Linear crosslinking

Dendrimers are a relatively new class of macromolecules different from the conventional linear, crosslinked, or branched polymers. Dendrimers are particularly interesting because of their nanoscopic dimensions and their regular, well-defined, and highly branched three-dimensional architecture. In contrast to polymers, these new types of macromolecules can be viewed as an ordered ensemble of monomeric building blocks. Their tree-like, monodispersed structures lead to a number of interesting characteristics and features globular, void-containing shapes, and unusual physical properties [107-111]. 

Abiotic hydrolysis of linear, crosslinked and porous PCL resulted in formation of 6-hydroxyhexanoic acid (HHA) and water-soluble oligomers [73]. As seen in Fig. 4 the introduction of crosslinks considerably increased the hydrolysis rate and formation of monomeric 6-hydroxyhexanoic acid. This was mainly explained by the lower degree of crystallinity for the crosslinked PCL homopolymer. 

Dendritic species represent the most recently discovered class of branched macromolecular architecture. Major developments in linear, crosslinked, and branched architectures date back roughly to the 1930s, 1940s, and 1960s, respectively. The first synthetic dendritic species were reported in 1978 [1] however, much of the work in this area began to build momentum only in the mid-1980s. A chronology of the key developments in dendritic polymers is provided in Table 30.1. 

Synthetic polymers can be divided into four key architectural classes linear, crosslinked, branched and dendritic structures. The first three types have been studied extensively in the past. The fourth comprises the more recently developed, nature-inspired dendrimers, and derivatives. 

Type I A metal ion, a metal complex or metal chelate is connected with a linear or crosslinked macromolecule by covalent, coordinative, chelate, ionic or Ti-type bonds (Figure 1). This type I is realized by binding of the metal part at a linear, crosslinked polymer or at the outer or interior surface of an inorganic support. Another possibility uses the polymerization or copolymerization of metal containing monomers. 

The results of mechanical tests indicate that the genipin stent has a significantly higher ultimate compression load (1,123 77 mN) and collapse pressure (2.5 0.1 bar) than the epoxy stent (856 148 mN, 1.9 0.1 bar). These results are attributable to the various crosslinking structures that are formed in stent matrices (Fig. 17) [176]. The two epoxide functional groups in the epoxy compound that was used in the study crosslinked the amine groups of chitosan in the stent matrix [177]. In this way, a linearly crosslinked structure between the adjacent chitosan molecules may be formed intermolecularly. 

Cycloahphatic diamines react with dicarboxyUc acids or their chlorides, dianhydrides, diisocyanates and di- (or poly-)epoxides as comonomers to form high molecular weight polyamides, polyimides, polyureas, and epoxies. Polymer property dependence on diamine stmcture is greater in the linear amorphous thermoplastic polyamides and elastomeric polyureas than in the highly crosslinked thermo set epoxies (2—4). 

Acyclic C5. The C5 petroleum feed stream consists mainly of isoprene which is used to produce rubber. In a separate stream the linear C5 diolefin, piperylene (trans and cis), is isolated. Piperylene is the primary monomer in what are commonly termed simply C5 resins. Small amounts of other monomers such as isoprene and methyl-2-butene are also present. The latter serves as a chain terminator added to control molecular weight. Polymerization is cationic using Friedel-Crafts chemistry. Because most of the monomers are diolefins, residual backbone unsaturation is present, which can lead to some crosslinking and cyclization. Primarily, however, these are linear acyclic materials. Acyclic C5 resins are sometimes referred to as synthetic polyterpenes , because of their similar polarity. However, the cyclic structures within polyterpenes provide them with better solvency power and thus a broader range of compatibility than acyclic C5s. 

Polyisoprene can be UV or e-beam cured [43,44]. The 3,4 units are particularly prone to crosslinking at low dose [45]. SIS and SBS are also crosslinkable, even conventional linear materials with low vinyl content however, small amounts of liquid trithiol or triacrylate compounds speed cure dramatically [44]. Like UV, e-beam cure is strongly affected by tackifier choice. Hydrogenated, non-aromatic resins provide much less interference with cure [36,37]. 

A typical maleimide resin is synthesized by the Michael addition of MDA and BMI (Fig. 4). If the stoichiometrically equal amounts of MDA and BMI are added into the reaction solvent under controlled temperature, linear, high molecular weight polyaminoimide (PAI) results. To obtain crosslinkable oligomer (pre-polymer) with maleimide end groups, a calculated 1.1-1.8 times an excess... 

As already mentioned, aromatie polymers are thermally stable but aliphatic portions of them are not as thermally stable. Typical maleimide resins have aliphatic units. This is inevitable because the Michael addition was used to prepare the maleimide-based oligomers. On the other hand, if an adhesive consists of a linear thermoplastic polymer, it is not usable at temperatures above its softening temperature. Introdueing chemical crosslinking is one way to prevent thermal weakening of a material. 

Removal of diluent by an extraction process To obtain the final stable macroporous structure, the liquid organic diluents and the linear polymer are removed from the crosslinked structure by extraction with a good solvent for the inert diluents and particularly for the linear polymer. Toluene or methylene chloride are usually preferred for the removal of linear polystyrene from the divinylbenzene crosslinked macroporous polystyrene particles [125,128]. The extraction is carried out within a Soxhelet apparatus at the boiling point of the selected solvent over a period usually more than 24 h. 

In the case of the segmented polymers, the domains that form during phase separation will lead to the rapid buildup of viscosity and gelation, much like a crosslinking urethane, although these polymers are linear. An an-ologous expression for the viscosity rise in these systems is given by [36] ... 

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). 

The acid-catalyzed reaction occurs by an electrophilic substitution where formaldehyde is the electrophile. Condensation between the methylol groups and the benzene rings results in the formation of methylene bridges. Usually, the ratio of formaldehyde to phenol is kept less than unity to produce a linear fusible polymer in the first stage. Crosslinking of the formed polymer can occur by adding more formaldehyde and a small amount of hexamethylene tetramine (hexamine. 

Assuming maximum corrosion resistance is required, then an anticorrosive primer will be needed, with best protection coming from a crosslinked epoxy stoving primer. Most other properties are dominated by the finish, which will be based on a high molecular weight-polymer, either linear or (more usually) crosslinked. The precise selection of the polymer depends on the balance of properties required, but will be constrained by the type and rate of curing necessary. 

The possibility of conformational changes in chains between chemical junctions for weakly crosslinked CP in ionization is confirmed also by the investigation of the kinetic mobility of elements of the reticular structure by polarized luminescence [32, 33]. Polarized luminescence is used for the study of relaxation properties of structural elements with covalently bonded luminescent labels [44,45]. For a microdisperse form of a macroreticular MA-EDMA (2.5 mol% EDMA) copolymer (Fig. 9 a, curves 1 and 2), as compared to linear PM A, the inner structure of chain parts is more stable and the conformational transition is more distinct. A similar kind of dependence is also observed for a weakly crosslinked AA-EDMA (2.5 mol%) copolymer (Fig. 9b, curves 4 and 5). 

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