Crosslinking thermosetting polymers

A thermoset polymer does not flow when it is heated and subjected to pressure. Thermoset polymers consist of an interconnected network of chains that are permanently chemically connected to their neighbors, either directly or via short bridging chains, as shown in Fig. 1.4. We refer to such networks as being crosslinked. Thermoset polymers do not dissolve in solvents, but they can soften and swell. 

Figure 1.23 Intermediary of (III) branched and (IV) dendritic architecture in the conversion of (I) linear thermoplastics to (II) crosslinked thermoset polymers. Intermediary of (IVb) dendrigrafts and (IVc) dendrimers in the formation of megamers...

General purpose thermosets, such as phenolic (PF), melamine (MF), and epoxy plastics, are more resistant to heat than the general purpose thermoplastics. These crosslinked thermoset polymers do not have true Tm values but decompose at elevated temperatures. 

Explosives projectiles and the oxidizer and fuel in rocket motors are held by a binder, which usually is a crosslinked thermosetting polymer. The binder can complicate solvent extraction of explosives or the aqueous dissolution of water-soluble oxidizers. 

Uses Epoxy tor adhesive, casting, potting, encapsulation, and wet layup applies., marine/protective coatings Features After cure, yields highly crosslinked thermoset polymers a high-visc., fast-reacting resin for adhesive applies. 

Precipitate can also form fiom a step reaction. Precipitation polymerizations of prepolymers to form crosslinked, thermoset polymers is a very common commercial reaction of the epoxy resins and phenol-methanal, network polymers covered in this book. These reactions work best when the reaction is slow, mildly exothermic, and undergoes a viscous to solid transformation late in the synthesis. 

Coefficients of linear thermal expansion a , for typical crosslinked thermoset polymers over the temperature range 10-70 °C, (i.e., below the T ), are in the range 60-100 ppm K. (Coefficients of volume expansion approximate to 3a .) This range of values is high... 

For some highly crosslinked thermosetting polymers with rigid backbones, topological restrictions limit the maximum attainable conversion. For the reaction between epoxidized novolacs and cresol-based novolacs, a maximum conversion, Xmax= 0.80 was reported (Hale et al., 1991). A similar value of x ,ax was reported for the cure of an epoxidized novolac with 4,4 -diaminodiphenylsulfone (DDS) (Oyanguren and WilKams, 1993a). In these cases, partially reacted networks may be modeled as a random solution of reacted functionalities with a concentration equal to x/x ax... 

Anaerobics are usually formulated with di- or trifunctional methacrylate monomers that can be polymerised rapidly to form a tightly crosslinked thermoset polymer. Typical examples are triethylene glycol dimethacrylate, and ethoxylated bisphenol A dimethacrylate. Other monomers are used to modify the properties. Examples are hydroxyethyl or hydroxypropyl methacrylate and acrylic or methacrylic acid these help to adjust viscosity, cure speeds and adhesive strength as seen in Equations 2.3-2.S ... 

The use of multifunctional monomers in anaerobics leads to a highly crosslinked thermoset polymer that is heat-resistant and has excellent resistance to oil and solvents. Anaerobics cure very quickly on clean surfaces made of iron, steel or brass where transition metal ions catalyse the initiation of polymerisation. However, they cure at a slower rate on plated surfaces, on oily surfaces, or in the presence of certain rust-inhibiting chemicals such as chromates. For very inactive surfaces or for fixing on plastics, surface primer solutions (usually amines or copper salts) can be used. 

Monomer(s) of thermoplastic polymers swollen in crosslinked thermoset polymer... 

In these reactions, the monomers have two functional groups (whether one or two monomers are used), and a linear polymer results. With more than two functional groups present, crosslinking occurs and a thermosetting polymer results. Example of this type are polyurethanes and urea formaldehyde resins (Chapter 12). 

Amino resins are those polymers prepared by reaction of either urea or melamine with formaldehyde. In both cases the product that results from the reaction has a well crosslinked network structure, and hence is a thermoset polymer. The structures of the two parent amino compounds are shown in Figure 1.1. 

