Identifiers | |
---|---|
ChemSpider |
|
ECHA InfoCard | 100.105.516 |
CompTox Dashboard (EPA) | |
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). |
Phenol formaldehyde resins (PF) (phenolic resins or phenoplasts [1] ) are synthetic polymers obtained by the reaction of phenol or substituted phenol with formaldehyde. Used as the basis for Bakelite, PFs were the first commercial synthetic resins. They have been widely used for the production of molded products including billiard balls, laboratory countertops, and as coatings and adhesives. They were at one time the primary material used for the production of circuit boards but have been largely replaced with epoxy resins and fiberglass cloth, as with fire-resistant FR-4 circuit board materials.
There are two main production methods. One reacts phenol and formaldehyde directly to produce a thermosetting network polymer, while the other restricts the formaldehyde to produce a prepolymer known as novolac which can be moulded and then cured with the addition of more formaldehyde and heat. [2] [3] There are many variations in both production and input materials that are used to produce a wide variety of resins for special purposes.
Phenol-formaldehyde resins, as a group, are formed by a step-growth polymerization reaction that can be either acid- or base-catalysed. Since formaldehyde exists predominantly in solution as a dynamic equilibrium of methylene glycol oligomers, the concentration of the reactive form of formaldehyde depends on temperature and pH.
Phenol reacts with formaldehyde at the ortho and para sites (sites 2, 4 and 6) allowing up to 3 units of formaldehyde to attach to the ring. The initial reaction in all cases involves the formation of a hydroxymethyl phenol:
The hydroxymethyl group is capable of reacting with either another free ortho or para site, or with another hydroxymethyl group. The first reaction gives a methylene bridge, and the second forms an ether bridge:
The diphenol (HOC6H4)2CH2 (sometimes called a "dimer") is called bisphenol F, which is an important monomer in the production of epoxy resins. Bisphenol-F can further link generating tri- and tetra-and higher phenol oligomers.
Novolaks (or novolacs) are phenol-formaldehyde resins with a formaldehyde to phenol molar ratio of less than one. In place of phenol itself, they are often produced from cresols (methylphenols). The polymerization is brought to completion using acid-catalysis such as sulfuric acid, oxalic acid, hydrochloric acid and rarely, sulfonic acids. [4] The phenolic units are mainly linked by methylene and/or ether groups. The molecular weights are in the low thousands, corresponding to about 10–20 phenol units. Obtained polymer is thermoplastic and require a curing agent or hardener to form a thermoset.
Hexamethylenetetramine is a hardener added to crosslink novolac. At a temperature greater than 90 °C, it forms methylene and dimethylene amino bridges. Resoles can also be used as a curing agent (hardener) for novolac resins. In either case, the curing agent is a source of formaldehyde which provides bridges between novolac chains, eventually completely crosslinking the system. [2]
Novolacs have multiple uses as tire tackifier, high temperature resin, binder for carbon bonded refractories, carbon brakes, photoresists and as a curing agent for epoxy resins.
Base-catalysed phenol-formaldehyde resins are made with a formaldehyde to phenol ratio of greater than one (usually around 1.5). These resins are called resoles. Phenol, formaldehyde, water and catalyst are mixed in the desired amount, depending on the resin to be formed, and are then heated. The first part of the reaction, at around 70 °C, forms a thick reddish-brown tacky material, which is rich in hydroxymethyl and benzylic ether groups.
The rate of the base-catalysed reaction initially increases with pH, and reaches a maximum at about pH = 10. The reactive species is the phenoxide anion (C6H5O−) formed by deprotonation of phenol. The negative charge is delocalised over the aromatic ring, activating sites 2, 4 and 6, which then react with the formaldehyde.
Being thermosets, hydroxymethyl phenols will crosslink on heating to around 120 °C to form methylene and methyl ether bridges through the elimination of water molecules. At this point the resin is a 3-dimensional network, which is typical of polymerised phenolic resins. The high crosslinking gives this type of phenolic resin its hardness, good thermal stability, and chemical imperviousness. Resoles are referred to as "one step" resins as they cure without a cross linker unlike novolacs, a "two step" resin.
Resoles are major polymeric resin materials widely used for gluing and bonding building materials. Exterior plywood, oriented strand boards (OSB), engineered high-pressure laminate are typical applications.
When the molar ratio of formaldehyde:phenol reaches one, in theory every phenol is linked together via methylene bridges, generating one single molecule, and the system is entirely crosslinked. This is why novolacs (F:P <1) do not harden without the addition of a crosslinking agents, and why resoles with the formula F:P >1 will.
