Living radical polymerization segmented block copolymers

Block copolymers between alkyl acrylates such as B-4,358 B-5,202,203 and B-6,203 on the other hand, have been synthesized by the macroinitiator methods mostly with copper catalysts. Star block copolymers with a soft poly(MA) core and a hard poly(isobomyl acrylate) shell were synthesized by using multifunctional initiators.358 Poly(tBA) segments in B-5 and B-6 can be converted into hydrophilic poly(acrylic acid).203 Block copolymers between />methylstyrene and styrene (B-7) were also prepared by the rhenium-catalyzed living radical polymerization in conjunction with an alkyl iodide initiator.169... 

Among these reactions, the Cu(l)-catalyzed azide-alkyne cycloaddition (CuAAC) is the most widely used. This reaction has been implemented for the preparation of segmented block copolymers from polymerizable monomers by different mechanisms. For example, Opsteen and van Hest [22] successfully prepared poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA) and PEO-b-PSt by using azide and alkyne end-functionalized homopolymers as the click reaction components (Scheme 11.2). Here, PEO, PSt, and PMMA homopolymers were obtained via living anionic ring-opening polymerization (AROP), atom transfer radical polymerization (ATRP), and postmodification reactions. Several research groups have demonstrated the combination of different polymerization techniques via CuAAC click chemistry, in the synthesis of poly(e-caprolactone)-b-poly(vinyl alcohol) (PCL-b-PVA)... 

Coca, S., and Matyjaszewski, K. (1997). Block copolymers by transformation of living carbocationic into living radical polymerization. II. ABA-type block copolymers comprising rubbery polyisobutene middle segment. J. Polym. Sci., Part A Polym. Chem., 35(16) 3595-3601. 

The polymerization methods leading to linear diblock, triblock or segmented block copolymers are based on two general reaction schemes. In a first one, a or a, oj active sites are generated on a polymer chain poly A which then initiate the polymerization of a second monomer B. Such a polymerization can be of free radical, anionic or cationic type and preferably of living type which proceed without termination and transfer reactions. The concept of this synthesis is given in Figure 7.2. 

The establishment of the living radical polymerization of NIPAM encouraged not only many polymer chemists but also polymer physicists to prepare functionalized NIPAM polymers with various controlled sequences and/or shapes, as discussed in this chapter. In the following parts, block, random, or graft copolymers will be simply designated by the acronym A-B for a diblock copolymer, A-B-A for an ABA-type triblock copolymer, A-B-C for an ABC-type triblock copolymer, A-co-B for a random copolymer, A-g-PNIPAM for grafting of NIPAM segments onto the polymer A. For example, PNIPAM-PEO stands for a diblock copolymer of PNIPAM and PEO. 

There is little doubt the advent of controlled/living radical polymerization (CRP) has revolutionized modern polymer science. Perhaps more than any synthetic development of the last several decades, CRP has unlocked access to a plethora of new functional and well-defined polymers to address a variety of complex applications. Previously considered useful for primarily the facile and rapid preparation of high molecular weight polymers for mostly commodity applications, radical polymerization can now be readily employed to prepare specialty materials based on (co)polymers that are well-defined, have controlled molecular weights and end group functionality, complex topologies, and predefined segment sequences e.g., block copolymers). 

Various types of well-defined block copolymers containing polypropylene segments have been synthesized by Doi et al. on the basis of three methods (i) sequential coordination polymerization of propylene and ethylene 83-m>, (ii) transformation of living polypropylene ends to radical or cationic ones which initiate the polymerization of polar monomers 104, u2i, and (iii) coupling reaction between iodine-terminated monodisperse polypropylene and living polystyrene anion 84). In particular, the well-defined block copolymers consisting of polypropylene blocks and polar monomer unit blocks are expected to exhibit new characteristic properties owing to the effect of microphase separation. 

There are essentially two methods used for the production of commercial FTPEs. The first is referred to as iodine transfer polymerization, which is similar to the living anionic polymerization used to make block copolymers such as styrene-butadiene-styrene (e.g., Kraton ). The difference is that this living polymerization is based on a free radical mechanism. The products consist of soft segments based on copolymers of vinylidene fluoride (VDF) with hexafluoropropylene (HFP) and... 

The number and order of sequences may be more complicated. Block copolymers are usually made by free radical or living polymerizations. These processes can produce polymers that consist of a pure A block connected to a pure B block, with no interphase zone of mixed A and B structure. The preparation of block copolymers is not limited to monomers A and B, but can also encompass segments of random copolymers. For example, a block of a random copolymer AB can be connected to a block of polymer A or B. Moreover, the point of attachment of the blocks can be either at the end or the middle of the polymer chain. Several examples of the various types of block copolymers possibly follow ... 

Several methods can be used to synthesize block copolymers. Using living polymerization, monomer A is homopolymerized to form a block of A then monomer B is added and reacts with the active chain end of segment A to form a block of B. With careful control of the reaction conditions, this technique can produce a variety of well-defined block copolymers. This ionic technique is discussed in more detail in a later section. Mechanicochemical degradation provides a very useful and simple way to produce polymeric free radicals. When a rubber is mechanically sheared (Ceresa, 1965), as during mastication, a reduction in molecular weight occurs as a result of the physical pulling apart of macromolecules. This chain rupture forms radicals of A and B, which then recombine to form a block copolymer. This is not a preferred method because it usually leads to a mixture of poorly defined block copolymers. 

Block copolymers were first produced from vinyl monomers using free radically initiated polymerization processes but the full potential of block polymeric materials was not realized until the discovery of the polyurethanes. The polyurethanes,in common with segmented polyesters, were often soluble in simple solvents but in the solid state were physically cross-linked by virtue of the two-phase morphology of these materials. It was the development of living polymerizations which permitted, for the first time, the efficient synthesis of block polymers from vinyl monomers, particularly non-polar monomers. Structures of the type A-B, A-B-A, A-B-C and others could readily be achieved (where A, B, and C represent chemically distinct polymeric units) and it was Milkovich who demonstrated the importance of the tri-block structure in order to achieve good physical properties. 

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