Common Thermosetting Polymers

Alkyd Excellent dimensional stability and heat resistance, surfaces tough, good susceptibility to fillers and fibres. 

Epoxy High physical strength and dimensional stability. Some types cold curing. Good filler susceptibility. 

Phenolic Low cost. Good physical strength and high temperature resistance. Good toughness with fillers and fibres. 

Polyester Good temperature and chemical stability. High physical strength with glass fibre reinforcement. 

Polyurethane High abrasion resistance, toughness and chemical resistance. 

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Thermosets are heavily cross-linked polymers which are normally rigid and intractable. They consist of a dense three-dimensional molecular network and, like rubbers, degrade rather than melt on the application of heat. Common thermosetting polymers include phenol-formaldehyde or urea-formaldehyde resins and high-performance adhesives such as epoxy resins. 

Polymer-matrix materials include a wide range of specific materials. Perhaps the most commonly used polymer is epoxy. Other polymers include vinyl ester and polyester. Polymers can be either of the thermoset type, where cross-linking of polymer chains is irreversible, or of the thermoplastic type, where cross-linking does not take place but the matrix only hardens and can be softened and hardened repeatedly. For example, thermoplastics can be heated and reheated, as is essential to any injection-molding process. In contrast, thermosets do not melt upon reheating, so they cannot be injection molded. Polyimides have a higher temperature limit than epoxies (650°F versus 250°F or 350°F) (343°C versus 121°C or 177°C), but are much more brittle and considerably harder to process. 

These are thermoset polymers made from phenol or, less commonly, phenolic-type compounds such as the cresols, xylenols, and resorcinol, together with formaldehyde. They had been known for some time - G.T (later Sir Gilbert) Morgan discovered them in the early 1890s when attempting (unsuccessfully) to make artificial dyestuffs by reaction of phenol with formaldehyde. But this knowledge had not been exploited before 1907, the year in which Leo... 

Composites consist of two (or more) distinct constituents or phases, which when combined result in a material with entirely different properties from those of the individual components. Typically, a manmade composite would consist of a reinforcement phase of stiff, strong material, embedded in a continuous matrix phase. This reinforcing phase is generally termed as filler. The matrix holds the fillers together, transfers applied loads to those fillers and protects them from mechanical damage and other environmental factors. The matrix in most common traditional composites comprises either of a thermoplastic or thermoset polymer [1]. 

The PGS obtained by Wang and coworkers was a kind of thermoset elastomer with the Young s modulus of 0.282 0.025 MPa, a tensile strain of at least 267 zE 59.4%, and a tensUe strength was at least 0.5 MPa. The mechanical properties of PGS were well consisted with that of some common soft tissues. Although PGS is a thermoset polymer, its prepolymer can be processed into various shapes by solving it in common organic solvents such as 1,3-dioxolane, tetrahydrofuran, isopropanol, ethanol, and iV,M-dimethylformamide. Porous scaffolds can be fabricated by salt leaching. 

This is a very broad class of compounds commonly used in coatings. Over 400-500 different alkyd resins are commercially available. They are polyesters containing unsaturation that can be cross-linked in the presence of an initiator known traditionally as a drier. A common example is the alkyd formed from phthalic anhydride and a glyceride of linolenic acid obtained from various plants. Cross-linking of the multiple bonds in the long unsaturated chain R produces the thermoset polymer by linking R groups of separate molecules with each other. 

The chemical structures of thermosets are generally much more diverse than the commodity thermoplastics. The most common types of thermosets are the phenol-formaldehydes (PF), urea-formaldehydes (UF), melamine-formaldehydes (MF), epoxies (EP), polyurethanes (PU), and polyimides (PI). Appendix 2 shows the chemical structure of these important thermosetting polymers. 

Unlike ductile metals, composite laminates containing fiber-reinforced thermosetting polymers do not exhibit gross ductile yielding. However, they do not behave as classic brittle materials, either. Under a static tensile load, many of these laminates show nonlinear characteristics attributed to sequential ply failures. One of the difficulties, then, in designing with laminar composites is to determine whether the failure of the first ply constitutes material failure, termed first-ply failure (FPF), or if ultimate failure of the composite constitutes failure. In many laminar composites, ultimate failure occurs soon after first ply failure, so that an FPF design approach is justified, as illustrated for two common laminar composites in Table 8.9 (see Section 5.4.3 for information on the notations used for laminar composites). In fact, the FPF approach is used for many aerospace and aircraft applications. 

