Hydroxyl content

As will be seen shortly, an analogous result is obtained with the silica-water system, where the BET monolayer capacity of water calculated from the water isotherm is roughly equal to the hydroxyl content of the silica surface. 

The relationship between the BET monolayer capacity of physically adsorbed water and the hydroxyl content of the surface of silica has been examined by Naono and his co-workers in a systematic study, following the earlier work by Morimoto. Samples of the starting material—a silica gel—were heated for 4 hours in vacuum at a succession of temperatures ranging from 25 to 1000°C, and the surface concentration of hydroxyl groups of each sample was obtained from the further loss on ignition at 1100°C combined with the BET-nitrogen area. Two complete water isotherms were determined at 20°C on each sample, and to ensure complete... 

In Table 5.3, is compared with the total hydroxyl concentration (Ni, + N ) of the corresponding fully hydroxylated, sample. The results clearly demonstrate that the physical adsorption is determined by the total hydroxyl content of the surface, showing the adsorption to be localized. It is useful to note that the BET monolayer capacity n JH2O) (= N ) of the water calculated from the water isotherm by the BET procedure corresponds to approximately 1 molecule of water per hydroxyl group, and so provides a convenient means of estimating the hydroxyl concentration on the surface. Since the adsorption is localized, n.(H20) does not, of course, denote a close-packed layer of water molecules. Indeed, the area occupied per molecule of water is determined by the structure of the silica, and is uJH2O) 20A ... 

V, = hydroxyl content before isotherm determination (OH groups per 1(X) A ). 

This compound, designated Cyagard RF1204, has been recommended for use in polypropylene. Despite its high hydroxyl content, it is proposed not as a polyol but as a stable, high melting additive for polypropylene (108). 

Functional Group Analysis. The total hydroxyl content of lignin is determined by acetylation with an acetic anhydride—pyridine reagent followed by saponification of the acetate, and followed by titration of the resulting acetic acid with a standard 0.05 W sodium hydroxide solution. Either the Kuhn-Roth (35) or the modified Bethge-Liadstrom (36) procedure may be used to determine the total hydroxyl content. The aUphatic hydroxyl content is determined by the difference between the total and phenoHc hydroxyl contents. 

Table 5. Phenolic and Aliphatic Hydroxyl Contents of Milled Wood and Technical Lignins ...

Hydroxyl number and molecular weight are normally determined by end-group analysis, by titration with acetic, phthaUc, or pyromellitic anhydride (264). Eor lower molecular weights (higher hydroxyl numbers), E- and C-nmr methods have been developed (265). Molecular weight deterrninations based on coUigative properties, eg, vapor-phase osmometry, or on molecular size, eg, size exclusion chromatography, are less useful because they do not measure the hydroxyl content. 

Table 7. Excess Hydroxyl Content Required in Alkyd Formulations...

The metallic impurities of Type IV vitreous siUca are similar to those of Type III material, except for a negligible hydroxyl content. 

The oxidation of vitreous siUca appears to proceed by one of two mechanisms, depending on the material s hydroxyl content (109,111). In hydroxyl-containing material, the rapid oxidation probably occurs by the diffusion and removal of hydrogen, according to the following reaction ... 

Density. The density of transparent vitreous sihca is approximately 2.20 g/cm. Translucent and opaque glasses have lower densities owing to the entrapped bubbles. The density of translucent Vitreosil, for example, is 2.07—2.15 g/cm (87,119). The density of transparent vitreous sihca decreases with increasing hydroxyl content and with lower fictive (glass stmcture equihbrium) temperatures. The fictive temperature depends on the thermal history and on glass viscosity (120). 

Nuclear Magnetic Resonance (nmr). The nmr analysis has been used in the polymer industry for some time to measure properties such as amount and type of branching, polymerized ethylene oxide content, and hydroxyl content. The same techniques are applicable to waxes, and are used for both characterization and quality control. 

Moisture sensitivity and vapor-permeabiUty rate of cellulose acetate increase with decreasing acetyl (increasing hydroxyl) content. Thermoplastic characteristics are gready improved as the acetyl content is increased from ca 20% (DS(acetyl) = 1) to ca 39% (DS(acetyl) = 2.4) (9). 

The acetyl content of cellulose acetate may be calculated by difference from the hydroxyl content, which is usually determined by carbanilation of the ester hydroxy groups in pyridine solvent with phenyl isocyanate [103-71-9J, followed by measurement of uv absorption of the combined carbanilate. Methods for determining cellulose ester hydroxyl content by near-infrared spectroscopy (111) and acid content by nmr spectroscopy (112) and pyrolysis gas chromatography (113) have been reported. 

A number of grades of poly(vinyl formal) are commercially available (Formvar, Mowital) which vary in degree of polymerisation, hydroxyl content and residual acetate content. 

