Vinyl-phenolic adhesive formulation

A great many of outstanding adhesive formulations are based on epoxy resins. A broad spectrum of adhesive formulations with a wide range of available properties have resulted from the use of polymeric hardeners such as polyamides and polyamines, phenolics, isocyanates, alkyds, and combinations of amines with polysulfide elastomers, and the alloying of the epoxy with compatible polymeric film-formers, such as poly(vinyl acetate) and certain elastomers. 

Elastomer epoxies generally contain nitrile rubber as the elastomeric component. This system is also referred to as a modified or toughened epoxy. One of the applications of widest use is in films and tapes. Elastomer epoxies cure at low pressures and low temperatures over a short time interval. This is achieved by adding a catalyst to the adhesive formulation. Bond strengths of elastomer epoxies are lower than those of nylon epoxies. However, the major advantage of elastomer epoxies is their sub-zero peel strengths, which do not decrease as fast as those of nylon epoxies. In addition, the moisture resistance of elastomer epoxies is better than that of nylon epoxies but not as good as that of vinyl-phenolics or nitrile-phenolics. Limitations to the use of elastomer epoxies include poor water immersion resistance and poor properties when exposed to marine conditions. 

The phenolic family of adhesives are very diverse in their formulations and uses. Some are filled or modified with other polymers (vinyl, nitrile or epoxy). The composition depends largely on the intended use, e.g. for temperature and chemical resistance, or for water-proof wood bonding (phenol-resorcinol-formaldehyde). The majority are heat-curing although some wood-bonding adhesives can be cured at room temperature (RT). The comparison table includes Typical Use to differentiate between the types of adhesives. Phenolic adhesives are generally poorly represented by mechanical property data. 

Phenolic materials go back to the patents of Baekeland and are based upon the reaction of phenol and formaldehyde to yield a lower molecular weight resinous material that can be formulated with other resins and sometimes other curatives to yield a paste adhesive or a film adhesive. When phenol and formaldehyde are reacted in the presence of an acidic catalyst with an excess of phenol versus formaldehyde, they yield what are known as novolac resins. These materials are soluble in organic solvents and do not react further with themselves thus, they need to have a curative added. That curative is most often hexamethylene tetraamine. Another type of phenolic resin can be generated with an excess of formaldehyde and under basic conditions. These materials, known as resole phenolics, will react with themselves to yield a ftilly cured phenolic and thus must be stored frozen in order to limit this reaction. Thus, resole phenolics do not need an external CTOsslinker. Resole phenolics are widely used in the binding of paper products and the bonding of wood. Adhesives based upon these materials were brittle and could only be used to bond wood, where it is still widely used. A more widely usable adhesive was developed during World War II which modified the very brittle phenolic adhesive with poly(vinyl formal) resins. These materials were... 

Nitrile rubber is compatible with phenol-formaldehyde resins, resorcinol-formaldehyde resins, vinyl chloride resins, alkyd resins, coumarone-indene resins, chlorinated rubber, epoxies and other resins, forming compositions which can be cured providing excellent adhesives of high strength, high oil resistance and high resilience. On the other hand, NBR adhesives are compatible with polar adherends such as fibres, textiles, paper and wood. Specific formulations of NBR adhesives can be found in [12]. 

Alkenyloxystyrene monomers such as 4-allyloxystyrene are useful components of photocured cationically polymerizable compositions. Used alone or in combination with divinyl ethers they provide low viscosity formulations, which are excellent solvents for commercial onium salt photoinitiators. Photocuring rates are comparable to vinyl ether monomers and the initially photocured alkenyloxystyrene polymers may be further heat processed to yield crosslinked phenolic type resins having outstanding thermal resistance properties. The new materials have good adhesive properties and are potentially useful where a combination of ease of processability and high performance is required. 

In adhesives, because of their brittle nature, phenolics are generally formulated in add mixture with other polymers. They are used as the primary cross-linking agents for nitrile rubbers, poly(vinyl formal) and butyral resins, and epoxy resins. 

It was not until the commercialization of synthetic plastics resins in the 1930s that an almost unlimited variety of base materials became available for compounding into adhesives and sealants. Most of the thermoplastic resins were soluble in organic solvents and were used as solvent adhesives for molded plastic articles of the same base composition and sometimes for other materials. Poly(vinyl chloride) (PVC), a thermoplastic developed in 1927, is used today in solvent formulations to bond PVC articles such as coated fabrics, films, foams, and pipe. In the early 1930s, phenolics came into importance as adhesive resins. Before that time they were used as coating varnishes [9, p. 239). About 1931 development of the use of a new phenolic resin for plywoods and veneers began [9, p. 239]. 

PVAc-based commercial wood adhesives are evaluated using standard tests for non-structural applications, as reported in EN 205 [8], and they are classified in agreement with the standard EN-204 [9]. This standard allows to classify wood adhesives in 4 categories from D1 to D4. D1 adhesives show a good resistance only in dry conditions D2 adhesives should withstand a rather low water presence, such as in occasional exposure in kitchens and bathrooms D3 adhesives are suitable to come in contact with cold water, such as for outside windows and doors, kitchen and bathrooms furniture D4 adhesives are suitable to be used in extreme conditions (resistance to hot water). Vinyl acetate homopolymer can be used to formulate D1 or D2 adhesives. Vinyl acetate based adhesives cross-Unked with hardeners and urea-formaldehyde (UF) adhesives belong to class D3. Only the phenol-formaldehyde (PE), resorcinol-formaldehyde (RF) and melamine-formaldehyde (MF) adhesives, some special 2-component polyurethanes (PUs), and cross-linking vinyl adhesives belong to class D4. 

Although Redux is still in use today, it has largely been displaced by adhesives supplied in film form. The advantages of film adhesives over the Redux system are twofold (1) they are supplied at exactly the desired weight, and (2) the formulation is precisely controlled (i.e., the ratio of phenolic resin to vinyl resin). As a consequence the aircraft manufacturer is less dependent on the skill of the individual applying the adhesive. 

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