Secondary cross-linked

Use of dimethylaminoethyl (also rert-butylaminoethyl) methacrylate as a monomer permits the introduction of pendent amino groups which can serve as sites for secondary cross-linking, provide a way to make the copolymer acid-soluble, and provide anchoring sites for dyes and pigments. 

Another technique—pres sure-shift freezing—also shows promise. In this technique the material is subjected to high pressure (200 MPa) and cooled to -15 C. Under these conditions the water does not freeze. However, when the pressure is released suddenly, many small ice crystals form. This has two results the small ice crystals do not rupture any structures present, but by dehydrating the unfrozen material the remaining stmcture is aggregated and stiffened by the introduction of secondary cross-links. At low concentration of solids there are too few interconnecting chains for there to be a load-bearing continuum, and the material tends to flocculate and settle out. 

Hybrid and Secondary Cross-Linked Silicone IPNs... 

It is important to note that secondary cross-linking reactions, in this specific case due to the secondary amine in APTES, can be easily recognized by CP MAS NMR (Innocenzi, 2003). 

A third disadvantage of studying polymers with electron microscopy is the radiation damage due to the electron beam. There are several primary and secondary irradiation effects, which can, on one side, damage the polymer, but on the other hand, contribute to a contrast enhancement, for example, if in polymer blends the thickness or the density in one part of the specimen is reduced by evaporation of volatile fractions of polymer chains, as in PVC/SAN blends (see Fig. 3.15) or if secondary cross-linking effects in semicrystalline polymers are stronger in the amorphous regions than in the crystalline ones, as in PEs [1,15,16]. 

Hydrogen bonding stabilizes some protein molecules in helical forms, and disulfide cross-links stabilize some protein molecules in globular forms. We shall consider helical structures in Sec. 1.11 and shall learn more about ellipsoidal globular proteins in the chapters concerned with the solution properties of polymers, especially Chap. 9. Both secondary and tertiary levels of structure are also influenced by the distribution of polar and nonpolar amino acid molecules relative to the aqueous environment of the protein molecules. Nonpolar amino acids are designated in Table 1.3. 

The three levels of structure listed above are also useful categories for describing nonprotein polymers. Thus details of the microstructure of a chain is a description of the primary structure. The overall shape assumed by an individual molecule as a result of the rotation around individual bonds is the secondary structure. Structures that are locked in by chemical cross-links are tertiary structures. 

The presence of the unsaturated substituent along this polyester backbone gives this polymer crosslinking possibilities through a secondary reaction of the double bond. These polymers are used in paints, varnishes, and lacquers, where the ultimate cross-linked product results from the oxidation of the double bond as the coating cures. A cross-linked polyester could also result from reaction (5.J) without the unsaturated carboxylic acid, but the latter would produce a gel in which the entire reaction mass solidified and is not as well suited to coatings applications as the polymer that crosslinks upon drying. ... 

Esters. Most acryhc acid is used in the form of its methyl, ethyl, and butyl esters. Specialty monomeric esters with a hydroxyl, amino, or other functional group are used to provide adhesion, latent cross-linking capabihty, or different solubihty characteristics. The principal routes to esters are direct esterification with alcohols in the presence of a strong acid catalyst such as sulfuric acid, a soluble sulfonic acid, or sulfonic acid resins addition to alkylene oxides to give hydroxyalkyl acryhc esters and addition to the double bond of olefins in the presence of strong acid catalyst (19,20) to give ethyl or secondary alkyl acrylates. 

Radiation Effects. Polytetrafluoroethylene is attacked by radiation. In the absence of oxygen, stable secondary radicals are produced. An increase in stiffness in material irradiated in vacuum indicates cross-linking (84). Degradation is due to random scission of the chain the relative stabiUty of the radicals in vacuum protects the materials from rapid deterioration. Reactions take place in air or oxygen and accelerated scission and rapid degradation occur. 

Cross-linked polyester composites have a relatively low coefficient of thermal conductivity that can provide beneficial property retention in thick laminates at high temperatures as well as remove the need for secondary insulation. The coefficient of thermal expansion of glass-reinforced composites is similar to aluminum but higher than most common metals. 

Secondary bonds are considerably weaker than the primary covalent bonds. When a linear or branched polymer is heated, the dissociation energies of the secondary bonds are exceeded long before the primary covalent bonds are broken, freeing up the individual chains to flow under stress. When the material is cooled, the secondary bonds reform. Thus, linear and branched polymers are generally thermoplastic. On the other hand, cross-links contain primary covalent bonds like those that bond the atoms in the main chains. When a cross-linked polymer is heated sufficiently, these primary covalent bonds fail randomly, and the material degrades. Therefore, cross-linked polymers are thermosets. There are a few exceptions such as cellulose and polyacrylonitrile. Though linear, these polymers are not thermoplastic because the extensive secondary bonds make up for in quantity what they lack in quahty. 

Similarly, polymers dissolve when a solvent penetrates the mass and replaces the interchain secondary bonds with chain-solvent secondary bonds, separating the individual chains. This cannot happen when the chains are held together by primary covalent cross-links. Thus, linear and branched polymers dissolve in appropriate solvents, whereas cross-linked polymers are insoluble, although they may be swelled considerably by absorbed solvent. 

Elastomers or rubbers are almost-linear polymers with occasional cross-links in which, at room temperature, the secondary bonds have already melted. The cross-links provide the "memory" of the material so that it returns to its original shape on unloading. The common rubbers are all based on the single structure... 

Elastomers are a special sort of cross-linked polymer. First, they are really linear polymers with just a few cross-links - one every hundred or more monomer units - so that a molecule with a DP of 500 might have fewer than five cross-link points along its length. And second, the polymer has a glass temperature which is well below room temperature, so that (at room temperature) the secondary bonds have melted. Why these two features give an elastomer is explained later (Chapter 23). 

---