Copolymerization coupling reactions

Equations 1 to 3 show some of fixation reactions of carbon dioxide. Equations la and lb present coupling reactions of CO2 with diene, triene, and alkyne affording lactone and similar molecules [2], in a process catalyzed by low valent transition metal compounds such as nickel(O) and palladium(O) complexes. Another interesting CO2 fixation reaction is copolymerization of CO2 and epoxide yielding polycarbonate (equation 2). This reaction is catalyzed by aluminum porphyrin and zinc diphenoxide [3],... 

Another C-C coupling reaction is the copolymerization of ethene and carbon monoxide 119). The presence of water increased the copolymerization productivity up to 3.7 times, but the reason for the increase is not yet understood. 

CO, alternating copolymerization, 273-274 Cp2ZrCl2/LiAlH4, 32 Cross-coupling reactions, 266-270 Cyclopentadienyl-free (butadiene)M(IV) complexes, 118-120... 

Woodgate et al. [51] applied the C-H/acetylene coupling to the ortho-selective alkenylation of terpene derivatives (Eq. 27). The basic feature of this reaction is the same as the alkenylation reaction of Murai et al. The combination of acetophenone and diynes provides a new entry for the copolymerization of aromatic ketones with acetylenes. Weber et al. [50] studied extensive reactions of ruthenium-catalyzed C-H/acetylene coupling with respect to the step-growth copolymerization of aromatic ketones and acetylenes (Eq. 28). These coupling reactions provide a new route to the preparation of trisubstituted styrene derivatives. 

The new copolymeric materials were synthesized via a Wurtz-type coupling reaction (equation 9)... 

Neutral catalysts or catalyst precursors based on fluorinated ligand systems have been applied in compressed CO2 to a broad range of transformations such as Zn- and Cr-catalyzed copolymerization of epoxides and CO2 [53, 54], Mo-catalyzed olefin metathesis [9], Pd-catalyzed coupling reactions [43, 55, 56] and Pd-catalyzed hydrogen peroxide synthesis [57]. Rhodium complexes with perfluoroalkyl-substituted P ligands proved successful in hydroformylation of terminal alkenes [28, 42, 44, 58], enantioselective hydroformylation [18, 59, 60], hydrogenation [61], hydroboration [62], and polymerization of phenylacetylene... 

Pd is also a potential contaminant and Nobile and coworkers recently employed a polymer-supported palladium complex (Pd-pol, Figure 5.3.1), obtained by copolymerization of Pd(AAEMA)2 with ethyl methacrylate and ethylenene glycol dimethacrylate (AAEMA is the deprotonated form of 2-(acetoacetoxy)ethyl methacrylate), as a catalyst in Stille cross-coupling reactions [Equation (5.3.14)]. The reaction can be performed in air without any activating ligand and with non-dried solvents. The catalyst can be recycled several times. 

A macroporous reactive polymer was prepared by copolymerization of the methacrylate esters 75 and 76, using the methacrylate ester 77 as crosslinking agent. After removal of the benzylidene protecting groups the polymer could be diazotized and used for immobilizing phenolic analytes by a coupling reaction. The azo dye formed on the polymer was split by hydrolysis of the ester and quantitatively determined by LC. ... 

Sasai developed miceUe-derived polymer-supported catalysts for a variety of enantioselective reactions, including diethylzinc addition [18]. The surfactant monomer 20 having tetraethylene glycol chains formed micelles in water and, followed by copolymerization with styrene, gave the spherical polymer. A coupling reaction of the polymer with a BINOL derivative and deprotection of the methoxymethyl groups of the BINOL moiety afforded the desired chiral polymer 21, as shown in Scheme 3.5. The catalytic asymmetric ethylation of benzaldehyde was... 

Copolymerization of N-alkylazlrldlnes with g-proplolactone. g-proplolactone (PL) reacts with tertiary amines to form the corresponding zwltterlon (7 ). If an N-substltuted azlrldlne Is used, a zwltterlon containing an azlrldlnlum Ion and a carboxylate Ion Is formed. This zwltterlon can Initiate a cationic polymerization of the azlrldlne or an anionic polymerization of the lactone or undergo a coupling reaction with another (monomeric or polymeric) zwltterlon. 

Doerffler and Patten have recently described a similar methodology for the formation of a less densely packed backbone where grafted polymers (macromolecules derived from only one monomer) were prepared strictly by ATRP [125]. The copolymerization of 4-acetoxymethyl- or 4-methoxymethylstyrene with styrene yielded a pendant functional macroinitiator with latent initiation sites . Transformation of the ester or ether to benzyl bromide substituents provided the alkyl halide necessary for the grafting reactions. The increased poly-dispersities observed above 20% monomer conversion were attributed to internal coupling reactions between the grafted chains. 

Polymers bearing CD moieties have been synthesized by cross-linking of CDs using epichlorohydrin [69, 70], by coupling reaction between modified or native CDs and polymers [71-75], and by homo- and copolymerization of monomers bearing CD moieties [76-78]. 

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