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). [1] 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 (catalyst, hardener ). Curing results in chemical reactions that create extensive cross-linking between polymer chains to produce an infusible and insoluble polymer network.
The starting material for making thermosets is usually malleable or liquid prior to curing, and is often designed to be molded into the final shape. It may also be used as an adhesive. Once hardened, a thermoset cannot be melted for reshaping, in contrast to thermoplastic polymers which are commonly produced and distributed in the form of pellets, and shaped into the final product form by melting, pressing, or injection molding.
Curing a thermosetting resin transforms it into a plastic, or elastomer (rubber) by crosslinking or chain extension through the formation of covalent bonds between individual chains of the polymer. Crosslink density varies depending on the monomer or prepolymer mix, and the mechanism of crosslinking:
Acrylic resins, polyesters and vinyl esters with unsaturated sites at the ends or on the backbone are generally linked by copolymerisation with unsaturated monomer diluents, with cure initiated by free radicals generated from ionizing radiation or by the photolytic or thermal decomposition of a radical initiator – the intensity of crosslinking is influenced by the degree of backbone unsaturation in the prepolymer; [2]
Epoxy functional resins can be homo-polymerized with anionic or cationic catalysts and heat, or copolymerised through nucleophilic addition reactions with multifunctional crosslinking agents which are also known as curing agents or hardeners. As reaction proceeds, larger and larger molecules are formed and highly branched crosslinked structures develop, the rate of cure being influenced by the physical form and functionality of epoxy resins and curing agents [3] – elevated temperature postcuring induces secondary crosslinking of backbone hydroxyl functionality which condense to form ether bonds;
Polyurethanes form when isocyanate resins and prepolymers are combined with low- or high-molecular weight polyols, with strict stoichiometric ratios being essential to control nucleophilic addition polymerisation – the degree of crosslinking and resulting physical type (elastomer or plastic) is adjusted from the molecular weight and functionality of isocyanate resins, prepolymers, and the exact combinations of diols, triols and polyols selected, with the rate of reaction being strongly influenced by catalysts and inhibitors; polyureas form virtually instantaneously when isocyanate resins are combined with long-chain amine functional polyether or polyester resins and short-chain diamine extenders – the amine-isocyanate nucleophilic addition reaction does not require catalysts. Polyureas also form when isocyanate resins come into contact with moisture; [4]
Phenolic, amino, and furan resins all cured by polycondensation involving the release of water and heat, with cure initiation and polymerisation exotherm control influenced by curing temperature, catalyst selection or loading and processing method or pressure – the degree of pre-polymerisation and level of residual hydroxymethyl content in the resins determine the crosslink density. [5]
Polybenzoxazines are cured by an exothermal ring-opening polymerisation without releasing any chemical, which translates in near zero shrinkage upon polymerisation. [6]
Thermosetting polymer mixtures based on thermosetting resin monomers and pre-polymers can be formulated and applied and processed in a variety of ways to create distinctive cured properties that cannot be achieved with thermoplastic polymers or inorganic materials. [7] [8]
Thermosetting plastics are generally stronger than thermoplastic materials due to the three-dimensional network of bonds (crosslinking), and are also better suited to high-temperature applications up to the decomposition temperature since they keep their shape as strong covalent bonds between polymer chains cannot be broken easily. The higher the crosslink density and aromatic content of a thermoset polymer, the higher the resistance to heat degradation and chemical attack. Mechanical strength and hardness also improve with crosslink density, although at the expense of brittleness. [9] They normally decompose before melting.
Hard, plastic thermosets may undergo permanent or plastic deformation under load. Elastomers, which are soft and springy or rubbery and can be deformed and revert to their original shape on loading release.
Conventional thermoset plastics or elastomers cannot be melted and re-shaped after they are cured. This usually prevents recycling for the same purpose, except as filler material. [10] New developments involving thermoset epoxy resins which on controlled and contained heating form crosslinked networks permit repeatedly reshaping, like silica glass by reversible covalent bond exchange reactions on reheating above the glass transition temperature. [11] There are also thermoset polyurethanes shown to have transient properties and which can thus be reprocessed or recycled. [12]
When compounded with fibers, thermosetting resins form fiber-reinforced polymer composites, which are used in the fabrication of factory-finished structural composite OEM or replacement parts, [13] and as site-applied, cured and finished composite repair [14] [15] and protection materials. When used as the binder for aggregates and other solid fillers, they form particulate-reinforced polymer composites, which are used for factory-applied protective coating or component manufacture, and for site-applied and cured construction, or maintenance purposes.
Application/process uses and methods for thermosets include protective coating, seamless flooring, civil engineering construction grouts for jointing and injection, mortars, foundry sands, adhesives, sealants, castings, potting, electrical insulation, encapsulation, solid foams, wet lay-up laminating, pultrusion, gelcoats, filament winding, pre-pregs, and molding.
Specific methods of molding thermosets are:
Polyurethane refers to a class of polymers composed of organic units joined by carbamate (urethane) links. In contrast to other common polymers such as polyethylene and polystyrene, polyurethane is produced from a wide range of starting materials. This chemical variety produces polyurethanes with different chemical structures leading to many different applications. These include rigid and flexible foams, and coatings, adhesives, electrical potting compounds, and fibers such as spandex and polyurethane laminate (PUL). Foams are the largest application accounting for 67% of all polyurethane produced in 2016.
