Precursor block copolymers

As previously described, all microspheres discussed in this chapter were synthesized from AB type diblock copolymers. Precursor block copolymers, poly(styrene-b-4-vinyl pyridine) (P[S-b-4VP]) diblock copolymers, were synthesized using the additional anionic polymerization technique [13]. The basic properties of the block copolymers were determined elsewhere [24,25] and are listed... 

In a more general way, the loading of metal salts into preformed block copolymer micelles has become the most used route for the incorporation of precursors into block copolymer nanostructures because it allows precursor loading with tolerable loading times, it is quite versatile, and it is applicable to a wide variety of precursor/block copolymer/solvent systems. The accordingly synthesized polymer-coated metallic or semiconducting nanoparticles exhibit increased stability, which results in, e.g., protection against oxidation as illustrated by Antonietti et al. [108]. 

It is further noteworthy that a large variety of other aggregate structures (micellar rods, toroids, etc.) could be produced depending on the protein and the composition of the precursor block copolymer. 

Kostakis, K. Mourmouris, S. Pitsikalis, M. Hadjichristidis, N. Polymerization of acrylates and bulky methacrylates with the use of zirconocene precursors Block copolymers with methyl methacrylate. J. Polym. ScL, Part A Polym. Chem. 2005, 43, 3337-3348. 

The same precursor block copolymer, PS-PI, was treated with C6F13 (CH2)2Si(CH3)2H under Pt-catalyzed hydrosilylation reaction conditions. The corresponding perfluoroalkyl groups were introduced into the vinyl groups in the PI segment to directly produce the target block copolymer as shown in Scheme 23.4 (Hwang et al, 1995 Jeyaprakash et al, 2000). 

Another method for preparation of multisegmented block copolymers has been developed based on click chemistry. An example is the initial preparation of a,co-diazido-terminated PS-I7-PEO-I7-PS followed by coupling with propargyl ether in DMF in the presence of a CuBr/PMDETA catalyst. The same catalyst could be used for both the formation of the first precursor block copolymer and the chain-extended multiblock copolymer as shown in Scheme 17. ... 

The C-S bond of the sulfide end groups can be relatively weak and susceptible to thermal and photo- or radical-induced homolysis. This means that certain disulfides [for example 7-9] may act as iniferters in living radical polymerization and they can be used as precursors to block copolymers (Sections 7.5.1 and 9.3.2). 

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. 

Anionic polymerization of lactams was shown to proceed according to what is called the activated monomer mechanism. With bischloroformates of hydroxy-terminated poly(tetramethyleneglycol) and poly(styrene glycol) as precursors for a polymeric initiator containing N-acyl lactam ends, block copolymers with n-pyrrol-idone and e-caprolactam were obtained by bulk polymerizations in vacuum at 30 and 80 °C, respectively361. ... 

Anionic polymerizations are well suited for the synthesis of polymers fitted at chain end with reactive functions. Block copolymers can result from reactions between suitable functions carried by two different functional precursors. In some cases the carbanionic sites themselves are the reactive functions. In other cases, functional polymers (obtained anionically, or by other methods) can be reacted with low molecular weight coupling agents. Here are a few examples ... 

Polystyrene-polyamide block copolymer synthesis 63> also involves some kind of site transformation. The polystyrene precursor is fitted at chain end with a function... 

Simon P.F.W., Ulrich R., Spiess H.W., and Wiesner U. Block copolymer-ceramic hybrid materials from organically modified ceramic precursors, Chem. Mater., 13, 3464, 2001. 

Scheme 2. Encapsulation of size- and shape-controlled Pt nanoparticles under neutral hydrothermal synthesis conditions of SBA-15. Silica templating block copolymers and silica precursors were added to PVP-protected Pt nanoparticle solutions and subjected to the standard SBA-15 silica synthesis conditions. Neutral, rather than acidic pH conditions were employed to prevent particle aggregation and amorphous silica formation [16j. (Reprinted from Ref. [16], 2006, with permission from American Chemical Society.)...

By employing anionic techniques, alkyl methacrylate containing block copolymer systems have been synthesized with controlled compositions, predictable molecular weights and narrow molecular weight distributions. Subsequent hydrolysis of the ester functionality to the metal carboxylate or carboxylic acid can be achieved either by potassium superoxide or the acid catalyzed hydrolysis of t-butyl methacrylate blocks. The presence of acid and ion groups has a profound effect on the solution and bulk mechanical behavior of the derived systems. The synthesis and characterization of various substituted styrene and all-acrylic block copolymer precursors with alkyl methacrylates will be discussed. 

Statistical and block copolymers based on ethylene oxide (EO) and propylene oxide (PO) are important precursors of polyurethanes. Their detailed chemical structure, that is, the chemical composition, block length, and molar mass of the individual blocks may be decisive for the properties of the final product. For triblock copolymers HO (EO) (PO)m(EO) OH, the detailed analysis relates to the determination of the total molar mass and the degrees of polymerization of the inner PPO block (m) and the outer PEO blocks (n). 

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