Phenol alcohol oligomers

Trade Names Containing lgepal OD410 Phenol alcohol. See Phenol Phenol, o-(t-butyl)-. See 2-t-Butylphenol Phenol calcium saH. See Calcium phenoxide Phenolcarbind. See Benzyl alcohol Phenol, dimethyl-. See Xylenol Phenol, 3,4-dimethyl-. See 3,4-Xylenol Phenol, dinonyh. See Dinonyl phenol Phenol-fonnaldehyde sulfonate Synonyms Resole sulfonate Classification Oligomer Properties Water-sol. 

Cmde diketene obtained from the dimeriza tion of ketene is dark brown and contains up to 10% higher ketene oligomers but can be used without further purification. In the cmde form, however, diketene has only limited stabHity. Therefore, especiaHy if it has to be stored for some time, the cmde diketene is distiHed to > 99.5% purity (124). The tarry distiHation residue, containing trike ten e (5) and other oligomers, tends to undergo violent Spontaneous decomposition and is neutralized immediately with water or a low alcohol. Ultrapure diketene (99.99%) can be obtained by crystallization (125,126). Diketene can be stabHized to some extent with agents such as alcohols and even smaH quantities of water [7732-18-5] (127), phenols, boron oxides, sulfur [7704-34-9] (128) and sulfate salts, eg, anhydrous copper sulfate [7758-98-7]. 

We have found that this sequence can be generally applied to the synthesis of hydroxypropyl derivatives of alcohols and phenols yields are uniformly acceptable and products of the desired degree of chain extension can be prepared completely free of lower and higher oligomers. The compounds shown in Table I were prepared using this chemistry. 

Benton and Schmitt38) described several carbonized syntactic materials using phenolic and carbon microspheres. The binders included wood resin, partially polymerized furfuryl alcohol, isotruxene, decacyclene, starch, and epoxy oligomers. Furfuryl alcohol and maleic anhydride were used as hardeners (Table 9). In addition solvents (metjiyl ethyl ketone, tetrahydrofuran, and acetone) were added to improve... 

Ferulic acid, a phenolic acid that can be found in rapeseed cake, has been used in the synthesis of monomers for ADMET homo- and copolymerization with fatty acid-based a,co-dienes [139]. Homopolymerizations were performed in the presence of several ruthenium-based olefin metathesis catalysts (1 mol% and 80°C), although only C5, the Zhan catalyst, and catalyst M5i of the company Umicore were able to produce oligomers with Tgs around 7°C. The comonomers were prepared by epoxidation of methyl oleate and erucate followed by simultaneous ring opening and transesterification with allyl alcohol. Best results for the copolymerizations were obtained with the erucic acid-derived monomer, reaching a crystalline polymer (Tm — 24.9°C) with molecular weight over 13 kDa. 

These anionic ring opening polymerizations are usually carried out either in bulk or in solution. A host of catalyst types are active. For synthetic references using specific catalysts, the reader is referred to several excellent sources (4,7,31,32). Representative catalysts include hydroxides, alcoholates, phenolates, silanolates, siloxanolates, mercaptides of the alkali metals, organolithium and potassium compounds, and quaternary ammonium and phosphonium bases and their silanolates and siloxanolates. Some physical characteristics of linear oligomers are given in Table 5 (10). 

In the case of phenol, with the free para position, due to the interaction between the phenolic group (acidic) and the aminic nitrogen (basic) of the amino alcohol, the ortho position is occupied first [9]. After the synthesis of Mannich bases, the water resulting from the reaction and the water from the aqueous solution of formaldehyde is distilled under vacuum, at 90-125 °C (preferably in the range 90-100 °C). A low range of distillation temperatures is preferred in order to avoid the tendency of the Mannich base to condensate to superior oligomers (with 2-3 aromatic nuclei), which increase substantially the viscosity of Mannich base and, of course, of final Mannich polyol. The mechanism of the Mannich reaction is considered to be a two-step mechanism. In the first step the reaction between formaldehyde and the primary or secondary amine (reaction 15.2) takes place, with the formation of an immonium cation [7-9, 22, 23]. 