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.
Phenol formaldehyde resins (PF) 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.
Polyurea is a type of elastomer that is derived from the reaction product of an isocyanate component and an amine component. The isocyanate can be aromatic or aliphatic in nature. It can be monomer, polymer, or any variant reaction of isocyanates, quasi-prepolymer or a prepolymer. The prepolymer, or quasi-prepolymer, can be made of an amine-terminated polymer resin, or a hydroxyl-terminated polymer resin.
In organic chemistry, a polyol is an organic compound containing multiple hydroxyl groups. The term "polyol" can have slightly different meanings depending on whether it is used in food science or polymer chemistry. Polyols containing two, three and four hydroxyl groups are diols, triols, and tetrols, respectively.
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 thermoset 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 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”.
Synthetic resins are industrially produced resins, typically viscous substances that convert into rigid polymers by the process of curing. In order to undergo curing, resins typically contain reactive end groups, such as acrylates or epoxides. Some synthetic resins have properties similar to natural plant resins, but many do not.
Polybenzoxazines, also called benzoxazine resins, are cured polymerization products derived from benzoxazine monomers.
Polyester resins are synthetic resins formed by the reaction of dibasic organic acids and polyhydric alcohols. Maleic anhydride is a commonly used raw material with diacid functionality in unsaturated polyester resins. Unsaturated polyester resins are used in sheet moulding compound, bulk moulding compound and the toner of laser printers. Wall panels fabricated from polyester resins reinforced with fiberglass—so-called fiberglass reinforced plastic (FRP)—are typically used in restaurants, kitchens, restrooms and other areas that require washable low-maintenance walls. They are also used extensively in cured-in-place pipe applications. Departments of Transportation in the USA also specify them for use as overlays on roads and bridges. In this application they are known AS Polyester Concrete Overlays (PCO). These are usually based on isophthalic acid and cut with styrene at high levels—usually up to 50%. Polyesters are also used in anchor bolt adhesives though epoxy based materials are also used. Many companies have and continue to introduce styrene free systems mainly due to odor issues, but also over concerns that styrene is a potential carcinogen. Drinking water applications also prefer styrene free. Most polyester resins are viscous, pale coloured liquids consisting of a solution of a polyester in a reactive diluent which is usually styrene, but can also include vinyl toluene and various acrylates.
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.
Reaction injection molding (RIM) is similar to injection molding except thermosetting polymers are used, which requires a curing reaction to occur within the mold.
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.
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.
Resin casting is a method of plastic casting where a mold is filled with a liquid synthetic resin, which then hardens. It is primarily used for small-scale production like industrial prototypes and dentistry. It can be done by amateur hobbyists with little initial investment, and is used in the production of collectible toys, models and figures, as well as small-scale jewellery production.
In polymer chemistry, the term prepolymer or pre-polymer, refers to a monomer or system of monomers that have been reacted to an intermediate-molecular mass state. This material is capable of further polymerization by reactive groups to a fully cured, high-molecular-mass state. As such, mixtures of reactive polymers with un-reacted monomers may also be referred to as pre-polymers. The term "pre-polymer" and "polymer precursor" may be interchanged.
Moisture-cure polyurethanes -- or polyurethane prepolymer -- are isocyanate-terminated prepolymers that are formulated to cure with ambient water. Cured PURs are segmented copolymer polyurethane-ureas exhibiting microphase-separated morphologies. One phase is derived from a typically flexible polyol that is generally referred to as the “soft phase”. Likewise the corresponding “hard phase” is born from the di- or polyisocyanates that through water reaction produce a highly crosslinked material with softening temperature well above room temperature.
Vitrimers are a class of plastics, which are derived from thermosetting polymers (thermosets) and are very similar to them. Vitrimers consist of molecular, covalent networks, which can change their topology by thermally activated bond-exchange reactions. At high temperatures, they can flow like viscoelastic liquids; at low temperatures, the bond-exchange reactions are immeasurably slow (frozen), and the Vitrimers behave like classical thermosets at this point. Vitrimers are strong glass formers. Their behavior opens new possibilities in the application of thermosets, such as a self-healing material or simple processibility in a wide temperature range.
Hydrogenated MDI (H12MDI or 4,4′-diisocyanato dicyclohexylmethane) is an organic compound in the class known as isocyanates. More specifically, it is an aliphatic diisocyanate. It is a water white liquid at room temperature and is manufactured in relatively small quantities. It is also known as 4,4'-methylenedi(cyclohexyl isocyanate) or methylene bis(4-cyclohexylisocyanate) and has the formula CH2[(C6H10)NCO]2.
Blocked isocyanates are organic compounds that have their isocyanate functionality chemically blocked to control reactivity. They are the product of an isocyanate moiety and a suitable blocking agent. It may also be a polyurethane prepolymer that is NCO terminated but this functionality has also been chemically reacted with a blocking agent. They are usually used in polyurethane applications but not always. They are extensively used in industrial applications such as coatings, sealants and adhesives.