Copolymerization of Phenolics

Phenolic compounds can be condensed forming aryl-aryl and aryl-oxygen-aryl (ether linkages) bonds to yield diaryl and diaryl ether polymers (59). These are in many ways similar to natural humic acids, confirming earlier research by others (60-62) that humic acids are formed from the copolymerization of phenolic compounds with amino acids, peptides, and amino sugars. 

Mita, N., Tawaki, S., Uyama H., and Kobayashi, S. 2001. Molecular weight control of polyphenols by enzymatic copolymerization of phenols. Polym. J., 33, 374-376. 

The functionality may vary with reaction conditions. For example, in base-catalyzed copolymerization of phenol and formaldehyde, both monomers are bifunctional at ambient temperature, but phenol becomes trifunctional if the temperature is raised sufficiently. Copolymerization at ambient temperature can produce essentially linear, liquid, resole-type "prepolymers" of low molecular weight. Upon acidification and heat-curing, methylene and ether crosslinks formed by the now trifunctional phenol units transform the polymer into an insoluble resin [7] (see next page). The original Bakelite was such a "thermosetting" product. 

A new class of polyaromatics was synthesized by peroxidase-catalyzed oxidative copolymerization of phenol derivatives with anilines. In the case of a combination of phenol and o-pheneylenediamine, FT-IR analysis showed the formation of the corresponding copolymer.75... 

Ethanal is the most important of these compounds (Table 2.6). The many ways it can be produced and its high reactivity (the CHO radical has extensive chemical affinities), as well as its rapid combination with sulfur dioxide at low temperatures and its organoleptic properties, make ethanal a very important component of wine. The presence of ethanal, produced by the oxidation of ethanol, is closely linked to oxidation-reduction phenomena. It is involved in the alcoholic fermentation mechanism. Furthermore, ethanal plays a role in the color changes occurring in red wines during aging by facilitating the copolymerization of phenols (anthocyanins and catechins) (Section 6.3.10). 

Another hybrid MIP example is represented by the copolymerization of phenol with a covalently constructed complex between 3-hydroxyphenyl boronic acid (functional monomer) and monosaccharide (template). The copolymer was deposited on a gold electrode by cyclic voltammetry using two successive scans [46]. The obtained polymer presented an irregular morphology with an average thickness of 36 nm. 

Uses ndReactions. The Prins reaction of 3-carene with formaldehyde in acetic acid gives mainly 2-carene-4-methanol acetate, which when saponified produces the 2-carene-4-methanol, both of which are commercial products of modest usage (60). 3-Carene (28) also reacts with acetic anhydride with a catalyst (ZnCl2) to give 4-acetyl-2-carene (29) (61), which is also a commercial product. Although 3-carene does not polymerize to produce terpene resins, copolymerization with phenol has been successfully commercialized by DRT in France (62). 

There have been other approaches to obtaining rubber/metal adhesion besides primers or additives consisting of phenolics or epoxies plus halogenated elastomers. For example, carboxylated polymers (olefins and diolefins copolymerized with acrylic acid monomers) have shown excellent adhesion to metals. Very little carboxyl is necessary, and polymers with carboxyl contents as low as 0.1% show good adhesion when laminated to bare steel. When these materials possess... 

Bollag J-M, S-Y Liu (1985) Copolymerization of halogenated phenols and syringic acid. Pest Biochem Physiol 23 261-272. 

Sernetz, F. G. Mulhaupt, R. Fokken, S. Okuda, J. Copolymerization of ethene with styrene using methylalumi-noxane-activated bis(phenolate) complexes. Macromolecules 1997, 30, 1562-1569. 

Preparation of Copolymers Containing Both Electrophilic and Nucleophilic Groups. Our first implementation of this reaction scheme involved the preparation of a series of copolymers incorporating both a latent electrophile and an electron-rich aromatic moiety which, being phenolic, also provides access to swelling-free development in aqueous medium. The copolymers are prepared as shown in Figure 1 by copolymerization of 4-t-butyloxycarbonyloxy-styrene with 4-acetyloxymethyl-styrene. Although the reactivity ratios of these two monomers are different [11], our study of this system has confirmed that they copolymerize essentially in random fashion. 

