and elastomers [68]. The Polycin line of polyols are prepared by transesterification of ricinoleic acid and derivatives. The producers (Vertellus) offer diol and triol products, as well as a recently developed series of diol and triol glyceryl ricinoleate esters that are stated to be prepared from 100% castor oil, making them fully renewable in content. The products are recommended for coatings, sealants, and adhesive applications. 

Some grades of polyurethane and polyester copolymers are used as hot-melt adhesives. Applications include shoe manufacture and as an adhesive interlayer in coextmsion. 

Originally for this work two-part polyurethane adhesives (100% solids) were used, mixed immediately beforehand, but material of this type is sensitive during setting to contact with water and rainfall soon after application was found to cause weakness. In consequence, moisture-curing polyurethane adhesives now are preferred such systems can be applied under most weather conditions, even at temperatures down to 5°C. 

The major synthetic adhesives used for bonding wood include urea, phenol, and melamine formaldehyde resorcinol formaldehyde, phenol resorcinol, and polyvinyl acetate emulsions. More recently one-component, moisture cured polyurethane adhesives have become popular for bonding wood. Natural adhesives such as casein and animal glues are also often used for general-purpose wood bonding. Epoxies have been used for certain specialized wood joining applications such as when wood is bonded to metal substrates. 

First-generation solventless polyurethane adhesives are one-component isocyanate terminated prepolymers formed by the reaction of MDI (4,4 methylene bis (phenyl isocyanate)), or other isocyanates with polyether and/ or polyester polyols. One-component 100% solids adhesives rely on moisture from the air or substrates or from induced moisture misting during the converting process, to cure the adhesive via an isocyanate/water reaction and subsequent polyurea-polyurethane polymer formation. Typically the high viscosity of the adhesive is such as to require adhesive delivery equipment and application rollers heated from 65-80 °C for use. They have a high level... 

Two-component polyurethane adhesives are the condensation product of a polyol with an organic isocyanate. The first component contains a prepolymer of the polyol, and polyisocyanate is the second component. These two components are thoroughly mixed before application. 

The main application of two-part polyurethane adhesives is for rapid bonding of wood-based materials, particularly for the assembly of housing components (Figure 4.5). 

Since these one-component polyurethane adhesives cure through reaction with water, one talks of moisture curing one-component polyurethane adhesives. Their characteristic feature is their excellent adhesiveness. Apart from adhesive applications, these formulations are applied to a great extent as sealing compounds, for example, as fitting foam glue or PU-foam (Section 4.9). 

The described polyurethane adhesives are applied depending on the materials to be bonded and the given application conditions in the different fields of industry,... 

Application as RTV-1 systems requires preconditions comparable to moisturecuring one-component polyurethane adhesives (Section 4.2.2). In order to ensure that curing is possible only with sufficient moisture, care has to be taken... 

The use of polyurethane as a binder has found two interesting applications foundry cores and woodchip particleboard. The foundry industry has recognized the value of polyurethane adhesive binders to bind sand foundry cores for metal casting. This application is increasing steadily. The use of isocyanate binders for woodchip particleboard is receiving significant attention. The... 

Polyurethane adhesives were prepared by mixing polyol, diisocyanate (MDI, TDI or HDI), solvent (DMF, benzene or ethylace-tate), and catalyst (T-9) in the following fashion The diisocyanate dissolved in half of the total solvent volume was mixed with two-thirds of the polyol in one-fourth of the solvent in the presence of a trace of the catalyst. The mixture was heated to 50°C until an exothermic reaction starts then, heat was temporarily removed and reapplied for 10 min to maintain a temperature of 80°C. The rest of the polyol, catalyst, and solvent were then added and mixed completely. The resin was ready for application when the consistency of the mixture had reached a suitable level. The adhesive was spread on 11 3/4" x 4 1/2" x 3/4" wood (hard maple or southern pine) strips. The moist adhesive-coated surfaces were exposed to ambient air (vented hood) for 20-30 seconds if DMF was used as solvent, or for 3-5 minutes if either benzene or ethylacetate was used. After pressing (100 psi), the strips were cut into small shear blocks and tested according to ASTM Standard D905-49. Polyurethane coatings were prepared by mixing the polyol (80 parts) in ethylacetate (60 parts) and toluene (40 parts), with a solution of TDI (53 parts) in 80 parts ethylacetate and 30 parts toluene, and T-9 catalyst... 

A number of "crude" isocyanates (polymeric isocyanates), undistilled grades of MDI and TDI, are available in the market. Some of these products, such as various forms of crude MDI, have a functionality varying between 2 and 3. They have a lower reactivity and a lower vapor pressure than the corresponding pure isocyanate. They have found extensive use in one-shot rigid foams. However, they are also employed in coating, sealant, and adhesive applications. The Upjohn Chemical Division has published an excellent bulletin on the use and precautions in handling isocyanates, polyurethanes, and related materials (13A). 

The development of polyurethane adhesives can be traced back more than 60 years to the pioneering efforts of Otto Bayer and co-workers. Bayer extended the chemistry of polyurethanes initiated in 1937 [1] into the realm of adhesives about 1940 [2] by combining polyester polyols with di- and polyisocyanates. He found that these products made excellent adhesives for bonding elastomers to fibers and metals. Early commercial applications included life rafts, vests, airplanes, tires, and tanks [3]. These early developments were soon eclipsed by a multitude of new applications, new technologies, and patents at an exponential rate. 

Polyurethane adhesive consumption has been estimated at 217 million pounds (1991) having a value of approximately 301 million (see Fig. 2). Applications contributing to this volume are shown in Table 1. It is interesting to note that while the packaging market is the fourth-largest market in terms of pounds of urethane adhesives sold, it is substantially larger than the forest products market and the foundry core binder market in terms of... 

The transportation market has used polyurethane adhesives for such diverse applications as bonding FRP and sheet molding composite (SMC) panels in truck and car applications, polycarbonate headlamp assemblies, door panels, and weatherstrip flocking. 

The second major classification of common polyurethane adhesives is the two-component system. Two-component polyurethane adhesives are widely used where fast cure speeds are critical, as on OEM (original equipment manufacturers) assembly lines that require quick fixture of parts, especially at ambient or low bake temperatures. Two-component urethanes are required in laminating applications where no substrate moisture is available or where moisture cannot penetrate through to the adhesive bond. Two-component urethanes are also useful where CO2 (generated by a one-component moisture cure) or a volatile blocking agent would interfere with the adhesive properties. 

Apart from underbody coating (usually PVC based), which is not explained further, the majority of bonding and sealing products in the paint shop are also PVC compounds. Acrylate plastisols are not often used and polyurethane-based sealants are rarely found. The main applications are in seam sealing and antiflutter bonding. On a small scale there are adhesive applications to bond and seal caps and to fix sound deadeners. In addition, foams and butyls as well as bituminous or acrylic-based sealants are used to fill car body holes. 

In view of the above efforts, it is surprising that the majority of recent patents on adhesives are for solvent-based systems.The new inventions include a universal primer, an adhesive composition in which solvents have been selected based on Snyder s polarity (only solvents which belong to group III are useful in adhesive for automotive applications to avoid a deleterious effect on paint), a low VOC adhesive for pipes and fittings, a solvent-containing heat-resistant adhesive based on siloxane polyimide, a water-based polyimide adhesive,and two-component solvent-free polyurethane adhesive system for use in automotive door paneling. ... 

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