Many reactions familiar to organic chemists may be utilized to carry out step polymerizations. Some examples are given in Table 2.2 for polycondensation and in Table 2.3 for polyaddition reactions. These reactions can proceed reversibly or irreversibly. Those involving carbonyls are the most commonly employed for the synthesis of a large number of commercial linear polymers. Chemistries used for polymer network synthesis will be presented in a different way, based on the type of polymer formed (Tables 2.2 and 2.3). Several different conditions may be chosen for the polymerization in solution, in a dispersed phase, or in bulk. For thermosetting polymers the last is generally preferred. 

So many kinds of polymers exist that scientists have developed ways of categorizing them to make it easier to study and describe them. Polymers formed by addition or condensation reactions, for example, are placed in the same category because they are formed by a common chemical reaction and, in many cases, have common physical and chemical properties. Similarly, thermoplastic and thermosetting polymers are grouped together primarily because of their behaviors when exposed to heat, and, hence, applications for which they are likely to he most suitable. 

First, a common method of forming polymers by a radical reaction is discussed. After the structures of the addition polymers made by this method are examined, several other procedures that can be used to prepare these or similar polymers are presented. Next, the effect of the structure of a polymer on its physical properties is discussed. This provides a basis for understanding the properties and uses of a number of other addition polymers. Rubbers (elastomers) are then discussed followed by condensation polymers and thermosetting polymers. The chapter concludes with a brief examination of the chemical properties of polymers. 

A thermosetting polymer is one in which heat applied to a liquid or semi-solid resin causes a chemical change by which it becomes solid (sets). In fact several of them, such as epoxies, are commonly hardened by the use of a catalyst, called a... 

Catalysts are currently not covered specifically by EU directives on food contact plastics. They tend to decompose during the polymerisation process. Again, the degradation products are often predictable and may sometimes be found in the finished food contact material. However, catalysts are usually present at low levels and the degradation products are often volatile. For example, the common catalyst t-butyl perbenzoate may decompose to give benzene when used in some thermoset polymers.Tert-butyl peroxide is used as a catalyst in certain polymers and will decompose to give tert-butanol. 

As mentioned earlier, suspensions of particulate rods or fibers are almost always non-Brownian. Such fiber suspensions are important precursors to composite materials that use fiber inclusions as mechanical reinforcement agents or as modifiers of thermal, electrical, or dielectrical properties. A common example is that of glass-fiber-reinforced composites, in which the matrix is a thermoplastic or a thermosetting polymer (Darlington et al. 1977). Fiber suspensions are also important in the pulp and paper industry. These materials are often molded, cast, or coated in the liquid suspension state, and the flow properties of the suspension are therefore relevant to the final composite properties. Especially important is the distribution of fiber orientations, which controls transport properties in the composite. There have been many experimental and theoretical studies of the flow properties of fibrous suspensions, which have been reviewed by Ganani and Powell (1985) and by Zimsak et al. (1994). 

This is a huge general category of materials, which includes both thermoplastics and thermosetting polymers. Tabular data on the corrosion resistance of these materials in a wide range of environments are available from a variety of sources. Commonly used materials of construction in the CPI include polyvinyl chloride (PVC and CPVC), polyethylene, polypropylene, polystyrene, polycarbonate, polytetrafluoroethylene (PTFE), fiberglass composite materials, and a variety of epoxies used for coatings or adhesives. 

Unlike thermoplastics, which are simply melted, thermoset resins chemically react from low-viscosity liquids to solid materials during processing, a process termed curing. Structurally, thermosets differ from thermoplastics because of the presence of cross-links in the former, which means that thermosets cannot be reshaped or recycled once the chemical reaction occurs. One advantage of thermosets vs. thermoplastics is that wetting the filler becomes much easier with a low-viscosity material. By far the most common thermoset composite is automobile tires, which consist of a polymer made from styrene and butadiene monomers and carbon-black filler. The actual recipe used is much more complicated, and can include other monomers or polymers, as well as other fillers. In the absence of filler, the cured resin is rubbery at room temperature, which makes tires a... 

A thermosetting plastic is a polymer that can be caused to undergo cross-linking to produce a network polymer, called a thermoset polymer. Quite commonly, thermosetting resins are prepared, by intent, in only partially polymerized states (prepolymers), so that they can be deformed in a heated mold and then hardened by curing (cross-linking). 

Table 1. Comparison of common high performance thermosetting polymer matrices...

Thermosets. Fire retardancy in thermosetting polymers is achieved largely by the use of reactive fire retardants because the common fire-retarding additives lack permanence. The flammability of thermosetting materials can be reduced by the additions of inorganic fillers and/or reactive flame retardant components. Flame-retardant vinyl monomers or other cross-linking agents are also frequently employed. 

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