Linear block copolymers

Poly(ethylene oxide)-/>-polyethyleneimine (PEO-6-PEI) Block copolymer, linear PEI segment Synthesis of carrier (Akiyama et al., 2000)... 

The main architectures of PLL-based block copolymers (linear and asymmetric), graft and more complex architectures are presented in Figure 4.5. The synthetic approaches for their preparation will be reviewed in the following sections. 

There are different types of block copolymers linear ABA, AB, and branched (AB) with various ratios of A to B (A is polystyrene, and B is polybutadiene, polyisoprene, or their hydrogenated derivatives). 

Similarly, the random introduction by copolymerization of stericaHy incompatible repeating unit B into chains of crystalline A reduces the crystalline melting point and degree of crystallinity. If is reduced to T, crystals cannot form. Isotactic polypropylene and linear polyethylene homopolymers are each highly crystalline plastics. However, a random 65% ethylene—35% propylene copolymer of the two, poly(ethylene- (9-prop5lene) is a completely amorphous ethylene—propylene mbber (EPR). On the other hand, block copolymers of the two, poly(ethylene- -prop5iene) of the same overall composition, are highly crystalline. X-ray studies of these materials reveal both the polyethylene lattice and the isotactic polypropylene lattice, as the different blocks crystallize in thek own lattices. 

Block (Star) Arrangement. The known star polymers, like their linear counterparts, exhibit microphase separation. In general, they exhibit higher viscosities in the melt than their analogous linear materials. Their rheological behavior is reminiscent of network materials rather than linear block copolymers (58). Although they have been used as compatibiUzers in polymer blends, they are not as effective at property enhancements as linear diblocks... 

With block copolymers two types of effect have been observed. In some instances a transition corresponding to each block is observable whilst in other cases a single transition is observed, usually close to that predicted by a linear relationship even where random copolymers show large deviations. This is because the blocks reduce both the contacts between dissimilar comonomer residues and also the disorder of the molecules which occurs in random copolymer systems. 

More recently Fina Chemicals have introduced linear SBS materials (Finaclear) in which the butadiene is present both in block form and in a mixed butadiene-styrene block. Thus comparing typical materials with a total styrene content of about 75% by weight, the amount of rubbery segment in the total molecule is somewhat higher. As a result it is claimed that when blended with polystyrene the linear block copolymers give polymers with a higher impact strength but without loss of clarity. 

The applicability of Noolandi and Hong s theory of compatibilization of immiscible blends using block copolymers has been extended to the reactive compatibilization technique by Thomas and coworkers [75,76]. According to Noolandi and Hong [77], the interfacial tension is expected to decrease linearly with the addition... 

The reaction of ACPC with linear aliphatic amines has been investigated in a number of Ueda s papers [17,35,36]. Thus, ACPC was used for a interfacia] polycondensation with hexamethylene diamine at room temperature [17] yielding poly(amide)s. The polymeric material formed carried one azo group per repeating unit and exhibited a high thermal reactivity. By addition of styrene and methyl methacrylate to the MAI and heating, the respective block copolymers were formed. 

Transfer constants of the macromonomers arc typically low (-0.5, Section 6.2.3.4) and it is necessary to use starved feed conditions to achieve low dispersities and to make block copolymers. Best results have been achieved using emulsion polymerization380 395 where rates of termination are lowered by compartmentalization effects. A one-pot process where macromonomers were made by catalytic chain transfer was developed.380" 95 Molecular weights up to 28000 that increase linearly with conversion as predicted by eq. 16, dispersities that decrease with conversion down to MJM< 1.3 and block purities >90% can be achieved.311 1 395 Surfactant-frcc emulsion polymerizations were made possible by use of a MAA macromonomer as the initial RAFT agent to create self-stabilizing lattices . 

Unusual reactivities of mechano-radicals have been reported in a few instances. To explain the pseudo first-order kinetics and the high yield of linear block copolymers formed during the mechanochemical degradation of a mixture of... 

Another important type of condensation polymer are the linear polyesters, such as poly (ethylene terephthalate) (PET) and poly (butylene terephthalate) (PBT). Copolymers of polyesters and PA have been studied in detail, and it has been shown that random copolyesteramides have a low structural order and a low melting temperature. This is even the case for structurally similar systems such as when the group between the ester unit is the same as that between the amide unit, as in caprolactam-caprolactone copolymers (Fig. 3.10).22 Esters and amide units have different cell structures and the structures are not therefore isomorphous. If block copolymers are formed of ester and amide segments, then two melting temperatures are present. 

The morphology of the ABA-type linear block copolymers is strongly influenced by the volume fraction of the two components. For example, in PS-EB-PS-type block copolymer as the volume fraction of PS is increased, the shape of the dispersed PS phase changes from spherical (comprising body-centered cubic spheres of PS dispersed in continuous soft phase) to cylindrical form (hexagonal packed cylinders of PS) [10,133,134]. When the volume fraction of the two phases... 

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