Epoxy resin nitrile system

Elastomers, plastics, fabrics, wood and metals can be joined with themselves and with each other using nitrile rubber/epoxy resin blends cured with amines and/or acidic agents. Ethylene-propylene vulcanizates can also be joined using blends of carboxylated nitrile rubber, epoxy resin and a reactive metal filler (copper, nickel, cobalt). However, one of the largest areas of use of nitrile rubber modified epoxy systems is in the printed circuit board area [12]. 

Composite Particles, Inc. reported the use of surface-modified rubber particles in formulations of thermoset systems, such as polyurethanes, polysulfides, and epoxies [95], The surface of the mbber was oxidized by a proprietary gas atmosphere, which leads to the formation of polar functional groups like —COOH and —OH, which in turn enhanced the dispersibility and bonding characteristics of mbber particles to other polar polymers. A composite containing 15% treated mbber particles per 85% polyurethane has physical properties similar to those of the pure polyurethane. Inclusion of surface-modified waste mbber in polyurethane matrix increases the coefficient of friction. This finds application in polyurethane tires and shoe soles. The treated mbber particles enhance the flexibility and impact resistance of polyester-based constmction materials [95]. Inclusion of treated waste mbber along with carboxyl terminated nitrile mbber (CTBN) in epoxy formulations increases the fracture toughness of the epoxy resins [96]. 

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. 

Relevant systems are mbber-toughened epoxy resins, high-impact acrylic (PMMA particles in mbber matrix, obtained by radical polymerization of 80/20 MMA/EVAc mixture), polyimide/silica hybrid materials (obtained using the sol-gel method), and a very high strength ( 60 MPa) mbbers (obtained by peroxide cure of a hydrogenated nitrile rubber/ zinc dimethacrylate system) [Inoue, 1995]. 

Another chosen example stems from the perceived benefits of combining solid and liquid carboxylic nitrile elastomers in the same modification scheme. This is particularly useful when a degree of tack is required in the system. Table VIII exhibits one approach for preparing such an elastomer-modified solid DGEBA resin. In this instance a resin (epoxide equivalent weight of 650) was prepared by advancing two available liquid epoxy resin adducts — one utilizing a liquid nitrile, the other a solid nitrile elastomer. 

Consequent to documentation surrounding methods of employing reactive nitrile elastomers to modify epoxy resins is a growing body of literature which serves to characterize and elucidate these systems. Such topics as morphology in the cured and uncured state, transitions from toughening to flexlbilization, viscoelastic effects, equilibrium physical properties and phase structure are available to the investigator (12-17). 

Small nitrile-rubber inclusions in epoxy resin electrical en-capsulants have been examined in both amine (29-31) and acid (32) epoxy cures, in filled and unfilled systems. The value of rubber inclusion in a boron trlfluorlde/amine complex epoxy cure has also been demonstrated (33), where elevated-temperature, high-humldlty testing showed electrical properties retention to be better than a comparable system cured with dodecenylsucclnic anhydride. Rubber benefits low-temperature properties specifically and thermocycling in general. It affects high temperature insulation properties negatively therefore, the amount of rubber incorporated must be judiciously chosen. 

One can rationalize a need for small rubber inclusions in some of the newer approaches to waterborne and high solids epoxy coating systems. Water-thinned epoxy coating compositions are described (48) where the two-component system consists of a nitrile rubber modified epoxy resin in the epoxide component and a styrene/ butadiene/methylmethacrylate latex modifier for an emulsion-based polyamide hardener component. Showing improved adhesion, impact and water resistance, the paint has good wetting characteristics and can be formulated to a high solids content at low viscosity. 

Flexible circuit boards consist primarily of polyimide-based carriers. The problem of bonding the copper foil on the polyimide carrier has not yet been solved satisfactorily. Due especially to their low bonding strength at elevated temperatures, the production of such materials is very limited. Nevertheless, adhesives for copper-polyimide systems were developed, where one-component epoxy resins (e.g., epoxy-polyester mixtures) and reactive hot melts (e.g., phenolic resin-nitrile rubbers) reached importance. 

Chiou and Bradley [81] conducted hydraulic burst and stress rupture tests on 1.28mm thick (58v/o 87/ 35/87° hoop filament wound) tubes made from E-glass fibre/Brunswick LRF-571 DGEBA epoxy resin. There were 6% voids in the laminate. A co-cured nitrile rubber liner was employed, partly to keep the inner surface dry and partly to ensure that pressure could still be maintained if the GRP cracked during the tests. The tests followed 6 months immersion in static simulated sea water (Aquarium Systems Instant Ocean, p = 1023 kgm, pH = 8.2). The tubes had a high (1.5%) moisture uptake, although some of this might have been free water in the voids, but saturation was not reached. 

In structural applications for epoxy resins, there are useful nitrile-epoxy systems that are prepared from (1) noncarboxylic nitrile rubber, which has been milled to reduce molecular weight and then transferred to solvents with the epoxy resins, and (2) specialty nitrile latexes, which are added directly to the epoxy resin and then vacuum-stripped to remove water. These approaches for preparing a nitrile-epoxy formulating base are not widely used and are confined primarily to adhesive applications. 

The liquid nitrile rubbers can be reacted into the epoxy matrix in one of two ways. If a carboxyl terminated material is used it is normally adducted or prepolymerized with an epoxy resin prior to formulating. The resulting epoxy adduct is then placed in the epoxy component of the composition. A second method of incorporating liquid nitrile materials would be to use an amine terminated rubber. In this case the material contributes amine reactivity and functions as a part of the hardener system. These materials were primarily developed to form stable admixes with amine containing epoxy hardeners. 

Pressure Sensitive. Mixtures of nitrile rubber and epoxy resin have been described to be useful as pressure sensitive adhesives. One such system combines nitrile rubber, a bisphenol A type epoxy resin methacrylate ester, a product... 

Carboxylic nitrile liquid and solid elastomers are used to prepare elastomer-modified epoxy liquid and solid resins when it is desirable to have the modifier in the epoxy portion of the system. This is effected through alkyl-hydroxy esterification reactions. This is covered in the literature for uncatalyzed liquid resins (9), for tert-amine catalyzed systems (10), for tert-phosphine catalyzed systems (11), for low molecular weight solid resins advanced from the liquid state (12) and for liquid and solid resins where an additional rubber vulcanization step is carried out in addition to the alkylhydroxy ester adducting step (13). Such adduct preparations offer formulation stability with a wide range of hardener types amines, anhydrides, catalytic, Lewis acids/bases. 

In most widely used two-polymer adhesives, the thermosetting component is phenolic. Phenolic resins are generally compatible, although not easily miscible, with a number of thermoplastic polymers. Particularly good compatibility is demonstrated between conventional alcohol-soluble phenolic resins and polyvinyl esters and acetals. Epoxies are important in two polymer adhesive systems. The most important thermoplastic components are the polyvinyl acetals (polyvinyl formal and butyral) and synthetic rubber, particularly nitrile rubber. Soluble nylons are also an important class. ... 

Phenolics or phenol-formaldehyde structural adhesives are chemically reactive systems that cure to form thermosets. In one-component systems, meltable powders (resols) are used as binders for particle board or as alloys (including nitrile-phenolics, vinyl - phenolics, and epoxy-phenolics), which are used in the structural bonding of metals. In two-component systems, the resin and catalyst are mixed and then heated to initiate curing. Both systems cure by a condensation reaction that produces a byproduct. 

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