Table I4.P shows the influence of these variables on some properties. The residual hydroxyl content is expressed in terms of poly(vinyl alcohol) content and residual acetate in terms of poly(vinyl acetate) content.

The hydroxyl content of commercial material is kept low but it is to be observed that this has an effect on the water absorption. Variation in the residual acetate content has a significant effect on heat distortion temperature, impact strength and water absorption. The incorporation of plasticisers has the usual influence on mechanical and thermal properties. 

Mention should also be made here of the extensive use of poly(vinyl alcohol) in potentially biodegradable applications. At appropriate hydroxyl contents these polymers will dissolve in water (see Chapter 14) and can apparently be conveniently washed away after use as a water-soluble packaging. Biodegradation does, however, appear to be slow and first requires an oxidative step involving enzymatic attack to a ketone such as polyenolketone, which then biodegrades more rapidly. 

Polyhydric Alcohols. (Polyols). An alcohol with three or more hydroxyl groups, each attached to a different carbon atom. They are w-sol and of sweetish taste, which tends to intensify with increasing hydroxyl content. Examples of polyols of ordn interest are listed below. Polyvinyl alcohol is considered in a separate entry as a polymer although it is defined as a polyhydric alcohol. Polyols, when nitrated, make excellent expls, proplnt binders, plasticizers, etc. Prepn can follow the procedure of Lenth DuPuis (Ref 3) which uses a methanol suspension of either sucrose or dextrose and a special Cu-Al oxide catalyst to yield 60-65% distillable polyols at 240° and 1500psi Refs 1) Beil — refs found under individual compds 2) CA, under Alcohols, Polyhydric for compds of current ordn interest 3) C.W. Lenth R.N. DuPuis, "Polyhydric Alcohol Production by Hydrogenolysis of Sugars in the Presence of Copper-Aluminum Oxide , IEC 37, 152-57 (1945) CA 39, 1391 (1945)... 

We found, however, that even highly concentrated lithium (9M) or sodium (3M) solutions did not reduce coal in a manner that increased its hydroxyl content and in parallel tests, 100% unreacted p-phenoxy phenol was always recovered from the lithium solutions ... 

Treatment of low-rank coal (or of a vitrinite fraction from such coal) with variously concentrated solutions of potassium in liquid ammonia did not cause an increased -OH content in the reacted material. Nor was the hydroxyl content affected by such treatment after prior exhaustive methylation of the coal with dimethyl sulphate and CO acetone (13). On the other hand,... 

After prolonged degassing of a large batch of PPG, analyses showed that its hydroxyl, unsaturation, and water contents were 0.97 meq/g, 0.033 meq/g, and 0.0035%, respectively. The hydroxyl content was determined by an acetylation method, carried out with acetic anhydride (10). The amounts of unsaturation and water were determined by the mecuric acetate and Karl Fischer methods (10), respectively. The obtained analytical results indicate that the number-average molecular weight of the dihydroxy material is 2062, provided its molecular weight is arbitrarily assumed to be twice that of the monohydroxy material, and that the mole fraction of the monohydroxy poly (propylene oxide) is 0.066. This value corresponds to a number-average functionality of 1.93 for the PPG. 

The hydroxylic content of the dextran sugar backbone makes the polymer very hydrophilic and easily modified for coupling to other molecules. Unlike PEG, discussed previously, which has modifiable groups only at the ends of each linear polymer, the hydroxyl functional groups of dextran are present on each monomer in the chain. The monomers contain at least 3 hydroxyls (4 on the terminal units) that may undergo derivatization reactions. This multivalent nature of dextran allows molecules to be attached at numerous sites along the polymer chain. 

The surface wettability of heat-treated wood decreases due to a reduction in the hydroxyl content of the modified wood (Pdtrissans etal., 2003). There is a reduction in the water-sorption capacity, which is related to a reduction in the number of primary sorption sites (OH groups) within the wood cell wall, largely as a result of the removal/degradation of the hemicellulosic component. As remarked upon earlier, hygroscopic properties are strongly influenced by the treatment method employed. Podgorski etal. (2000) heated... 

Masking of some of the cell wall hydroxyl content occurs, which can be a contributory factor in reducing water vapour sorption. The efficiency of OH masking depends upon the efficiency of diffusion of the cell waU bulking agent. 

Since lignin is not a uniform entity, chemical criteria for its characterization have centred around analytical detenninations of its functional groups, e.g. total hydroxyl content, phenolic hydroxyls (56), methoxyl and other ether groups, benzyl alcohol groups (7a), carbonyl groups (6), etc., and estimations of its content of special structural features, e.g. phenylcoumaran units (5), biphenylyl linkages (123), etc. 

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