Polymers Copper Complexes

Challa, G., Meinders, H. C. Copper-polymer complexes as catalysts for oxidative coupling reactions. J. Mol. Catal. 1977, 3,185-190. 

Copper-Polymer Complexes as Catalysts for Oxidative Coupling Reactions... 

Copper-polymer complexes also retain an important position as regards binding with ethylene. When a solid polymer complex was prepared from polystyrene beads, copper(I) chloride, and aluminum chloride, absorption at room temperature by the polymer complex was rapid, and the equilibrium molar ratio of absorbed ethylene to the admitted copper(I) chloride was 1.40. The amount of ethylene absorbed by 1 g of the polymer complex solid was 89 cm STP) [56]. 

Acetylene is condensed with carbonyl compounds to give a wide variety of products, some of which are the substrates for the preparation of families of derivatives. The most commercially significant reaction is the condensation of acetylene with formaldehyde. The reaction does not proceed well with base catalysis which works well with other carbonyl compounds and it was discovered by Reppe (33) that acetylene under pressure (304 kPa (3 atm), or above) reacts smoothly with formaldehyde at 100°C in the presence of a copper acetyUde complex catalyst. The reaction can be controlled to give either propargyl alcohol or butynediol (see Acetylene-DERIVED chemicals). 2-Butyne-l,4-diol, its hydroxyethyl ethers, and propargyl alcohol are used as corrosion inhibitors. 2,3-Dibromo-2-butene-l,4-diol is used as a flame retardant in polyurethane and other polymer systems (see Bromine compounds Elame retardants). 

The oxidative coupling of 2,6-dimethylphenol to yield poly(phenylene oxide) represents 90—95% of the consumption of 2,6-dimethylphenol (68). The oxidation with air is catalyzed by a copper—amine complex. The poly(phenylene oxide) derived from 2,6-dimethylphenol is blended with other polymers, primarily high impact polystyrene, and the resulting alloy is widely used in housings for business machines, electronic equipment and in the manufacture of automobiles (see Polyethers, aromatic). A minor use of 2,6-dimethylphenol involves its oxidative coupling to... 

Bonding Agents. These materials are generally only used in wire cable coat compounds. They are basically organic complexes of cobalt and cobalt—boron. In wire coat compounds they are used at very low levels of active cobalt to aid in the copper sulfide complex formation that is the primary adherance stmcture. The copper sulfide stmcture builds up at the brass mbber interface through copper in the brass and sulfur from the compound. The dendrites of copper sulfide formed entrap the polymer chains before the compound is vulcanized thus hoi ding the mbber firmly to the wire. 

However the formation of thin polymer film on the electrode, i.e. passivation of the electrode, resulted in cessation of the polymerization, which restricted the electro-oxidation as a polymerization procedure. The electro-oxidative polymerization as a method of producing poly(phenyleneoxide)s had not been reported except in one old patent, in which a copper-amine complex was added as an electron-mediator during the electrolysis (4). The authors recently found that phenols are electro-oxidatively polymerized to yield poly-(2,6-disubstituted phenyleneoxide)s, by selecting the electrolysis conditions This electro-oxidative polymerization is described in the present paper. 

Figure 3. Relationship between the polymer yield and the molecular weight, o Polymerization catalyzed by the copper-pyridine complex. Electrolysis...

Polymers containing chiral groups are useful for resolving racemic mixtures into the individual enantiomers [Kiniwa et al., 1987 Mathur et al., 1980 Wulff et al., 1980]. For example, the copper(II) complex of XXXXIII (either the R- or S-enantiomer) resolves racemates of amino acids [Sugden et al., 1980], The separation is based on the formation of a pair of diastereomeric complexes from the reaction of the polymer reagent with the two enantiomers. One of the enantiomers is complexed more strongly than the other and this achieves separation of the enantiomers. 

Compounds (20) and (21) undergo electrochemical oxidation to give films of poly(2-methyl-8-quinolinol) and poly(S-quinolinol) on a variety of metal substrates.60 Copper(II) can be com-plexed from aqueous media, but cobalt(II) requires an organic medium. X-ray photoelectron spectroscopy shows the copper(II) complex of films derived from (20) to be complexed to both N and O and also shows that water is absent from the primary coordination sphere. However, for cobalt(II) on the polymer derived from (21), water is present in the primary coordination shell. 

Organic compounds having labile hydrogens, such as phenols [41,42], phenylene-diamines [43], and acetylenes [44], can be oxidatively coupled in the presence of specific metal complexes to form polymeric compounds. The oxidative polymerization of 2,6-disubstituted phenols with a copper-amine complex produces poly(2,6-disubstituted phenylene ether) [45-51], Poly(2,6-dimethylphenylene ether) and poly(2,6-diphenylphenylene ether) are commercially produced from 2,6-dimethyl phenol and 2,6-diphenylphenol, respectively (Figure 5). These polymers exhibit excellent performance as engineering plastics. 

Oh BK, Meyerhoff ME. Spontaneous catalytic generation of nitric oxide from 5-01110801111018 at the surface of polymer films doped with lipophilic copper(II) complex. Journal of the American Chemical Society 2003, 125, 9552-9553. 

In the polycoupling reactions, the formation of the diyne units proceeded via a Glaser-Hay oxidative coupling route [35-38]. Despite its wide applications in the preparation of small molecules and linear polymers containing diyne moieties, its mechanism remains unclear [38-40]. It has been proposed that a dimeric copper acetylide complex is involved, whose collapse leads to the formation of the diyne product (Scheme 9). 

Fig. 16 A Optical micrograph of two-dimensional photopattern generated by photolysis of a metallized hb-PY (81) through a copper-negative mask. B Image with a higher magnification and C molecular structure of polymer complex 81...

---