Poly copper catalyst

The following questions on the electro-oxidative polymerization arose. First, why various phenol derivatives were smoothly polymerized which could not occur by the oxidation with the copper catalyst or lead dioxide. Secondly, why the activated phenol was reacted preferentially through C-0 coupling to form the poly(phenyleneoxide). The mechanism of the electro-oxidative polymerization is discussed below by using the example of 2,6-dimethylphenol. 

The second example is the electro-oxidative polymerization of phenols bearing functional substituents. It is known that salicylic acid forms a stable chelate with copper ion, thus the copper catalyst is deactivated and the polymerization does not occur. On the other hand, salicylic acid was electro-oxidatively polymerized to produce the poly(phenyleneoxide) bearing carboxylic group. 

Copper-catalyzed oxidations of phenols by dioxygen have attracted considerable interest owing to their relevance to enzymic tyrosinases (which transform phenols into o-quinones equation 24) and laccases (which dimerize or polymerize diphenols),67 and owing to their importance for the synthesis of specialty polymers [poly(phenylene oxides)]599 and fine chemicals (p-benzoquinones, muconic acid). A wide variety of oxidative transformations of phenols can be accomplished in the presence of copper complexes, depending on the reaction conditions, the phenol substituents and the copper catalyst.56... 

Recommended initiators for methacrylate polymerizations are 1-24 (X = Br) and 1-25 (X = Cl), both of which are unimer and dimer models of poly(methacry-late) dormant terminals, respectively. For example, PMMA with precisely controlled molecular weights, very narrow MWDs (MJMn — 1.1), and nearly perfect end-capping with halogen was obtained with the 1-25 (X = Cl)/Ru-5/Al(0-7-Pr)3 initiating system.60 197 Alternatively, arenesulfonyl chlorides can lead to well-controlled poly (methacrylate) s with narrow MWDs (MJMn = 1.1 —1.2) in combination with copper catalysts.126176... 

Almost all metal-catalyzed living polymerizations give polymers capped with halogens that are stable after the usual workup. These terminal halogens would be undesirable, because they may lower the polymer s thermal stability. Dehalogenation by tribu-tyltin hydride (EC-15) is of importance in this respect and effectively works for the bromide terminals in polystyrene, PMMA, and poly(MA) in the presence of copper catalysts.277... 

Block copolymers between alkyl acrylates such as B-4,358 B-5,202,203 and B-6,203 on the other hand, have been synthesized by the macroinitiator methods mostly with copper catalysts. Star block copolymers with a soft poly(MA) core and a hard poly(isobomyl acrylate) shell were synthesized by using multifunctional initiators.358 Poly(tBA) segments in B-5 and B-6 can be converted into hydrophilic poly(acrylic acid).203 Block copolymers between />methylstyrene and styrene (B-7) were also prepared by the rhenium-catalyzed living radical polymerization in conjunction with an alkyl iodide initiator.169... 

In a study, copper-catalyzed radical copolymerization of nBA and methacryloxy-capped poly(MMA) was compared with conventional radical copolymerization.267 431 The graft copolymers G-l obtained with copper catalysts are more homogeneous in terms of MWD (Mw/Mn 1.6 vs 3) and the number of side chains. This is attributed to diffusion control being less important in the metal-catalyzed radical polymerization, where the growing radical species is rapidly converted into the dormant covalent species. 

There are several examples of graft copolymers obtained from macromonomer prepared by the metal-catalyzed polymerizations. Conventional radical copolymerization of TV-vinylpyrrolidione and vinyl acetate-capped polystyrene synthesized with copper catalysts gave graft copolymers G-2, which formed hydrogels in water.337 Electrochemical copolymerization of pyrrole and thiophene-capped poly(MMA) affords G-3.335... 

Dias et al,35 reported that high-quality poly aniline can be prepared catalytically in MeCN using aniline, HC1, H2O2, and the copper catalyst [CuCl(MeTpMs)]. Controlled, copper-catalyzed functionalization of polyolefins by using [Cu(Tpx)L] (L = MeCN) complexes has been reported by Perez and coworkers.36... 

Controlled/ Living radical polymerization (CRP) of vinyl acetate (VAc) via nitroxide-mediated polymerization (NMP), organocobalt-mediated polymerization, iodine degenerative transfer polymerization (DT), reversible radical addition-fragmentation chain transfer polymerization (RAFT), and atom transfer radical polymerization (ATRP) is summarized and compared with the ATRP of VAc catalyzed by copper halide/2,2 6 ,2 -terpyridine. The new copper catalyst provides the first example of ATRP of VAc with clear mechanism and the facile synthesis of poly(vinyl acetate) and its block copolymers. 