Polyurethanes are thermoset polymers formed from di-isocyanates and poly functional compounds containing numerous hydroxy-groups. Typically the starting materials are themselves polymeric, but comprise relatively few monomer units in the molecule. Low relative molar mass species of this kind are known generally as oligomers. Typical oligomers for the preparation of polyurethanes are polyesters and poly ethers. These are usually prepared to include a small proportion of monomeric trifunctional hydroxy compounds, such as trimethylolpropane, in the backbone, so that they contain pendant hydroxyls which act as the sites of crosslinking. A number of different diisocyanates are used commercially typical examples are shown in Table 1.2. 

The final physical properties of thermoset polymers depend primarily on the network structure that is developed during cure. Development of improved thermosets has been hampered by the lack of quantitative relationships between polymer variables and final physical properties. The development of a mathematical relationship between formulation and final cure properties is a formidable task requiring detailed characterization of the polymer components, an understanding of the cure chemistry and a model of the cure kinetics, determination of cure process variables (air temperature, heat transfer etc.), a relationship between cure chemistry and network structure, and the existence of a network structure parameter that correlates with physical properties. The lack of availability of easy-to-use network structure models which are applicable to the complex crosslinking systems typical of "real-world" thermosets makes it difficult to develop such correlations. 

When a thermoplastic polyurethane elastomer is heated above the melting point of its hard blocks, the chains can flow and the polymer can be molded to a new shape. When the polymer cools, new hard blocks form, recreating the physical crosslinks. We take advantage of these properties to mold elastomeric items that do not need to be cured like conventional rubbers. Scrap moldings, sprues, etc. can be recycled directly back to the extruder, which increases the efficiency of this process. In contrast, chemically crosslinked elastomers, which are thermosetting polymers, cannot be reprocessed after they have been cured. 

Thermoset polymers (sometimes called network polymers) can be formed from either monomers or low MW macromers that have a functionality of three or more (only one of the reagents requires this), or a pre-formed polymer by extensive crosslinking (also called curing or vulcanisation this latter term is only applied when sulfur is the vulcanising or crosslinking agent.) The crosslinks involve the formation of chemical bonds — covalent (e.g., carbon-carbon bonds) or ionic bonds. 

Classifying polymers in their crosslinked state according to end-use properties, polymer networks include vulcanized rubbers, crosslinked thermosetting materials, protective coatings, adhesives, polymeric sorbents, microelectronics materials, soft gels, etc. Polymer networks in contrast to uncrosslinked polymers,... 

The crosslinking reaction is an extremely important one from the commercial standpoint. Crosslinked plastics are increasingly used as engineering materials because of their excellent stability toward elevated temperatures and physical stress. They are dimensionally stable under a wide variety of conditions due to their rigid network structure. Such polymers will not flow when heated and are termed thermosetting polymers or simply thermosets. More than 10 billion pounds of thermosets are produced annually in the United States. Plastics that soften and flow when heated, that is, uncrosslinked plastics, are called thermoplastics. Most of the polymers produced by chain polymerization are thermoplastics. Elastomers are a category of polymers produced by chain polymerization that are crosslinked (Sec. 1-3), but the crosslinking reactions are different from those described here (Sec. 9-2). 

The purpose of the second dwell is to allow crosslinking of the matrix to take place. It is during the second dwell when the strength and related mechanical properties of the composite are developed. To characterize the exothermic crosslinking reaction of a thermosetting polymer matrix, a thermal cure monitor technique such as Differential Scanning Calorimetry... 

Thermal stability as measured by these ramped TGA experiments of the sort previously described are not the definitive test of a polymer s utility at elevated temperature. Rather, for a polymer to be useful at elevated temperatures, it must exhibit some significant retention of useful mechanical properties over a predetermined lifetime at the maximum temperature that will be encountered in its final end use application. While many of the bisbenzocyclobutene polymers have been reported in the literature, only a few have been studied in detail with regards to their thermal and mechanical performance at both room and elevated temperatures. Tables 7-10 show some of the preliminary mechanical data as well as some other physical properties of molded samples of polymers derived from amide monomer 32, ester monomer 40, diketone monomer 14 and polysiloxane monomer 13. The use of the term polyamide, ester etc. with these materials is not meant to imply that they are to be regarded as merely modified linear thermoplastics. Rather, these polymers are for the most part highly crosslinked thermosets. 

Figure 29-2 Schematic representation of the conversion of an uncross-linked thermosetting polymer to a highly cross-linked polymer. The crosslinks are shown in a two-dimensional network, but in practice three-dimensional networks are formed.

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