In contrast, monolithic materials are easily amenable to any format. This has been demonstrated by using short monolithic rods prepared by copolymerization of divinylbenzene and 2-hydroxyethyl methacrylate in the presence of specifically selected porogens [93]. Table 2 compares recoveries of substituted phenols from both the copolymer and poly(divinylbenzene) cartridges and clearly confirms the positive effect of the polar comonomer. 

We have utilized somewhat less-effective optional approaches to copolymer purification with attendant catalyst recovery. One of these methods involved the replacement of the f-butyl substituents on the 5-position of the phenolate ligands with poly(isobutylene) (PIB) groups, as illustrated in Fig. 14 [39]. Importantly, this chromium(III) catalyst exhibited nearly identical activity as its 3,5-di-t-butyl analog for the copolymerization of cyclohexene oxide and carbon dioxide. The PIB substituents on the (salen)CrCl catalysts provide high solubility in heptanes once the copolymer is separated from the metal center by a weak acid. 

Hydrophobic monolithic methacrylate capillary columns have been introduced by copolymerization of butyl methacrylate and EDMA as cross-linking agent. The polymerization, however, was not thermally or photochemically but chemically initiated ammonium peroxodisulfate [154]. The resulting monolithic columns were applied to RP separation of small analytes like uracil, phenol, or alkylbenzenes. Reasonable results have been obtained under isocratic conditions, delivering typical values for theoretical plate height ranging between 40 and 50 pm. 

The same technique was applied to a mixture of polyethylene terephthalate and acrylic acid (34). The polymerizations were followed by looking at the acid number of the product the parameters studied were time, temperature, and monomer content see Fig.9a,b,c. The hydrophilicity, the solubility of the copolymer in benzyl alcohol, aniline, and a mixture of phenol and CHQ3 were increased by graft copolymerization. 

Electrochemical polymerization of phenols to non-conducting poly(phenylene ethers) has been described 112) and Oyama et al. recently claimed that phenol 191) and p,p -biphenol192) can be polymerized to uncharacterized conducting films. Kumar et al.193) claimed that it is possible to copolymerize phenol with pyrrole... 

The Feltzin mechanism 73) takes account of the presence of proton donors at the beginning of copolymerization. However, initiation probably proceeds in two ways 74) and depends on the type of the proton donor and its concentration in the copolymerization mixture. If HA in Eq. (45) is alcohol, phenol or moisture, initiation occurs according to Eq. (46), i.e. through interaction with the anhydride yielding an ammonium salt of the monoester. The formation of monoesters as primary active centres accounts here for the lower cocatalytic effect of phenols as compared with alcohols. If the proton donor is a carboxylic acid, activation of the tertiary amine (Eq. (63)) is followed by reaction with the epoxide according to Eq. (76)74. ... 

The emulsion copolymerization of BA with PEO-MA (Mw=2000) macromonomer was reported to be faster than the copolymerization of BA and MMA, proceeding under the same reaction conditions at 40 °C [100]. Polymerizations were initiated by a redox pair consisting of 1-ascorbic acid and hydrogen peroxide in the presence of a nonionic surfactant (p-nonyl phenol ethoxylate with 20 moles ethylene oxide). In the macromonomer system, the constant-rate interval 2 [9,10] was long (20-70% conversion). On the other hand, the interval 2 did not appear in the BA/MMA copolymerization and the maximum rate was lower by ca. 8% conversion min 1 and it was located at low conversions. 

The first report of the copolymerization of an epoxide, namely, ethylene oxide and C02 is contained in a patent by Stevens [6]. However, this process, when carried out in the presence of polyhydric phenols, provided polymers which were viscous liquids or waxes possessing copious polyether linkages with only a few incorporated C02 units. The earliest metal-catalyzed copolymerization of epoxides and C02 was reported in 1969 by Inoue and coworkers, who employed a heterogeneous catalyst system derived from a 1 1 mixture of diethylzinc and H20 [7, 8], Subsequently, Kuran and coworkers investigated a group of related catalysts prepared from diethylzinc and di- and triprotic sources such as pyrogallol, with a slight improvement over Inoue s system for the production of polypropylene carbonate) from PO and C02 [9],... 

In the first case PIB-Cl was dehydrochlorinated and metallated in a one pot procedure. This was followed by coupling of the resulting PIB anion with CEVE. In the second process, phenol was alkylated with PIB-Cl followed by a reaction with CEVE. The value of Fn determined by H NMR spectroscopy indicated close to quantitative functionalization. Copolymerization of the macromonomers has not been reported. 