Phenolic resins are found in myriad industrial products. Phenolic laminates are made by impregnating one or more layers of a base material such as paper, fiberglass, or cotton with phenolic resin and laminating the resin-saturated base material under heat and pressure. The resin fully polymerizes (cures) during this process forming the thermoset polymer matrix. The base material choice depends on the intended application of the finished product. Paper phenolics are used in manufacturing electrical components such as punch-through boards, in household laminates, and in paper composite panels. Glass phenolics are particularly well suited for use in the high speed bearing market. Phenolic micro-balloons are used for density control. The binding agent in normal (organic) brake pads, brake shoes, and clutch discs are phenolic resin. Synthetic resin bonded paper, made from phenolic resin and paper, is used to make countertops. Another use of phenolic resins is the making of duroplast, famously used in Trabant automobiles.
Phenolic resins are also used for making exterior plywood commonly known as weather and boil proof (WBP) plywood because phenolic resins have no melting point but only a decomposing point in the temperature zone of 220 °C (428 °F) and above.
Phenolic resin is used as a binder in loudspeaker driver suspension components which are made of cloth.
Higher end billiard balls are made from phenolic resins, as opposed to the polyesters used in less expensive sets.
Sometimes people select fibre reinforced phenolic resin parts because their coefficient of thermal expansion closely matches that of the aluminium used for other parts of a system, as in early computer systems [5] and Duramold.
The Dutch painting forger Han van Meegeren mixed phenol formaldehyde with his oil paints before baking the finished canvas, in order to fake the drying out of the paint over the centuries.[ citation needed ]
Atmospheric re-entry spacecraft use phenol formaldehyde resin as a key component in ablative heat shields (e.g. AVCOAT on the Apollo modules). As the heat shield skin temperature can reach 1000-2000 °C, the resin pyrolizes due to aerodynamic heating. This reaction absorbs significant thermal energy, insulating the deeper layers of the heat shield. The outgassing of pyrolisis reaction products and the removal of charred material by friction (ablation) also contribute to vehicle insulation, by mechanically carrying away the heat absorbed in those materials.
Phenol-formaldehyde is degraded by the white rot fungus Phanerochaete chrysosporium . [8]
Epoxy is the family of basic components or cured end products of epoxy resins. Epoxy resins, also known as polyepoxides, are a class of reactive prepolymers and polymers which contain epoxide groups. The epoxide functional group is also collectively called epoxy. The IUPAC name for an epoxide group is an oxirane.
In materials science, a thermosetting polymer, often called a thermoset, is a polymer that is obtained by irreversibly hardening ("curing") a soft solid or viscous liquid prepolymer (resin). Curing is induced by heat or suitable radiation and may be promoted by high pressure or mixing with a catalyst. Heat is not necessarily applied externally, and is often generated by the reaction of the resin with a curing agent. Curing results in chemical reactions that create extensive cross-linking between polymer chains to produce an infusible and insoluble polymer network.
A drying oil is an oil that hardens to a tough, solid film after a period of exposure to air, at room temperature. The oil hardens through a chemical reaction in which the components crosslink by the action of oxygen. Drying oils are a key component of oil paint and some varnishes. Some commonly used drying oils include linseed oil, tung oil, poppy seed oil, perilla oil, castor oil and walnut oil. The use of natural drying oils has declined over the past several decades, as they have been replaced by alkyd resins and other binders.
In chemistry and biology, a cross-link is a bond or a short sequence of bonds that links one polymer chain to another. These links may take the form of covalent bonds or ionic bonds and the polymers can be either synthetic polymers or natural polymers.
Micarta is a brand name for composites of linen, canvas, paper, fiberglass, carbon fiber, or other fabric in a thermosetting plastic. It was originally used in electrical and decorative applications. Micarta was developed by George Westinghouse at least as early as 1910 using phenolic resins invented by Leo Baekeland. These resins were used to impregnate paper and cotton fabric which were cured under pressure and high temperature to produce laminates. In later years this manufacturing method included the use of fiberglass fabric, and other resin types were also used. Today Micarta high-pressure industrial laminates are produced with a wide variety of resins and fibers. The term has been used generically for most resin impregnated fiber compounds. Common uses of modern high-pressure laminates include electrical insulators, printed circuit board substrates, and knife handles.
Powder coating is a type of coating that is applied as a free-flowing, dry powder. Unlike conventional liquid paint, which is delivered via an evaporating solvent, powder coating is typically applied electrostatically and then cured under heat or with ultraviolet light. The powder may be a thermoplastic or a thermosetting polymer. It is usually used to create a thick, tough finish that is more durable than conventional paint. Powder coating is mainly used for coating of metal objects, particularly those subject to rough use. Advancements in powder coating technology like UV-curable powder coatings allow for other materials such as plastics, composites, carbon fiber, and medium-density fibreboard (MDF) to be powder coated, as little heat or oven dwell time is required to process them.