Copolymers with styrene and alkyl methacrylates were synthesized also. The coupling method was initially developed by Asami et al. (200. 210) who succeeded in preparing polymerizable oligomers from living poly(THF) by coupling with vinyl phenolate (CH2=CH-C H -0 ) or with vinylbenzyl alcoholate (CH2=CH-C H -CH20 ). The horaopolymerization and copolymerization of these Macroraers were studied (209). 

About 15.3 million metric tons (16.8 million short tons) of propylene were produced for commercial sale in the United States in 2004. About 39 percent of that amount was used for the production of polypropylene. Almost all of the remaining production was also used for the synthesis of chemical compounds, especially acrylonitrile (14 percent), propylene oxide (11 percent), cumene (10 percent), oxo alcohols (8 percent), isopropyl alcohol (7 percent), oligomers (5 percent) and acrylic acid (3 percent). Acrylonitrile, propylene oxide, oxo alcohols, and acrylic acids are all used primarily for the production of various types of polymers. Cumene is itself used as a raw material in the production of other organic compounds, especially acetone and phenol. 

Alkylphenol ethoxylates are important kinds of nonionic surfactants. A characteristic feature of the catalytic ethoxylation of alkylphenols is the enhanced reactivity of phenol hydroxyl for ethylene oxide in comparison with alcohols. Esters of ethylene glycol and alkylphenol behave already as an alcohol. Therefore di-, tri-, and m-mers are allowed to form only after the complete consumption of the starting material. All commercial ethoxylated alkylphenols are mixtures of oligomer-homologues having a Poisson-like distribution with some PEG and catalyst as impurities. Both alkylphenols and dialkylphenols are useful for ethoxylation as a hydrophobic moiety. Among the alkylphenols, isooctylphenol and isononylphenol are most widely used. They are synthesized by the Friedel-Crafts alkylation of phenol with butene dimer and mixture of propene trimers, respectively. 

Epoxy-amine systems follow an addition step-growth polymerisation mechanism. The two principal reactions of primary and secondary amines with epoxy oligomers are shown in Reaction scheme 1 [30]. These reactions are catalysed by acids, phenols and alcohols (e.g. impurities in commercial epoxy resins). The presence of water causes a tremendous acceleration, but does not alter the network structure. The hydroxyl groups formed by the amine-epoxy addition steps are also active catalysts, so that the curing reaction usually shows an accelerating effect in its early stage (autocatalysis). 

In the presence of alcohols, the reactive species is a carbenium ion (4), formed from the hemiacetal (5) (Eq. 7). Efforts to synthesize model compounds continue the work started by Bender and coworkers. A series of new dimeric and trimeric compounds, derived from o-cresol, have been synthesized and their structures determined by IR, NMR, and elemental analysis. Additional homologues of p-cresol have been prepared by Kammerer and Niemann, to study the melting behavior of a wide range of methylene-bridged phenol oligomers. Prepolymer formation, namely novolac production, has been studied in batch and continuous flow reac-... 

There are several ways in which phenols have been categorized. Harbome and Simmonds categorized polyphenols based on the number of carbon atoms, which includes simple phenols (Ce) phenolic acids and related compounds (Ce—Ci) acetophenones and phenyl acetic acids (Cg—C2) cinnamic acids, cinamyl aldehydes, and alcohols (Cg—C3) coumarins, isocoumarins, and chromones (Cg—C3) flavonoids (C15) biflavonyls (C30) stilbenes (Cg—C2—Cg) benzophenones and xanthones (Cg—C2—Cg) quinones (Cg, Cio, Cm) betacyanins (Cjg) and lignans, lignins, tannins, and phlobaphenes (which are dimmers, oligomers, or polymers) [19]. Polyphenols have also been categorized by some researchers based on their... 

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