Copolymers architecture

Several groups have engaged in the study of linear polymer-dendrimer conjugates (i.e. architectural copolymers). These structures combine block copolymer and dendrimer branching features within one molecular architecture [69-71],... 

Controlling the size, shape and ordering of synthetic organic materials at the macromolecular and supramolecular levels is an important objective in chemistry. Such control may be used to improve specific advanced material properties. Initial efforts to control dendrimer shapes involved the use of appropriately shaped core templates upon which to amplify dendritic shells to produce either dendrimer spheroids or cylinders (rods). The first examples of covalent dendrimer rods were reported by Tomalia et al. [43] and Schluter et al. [44], These examples involved the reiterative growth of dendritic shells around a preformed linear polymeric backbone or the polymerization of a dendronized monomer to produce cylinders possessing substantial aspect ratios (i.e. 15-100) as observed by TEM and AFM. These architectural copolymers consisting of linear random... 

SEC with viscometric detection this elegant method permits the on-line measurement of Mark-Houwink coefficients for copolymers of various architectures copolymer M measurement applying Goldwasser s formula (13) is an additional benefit. 

Controlled free-radical polymerization (CFRP) has been used successfully to produce block, graft, and other controlled architecture copolymers within the last decade for a variety of free radically polymerizable monomers. The main techniques include reversible addition fragmentation and transfer (RAFT) polymerization, stable free-radical polymerization (SFRP) mediated by nitroxide/alkoxyamine based radicals, atom transfer radical polymerization (ATRP), diphenyl ethylene (DPE) mediated polymerization, and novel precipitation/emulsion polymerization based methods like free-radical retrograde precipitation polymerization (FRRPP). ... 

A few other methods have been used to prepare polypeptide hybrid copolymers. Inoue polymerized Bn-Glu NCA off of amine-functionalized styrene derivatives, and then copolymerized these end-functionalized polypeptides with either styrene or methyl methacrylate using free radical initiators to yield hybrid comb architecture copolymers [38]. Although unreacted polypeptide was identified and removed by fractionation, copolymers were obtained with polypeptide content that increased with feed ratio. There was no mention if the polypeptide interfered with the radical chemistry. In similar work, Imanishi and coworkers converted the amine-ends of polypeptides to haloacetyl groups that were used to initiate the free radical polymerization of either styrene or methylmethacrylate to yield hybrid block copolymers [39]. Studies using CPC showed that the crude product contained mixtures of copolymers and homopolymers, and so removal of the homopolymers by extraction was necessary. 

Figure 20 A rotaxane with dendritic stoppers. An example of a dendritic-linear-cyclic architectural copolymer. (Courtesy Chem. Rev. 97 1701, 1997. Copyright 1997 American Chemical Society.)...

Cylindrical, rod-shaped dendrimer assemblies were first synthesized by TomaUa et al. as early as 1987 [35,37,177]. These structures represent some of the first examples of hybridized dendritic architecture. Since they possess a linear polymeric core and dendritic arms, they are called architectural copolymers or dendronized, linear polymers. This work was recently reported in detail [160]. The method involved the divergent dendronization of //near poly(ethyleneimine) (PEI) cores... 

Percec and coworkers [184] utilized a similar strategy for the conversion of perfluorinated alkylene functionalized 3,4,5-trihydroxy benzoic acid-type dendrons into methyl methacrylate functionalized dendritic macromonomers. Characterization of the resulting linear-dendritic architectural copolymers involved DSC, x-ray diffraction, and thermal optical polarized microscopy. It was concluded that the self-assembly of the pendant dendritic mesogens forced the linear backbone into a tilted, helical ribbon-type structure. The self-assembly behavior was largely controlled by the multiplicity, composition, and molecular weights of the pendant dendritic mesogens. 

Grafting the required monomer to introduce the desired function properly has been thoroughly investigated by many authors and recently reviewed [112]. The corresponding materials offer a wide range of weU-architectured copolymers involved... 

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