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1.
D. R. Weimer L. D. Lindemuth W. L. Groves 《Journal of the American Oil Chemists' Society》1967,44(3):171-174
Refractive index is a rapid and consistent method of analysis for alcohols and nonionics from normal alcohols and ethylene
oxide. Correlations of refractive index with hydroxyl number of alcohols and nonionics are excellent and measurement error
is considerably lower for refractive index. Refractive index affords a measurement of the amount of ethylene oxide in nonionics
and can be used as a replacement for the 1% cloud point analysis. The ethylene oxide adduct distribution has no effect on
refractive index. Specific adducts, a narrow range of adducts made by acid catalyzed ethoxylation and a broad range of adducts
made by base catalyzed ethoxylation give the same refractive index value for any given ethylene oxide content.
Applications for the refractive index method for the laboratory and plant are: alcohol blending control, calculation of ethylene
oxide requirements for ethoxylation, nonionic control analysis, calculations of hydroxyl number for sulfations. Also, refractive
index can help identify laboratory samples, indicate the 1% cloud point and predict the phase character of nonionics. 相似文献
2.
N. Schönfeldt 《Journal of the American Oil Chemists' Society》1955,32(2):77-79
Summary A method for quantitative determination of ethylene oxide adducts is described. By precipitation in hydrochloric acid solution
with a known quantity of ferrocyanic acid, filtration, and titration with zinc sulfate, the consumption of ferrocyanic acid
can be determined. From the results a m.d. of less than 8% was calculated, the corresponding figure for adducts containing
more than 9 ethylene oxide units does not surpass 5%. The reaction takes place on the ethylene oxide chain in the compound.
To precipitate an adduct containing 6 units ethylene oxide approximately one mole of ferrocyanic acid is necessary. 相似文献
3.
Thomas K. Miwa Richard V. Madrigal William H. Tallent Ivan A. Wolff 《Journal of the American Oil Chemists' Society》1968,45(3):159-164
Both liquid and solid surface-active adducts of brassylic (tridecanedioic) acid were prepared by potassium hydroxide-catalyzed addition of ethylene oxide gas to the molten acid. The number-average molecular weights \(\left( {\overline {MW} _n } \right)\) of the adducts ranged from 500 to 3,000. These adducts cover a wide span in the ratios of hydrophilic to lipophilic portions of the molecule. They are unique in that hydrophilic end-groups sandwich a rather long chain of lipophilic methylene units. Treatment of some adducts with hot, saturated, aqueous sodium chloride induced transesterification and produced hydroxyl-terminated, multi-brassylic, poly(ethylene glycol) esters of MWn 1,000 to 4,000, all of which were efficient surface-active agents. Average degrees of polymerization of the poly(ethylene oxide) (PEO) chains were determined by a) functional group analysis, b) weight increase, and c) methanolysis of the products, followed by gas-chromatographic analysis of the isolated poly(ethylene glycol) fraction. Surface tension, critical micelle concentration, emulsion stability, and efficiency as an emulsifying agent in the aqueous polymerization of vinyl acetate were measured to evaluate surfactant properties of products in which the degrees of polymerization of the PEO chains ranged from 1.4 to 44. 相似文献
4.
Lloyd E. Weeks John T. Lewis Martin E. Ginn 《Journal of the American Oil Chemists' Society》1958,35(4):149-152
Summary and Conclusions A critical review of the literature was made in search of suitable methods for analyzing ethylene oxide condensates. These
studies led to the development of a rapid empirical titrimetric method for measuring nonionic hydrophobicity based on a water
titration of a condensate dissolved in dimethylformamide (DMF) and benzene. The end-point is identified by a definite solution
turbidity. Calibration curves were prepared from known condensates.
This method should be useful for analysis of adducts in plant quality control and also for nonionics with known hydrophobes.
Ether type adducts can not. (Ethylene oxide in esters can be calculated from their saponification values.) Examples of adducts
which can be identified by the titrimetric method are those based on fatty alcohols and alkylphenols. Proprietary nonionics
analyzed by the DMF method had ethylene oxide values in agreement with those claimed by the manufacturers. DMF data also compare
favorably with that by hydriodic acid cleavage. 相似文献
5.
