Branched Polymers I by Bernadette Charleux, Rudolf Faust (auth.), Dr. Jacques

By Bernadette Charleux, Rudolf Faust (auth.), Dr. Jacques Roovers (eds.)

While books were written on many themes of Polymer technology, no compre hensive treatise on lengthy chain branching has ever been composed. This sequence of stories in quantity 142 and 143 of Advances in Polymer technology attempts to fill this hole via highlighting lively components of analysis on branched polymers. lengthy chain branching is a phenomenon saw in man made polymers and in a few normal polysaccharides. It has lengthy been well-known as a massive mole cular parameter of macromolecules. Its presence used to be first surmised by means of H. Stau dinger and G. V. Schuh (Ber. sixty eight, 2320, 1935). curiously, their approach to iden tification through the irregular relation among intrinsic viscosity and molecular weight has survived to at the present time. certainly, the main refined technique for research of lengthy chain branching makes use of measurement exclusion fractionation with the simultaneous recording of mass, molecular weight and intrinsic visco sity of the fractions. within the Forties and Nineteen Fifties, random branching in polymers and its influence on their houses used to be studied through Stockmayer, Flory, Zimm and so forth. Their paintings is still a milestone at the topic to today. Flory committed numerous chapters of his "Principles of Polymer Chemistry" to non linear polymers. specifically very important at the moment used to be the view that randomly branched polymers are inter mediates to polymeric networks. additional advancements in randomly branched polymers got here from the creation of percolation concept. the fashionable aspec ts of this subject are elaborated right here within the bankruptcy by means of W. Burchard.

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The experimental results indicated that poly(IBVE) with a functional a-end group could be synthesized using living cationic polymerization without any significant side reactions affecting the integrity of the functional group. Coupling reaction with 25 was performed at the same conditions as previously described and the same conclusions could be drawn. Based on SEC analysis the initial peak shifted towards higher MWs and the MWD remained narrow. This was especially the case 34 B. Charleux, R. Faust for the coupled products with acetoxy and methacryloyloxy functionality (yield>95%).

First, three arm star PIB (Mn=30,000 g mol–1) was prepared by living cationic 30 B. Charleux, R. Faust Table 2. Multiarm star polymers and copolymers synthesized using a multifunctional initiator Monomers Multi-functional initiatorType of star Reference IBVE 8, 9 10 11, 12 13 14–17 18 19 20, 21 8 14, 15 20, 21 14 14 14 [19, 20] [21, 22] [23] [24, 25] [26–34] [35] [36] [37] [38] [39, 40] [41] [42] [43] [44] p-MOS S IB IBVE/AcOVE IB/S IB/p-MeS IB/THF IB/MMA A3 A4 A3 A6 A3 A4 A6 A8 (AB)3 (AB)3 (AB)8 (AB)3 (AB)3 (AB)3 polymerization of IB using a trifunctional initiator (tricumyl chloride, 14), and the living ends were quantitatively capped with 1,1-diphenylethylene.

To overcome the problems outlined above a semi-continuous polymerization technique has been introduced [27]. In this technique a mixed monomer/inifer feed is added at a sufficiently low constant rate to a well stirred, dilute BCl3 charge. Due to stationary conditions maintained during the whole polymerization, well-defined telechelic products with symmetrical end groups and theoretical polydispersities could be obtained. The kinetics of the polymerization has been discussed and the DPn equation has been derived.

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