System, hybrid epoxy

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. 

A variety of polymers, both thermosets as well as thermoplastics, can be blended and coreacted with epoxy resins to provide for a specific set of desired properties. The most common of these are nitrile, phenolic, nylon, poly sulfide, and polyurethane resins. At high levels of additions these additives result in hybrid or alloyed systems with epoxy resins rather than just modifiers. They differ from reactive diluents in that they are higher-molecular weight-materials, are used at higher concentrations, and generally have less deleterious effect on the cured properties of the epoxy resin. 

Typically tape or film epoxy adhesives are modified with synthetic thermoplastic polymers to improve flexibility in the uncured film and toughness in the cured adhesive. Epoxy resins can also be blended with phenolic resins for higher heat resistance. The most common hybrid systems include epoxy-phenolics, epoxy-nylon, epoxy-nitrile, and epoxy-vinyl hybrids. These hybrid film adhesives are summarized in Table 13.2, and structural properties are shown in Table 13.3. 

Several hybrid epoxy emulsions have been commercially prepared. An epoxy emulsion blended with waterborne aliphatic urethanes exhibited peel strength on aluminum of 10 lb/in—1.5 times greater than with the polyurethane itself. The optimum concentration of urethane in the final emulsion was about 50 percent by weight.13 Epoxy-phenolic dispersions have also been developed to provide waterborne adhesive systems with high glass transition temperature and chemical resistance. 

Another development has been reported by P.A. Lucas, W.E. Stamer and S.G. Musselman of Air Products and Chemicals Inc. (Lucas et al., 1994). An acrylate functional urethane flexibiliser has been used to modify epoxy resin, which optimises reactivity and is more compatible with epoxy. Urethane-acrylate flexibiliser offers very tough hybrid epoxy systems meeting the more demanding requirements of civil engineering applications. 

Table 3.5. Mechanical properties of hybrid epoxy systems modified with CTBN/EX-PANCEL [9]...

In contrast to the PBT/Cloisite 6A and PBT/Cloisite lOA systems, adding epoxy resin to the PBT/Cloisite SOB nanocomposites is an effective way to improve the nanostructure of the corresponding hybrids. The XRD pattern also indicates a high degree of intercalation with layer spacings higher than 4-5 nm, and/or exfoliation of the Cloisite SOB silicate layers. 

Aromatic tertiary amines ean also be used as part of the initiator system [58]. Glyeidyl methaerylate or methaerylie aeid have been used to hybridize acrylie adhesives based on this eure ehemistry with epoxies [59]. The epoxy funetionality is reaetive with the earboxylie aeid groups on the monomer. 

Hybrid systems of acrylics with other technologies have been reported. Aciylic and epoxy polymers can be coupled through the use of 2-methacryloloxyethyl phosphate. The phosphoric acid functionality reacts with epoxy and the methacrylate group copolymerizes with the acrylic backbone [ 145] (Scheme 14). 

L. Mascia and T. Tang, Ceramers based on crosslinked epoxy resins-silica hybrids low surface energy systems, J. Sol-Gel Sci. Technol., 1998, 13, 405. 

In protein microarrays, capture molecules need to be immobilized in a functional state on a solid support. In principle, the format of the assay system does not limit the choice of appropriate surface chemistry. The same immobilization procedure can be applied for both planar and bead-based systems. Proteins can be immobilized on various surfaces (Fig. 1) (12). Two-dimensional polystyrene, polylysine, aminosilane, or aldehyde, epoxy- or thiol group-coated surfaces can be used to immobilize proteins via noncovalent or covalent attachment (13,14). Three-dimensional supports like nitrocellulose or hydrogel-coated surfaces enable the immobilization of the proteins in a network structure. Larger quantities of proteins can be immobilized and kept in a functional state. Affinity binding reagents such as protein A, G, and L can be used to immobilize antibodies (15), streptavidin is used for biotinylated proteins (16), chelate for His-tagged proteins (17, 18), anti-GST antibodies for GST fusion proteins (19), and oligonucleotides for cDNA or mRNA-protein hybrids (20). 

These blends can take a number of different forms. The added resin may be reacted with the epoxy resin, or it may be included as an unreacted modifier. The modifier may be blended into a continuous phase with the epoxy resin (epoxy alloys) or precipitated out as a discrete phase within the epoxy resin matrix (as is generally done in the case of toughening modifiers). Epoxy hybrid adhesives are often used as film (supported and unsupported) or tape because of the ease with which formulated systems can be dissolved into solvent and applied to a carrier or deposited as a freestanding film. Some systems, notably epoxyurethanes and epoxy-poly sulfides, can be employed as a liquid or paste formulation because of the low-viscosity characteristics of the components. 

TABLE 7.1 Common Epoxy Hybrid Adhesive Systems... 

The first group, resins that are used primarily to toughen epoxy adhesive systems, is described in Chap. 8. This chapter focuses on the resinous modifiers that are used as alloy blends. Characteristics of commercially available epoxy alloy adhesives are presented in Table 7.1. Tensile shear and peel strengths that are typical of these hybrid adhesives are compared in Table 7.2. 

Blocked isocyanate prepolymers have been mixed with epoxy resins and cured with amines.18,19 These blocked prepolymers will initially react with the amines to form amine-terminated prepolymers that crosslink the epoxy resin. Urethane amines are also offered commercially for use with epoxy resins to develop hybrid adhesive systems.20... 

The number of possible hybrid systems that can be manufactured with epoxy resins is nearly infinite, and many adhesive formulations have been attempted in a quest to improve the main disadvantages of a cured epoxy brittleness and rigidity. 

Functionalized, liquid polybutadiene derivatives have also been developed as hybrid flexiblizers for epoxy resins. Carboxyl-terminated butadiene/acrylonitrile polymers, butadiene homopolymers, and maleic anhydride-amino acid grafted butadiene homopolymers have been used as flexibilizers to impart good low-temperature strength and water resistance to DGEBA-based epoxy adhesives. An epoxy system toughened by polybutadiene with maleic anhydride is claimed to provide a hydrophobic backbone, low viscosity, softness, and high tensile strength and adhesion (Table 7.10). 

These hybrids generally yield improved flexibility and toughness, but they are more commonly used in epoxy coating formulations than in adhesive systems. 

By adding nonepoxy flexibilizing resins to the formulation to create an epoxy-hybrid adhesive system... 

However, newer adhesives systems having moderate temperature resistance have been developed with improved toughness but without sacrificing other properties. When cured, these structural adhesives have discrete elastomeric particles embedded in the matrix. The most common toughened hybrids using this concept are acrylic and epoxy systems. The elastomer is generally a amine- or carboxyl-terminated acrylonitrile butadiene copolymer (ATBN and CTBN). 

There are several common forms of solid epoxy adhesives. These include film, tape, powder, and preformed shapes. Certain formulations are better suited for specific forms. For example, casting of tape or film adhesive from solvent solutions lends itself to working with multicomponent hybrid systems, where each resin can be solubilized and blended together in a universal solvent. B-staged systems are generally more brittle and better suited for powders or preformed adhesives. 

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