Polycondensates, cross-linking

The second largest use at 21% is for unsaturated polyester resins, which are the products of polycondensation reactions between molar equivalents of certain dicarboxyhc acids or thek anhydrides and glycols. One component, usually the diacid or anhydride, must be unsaturated. A vinyl monomer, usually styrene, is a diluent which later serves to fully cross-link the unsaturated portion of the polycondensate when a catalyst, usually a peroxide, is added. The diacids or anhydrides are usually phthahc anhydride, isophthahc acid, and maleic anhydride. Maleic anhydride provides the unsaturated bonds. The exact composition is adjusted to obtain the requked performance. Resins based on phthahc anhydride are used in boat hulls, tubs and spas, constmction, and synthetic marble surfaces. In most cases, the resins contain mineral or glass fibers that provide the requked stmctural strength. The market for the resins tends to be cychcal because products made from them sell far better in good economic times (see Polyesters,unsaturated). 

The hydrolysis and polycondensation reactions initiate at numerous sites within the TMOS/H2O solution as mixing occurs. When sufficient intercoimected Si—O—Si bonds are formed in a region, the material responds cooperatively as colloidal (submicrometer) particles or a sol. The size of the sol particles and the cross-linking within the particles, ie, the density, depends on the pH and R ratio, where R = [H2 0]/[Si(0R)4]. 

In conclusion, the self-condensation of 2-furaldehyde promoted by heat occurs with the formation of di- and trifurylic intermediates. The functionality of the growing chain increases after each oligomerization step until gelation and precipitation of the resin occurs. Thus, the process is non-linear from the onset since the condensation product 4 possesses three sites for further attack, namely the free C-5 position and the two formyl groups. It is interestering to note that while the polycondensation of 2-furfuryl alcohol is essentially linear and cross-linking is due to side reactions, the thermal resinification of 2-furaldehyde is intrinsically non-linear and gel formation occurs at earlier conversions. 

Polycondensation pol5mers, like polyesters or polyamides, are obtained by condensation reactions of monomers, which entail elimination of small molecules (e.g. water or a hydrogen halide), usually under acid/ base catalysis conditions. Polyolefins and polyacrylates are typical polyaddition products, which can be obtained by radical, ionic and transition metal catalyzed polymerization. The process usually requires an initiator (a radical precursor, a salt, electromagnetic radiation) or a catalyst (a transition metal). Cross-linked polyaddition pol5mers have been almost exclusively used so far as catalytic supports, in academic research, with few exceptions (for examples of metal catalysts on polyamides see Ref. [95-98]). 

As mentioned previously, the main drawbacks of the thermal route to poly-borylborazine are (1) the presence of both direct intercyclic bonds and three-atom bridges between the rings, and (2) a difficulty in controlling the polycondensation rate. One solution we investigated to address these drawbacks is a route based on the room temperature reaction of /i-chloroborazine with trialkylaminoborane.31 32 We used 2-methylamino-4,6-dichloroborazine instead of 2,4,6-trichloroborazine to prepare a two-point polymer (scheme 4), which is theoretically less cross-linked. 

In the second, complementary, approach the polycondensation of silica polymer is followed by the formation of an organic network made by cross-linking reaction of monomers covalently bound to silicon compounds (Scheme 4.1) resulting in polymeric materials with outstanding protective abilities, including thermal, mechanical and corrosion resistance. 

Synthetic peptides have been extensively used to study the thermal stability and folding of the triple helix. These peptides can be synthesized as either single chains or cross-linked peptides. Early on, such peptides were synthesized by polycondensation of tri- or hexapeptides, which led to a broad mass distribution that was difficult to separate. With the advances of solid-phase synthesis methods, peptides with defined chain length became available. The most studied collagen-like peptides are (Gly-Pro-Pro) or (Pro-Pro-Gly) and (Gly-Pro-4(if)Hyp) or (Pro-4(if)Hyp-Gly) with n varying from 5 to 15. Sutoh and Noda" " introduced the concept... 

Hydrolytic polycondensation of trifunctional monomers of the type XSiYj leads to cross-linked three-dimensional as well as network and cis-syndiotactic (ladder-type) polymers, (XSiOj 5) With increasing amount of solvent, however, the cor-... 

For a linear polymer to be synthesized by the polycondensation or polymerization mechanism, each molecule of the oligomer must have f = 2 for single-act or f = 1 for two-act RFG. To obtain cross-linked polymers the system must contain components of f > 3 for single-act RFG (three-dimensional polycondensation) or with f > 2 for two-act groups. 

The same concept was used in polycondensation systems for the preparation of branched and cross-linked polymers [121]. Copolyurethanes 73 were prepared from tetra(ethylene glycol), bis(5-hydroxymethyl-l,3-phenylene)-32-crown-10 (74)... 

The complete balance of the upturn by the polydispersity is only obtained for random branching processes. Often the reaction is impeded by serious constraints, or the primary chains before cross-linking are monodisperse. Then the resultant final molecular-weight distribution is narrower than in the random case, and the characteristic upturn as a result of branching, develops again. A strange coincidence in behavior is observed with star-molecules, where the rays are polydisperse, and with the ABC-type polycondensates. In both cases the particle-scattering factors can be expressed as ... 

In Chap. C we have discussed in some detail the application of the cascade theory to polycondensates in their unperturbed state. In Chap. D some experimental results were already given for cross-linked or vulcanisated linear chains. In this chapter we shall now outline in brief how cross-linking chain reactions or the vulcanization of preformed chains of an arbitrary length distribution can be treated by cascade theory. Second, we shall discuss how heterogeneities in branching or a rigidity of a certain domain can be taken into account. 

The principles of the calculation by means of the cascade theory is sketched in Fig. 58 and compared with the random polycondensation. Instead of selecting a single monomeric unit as root of a tree, a whole primary chain is placed on the zero-th generation, and the same is done for all the other primary chains from the cross-linked polymer. 

S.S -Tetrahydroxy-S -tetramethyl spirobisindane (TTSBI) was depro-tonated with f-BuOK and polycondensed with di(ethylene glycol) tosylate or tri(ethylene glycol) tosylate as shown in Fig. 46. At concentrations of 0.1 or 0.2 mol/L no cross-linking was observed and multicyclic polyethers were isolated in high yields (up to 99%). The formed polymer was an amorphous character with two glass-transition temperatures [151]. 

Depending on the reaction conditions, the solvent used and the length of the radical at the Si atom, the hydrolytic condensation of trifunctional halogen-containing compounds drastically changes the structure, composition and properties of polyorganosiloxanes formed as a result of hydrolytic condensation and polycondensation. This leads to the formation of branched (I), ladder (II) or cross-linked molecular structures in the polymer. 

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