Copolymer polydispersity

The calculation of copolymer molar mass averages and so on, and copolymer polydispersity D is done as in conventional GPC calculations using the copolymer molar mass calculated from Eq. (3). 

Copolymer molar mass averages etc. and copolymer polydispersity... 

The calculation of copolymer molar mass averages and copolymer polydispersity is made as in conventional SEC... 

Comonomer is exhausted at relatively low conversion (20), but a random copolymer is nevertheless obtained. This is because a very facile transacetalisation reaction allows for essentially random redistribution of the comonomer units (18) and also results in a polydispersity index near 2.0 (21). 

The new knowledge and understanding of radical processes has resulted in new polymer structures and in new routes to established materials many with commercial significance. For example, radical polymerization is now used in the production of block copolymers, narrow polydispersity homopolymers, and other materials of controlled architecture that were previously available only by more demanding routes. These commercial developments have added to the resurgence of studies on radical polymerization. 

See also PBT degradation structure and properties of, 44-46 synthesis of, 106, 191 Polycaprolactam (PCA), 530, 541 Poly(e-caprolactone) (CAPA, PCL), 28, 42, 86. See also PCL degradation OH-terminated, 98-99 Polycaprolactones, 213 Poly(carbo[dimethyl]silane)s, 450, 451 Polycarbonate glycols, 207 Polycarbonate-polysulfone block copolymer, 360 Polycarbonates, 213 chemical structure of, 5 Polycarbosilanes, 450-456 Poly(chlorocarbosilanes), 454 Polycondensations, 57, 100 Poly(l,4-cyclohexylenedimethylene terephthalate) (PCT), 25 Polydimethyl siloxanes, 4 Poly(dioxanone) (PDO), 27 Poly (4,4 -dipheny lpheny lpho sphine oxide) (PAPO), 347 Polydispersity, 57 Polydispersity index, 444 Poly(D-lactic acid) (PDLA), 41 Poly(DL-lactic acid) (PDLLA), 42 Polyester amides, 18 Polyester-based networks, 58-60 Polyester carbonates, 18 Polyester-ether block copolymers, 20 Polyester-ethers, 26... 

This polymeric oxocarbenium salt readily initiates the cationic ring opening polymerization of oxolane to produce a polystyrene-polyTHF block copolymer. Molecular weight control is provided, polydispersity is narrow and compositional heterogeneity is small59). 

Once all the remaining sites have reacted a polystyrene fitted with grafts of known length at approximately constant intervals is obtained. As the backbone arises by polycondensation, fractionation is necessary when samples of low polydispersity are needed. Whether the grafts are distributed regularly or randomly hardly affects the behavior of the graft copolymer 91). 

The general structure of linear low density polyethylene is shown in Fig. 18.2 c). Linear low density resins are copolymers of ethylene and 1-alkenes principally 1-butene, 1-hexene, and 1-octene. Comonomer levels range from approximately 2 to 8 mole %. This family of polyethylene is widely known as LLDPE. Linear low density polyethylenes are polydisperse with regard to molecular weight and branch distribution. 

For analyzing structure-property relationships, a variety of PEO-g-PVA copolymers were prepared, differing in the VAc-to-PEO ratio and the molar mass of PEO. The analysis of the copolymers by IR and 1H- and 13C-NMR showed the presence of both PEO and PVA. A small C=0 absorption was still present and was explained by a nonquantitative saponification. SEC showed polydispersities (Mw/M ) of around 5, with a small tailing to the low molar mass side. The latter was probably caused by the relatively low molar mass PVA homopolymer formed by the chain transfer reaction of VAc, both to the PEO and its acetate functionality. 

Triblock copolymers of the ABA type may be analyzed similar to the analysis of diblock copolymers. The two possible cases for this type of investigation are (a) the analysis with respect to the inner block B using the critical conditions of the outer blocks A and A, and (b) the analysis of the outer blocks A and A using the critical conditions of the inner block B. It is particularly useful to carry out experiments at the critical point of A and A. The separation then occurs with respect to the chain length of B, yielding fractions that are monodisperse with respect to B and polydisperse with respect to A and A. These fractions can be analyzed selectively with respect to the outer blocks A and A in separate experiments (Entelis et al., 1986 Adrian et al., 1998 Pasch and Augenstein, 1993, 1994, 2002 Pasch, 1997, 2000, 2004 Kilz and Pasch, 2000). 

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