Norman T. Crabb Harry E. Persinger 《Journal of the American Oil Chemists' Society》1968,45(9):611-615
Cobalt thiocyanate is used as a colorimetric reagent to determine traces of polyoxyethylene nonionic surfactants. It has been
established that when there is an insufficient number of oxide units per hydrophobe the color intensity is markedly diminished,
and with smaller numbers of oxide units the color fails to form altogether. the exact number of oxide units at which the colorimetric
procedure fails has not been established previously, due to the unavailability of the pure individual ethylene oxide adducts.
The individual ethylene oxide adducts of high purity were obtained by liquid chromatography on silica gel. The mixed solvent
used was originally developed for thin-layer chromatography and was applied without change to column chromatography. The composition
of the separated isomers has been determined by infrared, ultraviolet, nuclear magnetic resonance, and mass spectroscopy.
The apparent molar absorption coefficients have been obtained for the individual cobalt thiocyanate complexes both in benzene
and chlorform. For the low molecular weight adducts studied, the efficiency of color development and extraction into the organic
phase has been found to be dependent on the concentration of the cobalt thiocyanate reagent. A saturated aqueous solution
of cobalt thiocyanate was found to be preferable and benzene was found to be a more reliable extractant than chloroform.
The apparent molar absorption coefficients do not vary linearly with chain length at low molecular weights and the minimum
number of ethylene oxide units that will form an extractable color with the saturated reagent was found to be 3. 相似文献
6.
A high performance liquid chromatography (HPLC) method using adsorption columns combined with linear gradient elution has
been developed for the determination of ethylene oxide (EO) distribution in nonionic surfactants. The quantitative ethoxylate
adduct distribution in single-carbon-number and mixed-carbon-number primary alcohol-based samples can be obtained. The HPLC
method is also applicable for determining the molar EO distributions in diverse ethylene oxide adduct compounds such as alkylphenol
ethoxylates, branched alcohol ethoxylates and secondary alcohol ethoxylates. Nonionic surfactant samples containing adducts
up to 25 mol have been successfully separated and the individual adducts quantitated. 相似文献
7.
J. Szymanowski 《European Journal of Lipid Science and Technology》1982,84(6):245-248
The concept of the effective chain length and the hydrophobicity index was modified and adopted for block copolymers of ethylene and butylene oxides. The effective contents of the polyoxyethylene chain and hydrophilicity indices were determined, and an improved equation for the calculation of HLB values of ethylene and butylene oxide block copolymers is proposed. The method for the estimation of the polarity index is also given. 相似文献
8.
The work contains an analysis of the possibility of estimating the average structure of block copolymers of ethylene and of the parameters characterizing the state of hydrophilic—lipophilic balance. Based on the polarity index (PI), water value [WV] and emulsion inversion point (EIP) it is possible to deter-mine the average Polyethylene group content with an accuracy of 7% relativity, the polyoxybutylene group “molecular mass” at 12%, and the copolymer molecular mass at 15%. 相似文献
9.
The relative reaction constants for the base-catalyzed ethoxylation of primary straight chain alcohols have been determined
for the unreacted alcohol and the first three ethylene oxide adducts. The distribution of the ethoxylates was found using
molecular distillation, nuclear magnetic resonance analysis and gas liquid partition chromatography.
A mathematical model describing the distributions was set up and programmed on a 7090 digital computer. Solution of the program
gave the relative reaction constants for the alcohol and the first three adducts.
The relative reactivities of the adducts in the base-catalyzed ethoxylation of primary straight chain alcohols are shown to
increase with adduct number, but tend to a constant value as the adduct number increases. Results also show that alcohols
from C6 to C18 are equally reactive to ethylene oxide on a molar basis. 相似文献
10.
11.
Individual ethylene oxide adducts of high purity have been separated chromatographically from commercial grade nonylphenoxypoly
(oxyethylene)-ethanol (TERGITOL nonionic NP surfactants) and studied by time-of-flight mass spectrometric techniques. The
1–9 mole ethylene oxide adducts of nonylphenol produced clearcut spectra with a small number of fragment ions. Four groups
of different ion types have been established and some remarks concerning their formation are given. Molecular ions for the
nine adducts, through mass 616, were observed in good abundances because of the low-energy and high-speed capabilities of
the instrument. However, no single structure for an adduct can be proposed because the nonyl portions of the compounds are
isomeric mixtures. The ionization characteristics of the NPEn compounds reveal that the aromatic and alkyl portions of the molecules are easily activated. Tergitol nonionic NP surfactants
have branched alkyl substituents and are not completely biodegradable. Therefore it is speculated that the biodegradation
process leads to exposure of the highly branched alkylaromatic portions of the molecules in a manner comparable to mass spectral
fragmentation processes. 相似文献
12.
