Polymerization strain

Living anionic ring-opening polymerization, strained metallocenophanes, 12, 326 Living polymerization acetylenes... 

The preceding research on the model maxillofacial material was followed by TMDSC study of several representative elastomeric impression materials, which are extensively used in dentistry for the accurate fabrication of inlays and crowns from dental alloys, metal-ceramic restorations, and fixed and removable partial dentures [1-3]. There have been numerous studies reporting the clinically relevant properties of these impression materials (viscosity before setting by polymerization, strain in compression after setting, permanent deformation for simulated in vivo removal of the impressions, and tear strength of the thin impressions). However, only minimal research has been reported [44] on some thermal properties of impression materials obtained by conventional DSC. Our pioneering TMDSC study [45] was designed to obtain fundamental information about impression materials and seek correlations with their relevant properties. 

Calderon was the first to find a catalyst system that would initiate both ring-opening polymerization of olefins (subsequendy named ROMP by Tim Swager when he was a student at Caltech) and acydic metathesis of simple olefins. Up until his findings, most catalysts for acydic metathesis were heterogeneous systems, and metal salts were used to polymerize strained olefins such as norbomenes. Beautiful work was carried out using the poorly defined systems to work out the stereochemistry and mechanism of metathesis. This beautiful work provides an excellent backdrop for the work described here. This section will focus on the use of well-defined complexes as initiators for the living polymerization of cydic olefins. 

The (CEF) model (see Chapter 1) provides a simple means for obtaining useful results for steady-state viscometric flow of polymeric fluids (Tanner, 1985). In this approach the extra stress in the equation of motion is replaced by explicit relationships in terms of rate of strain components. For example, assuming a zero second normal stress difference for veiy slow flow regimes such relationships arc written as (Mitsoulis et at., 1985)... 

The various elastic and viscoelastic phenomena we discuss in this chapter will be developed in stages. We begin with the simplest the case of a sample that displays a purely elastic response when deformed by simple elongation. On the basis of Hooke s law, we expect that the force of deformation—the stress—and the distortion that results-the strain-will be directly proportional, at least for small deformations. In addition, the energy spent to produce the deformation is recoverable The material snaps back when the force is released. We are interested in the molecular origin of this property for polymeric materials but, before we can get to that, we need to define the variables more quantitatively. 

Terephthahc acid (TA) or dimethyl terephthalate [120-61 -6] (DMT) reacts with ethyleae glycol (2G) to form bis(2-hydroxyethyl) terephthalate [959-26-2] (BHET) which is coadeasatioa polymerized to PET with the elimination of 2G. Moltea polymer is extmded through a die (spinneret) forming filaments that are solidified by air cooling. Combinations of stress, strain, and thermal treatments are appHed to the filaments to orient and crystallize the molecular chains. These steps develop the fiber properties required for specific uses. The two general physical forms of PET fibers are continuous filament and cut staple. 

More recently, Raman spectroscopy has been used to investigate the vibrational spectroscopy of polymer Hquid crystals (46) (see Liquid crystalline materials), the kinetics of polymerization (47) (see Kinetic measurements), synthetic polymers and mbbers (48), and stress and strain in fibers and composites (49) (see Composite materials). The relationship between Raman spectra and the stmcture of conjugated and conducting polymers has been reviewed (50,51). In addition, a general review of ft-Raman studies of polymers has been pubUshed (52). 

The polymerizations of tetrahydrofuran [1693-74-9] (THF) and of oxetane [503-30-0] (OX) are classic examples of cationic ring-opening polymerizations. Under ideal conditions, the polymerization of the five-membered tetrahydrofuran ring is a reversible equiUbtium polymerization, whereas the polymerization of the strained four-membered oxetane ring is irreversible (1,2). 

The four-membered oxetane ring (trimethylene oxide [503-30-0]) has much higher ring strain, and irreversible ring-opening polymerization can occur rapidly to form polyoxetane [25722-06-9] ... 

Because of the high ring strain of the four-membered ring, even substituted oxetanes polymerize readily, ia contrast to substituted tetrahydrofurans, which have tittle tendency to undergo ring-opening homopolymerization (5). 

The chemistry of polymerization of the oxetanes is much the same as for THE polymerization. The ring-opening polymerization of oxetanes is primarily accompHshed by cationic polymerization methods (283,313—318), but because of the added ring strain, other polymerization techniques, eg, iasertion polymerization (319), anionic polymerization (320), and free-radical ring-opening polymerization (321), have been successful with certain special oxetanes. 

A sliding plate rheometer (simple shear) can be used to study the response of polymeric Hquids to extension-like deformations involving larger strains and strain rates than can be employed in most uniaxial extensional measurements (56,200—204). The technique requires knowledge of both shear stress and the first normal stress difference, N- (7), but has considerable potential for characteri2ing extensional behavior under conditions closely related to those in industrial processes. 

The search for new, high performance materials requites the synthesis of weU-defined, narrow molecular weight distribution, cycHc-free, homo- and copolymers. Synthesis of these polymers can be accompHshed by the kinetically controUed polymerization of the strained monomer. 

A drawback to the Durham method for the synthesis of polyacetylene is the necessity of elimination of a relatively large molecule during conversion. This can be overcome by the inclusion of strained rings into the precursor polymer stmcture. This technique was developed in the investigation of the ring-opening metathesis polymerization (ROMP) of benzvalene as shown in equation 3 (31). 

Many fibrous composites are made of strong, brittle fibres in a more ductile polymeric matrix. Then the stress-strain curve looks like the heavy line in Fig. 25.2. The figure largely explains itself. The stress-strain curve is linear, with slope E (eqn. 25.1) until the matrix yields. From there on, most of the extra load is carried by the fibres which continue to stretch elastically until they fracture. When they do, the stress drops to the yield strength of the matrix (though not as sharply as the figure shows because the fibres do not all break at once). When the matrix fractures, the composite fails completely. 

Fig. 25.9. The compressive stress-strain curve for a polymeric foam. Very large compressive strains ore possible, so the foam absorbs a lot of energy when it is crushed.

Polymeric materials exhibit mechanical properties which come somewhere between these two ideal cases and hence they are termed viscoelastic. In a viscoelastic material the stress is a function of strain and time and so may be described by an equation of the form... 

The individual laminae used by Tsai [4-6] consist of unidirectional glass fibers in a resin matrix (U.S. Polymeric Co. E-787-NUF) with moduli given in Table 2-3. A series of special cross-ply laminates was constructed with M = 1,2,3,10 for two-layered laminates and M = 1,2,5,10 for three-layered laminates. The laminates were subjected to axial loads and bending moments whereupon surface strains were measured. Accordingly, the stiffness relations as strains and curvatures in terms of forces and moments, that is. 

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