Star-shape polymers

Platinum-cobalt alloy, enthalpy of formation, 144 Polarizability, of carbon, 75 of hydrogen molecule, 65, 75 and ionization potential data, 70 Polyamide, 181 Poly butadiene, 170, 181 Polydispersed systems, 183 Polyfunctional polymer, 178 Polymerization, of butadiene, 163 of solid acetaldehyde, 163 of vinyl monomers, 154 Polymers, star-shaped, 183 Polymethyl methacrylate, 180 Polystyrene, 172 Polystyril carbanions, 154 Potential barriers of internal rotation, 368, 374... 

To make this review self-contained and to provide a foundatitMi for further discussion, we have included the experimental methods and theoretical models of mechanical degradation for linear chains in the second and third sections, respectively. From the fourth to seventh sections, the mechanochemistry of cyclic polymers, graft polymers, star-shaped polymers (star-shaped polymers), dendrimers, and hyperbranched polymers is summarized. In the eighth section, we survey the mechanochemistry of supramolecular aggregates and knotted polymers, where the topology constraints are temporal. We hope our overview can serve as a guideline for the future work in the field of polymer mechanochemistry. 

Their findings were that star polymers presented a lower surface tension that linear polystyrene and that this value decreased with increasing number of arms. This behavior was explained by a lattice model considering finite compressibility of the chain and density gradient in the polymer blend. Thus this study implied that when mixed with a linear polymer star-shaped macromolecules would segregate to reduce the surface tension. 

More recent examples include end-functionalized multiarmed poly(vinyl ether) (44), MVE/styrene block copolymers (45), and star-shaped polymers (46—48). With this remarkable control over polymer architecture, the growth of future commercial appHcations seems entirely likely. 

Transparent toughened polystyrene polymers are produced by blending polystyrene with SBS block copolymers (see Section 11.8). During the 1970s and 1980s most development was with block copolymers with a radial (or star) shape. Two types were developed block copolymers with a central butadiene block, and block copolymers with a central polystyrene block. 

The linear diblocks are then coupled by a polyfunctional coupling agent such as epoxidised linseed oil to give a star-shaped polymer. As already mentioned, commercial materials of this type have a tetramodal distribution. 

Two types of well defined branched polymers are acessible anionically star-shaped polymers and comb-like polymers87 88). Such macromolecules are used to investigate the effect of branching on the properties, 4n solution as well as in the the bulk. Starshaped macromolecules contain a known number of identical chains which are linked at one end to a central nodule. The size of the latter should be small with respect to the overall molecular dimensions. Comb-like polymers comprise a linear backbone of given length fitted with a known number of randomly distributed branches of well defined size. They are similar to graft copolymers, except that backbone and branches are of identical chemical nature and do not exhibit repulsions. 

The synthesis of tailor-made star-shaped polymers can be performed in several ways by means of a plurifunctional organometallic initiator, or by reacting a living precursor polymer with a plurifunctional reagent, to build the centra] body, or by block copolymerization involving a diunsaturated monomer (Scheme 3). 

The purpose of this review is to show how anionic polymerization techniques have successfully contributed to the synthesis of a great variety of tailor-made polymer species Homopolymers of controlled molecular weight, co-functional polymers including macromonomers, cyclic macromolecules, star-shaped polymers and model networks, block copolymers and graft copolymers. 

Fig. 19—Diagram of friction versus load of mono- and multilayer L-B films of star-shaped Cgo-Pst polymer.

The results show that the C5o-Pst star-shaped polymer L-B hlms are hrmly fixed on the surface of the substrate, even after the surface was scanned for many times. The topography, high density, order and preferred orientation of the hlms are dominating factors in friction. The C5o-Pst him could play a signihcant role in microtribological applications. 

The paper is organized in the following way In Section 2, the principles of quasi-elastic neutron scattering are introduced, and the method of NSE is shortly outlined. Section 3 deals with the polymer dynamics in dense environments, addressing in particular the influence and origin of entanglements. In Section 4, polymer networks are treated. Section 5 reports on the dynamics of linear homo- and block copolymers, of cyclic and star-shaped polymers in dilute and semi-dilute solutions, respectively. Finally, Section 6 summarizes the conclusions and gives an outlook. 

Star shaped macromolecules are polymers, where the one end of f > 2 (f functionality of the star) linear chains is chemically attached by covalent bonds to a small central linker unit, are the simplest form of branched polymers. Modern anionic polymerization techniques allow us to synthesize star systems with a large number of nearly monodisperse arms [133, 134],... 

Fig. 47a, b. Structure and dynamics of star-shaped polymers with different functionalities, a Kratky plot of the static structure factor (S(Q, 0) Q2 vs. Q Rg. b Q(Q)/Q3 vs. Q Rg, as derived from Eqs (94) and (123), assuming Rouse dynamics... 

When the various results obtained by combined elastic and quasielastic neutron scattering measurements on star shaped polymers in dilute solutions... 

Star-shaped polymer molecules with long branches not only increase the viscosity in the molten state and the steady-state compliance, but the star polymers also decrease the rate of stress relaxation (and creep) compared to a linear polymer (169). The decrease in creep and relaxation rate of star-shaped molecules can be due to extra entanglements because of the many long branches, or the effect can be due to the suppression of reptation of the branches. Linear polymers can reptate, but the bulky center of the star and the different directions of the branch chains from the center make reptation difficult. 

Samarium enolates 60 can be easily prepared by reduction of ct-bromocarboxylic acid esters with SmT. These enolates mediated well-defined synthesis of star-shaped block co-polymers 61 (Scheme 21 ).32 32l Sml3 also mediated the formation of samarium enolates. Phenacyl thiocyanate 6233 and cr-haloketone 6434 are converted to samarium(lll) enolate intermediates 63 and 65, respectively, which undergo addition to benzaldehyde derivatives affording the corresponding oy i-unsaturatcd ketones as shown in Schemes 22 and 23. 

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