Macromolecules crosslinked

By chemically creating crosslinks between previously formed linear or branched macromolecules (crosslinking of primary chains, as vulcanization does for natural rubber). 

From the data of DTA and TGA analyses illustrated in Fig. 4, its evident that the visible exo-peaks in the range of 140-150°C appear in DTA curves (Fig. 4a), which can be taken as evidence of a crosslinking reaction of acylated macromolecules at the expense of side chain... 

Modified PS by use of BF3-OEt2 catalyst had better properties comparised with virgin PS and other modified polymers. High thermostability and photosensitivity of modified PS compared with virgin PS are explained by the crosslinked structure of macromolecules formed during the processes of thermo- and phototreatment. 

The steady structure determined by the value of Kw (Fig. 1) for the entire class of carboxylic CP obtained by precipitation copolymerization is one of the most important factors determining the possibility of reversible bonding of proteins absorbed by carboxylic CP with a high sorption capacity [16,19]. Thus, for the MA-HHTT system (Fig. 2), a complete desorption of enzyme is carried out on crosslinked copolymers characterized by low Kw values. In crosslinked structures exhibiting looser structure (Kw P 1), owing to the mobility of chain fragments of CP especially in the process of desorption, the macromolecules of sorbed protein are irreversibly captured as a result of a marked polyfunctional interaction. 

This is one of the most universal techniques for obtaining hydrogels from water-soluble polymers. Crosslinked PEO, PVA, PAAm, PAAc and its salts, as well as some polymer blends were obtained by this method. Although all polymers mentioned above have their own specific features, in most cases the gelation doses do not exceed 1-2 Mrad, i.e. they are substantially lower than for the same polymer in bulk. This is due to the fact that in aqueous media crosslinking occurs indirectly, namely because of the OH radical formation and their attack on the macromolecules. There exists a developed theory of these processes [73],... 

Elasticity is another important property of SAH which distinguishes the swollen gel from a viscous (but capable of flowing) solution of the non-crosslinked macromolecules. 

The above results proved the potential viability of the adsorbed hydrophilic macromolecules as bonded phases in chromatography of biopolymers but it must be admitted that additional crosslinking of previously adsorbed macromolecules is usually needed in order to obtain stable composites. The cross-linked bonded polymeric phases, however, may suffer from the restricted flexibility of the chain segment and their steric repellency may be diminished. Moreover, the conformational adaptivity of cross-linked chains for binding with solutes is poorer than that of grafted or chemically bound macromolecules. 

The presence of double bonds in the macromolecule of these copolymers of type 9 makes it possible to crosslink the fibres by various methods32, 33. ... 

Covalent chemical bonds that occur between macromolecules are known as crosslinks. Their presence and density have a profound influence on both the chemical and mechanical properties of the materials in which they occur. 

As we have seen previously the presence of crosslinks between macromolecules influences the way in which these materials respond to heat. Uncrosslinked polymers will generally melt and flow at sufficiently high temperatures they are usually thermoplastic. By contrast, crosslinked polymers cannot melt because of the constraints on molecular motion introduced by the crosslinks. Instead, at temperatures well above those at which thermoplastics typically melt, they begin to undergo irreversible degradation. 

Crosslinking can be introduced into an assembly of polymer molecules either as the polymerisation takes place or as a separate step after the initial macromolecule has been formed. Typical of the first category are polymers made by step processes, often condensations, in which monomers of functionality greater than 2 are present. The relative concentration of such higher functionality monomers then determines the density of crosslinks in the final material. 

Although the name polyurethane might be taken as implying that these materials contain urethane groups (—NHCOO—) in the backbone of the macromolecule, for those polyurethanes in major commercial use this is not tme. For such materials the initial macromolecule tends to be a polyester or polyether it is the crosslinks that involve the formation of a polyurethane stmcture. 

All polymers are giant molecules made up of repeating units called monomers or mers. These units may be the same or different. The number of monomers that join to form a polymer or macromolecule is called the degree of polymerization and is theoretically infinite, but, in practice, the number of monomer units is commonly in the range of 1000 to 20,000 if no crosslinks are present. 

Finally, a new water-soluble polyphosphazene was recently synthesized that has the structure shown in 36 (46). This polymer has two attributes as a biomedical macromolecule. First, the pendent carboxylic acid groups are potential sites for condensation reactions with amines, alcohols, phenols, or other carboxylic acid units to generate amide, ester, or anhydride links to polypeptides or bioactive small molecules. Second, polymer forms ionic crosslinks when brought into contact with di- or trivalent cations such as Ca or Ai3+. The crosslinking process converts the water-soluble polymer to a hydrogel, a process that can be reversed when the system... 

Allcock, H. R., and Kwon, S., An ionically-crosslinkable poly-phosphazene Poly[di(carboxylatophenoxy)phosphazene] and its hydrogels and membranes. Macromolecules. 22. 75, 1989. 

Michaeli (1960) opposed these views. He concluded that whatever the exact mechanism was, the binding of divalent cations caused contraction and coiling of the polyelectrolyte as was the case with adds. He disagreed with the concept of ionic crosslinking. The phenomenon of precipitation could be explained simply in terms of reduced solubility. From this he concluded that precipitation took place in an already coiled molecule and the matrix consisted of spherical macromolecules containing embedded cations. 

Funke, Wa Microgels-Intramolecularly Crosslinked Macromolecules with a Globular Structure. VoL 136, pp. 137-232. 

The term "macromolecules" implies that the subject matter includes chain molecules that may be built up of repeat units, as well as more complex ring, branched, or crosslinked species (for example, see Organo-Oxo-Element Macromolecules Related to Sol-Gel Processes, and contributions by Murray (p. 408) or Seyferth (p. 143)). 

Metallophosphazenes are a new type of macromolecule designed to bridge the gap between polymers and metals. Although still at an exploratory stage of laboratory development, they may provide access to electronically-conducting polymers, magnetically-active polymers, macromolecular catalysts, electrode mediator systems, or polymers crosslinked by metal atoms. 

The connection between polymer chemistry and ceramic science is found in the ways in which linear macromolecules can be converted into giant ultrastructure systems, in which the whole solid material comprises one giant molecule. This transformation can be accomplished in two ways—first by the formation of covalent, ionic, or coordinate crosslinks between polymer chains, and second, by the introduction of crystalline order. In the second approach, strong van der Waals forces within the crystalline domains confer rigidity and strength not unlike that found when covalent crosslinks are present. 

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