Block copolymers poly segments

We recently have reported our initial studies on step-growth block copolymers containing segments of poly (aryl ethers) and poly (aryl carbonates) (9,10). The multiblock [ A-B ]n block copolymers were prepared by phosgenation in methylene chloride/pyridine solution either by what was termed an in situ or by a coupled oligomer technique (JO). The choice of polycarbonates and poly (aryl ethers) for initial studies was based on the several considerations. Copolymerization is feasible since the end groups in the two oligomers can be identical, as shown in Structures 1 and 2. Considerable information is available in the... 

The most characteristic feature of the cationic polymerization of cyclic acetals, however, is an excessive participation of the polymer chain in the polymerization processes. This is exemplified by the results of attempted synthesis of block copolymer containing segments of poly(l,3-dioxolane, DXL) and poly(l,3-dioxepane, DXP) [130]. 

Styrenic block copolymers and their compounds have been in widespread commercial use for many years, with many applications. With the latest technology, they have become particularly interesting as impact modifiers for plastics, both thermoplastics and thermosets. Most polymers are thermodynamically incompatible with others polymers and mixtures tend to separate into two phases, even when they are part of the same molecule, as in block copolymers. Poly(styrene-P-elastomer-P-styrene) copolymers, in which the elastomer is the main constituent, give a structure in which the polystyrene end-segments form separate spherical regions ( domains ) dispersed in a continuous phase. 

Recently, the enhanced control of bulk and surface ordering of polypeptides has been employed to drive the processing and self-assembly of conductive rigid segments. Mainly triblock copolymer structures have been studied (see the following section). Manners and Winnik (Wang et al., 2008) synthesized a new type of metaUopolymer-polypeptide block copolymer poly(ferrocenyldimethylsilane)-fc-poly(8-benzyloxycarbonyl-L-lysine) (PFS-( -PZLLys) and studied their self-organization behavior in both the bulk state and in solution. In the bulk state, a cylindrical in-lamellar structure was observed in a compositionally asymmetric sample. Rod-like micelles with a polyferrocenylsilane core formed in a polypeptide selective solvent alone or in the presence of a common solvent. 

All these elastomers, especially poly(ethylene- (9-butylene) and poly(ethylene- (9-propylene), are nonpolar. The corresponding block copolymers can thus be compounded with hydrocarbon-based extending oils, but do not have much oil resistance. Conversely, block copolymers with polar polyester or polyether elastomer segments have Htde affinity for such hydrocarbon oils and so have better oil resistance. 

In Chapters 3 and 11 reference was made to thermoplastic elastomers of the triblock type. The most well known consist of a block of butadiene units joined at each end to a block of styrene units. At room temperature the styrene blocks congregate into glassy domains which act effectively to link the butadiene segments into a rubbery network. Above the Tg of the polystyrene these domains disappear and the polymer begins to flow like a thermoplastic. Because of the relatively low Tg of the short polystyrene blocks such rubbers have very limited heat resistance. Whilst in principle it may be possible to use end-blocks with a higher Tg an alternative approach is to use a block copolymer in which one of the blocks is capable of crystallisation and with a well above room temperature. Using what may be considered to be an extension of the chemical technology of poly(ethylene terephthalate) this approach has led to the availability of thermoplastic polyester elastomers (Hytrel—Du Pont Amitel—Akzo). 

When ACPC was condensed with hexamethylene diamine in the presence of two other acid chlorides (seb-acoyl or adipoyl chloride), poly(amide)s 6.6 and 6.10 with various numbers of azo groups per repeating unit (between 0.14 and 1.0, depending on the ratio of the acid chlorides used) could be obtained [35,36]. Thus, block copolymers with a controlled segment length of the poly-(amide) blocks were attainable. 

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. 

Hedrick et al. reported imide aryl ether ketone segmented block copolymers.228 The block copolymers were prepared via a two-step process. Both a bisphenol-A-based amorphous block and a semicrystalline block were prepared from a soluble and amorphous ketimine precursor. The blocks of poly(arylene ether ether ketone) oligomers with Mn range of 6000-12,000 g/mol were coreacted with 4,4,-oxydianiline (ODA) and pyromellitic dianhydride (PMDA) diethyl ester diacyl chloride in NMP in the presence of A - me thy 1 morphi 1 i nc. Clear films with high moduli by solution casting and followed by curing were obtained. Multiphase morphologies were observed in both cases. 

Hydrosilation reactions have been one of the earlier techniques utilized in the preparation of siloxane containing block copolymers 22,23). A major application of this method has been in the synthesis of polysiloxane-poly(alkylene oxide) block copolymers 23), which find extensive applications as emulsifiers and stabilizers, especially in the urethane foam formulations 23-43). These types of reactions are conducted between silane (Si H) terminated siloxane oligomers and olefinically terminated poly-(alkylene oxide) oligomers. Consequently the resulting system contains (Si—C) linkages between different segments. Earlier developments in the field have been reviewed 22, 23,43> Recently hydrosilation reactions have been used effectively by Ringsdorf 255) and Finkelmann 256) for the synthesis of various novel thermoplastic liquid crystalline copolymers where siloxanes have been utilized as flexible spacers. Introduction of flexible siloxanes also improved the processibility of these materials. 

Walch E. and Caymans R.J., Synthesis and properties of poly(butylenes terephthalate)-b-polyisobutylene segmented block copolymers, Polymer, 35, 636, 1994. 

Deschamps AA, Grijpma DW, and Feijen J. Poly(ethylene oxide)/poly(butylenes terephthalate) segmented block copolymers The effect of copolymer composition on physical properties and degradation behavior. Polymer, 2001, 42, 9335-9345. 

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