Chain-extension polymerization

Recently, Cohn and Salomon synthesized and characterized a series of PLCL thermoplastic bioelastomers by two-step synthesis procedure. First, ring-opening polymerization of L-lactide initiated by the hydroxyl terminal groups of the PCL chain. Second, chain extension polymerization of these PLA-PCL-PLA triblocks initiated by the hexamethylene diisocyanate (HDl). 

The broad applicability of ATRP in the ionic liquid [BMIMjPFg was shown by extending it to the polymerization of N-substituted maleimides with styrene. The ATRP was initiated with dendritic polyaryl ether 2-bromoisobutyrate as the initiator at room temperature. The dendritic-linear block copolymers formed in the ionic liquid were characterized by low polydispersity (1.05[Pg.214]

Each of the units in the preceding structure are linked together into a polymer chain using chain extension polymerization. The resulting polymer themselves are also identified by a shorthand nomenclature. If the substitution is within the silicone polymer, that is, based on D, a comb polymer is achieved. 

The polymerization rates at appropriate power of miaowave irradiation wae faster than that unda conventional heating conditions at the same reaction temperature with or without benzoyl peroxide. Furthermore, it was proved by successful chain extension polymerization and NMR spertrum analysis that the nitroxide moiety did exist at the end of polymeric chain. ... 

Stabilizers and pigments are normally slurried with macroglycol and added to the polymeric glycol charge, prior to diisocyanate addition. Therefore, care must be taken to avoid additives that react significantly with diisocyanates or diamines under processing conditions. Also, stabilizers should be chosen that have no adverse catalytic effect on the prepolymer or chain-extension reactions. 

DNA polymerases normally use 3 -deoxynucleotide triphosphates as substrates for polymerization. Given an adequate concentration of substrate, DNA polymerase synthesizes a long strand of new DNA complementary to the substrate. The use of this reaction for sequencing DNA depends on the inclusion of a single 2/3 -dideoxynucleoside triphosphate (ddNTP) in each of four polymerization reactions. The dideoxynucleotides ate incorporated normally in the chain in response to a complementary residue in the template. Because no 3 -OH is available for further extension, polymerization is... 

The main industrial use of alkyl peroxyesters is in the initiation of free-radical chain reactions, primarily for vinyl monomer polymerizations. Decomposition of unsymmetrical diperoxyesters, in which the two peroxyester functions decompose at different rates, results in the formation of polymers of enhanced molecular weights, presumably due to chain extension by sequential initiation (204). 

The amine groups thus formed can also react vigorously with the isocyanate groups to continue the chain extension and cross-linking reactions. Hence, ia the systems there are simultaneous foaming, polymerization, and cross-linking reactions, which produce foam elastomers (or plastics). 

While the chemistry of radiation curable hot melt adhesives is the same as that used in liquid (syrup) adhesives and coatings discussed elsewhere in this volume, there is a fundamental difference between the objectives of reaction in the two types of systems. Syrups consist largely or entirely of reactive monomeric and/or oligomeric materials. Radiation is used to initiate the polymerization of virtually the entire mass. In contrast, hot melts generally contain polymers initially, and these polymers are capable of reaction via radiation to produce chain extension and... 

Macromonomers such as 66, 68 and 94 are themselves catalytic chain transfer agents (Section 6.2.3.4) and transfer to macromonomer is one mechanism for chain extension of the initially formed species. The adduct species in the case of monomeric radical adding dimer (100) may also react by chain transfer to give 101 which is inert under polymerization conditions (Scheme 6.25). Polymerizations to... 

Chemical analyses reveal that measurable amounts of uranyl ion are actually present in Pu(IV) polymers grown in mixtures of Pu(IV) and uranyl nitrate suggesting that uranyl ion is being taken up in the polymer network and consequently hampers the growth through a chain termination process as suggested in Fig. 3. The uranyl serves to terminate active sites because it does not typically form extensive polymeric aggregates as does Pu(IV) instead it tends only to dimerize and, at most, tri-merize (4). 

Cements, polyester, 30 CFCs. See Chlorofluorocarbons (CFCs) Chain conformation, 54 Chain extenders, 213-214 structure of, 219 Chain extension, 216 Chain-growth polymerizations, 4 Char formation, 421, 423 Chelated phosphine ligands, 488 Chemical recycling, 208 Chemical structure... 

Addition polymers, which are also known as chain growth polymers, make up the bulk of polymers that we encounter in everyday life. This class includes polyethylene, polypropylene, polystyrene, and polyvinyl chloride. Addition polymers are created by the sequential addition of monomers to an active site, as shown schematically in Fig. 1.7 for polyethylene. In this example, an unpaired electron, which forms the active site at the growing end of the chain, attacks the double bond of an adjacent ethylene monomer. The ethylene unit is added to the end of the chain and a free radical is regenerated. Under the right conditions, chain extension will proceed via hundreds of such steps until the supply of monomers is exhausted, the free radical is transferred to another chain, or the active site is quenched. The products of addition polymerization can have a wide range of molecular weights, the distribution of which depends on the relative rates of chain grcnvth, chain transfer, and chain termination. 

The polymerization process for nylon 6 consists primarily of the three types of reaction illustrated in Fig. 23.6. Each of the reactions is reversible, tvith the equilibrium of the products being controlled primarily by the concentration of water in the reaction vessel. The reaction is initiated by the hydrolytic ring opening of caprolactam to form 6-aminohexanoic acid, as shown in Fig. 23.6 a). Chain extension of the type shotvn in Fig. 23.6 b) dominates when water is abundant (10 to 20%) in the reaction mixture. At lower water levels (2 to 5%) chains grow primarily by the mechanism shown in Fig. 23.6 c). In order to limit the average molecular... 

Single stage polymerization generates much more heat than the polymerization of a prepolymer in the chain extension stage of the two stage polymerization process. Why is this so, and what benefit is there in having a lower heat of polymerization ... 

For the hydrosilylation reaction various rhodium, platinum, and cobalt catalysts were employed. For the further chain extension the OH-functionalities were deprotected by KCN in methanol. The final step involved the enzymatic polymerization from the maltoheptaose-modified polystyrene using a-D-glucose-l-phosphalc dipotassium salt dihydrate in a citrate buffer (pH = 6.2) and potato phosphorylase (Scheme 59). The characterization of the block copolymers was problematic in the case of high amylose contents, due to the insolubility of the copolymers in THF. 

These iniferter sites containing an N-H group can be easily transformed into the corresponding thiol which leads to disulfide by oxidative coupling and can form chelation with metal ions (Eq. 47) [171,172]. Poly(St) prepared for polymerization with 44 and 45 was applied to the chain-extension reaction by the S-S bond or chelation bond formations. 

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