Detailed experiments revealed that there is a gradual accumulation of dissolved toxic soluble products during the treatment of phenols [100]. Subsequent experiments showed that when phenolic substrates were treated in mixtures, the copolymerized products tended to be of reduced toxicity [101]. This is of practical importance given that many wastewaters are contaminated with a variety of phenols. The mutagenicity of reaction... 

The telechelica,(i -bis(2,6-dimethylphenol)-poly(2,6-dimethylphenyl-ene oxide) (PP0-20H) [174-182] is of interest as a precursor in the synthesis of block copolymers [175] and thermally reactive oligomers [179]. The synthesis has been accomplished by five methods. The first synthetic method was the reaction of a low molecular weight PPO with one phenol chain end with 3,3, 5,5 -tetramethyl-l,4-diphenoquinone. This reaction occurred by a radical mechanism [174]. The second method was the electrophilic condensation of the phenyl chain ends of two PPO-OH molecules with formaldehyde [177,178], The third method consists of the oxidative copolymerization of 2,6-dimethylphenol with 2,2 -di(4-hydroxy-3,5-di-methylphenyl)propane [176-178]. This reaction proceeds by a radical mechanism. A fourth method was the phase transfer-catalyzed polymerization of 4-bromo-2,6-dimethylphenol in the presence of 2,2-di(4-hy-droxy-3,5-dimethylphenyl)propane [181]. This reaction proceeded by a radical-anion mechanism. The fifth method developed was the oxidative coupling polymerization of 2,6-dimethylphenol (DMP) in the presence of tetramethyl bisphenol-A (TMBPA) [Eq. (57)] [182],... 

The t-BOC protected copolymers were prepared both by copolymerization of the t-BOC protected hydroxyphenylmaleimide monomer with styrene and by modification of preformed phenolic copolymers of various molecular weights as shown in Scheme I. In both cases the copolymer compositions were foxmd to be 1 1 based on NMR results and elemental analyses. The NMR and IR spectra obtained from copolymers from both routes were identical. The 13C and IH NMR spectra of the modified polymer are shown in Figures 1 and 2. These data substantiate the completeness of the protection reaction of the preformed phenolic copolymer. The copolymers are presumed to be predominately alternating since these comonomers represent an example of the classic general alternating copolymerization case of an electron rich comonomer (styrene) and an electron poor comonomer (N-substituted maleimide) (13). 

Features of the free-radical initiation processes are similar for both the homopolymerization of functionalized monomers and copolymerization of the latter with conventional monomers. Common chemical initiators were applied. Azo-bis(isobutyro nitrile) was mostly used in bulk polymerization. No interference with phenolic hydroxy groups was observed in polymerization of 2-hydroxybenzo-phenoiKs, acetophenones, salicylates and of their derivatives [47]. The most rigorous eliinination of oxygen from the reaction mixture was necessary to achieve polymerization of monomeric hindered phenolic antioxidants or derivatives of 2-(2-hydroxyphenyl)benzotriazole [48]. An oxygen-free atmosphere is also an advantage for aromatic amines. A higher initiator level and/or increased temperature appear to be necessary to achieve normal polymerization rates with (D-functionalized monomers [46]. 

The mechanistic principle of the chain transfer exploiting functionalized transfer agents was used for the synthesis of polymer bound CB AO, attached to the polymer chain via the sulfur atom. Weinstein [73, 74] used phenolic and aminic thiols 79, 81 and disulfides 80, 82 as generators of thiyls during free-radical bulk or emulsion copolymerization of butadiene or isoprene with styrene. Systems formed can be considered as bifunctional physically persistent stabiUzers combining CB and HD fiinctions. 

The second class of catalysts are zinc(II) mono- or dialkoxides obtained from polyhydric phenols and dialkylzinc with partly polymeric stmctures. This system, extensively studied by Kuran [84], is an optimization of the water/diethylzinc and polyphenol/diethylzinc systems developed by Inoue [85]. The use of soluble zinc phenoxides and their analogous cadmium complexes as catalyst for the copolymerization of CO2 and epoxide was studied extensively by the Darensbourg group [86]. This work focused on the use of mononuclear phenoxide derivatives with bulky substituents, e. g., phenyl- and fe/t-butyl groups, on the aromatic ring to a homogeneous catalytic system and thus enhance the activity of the Zn phenoxides. The catalysts developed are stabilized through ancillary neutral... 

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