Wood glue is an adhesive used to tightly bond pieces of wood together. Many substances have been used as glues. Traditionally animal proteins like casein from milk or collagen from animal hides and bones were boiled down to make early glues. They worked by solidifying as they dried. Later, glues were made from plant starches like flour or potato starch. When combined with water and heated, the starch gelatinizes and forms a sticky paste as it dries. Plant-based glues were common for books and paper products, though they can break down more easily over time compared to animal-based glues. Examples of modern wood glues include polyvinyl acetate (PVA) and epoxy resins. Some resins used in producing composite wood products may contain formaldehyde. As of 2021, “the wood panel industry uses almost 95% of synthetic petroleum-derived thermosetting adhesives, mainly based on urea, phenol, and melamine, among others”.
Polybenzoxazines, also called benzoxazine resins, are cured polymerization products derived from benzoxazine monomers.
Curing is a chemical process employed in polymer chemistry and process engineering that produces the toughening or hardening of a polymer material by cross-linking of polymer chains. Even if it is strongly associated with the production of thermosetting polymers, the term "curing" can be used for all the processes where a solid product is obtained from a liquid solution, such as with PVC plastisols.
Melamine resin or melamine formaldehyde is a resin with melamine rings terminated with multiple hydroxyl groups derived from formaldehyde. This thermosetting plastic material is made from melamine and formaldehyde. In its butylated form, it is dissolved in n-butanol and xylene. It is then used to cross-link with alkyd, epoxy, acrylic, and polyester resins, used in surface coatings. There are many types, varying from very slow to very fast curing.
Polymer engineering is generally an engineering field that designs, analyses, and modifies polymer materials. Polymer engineering covers aspects of the petrochemical industry, polymerization, structure and characterization of polymers, properties of polymers, compounding and processing of polymers and description of major polymers, structure property relations and applications.
Cyanate esters are chemical compounds in which the hydrogen atom of the cyanic acid is replaced by an organyl group. The resulting compound is termed a cyanate ester, with the formula R−O−C≡N, where R is an organyl group. Cyanate esters contain a monovalent cyanate group −O−C≡N.
A thermoset polymer matrix is a synthetic polymer reinforcement where polymers act as binder or matrix to secure in place incorporated particulates, fibres or other reinforcements. They were first developed for structural applications, such as glass-reinforced plastic radar domes on aircraft and graphite-epoxy payload bay doors on the Space Shuttle.
Bisphenol A diglycidyl ether is an organic compound and is a liquid epoxy resin. The compound is a colorless viscous liquid. It is a key component of many epoxy resin formulations. Addition of further Bisphenol A and a catalyst and heat can produce Bisphenol A glycidyl ether epoxy resins of higher molecular weight that are solid.
Nylon 1,6 is a type of polyamide or nylon. Unlike most other nylons, nylon 1,6 is not a condensation polymer, but instead is formed by an acid-catalyzed synthesis from adiponitrile, formaldehyde, and water. The material was produced and studied by researchers at DuPont in the 1950s. Synthesis can be performed at room temperature in open beakers.
In materials science, a polymer matrix composite (PMC) is a composite material composed of a variety of short or continuous fibers bound together by a matrix of organic polymers. PMCs are designed to transfer loads between fibers of a matrix. Some of the advantages with PMCs include their light weight, high resistance to abrasion and corrosion, and high stiffness and strength along the direction of their reinforcements.
Furan resin refers to polymers produced from various furan compounds, of which the most common starting materials are furfuryl alcohol and furfural. In the resin and in the cured polyfurfurol, the furan rings are not connected by conjugation. The resins are generally used as binders for sand castings. The furan monomer is typically converted to a free-flowing resin with mild acid catalysis. Curing is achieved using strong acid.
Novolaks are low molecular weight polymers derived from phenols and formaldehyde. They are related to Bakelite, which is more highly crosslinked. The term comes from Swedish "lack" for lacquer and Latin "novo" for new, since these materials were envisioned to replace natural lacquers such as copal resin.
Castor oil glycidyl ether is a liquid organic chemical in the glycidyl ether family. It is sometimes called castor oil triglycidyl ether. It has the theoretical formula C66H116O12. There are two CAS numbers in use, 14228-73-0 and 74398-71-3. The IUPAC name is 2,3-bis[[(E)-12-(oxiran-2-ylmethoxy)octadec-9-enoyl]oxy]propyl (E)-12-(oxiran-2-ylmethoxy)octadec-9-enoate. A key use is acting as a modifier for epoxy resins as a reactive diluent that adds flexibility and improved mechanical properties.
2,4,6-Tris(dimethylaminomethyl)phenol is an aromatic organic chemical that has tertiary amine and phenolic hydroxyl functionality in the same molecule. The formula is C15H27N3O and the CAS Registry Number is 90-72-2. It is REACH registered and the European Community Number is 202-013-9.