Treatment of m-diethynylbenzene with a copper catalyst and dioxygen gave a poly(phenylene butadismylene) (315). Use of Cu-incorporated mesoporous materials as the oxidative polymerization catalyst for l,4-dieth5mylbenzene produced highly conjugated poly(l,4-phenylene-l,4-butadi5mylene) (316). 

A variety of transition metal complexes, especially those of cobalt and copper, catalyze the oxidation of phenols. Autoxidations of 2,6-disubstituted phenols in organic solvents produce mainly the 2,6-disubstituted-1,4-benzoquinone and the 3,5,3, 5 -tetrasubstituted-4,4 -diphenoquinone with Co catalysts and certain copper catalysts (eq. Poly(2,6-... 

Yoshimiu-a and Iwasaki of Sumitomo Chemical Co. have synthesized aromatic ionomers containing pendant perfluorosulfonic acid groups (Fig. 7.29) [79]. Poly (arylene ether sulfone) was brominated and then perfluorosulfonated via Ullmann coupling reaction in the presence of copper catalyst. The lEC was controllable up to 1.58 meq/g. The obtained ionomer membranes behaved very differently from the typical sulfonated aromatic ionomer membranes. Characteristic hydrophobic/hydro-philic separation (ca. 3-4 nm) was observed in the smaU-angle X-ray scattering (SAXS) analyses of the hydrated samples. The ionic clusters were slightly smaller... 

A novel approach to semicrystalline poly(aryl ether ketones) involves the reaction of 4,4"-dichlorobenzophenone with sodium carbonate in the presence of a silica/copper catalyst in diphenylsulfone at 280 - 320 C (26). Under these conditions, the sodium carbonate/catalyst combination behaves as a... 

Poly(aryl ethers) have been prepared by Ullman coupling of bisphenols and dibromoarylenes in the presence of a copper catalyst (111). This methodology does not require the presence of an activating group for halo-displacement hence aromatic ether polymers can be prepared without polar functionahty. 

Trilialophenols can be converted to poly(dihaloph.enylene oxide)s by a reaction that resembles radical-initiated displacement polymerization. In one procedure, either a copper or silver complex of the phenol is heated to produce a branched product (50). In another procedure, a catalytic quantity of an oxidizing agent and the dry sodium salt in dimethyl sulfoxide produces linear poly(2,6-dichloro-l,4-polyphenylene oxide) (51). The polymer can also be prepared by direct oxidation with a copper—amine catalyst, although branching in the ortho positions is indicated by chlorine analyses (52). 

Low molecular weight poly(l,3-phenylene oxide) [25190-64-1] has been prepared from the sodium salt of y -chlorophenol with copper as a catalyst... 

Salts of neodecanoic acid have been used in the preparation of supported catalysts, such as silver neodecanoate for the preparation of ethylene oxide catalysts (119), and the nickel soap in the preparation of a hydrogenation catalyst (120). Metal neodecanoates, such as magnesium, lead, calcium, and zinc, are used to improve the adherence of plasticized poly(vinyl butyral) sheet to safety glass in car windshields (121). Platinum complexes using neodecanoic acid have been studied for antitumor activity (122). Neodecanoic acid and its esters are used in cosmetics as emoUients, emulsifiers, and solubilizers (77,123,124). Zinc or copper salts of neoacids are used as preservatives for wood (125). 

Poly(phenylene ether). The only commercially available thermoplastic poly(phenylene oxide) PPO is the polyether poly(2,6-dimethylphenol-l,4-phenylene ether) [24938-67-8]. PPO is prepared by the oxidative coupling of 2,6-dimethylphenol with a copper amine catalyst (25). Usually PPO is blended with other polymers such as polystyrene (see PoLYETPiERS, Aromatic). However, thermoplastic composites containing randomly oriented glass fibers are available. 

The Ullman reaction has long been known as a method for the synthesis of aromatic ethers by the reaction of a phenol with an aromatic halide in the presence of a copper compound as a catalyst. It is a variation on the nucleophilic substitution reaction since a phenolic salt reacts with the halide. Nonactivated aromatic halides can be used in the synthesis of poly(arylene edier)s, dius providing a way of obtaining structures not available by the conventional nucleophilic route. The ease of halogen displacement was found to be the reverse of that observed for activated nucleophilic substitution reaction, that is, I > Br > Cl F. The polymerizations are conducted in benzophenone with a cuprous chloride-pyridine complex as a catalyst. Bromine compounds are the favored reactants.53,124 127 Poly(arylene ether)s have been prepared by Ullman coupling of bisphenols and... 

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