Solubility phenols, 567 polymers

The peroxidase-catalyzed polymerization of m-alkyl substituted phenols in aqueous methanol produced soluble phenolic polymers. The mixed ratio of buffer and methanol greatly affected the yields and the molecular weight of the polymer. The enzyme source greatly affected the polymerization pattern of m-substituted monomers. Using SBP catalyst, the polymer yield increased as a function of the bulkiness of the substituent, whereas the opposite tendency was observed when HRP was the catalyst. 

Various bisphenol derivatives were also polymerized by peroxidase under selected reaction conditions, yielding soluble phenolic polymers. Bisphenol-A was polymerized by peroxidase catalyst to give a polymer soluble in acetone, DMF, DMSO, and methanol. The polymer was produced in higher yields using SBP as a catalyst. This polymer showed a molecular weight of 4 x 10 and a 7g at 154°C. The HRP-catalyzed polymerization of 4,4 -biphenol produced a polymer showing high thermal stability. ... 

The formation of phenolic polymers by Claisen Rearrangement of poly(4-allyloxystyrenes) under acid catalyzed thermolysis conditions has previously been reported in connection with the development high resolution photoresists (14,15). This work was primarily focused on the production of soluble phenolic polymers that could be imaged on the basis of differential dissolution. In this regard, allyloxysty-rene polymers bearing alkyl substituents at the a-position to the ether oxygen atom... 

Tannins are water-soluble phenolic compounds which are usually extracted from plant material by hot water. After lignins, they are the second most abundant group of plant phenolics. Their tanning property is due to their capacity to combine with proteins. However, they can also complex with other polymers such as alkaloids, cellulose, and pectins. 

Imidisation of PCA based on 4,4 -di-(/7-aminophenoxy)-benzophenone was accompanied by the precipitation of the polymers from the reaction solutions, which is partially due to crystallinity in the polyimides formed. This appears to hinder the solubility of the polymers in amide and phenolic solvents. Polyimides based on l,l-dichloro-2,2-di-(/7-aminophenoxyphenyl)-ethylene are more soluble. The polymer formed from this diamine and the dianhydride of benzophenone-3,3 -4,4 -tetracarboxylic acid is soluble in a TCE/phenol (3 1) mixture. 

Another recent example by Peukert and Jacobsen (199) took advantage of the first polymer supported Jacobsen s catalyst 8.53 (Fig. 8.31) comparable with the soluble catalyst in asymmetric epoxidation and its full characterization (200, 201). The supported catalyst, prepared from the activated carbonate of hydroxymethyl PS and from a soluble phenolic catalyst (201), was used to catalyze the opening of racemic alkyl epoxides (Mi, Fig. 8.31) with substituted phenols and yielded the 50-member aryloxy alcohol library L15 with good enantiomeric purity (average >90%, never below 80% e.e.). 8.53 was also used to produce the chiral intermediate monomer set M3 (Fig. 8.31) which was used to make two 50-member chiral libraries L16 (1,4-diary-loxy 2-propanols) and L17 (3-aryloxy-2-hydroxy propanamines) with excellent enantiomeric excess following the straightforward synthetic schemes reported in Fig. 8.31. 

The ketene intermediate reacts with water present in the phenolic polymer base or in subsequent alkaline developer to form a soluble Indene carboxylic acid. 

Phenol, the simplest and most important phenolic compound in industrial fields, is a multifunctional monomer for oxidative polymerization, and hence, conventional polymerization catalysts afford an insoluble product with uncontrolled structure. On the other hand, the peroxidase catalysis induced the polymerization in aqueous organic solvent to give a powdery polymer consisting of phenylene and ox-yphenylene units showing relatively high thermal stability (Scheme 2).5,6 In the HRP and soybean peroxidase (SBP)-catalyzed polymerization in the aqueous 1,4-dioxane, the resulting polymer showed low solubility the polymer was partly soluble in N,N-dimethylformamide (DMF) and dimethyl sulfoxide and insoluble in other common organic solvents.5 On the other hand, the aqueous methanol solvent af-... 

The first chemically amplified resist was designed by G.H. Smith and J. A. Bonham of the 3M Company for which they were granted a U.S. patent in 1973. It was used in the acid-catalyzed deprotection of tetrahydropyranal ether from a polymer of tetrahydropyranal ether of novolac to generate a base-soluble phenol (novolac), as shown in Scheme 7.27. Incidentally, this work was never published in the open literature and was never exploited by 3M, and remained lost in the patent literature for a considerable length of time. 

Poly(N-vinyl-pyrrolidone), or PNVP, is a biocompatible, water-soluble (JJ ) polymer that has previously been used as a synthetic blood plasma extender, as a component of soft contact lenses, and in a complex with iodine as the commercially available topical antiseptic Betadine ( ). It also forms a remarkable variety of chemically specific complexes with drugs and hormones such as the tetracyclines, phenothiazine antipsychotics, the antiepileptic drug phenytoin, procaine local anesthetics, and methyldopa antiparkinsonian drugs ( ). In its insoluble, chemically cross-linked form, PNVP has also been used as a concentrating agent for a variety of phenols and catechol compounds (22). 

The peroxidase-catalyzed oxidative coupling of phenols proceeds rapidly in aqueous solution, giving rise to the formation of oligomeric compounds that, unfortunately, have not well been characterized, as most of them demonstrate a low solubility towards common organic solvents and water. In 1987, the enzymatic synthesis of a new class of phenolic polymer was first reported [15], whereby an oxidative polymerization of p-phenylphenol, using HRP as catalyst, was carried out in a mixture of water and water-miscible solvents such as 1,4-dioxane, acetone. 

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