Synthesis of Macromolecules

Much of the effort of organic chemists since about 1930, especially in industrial research laboratories, has been directed toward the synthesis of polymeric materials, and many such substances have come to play a prominent role in industry and commerce. In this chapter, some of the reactions that are utilized to create useful polymers will be illustrated. It will be seen from the discussion that the basic mechanisms of polymerization reactions are the same as those encountered in the reactions of small organic molecules, and that the special features of polymerizations are the result of the high molecular weights of the molecules involved. 

Three broad types of polymerization processes are generally recognized chain-addition polymerization, step-growth polymerization, and coordination polymerization. 

Chain-Addition Polymerization. The characteristic pattern of chain-addition polymerization is the one-by-one attachment of individual monomer units to the growing polymer chain. Addition of each successive monomer unit regenerates a 

Step-Growth Polymerization. In step-growth polymerization, the monomer units are not added one by one. Instead, there is a gradual buildup of chain length and 

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Qiu et al. [241 have reported the synthesis of macromolecules having 4-tolylureido pendant groups, such as poly(N-acryloyl-N -4-tolylurea-cvi ethyl acrylate) [po-ly(ATU-co-EA)] 18, and poly(N-methacryloyl-A/ -4-tol-ylurea-co-EA) [poly(MTU-co-EA)] 19, from the copolymerization of ATU and MTU with EA, respectively. Graft copolymerization of acrylamide onto the surface of these two copolymer films took place using the Ce(lV) ion as initiator. The graft copolymerization is proposed as Scheme (12). 

Energy for maintenance is the energy required for survival, or non-growth related purposes. It includes activities such as active transport across membranes and turnover (replacement synthesis) of macromolecules. 

Abstract During the past decade, atom transfer radical polymerization (ATRP) has had a tremendous impact on the synthesis of macromolecules with well-defined compositions, architectures, and functionalities. Structural features of copper and copper(II) complexes with bidentate, tridentate, tetradentate, and multidentate nitrogen-based ligands commonly utilized in ATRP are reviewed and discussed. Additionally, recent advances in mechanistic understanding of copper-mediated ATRP are outlined. 

Over the past decade, copper-catalyzed atom transfer radical polymerization (ATRP) has had a tremendous impact on the synthesis of macromolecules with well-defined architectures, functionalities, and compositions. Structural and mechanistic... 

F.J. Martin, PhD Thesis, Theoretical Synthesis of Macromolecules From Transferable Functional Groups, McMaster University, 2001. 

Natta, G. (1963) From the stereospecific polymerization to the asymmetric autocatalytic synthesis of macromolecules, Nobel Lecture, 12 December, 1963. 

Figure 9.30 Flow diagram of the energy chain from food to essential processes in human life. The ATP utilised by the NayK ATPase maintains the ion distribution in nerves that is essential for electrical activity and, in addition, maintains neurotransmitter synthesis, both of which provide communication in the brain and hence consciousness, learning and behaviour (Chapter 14). ATP utilisation by myosin ATPase is essential for movement and physical activity. ATP utilisation by the flagellum of sperm is essential for reproduction and ATP utilisation for synthesis of macromolecules is essential for growth.

Biological evolution itself seems to be associated with a much warmer, denser and damper environment than can be encountered in these clouds, corresponding rather to planetary conditions. In such surroundings, the synthesis of macromolecules can proceed at a much more lively rate. These... 

Table 2.2. Synthesis of macromolecules by chain growth polymerization...

Table 2.3. Synthesis of macromolecules by step growth polymerization (polycondensation)...

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