Gas-liquid chromatography (GLC) of ethylene oxide adducts of fatty alcohols is carried out after conversion of the alcohols
to aetate esters. This conversion permits detection of higher mol wt compounds. Separate peaks for adducts with up to 13 units
of ethylene oxide are obtained for a product derived from dodecyl alcohol. The procedure is used to follow the course of a
molecular distillation of an adduct prepared from hexadecyl alcohol and an example is also shown for an adduct derived from
a mixture of dodecyl and tetradecyl alcohols.
Presented at the AOCS Meeting in Minneapolis, 1963. 相似文献
13.
The solubility of ethylene and butylene oxide block copolymers in water was investigated. The turbidity of water dispersion and the water number were determined, and empirical statistically valid equations correlating these parameters with the molecular mass of the polyoxyethylene chain were derived. The hydrophilicity of block copolymers defined by the degree of transmittance and the water number was compared with hydrophilicity derived from the polarity index. 相似文献
14.
Donald R. Larkin Charles C. Hobbs 《Journal of the American Oil Chemists' Society》1988,65(11):1838-1846
A process was developed for condensing different mol ratios of dodecanol, formaldehyde and ethylene oxide to form a series
of adducts with useful detergent properties. These products are analogous to the commercially important class of nonionic
surfactants produced by treating fatty alcohols with ethylene oxide to produce a homologous series of adducts. The structures
were shown to be represented by RO[(CH2O)x(CH2CH2O)y]R where R is either dodecyl or hydrogen, x and y are integers (including zero), and it is understood that the oxymethylene
and oxyethylene groups are intermingled in the ether chains. Unfortunately, we were unable to produce commercially viable
detergent compositions. For these, our calculations indicate that a dodecanol:HCHO:EO mol ratio between 1:3:4 and 1:5:2 would
be necessary both for good detergency and good economics. With acidic catalysts such as BF3, the condensation is facile and product with desired overall mol ratios can be produced. However, much of the formaldehyde
and ethylene oxide are incorporated into by-products that either detract from the detergency properties (e.g., terminal ethers
where both R groups are dodecyl) or make the mixtures unacceptable as detergents (e.g., 1,4-dioxane). Because of the presence
of terminal ethers, the detergent properties are similar to those of propylene oxide adducts rather than ethylene oxide adducts.
With selected basic catalysts most of the harmful by-products can be eliminated, but the reaction rates and conversions are
unsatisfactory. Basic catalysts that give high reaction rates convert most of the formaldehyde fed to methyl formate. 相似文献
15.
Polyglycol nonionic surfactants are widely used in industrial and consumer products. Two classes of these surfactants, made
from selected combinations of 1,2-butylene oxide, propylene oxide and ethylene oxide, were compared to alcohol ethoxylate
(AE) and nonyl phenol ethoxylate nonionic surfactants in this study. Polyglycol copolymers consisted of either a polypropylene
glycol (PPG) or polybutylene glycol (PBG) central hydrophobe. Ethoxylation of the hydrophobes produced polyethylene glycol
hydrophilic blocks. Differences in hydrophobe polarity were determined by inverse gas chromatography (IGC). IGC is a useful
analytical method by which the physical and chemical characteristics of a material are studied. The stationary surfactant
material under study was coated onto an inert support and used as the packing for the column. A probe mixture, containing
simple organic molecules of varying polarity, was injected, and the retention characteristics were measured. The retention
characteristics of the standard probe mixture were used to reveal relative polarity information about the stationary surfactant
coatings. Polarities of the four hydrophobes were (in decreasing order): PPG, PBG, nonyl phenyl and fatty alkyl. Comparisons
were then made between the calculated hydrophile-lipophile balance values and polarity indices of the hydrophobes and their
ethoxylates. The effects of hydroxyl groups on polarity were also studied and quantified. 相似文献
16.
