Constituting-block copolymers

Yet another variant of self-assembly relies on the repulsion between blocks of suitably constituted block copolymers, leading to fine-scale patterns of organisation. One very recent description of this approach is by de Rosa et al. (2000). Details of this kind of approach as cultivated at Oak Ridge National Laboratory can also be found on the internet (ORNL 2000). 

Despite the fact that Milner s theory was originally developed for miktoarm-star copolymers, it can also be adopted for more complex branched structures. This empirical concept termed constituting-block copolymers approximates the architecture of branched molecules to be composed of an array of A2B and A2B2 miktoarms. This approach is capable of predicting the morphology of architectures as complex as centipedes or barbed wires, as shown in a very recent publication [125]. 

Thanks to their multiphase constitution, block copolymers have the originality to add advantageously the properties of their constitutive sequences. These very attractive materials can display novel properties for new technological applications. In this respect, thermoplastic elastomers are demonstrated examples (l, 2, 3) they are currently used without any modification as elastic bands, stair treads, solings in the footwear industry, impact resistance or flexibility improvers for polystyrene, polypropylene and polyethylene whereas significant developments as adhesives and adherends are to be noted (5.). 

Polyall lene Oxide Block Copolymers. The higher alkylene oxides derived from propjiene, butylene, styrene (qv), and cyclohexene react with active oxygens in a manner analogous to the reaction of ethylene oxide. Because the hydrophilic oxygen constitutes a smaller proportion of these molecules, the net effect is that the oxides, unlike ethylene oxide, are hydrophobic. The higher oxides are not used commercially as surfactant raw materials except for minor quantities that are employed as chain terminators in polyoxyethylene surfactants to lower the foaming tendency. The hydrophobic nature of propylene oxide units, —CH(CH2)CH20—, has been utilized in several ways in the manufacture of surfactants. Manufacture, properties, and uses of poly(oxyethylene- (9-oxypropylene) have been reviewed (98). 

There are additional factors that may reduce functionality which are specific to the various polymerization processes and the particular chemistries used for end group transformation. These are mentioned in the following sections. This section also details methods for removing dormant chain ends from polymers formed by NMP, ATRP and RAFT. This is sometimes necessary since the dormant chain-end often constitutes a weak link that can lead to impaired thermal or photochemical stability (Sections 8.2.1 and 8.2.2). Block copolymers, which may be considered as a form of end-functional polymer, and the use of end-functional polymers in the synthesis of block copolymers are considered in Section 9.8. The use of end functional polymers in forming star and graft polymers is dealt with in Sections 9.9.2 and 9.10.3 respectively. 

Covalently connecting two incompatible polymers at their ends leads to a fascinating class of self-assembling materials [1]. Block copolymers constitute a well-studied and well-documented set of nanostructured hybrid materials [2], Many synthetic techniques are available for generating AB diblock, ABA triblock, ABC triblock and even more complicated block architectures [3,4], Furthermore, the thermodynamics governing the self-assembly... 

Note In the constituent macromolecules of a block copolymer, adjacent blocks are constitutionally different, i.e., adjacent blocks comprise constitutional derived from different species of monomer or from the same species of monomer but with a different composition or sequence distribution of constitutional units. 

A block polymer is a polymer comprising molecules in which there is a linear arrangement of blocks, a block being defined as a portion of a polymer molecule in which the monomeric units have at least one constitutional or configurational feature absent from the adjacent portions [4]. In a block copolymer, the distinguishing feature is constitutional, i.e. each of the blocks comprises units derived from a characteristic species of monomer. 

Polyurethane multiblock copolymers of the type described by Eqs. 2-197 and 2-198 constitute an important segment of the commercial polyurethane market. The annual global production is about 250 million pounds. These polyurethanes are referred to as thermoplastic polyurethanes (TPUs) (trade names Estane, Texin). They are among a broader group of elastomeric block copolymers referred to as thermoplastic elastomers (TPEs). Crosslinking is a requirement to obtain the resilience associated with a rubber. The presence of a crosslinked network prevents polymer chains from irreversibly slipping past one another on deformation and allows for rapid and complete recovery from deformation. 

Treatment of polyisobutylene (which contains terminal double bonds) with ozone followed by thermolysis produces polymeric radicals. Isobutylene-styrene block copolymer is formed when thermolysis is performed in the presence of styrene, but the process is not efficient because polystyrene and polyisobutylene homopolymers constitute more than half of the product [Cunliffe et al., 2001]. 

Like the homopolymers, fairly thin polymer thicknesses were observed for the copolymers [72]. Again for these block copolymer brushes, the MW and PDI are unknown, much less the actual constitution and voliune of the blocks on the polymer brush. The presence of the blocks can be confirmed where the sequence of the polymerization procedure assures consumption... 

With the exception of DNA catenanes and protein catenanes, and despite various synthetic attempts, only one polymeric catenane structure, i.e. the catenated block copolymer 72, is known [31]. Evidently, the fact that the two constitutive cyclic polymers have two different chemical structures greatly facilitates the syn-... 

Based on thermodynamic considerations, criteria for the existence of domains in the melt in simple shear fields are developed. Above a critical shear stress, experimental data for the investigated block copolymers form a master curve when reduced viscosity is plotted against reduced shear rate. Furthermore the zero shear viscosity corresponding to data above a critical shear stress follow the WLF equation for temperatures in a range Tg + 100°C. This temperature dependence is characteristic of homopolymers. The experimental evidence indicates that domains exist in the melt below a critical value of shear stress. Above a critical shear stress the last traces of the domains are destroyed and a melt where the single polymer molecules constitute the flow units is formed in simple shear flow fields. 

A number of investigations concerning the morphology of AB and ABA block copolymers have shown that these systems normally exhibit phase separation if the blocks consist of sufficiently long chains. One block type often is found to constitute a dispersed phase in a continuous matrix of the second block type. 

The use of polysilanes as photoinitiators of radical polymerization was one of the hrst means whereby they were incorporated within block copolymer structures [38 0], albeit in an uncontrolled fashion. However the resulting block copolymer structures were poorly defined and interest in them principally lay in their application as compatibilisers for polystyrene (PS) and polymethylphenylsilane blends PMPS. The earliest synthetic strategies for relatively well-defined copolymers based on polysilanes exploited the condensation of the chain ends of polysilanes prepared by Wurtz-type syntheses with those of a second prepolymer that was to constitute the other component block. Typically, a mixture of AB and ABA block copolymers in which the A block was polystyrene (PS) and the B block was polymethylphenylsilane (PMPS) was prepared by reaction of anionically active chains ends of polystyrene (e.g. polystyryl lithium) with Si-X (X=Br, Cl) chain ends of a,co-dihalo-polymethylphenylsilane an example of which is shown in Fig. 2 [43,44,45]. Similar strategies were subsequently used to prepare an AB/ABA copolymer mixture in which the A block was poly(methyl methacrylate) (PMMA) [46] and also a multi- block copolymer of PMPS and polyisoprene (PI) [47]. 

Among the structural factors that should be controlled in polymer syntheses (Fig. 1, Section I), perhaps the least exploited is the sequence of constitutional repeat units along a polymer main chain. We have already discussed the syntheses of block copolymers, where two or more homopolymer segments are connected, such as AAAAA-BBBBB- -, which is among the most primitive examples of sequence control in synthetic polymers. 

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