Ring-opening carboxylative polymerization

The living character of the ring opening metathesis polymerization described earlier in this review enables a simple preparation of functionalized norbornene-based monoliths. Adding one more in situ derivatization step that involves functional norborn-2-ene and 7-oxanorborn-2-ene monomers that react with the surface-bound initiator, the pores were provided with a number of typical functional groups such as carboxylic acid, tertiary amine, and cyclodextrin [58,59]. 

A screening of ruthenium(II) carboxylates and several ruthenium(II) chloride complexes has identified tetrakis(trifluoroacetato)diruthenium as an excellent catalyst for the cyclo-propanation of cyclooctene with ethyl diazoacetate (60°C, excess of alkene, 0.75 mol% of catalyst yield of ethyl bicyclo[6.1,0]nonane-9-carboxylate 99% endojexo 1.65)." With several other ruthenium(II) complexes, ring-opening metathesis polymerization of cyclooctene competes strongly with the cyclopropanation reaction. 

Scheme 7.36 Synthetic scheme for the polymerization of norbornene and its derivatives via free radical polymerization (FRP), ring-opening metathesis polymerization (ROMP), and vinyl addition polymerization (VAP) techniques. Polymers I, II, and III are isomers that differ in their enchainment and physical properties. Co- and terpolymerization of norbornene and derivatives of norbornene with other alicyclic monomers such as maleic anhydride, methyltetracyclododecene carboxylic acid, etc. are also successfully synthesized with this scheme. (Note that 2, 3- and 2,7-enchainments of repeating units are reported in type I polymers. °°)...

It must have a carboxyl group (- COOH) at the other end to react with e-caprolactam, which is a nylon 6 monomer, for ring opening and polymerization. 

Schitter, R. M. E. Steinhausler, T. Stelzer, F. Ring opening metathesis polymerization of methyl-A-(l-phenylethyl)-2-azabicyclo[2.2.1]hept-5-ene-3-carboxylate. J. Mol. Catal. 1997, 115, 11-20. 

Morita, T, Maughon, B.R., Bielawski, C.W., and Grubbs, R.H. (2000) A ring-opening metathesis polymerization (ROMP) approach to carboxyl- and amino-terminated telechelic poly(butadiene)s. Macromolecules, 33,6621-6623. 

The main polymerization method is by hydrolytic polymerization or a combination of ring opening as in (3.11) and hydrolytic polymerization as in (3.12).5,7 9 11 28 The reaction of a carboxylic group with an amino group can be noncatalyzed and acid catalyzed. This is illustrated in the reaction scheme shown in Fig. 3.13. The kinetics of the hydrolytic polyamidation-type reaction has die form shown in (3.13). In aqueous solutions, die polycondensation can be described by second-order kinetics.29 Equation (3.13) can also be expressed as (3.14) in which B is die temperature-independent equilibrium constant and AHa the endialpy change of die reaction5 6 812 28 29 ... 

Polymerization of oxiranes with succinic anhydride proceeded in the presence of PPL at 60 °C or 80 °C [63]. The ring-opening of the oxirane might proceed by a carboxylic acid catalyst, which is formed by the reaction of succinic anhydride with serine residue of the lipase catalyst. 

Although the first examples of hyperbranched polymers proposed by Flory involved condensation-type polymerization strategies, the first well-characterized hyperbranched example involved the ring-opening polymerization of 2-carboxylic-2-oxazoline derivatives. As early as 1988, Odian and Tomalia [2] reported the ring-opening polymerization of these derivatives to form random... 

Since it was shown that free radical ring-opening polymerization (2) made it possible to introduce functional groups, such as esters C3j, carbonates (4), thioesters (5), and amides (6), into the backbone of an addition polymer, it was reasoned that simple hydrolysis would produce the desired oligomers that could be terminated with various combinations of hydroxyl, amino, thiol, and carboxylic acid groups. 

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