Natchanun Leepipatpiboon Ura Pancharoen Prakorn Ramakul 《Korean Journal of Chemical Engineering》2013,30(1):194-200
The separation of cobalt(II) and nickel(II) ions by HFSLM has been presented. The feed solution is 0.5M thiocyanate containing 300 ppm each of cobalt(II) and nickel(II) ions, whereas extractant is Alamine300 and the stripping solution is ammonia. Cobalt(II) is more preferable with Alamine300 than nickel(II). The effects of pH, Alamine300 concentration and ammonia concentration were investigated. Seven diluents were used: hexane, decanol, chlorobenzene, benzene, dichloromethane, ethylene dichloride and chloroform with different polarity indexes, from 0.1–4.1. Nickel(II) ion which is unpreferable with Alamine300 was used as a tracer to determine the membrane stability. The polarity of the diluents was found to be the main factor influencing the extraction performance and stability of a liquid membrane. The decreasing of polarity of the diluent can prolong the membrane stability, but the percentages of extraction and stripping decreased. The longest lifetime, 200 minutes, was obtained by using hexane as a diluent with the polarity index of 0.1. 相似文献
17.
The addition reactions of ethylene oxide and/or propylene oxide catalyzed by KOH and initiated with compounds containing free hydroxyls are followed by secondary reactions which vary the expected molecular weight. By using ethylene oxide, diols are formed and by using propylene oxide, both diols and unsaturated monofunctional compounds are formed. These products are usually characterized by their hydroxyl number. The average molecular weight is found by taking into consideration the starter functionality only. There are often some behavioral differences among similar products owing to the different quantity and chain length of the secondary products contained therein. The secondary products are analyzed and the quantity of the secondary products were determined from the hydroxyl number values and from the unsaturation of reagents and products. In the case of monofunctional adducts using the calculation method, the results have been experimentally confirmed. 相似文献
18.
The gas chromatographic analysis of various kinds of nonionic surfactants has been carried out after chemical decomposition
using the mixed anhydride of acetic and p-toluene sulfonic acids which acts as a reagent for cleavage of ether linkages. The
gas chromatographic peaks of the reaction products show the alkyl distributions of the hydrophobic groups of ethylene oxide
adducts. The alkyl compositions closely agree with those of the starting materials. In this way, the hydrophobic groups of
polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl amine, and polyoxyethylene alkyl thioether
have been analyzed. At the same time, the hydrophilic group, namely polyoxyethylene group, can be identified in the form of
ethylene glycol diacetate. 相似文献
19.
H. L. Sanders J. B. Braunwarth R. B. McConnell R. A. Swenson 《Journal of the American Oil Chemists' Society》1969,46(3):167-170
It is well known that long chain alcohols and phenols cannot react with ethylene oxide in the absence of catalysts, whereas
primary fatty amines can take up at least two moles of oxide to form tertiary amines. It has been found that further ethoxylation
of this two mole adduct in the absence of added catalyst can proceed only if ethoxylation temperatures are lowered considerably.
The present paper demonstrates that this low-temperature ethoxylation is really catalyzed by a previously overlooked highly
alkaline compound generated during the course of the reaction. It is shown that this is a long-chain quaternary ammonium compound,
and the mechanism of its formation is described. As the addition of ethylene oxide proceeds, this quaternary gradually decomposes
and the reaction essentially comes to a halt when it has all disappeared. 相似文献
20.
Richard R. Egan Gary W. Earl Jeannene Ackerman 《Journal of the American Oil Chemists' Society》1984,61(2):324-329
A number of unsaturated fatty alcohols are known, but only those of the C16 and C18 chain lengths are of much importance. In particular, oleyl alcohol., 9,10-octadecenol-1, is by far the most important. A
variety of grades of oleyl alcohols is produced and used in the USA ranging from high purity material having iodine values
(IV) of 90–95 to those having IV of 45–55, with the other components being primarily cetyl (hexadecanol-1) and stearyl (octadecanol-1)
alcohols. This paper takes a brief look at the various grades of unsaturated alcohols used in the USA, methods of preparation,
and the change in physical and chemical properties as the octadecanol-1 content and IV decline. Uses of these alcohols industrially
and in cosmetic and pharmaceutical preparations are also discussed. Unsaturated alcohols are useful chemical intermediates
since they have two reactive sites, the hydroxyl group and the carbon-carbon double bond. Particular attention is paid to
the properties, uses and potential uses of some of their sulfates, ether sulfates, ethylene oxide adducts and ethylene/propylene
oxide adducts as detergents and emulsifiers for ultimate use in cosmetics and light-duty and heavy-duty systems. Current estimated
consumption of unsaturated alcohols in the USA is discussed. 相似文献