CA1049046A - Vinylidene alcohol compositions - Google Patents
Vinylidene alcohol compositionsInfo
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- CA1049046A CA1049046A CA73170589A CA170589A CA1049046A CA 1049046 A CA1049046 A CA 1049046A CA 73170589 A CA73170589 A CA 73170589A CA 170589 A CA170589 A CA 170589A CA 1049046 A CA1049046 A CA 1049046A
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Abstract
Abstract of the Disclosure Particular compositions of vinylidene alcohols are provided which are distinguishably characterized by their structure, their bio-degradable nature, and by their very low pour point characteristics.
These compositions can be used to provide useful surfactants and de-tergents and to form distinctive ethoxylate derivatives having unusual attributes, such as biodegradability, very high rates of water solu-bility, nongelling tendencies, and superior wetting ability; and cer-tain of these ethoxylate compositions are synergistic in wetting abi-lity and, unlike related ethoxylates of conventional alcohols, the ethoxylates of certain compositions possess cloud point temperatures within an especially desired range.
These compositions can be used to provide useful surfactants and de-tergents and to form distinctive ethoxylate derivatives having unusual attributes, such as biodegradability, very high rates of water solu-bility, nongelling tendencies, and superior wetting ability; and cer-tain of these ethoxylate compositions are synergistic in wetting abi-lity and, unlike related ethoxylates of conventional alcohols, the ethoxylates of certain compositions possess cloud point temperatures within an especially desired range.
Description
lV49046 VINYLIDENE ALCOHOL COMPOSITIONS
This invention relates to the field of synthetic alcoholsand to products useful for forming synthetic surfactants. Novel com-positions exhibiting unusual characteristics and superior properties are included.
Alcohols derived from both natural and synthetic origins have been widely utilized in a variety of applications. Exemplary areas in which such alcohols and their derivatives have been employed include their application in plasticizers, textile treatments, lub-ricants, polyurethanes, amines, alkyd coatings, surfactants, and the like. The employment of alcohols in the surfactant area is notably increasing in importance.
Surfactants, such as the alcohol alkoxylates, have been broadly employed by the detergent and other related industries, as wetting agents, solubilizing agents, washing agents, foaming agents, emulsifying agents, rewetting agents, dispersing agents, scouring agents, ant the like.
Since the various surfactant applications of such alcohols are so myriad and categorically nondistinctive, a more convenient manner of characterizing the surfactants than by their utility is to use a system wherein they are classified as anionic, cationic, ampho-~teric, or nonionic, depending upon the nature of the ionic charge, if any, of the hydrophilic moiety of the surfactant.
Nonionic type surfactants to which the subject invention is related have been derived from alcohols by condensing them with alkylene oxides.
rhese as well as the other surfactant types may, or may not - exhibit a sufficient combination of properties so that they can be used beneficially in more than one application.
~, .
.. .. . .. . .
~49~46 Regardless of whether a material has a rather wide or narrow range of useful functions, there are some relatively basic and cogent criteria that in reality can dictate the suitability and/or acceptability of an alcohol and its surfactant derivatives.
For example, a synthetic surfactant may be an excellent detergent and wetter and yet not be biodegradable. This fact would, in effect, bar acceptability of this surfactant by the public and/or the industry.
In like manner, a surfactant may have excellent and varied activities but exist in such a physical state that its use is incon-venient, if not prohibited in many applications. Accordingly, the surfactant may under conditions normal to its application undergo : gelling and thus become an unusable product. The product may have a prohibitive slow rate of solution in water or have an undesirable cloud point, whereby the value of the surfactant is substantially diminishet.
The possession of such attributes as biodegradability, non-gelling tendencies, a rapid rate of solution in water, and a desir-able cloud point, are, in effect, conditions precedent to the bene-ficial utilization of a surfactant's basic functions.
Obviously, the worth of an alcohol-derived surfactant is .
heavily dependent on the characteristics of the alcohol. The basic character of the alcohol determines, to a large extent, whether the alcohol can be satisfactorily and conveniently converted to a sur-factant material and whether the surfactant will successfully demon-strate the aforementioned attributes. In summary, the alcohol must be biodegradable and exist in a convenient form, such as in the liquid state at room temperature, in order to enable successful utilization in a wider variety of applications.
This invention relates to the field of synthetic alcoholsand to products useful for forming synthetic surfactants. Novel com-positions exhibiting unusual characteristics and superior properties are included.
Alcohols derived from both natural and synthetic origins have been widely utilized in a variety of applications. Exemplary areas in which such alcohols and their derivatives have been employed include their application in plasticizers, textile treatments, lub-ricants, polyurethanes, amines, alkyd coatings, surfactants, and the like. The employment of alcohols in the surfactant area is notably increasing in importance.
Surfactants, such as the alcohol alkoxylates, have been broadly employed by the detergent and other related industries, as wetting agents, solubilizing agents, washing agents, foaming agents, emulsifying agents, rewetting agents, dispersing agents, scouring agents, ant the like.
Since the various surfactant applications of such alcohols are so myriad and categorically nondistinctive, a more convenient manner of characterizing the surfactants than by their utility is to use a system wherein they are classified as anionic, cationic, ampho-~teric, or nonionic, depending upon the nature of the ionic charge, if any, of the hydrophilic moiety of the surfactant.
Nonionic type surfactants to which the subject invention is related have been derived from alcohols by condensing them with alkylene oxides.
rhese as well as the other surfactant types may, or may not - exhibit a sufficient combination of properties so that they can be used beneficially in more than one application.
~, .
.. .. . .. . .
~49~46 Regardless of whether a material has a rather wide or narrow range of useful functions, there are some relatively basic and cogent criteria that in reality can dictate the suitability and/or acceptability of an alcohol and its surfactant derivatives.
For example, a synthetic surfactant may be an excellent detergent and wetter and yet not be biodegradable. This fact would, in effect, bar acceptability of this surfactant by the public and/or the industry.
In like manner, a surfactant may have excellent and varied activities but exist in such a physical state that its use is incon-venient, if not prohibited in many applications. Accordingly, the surfactant may under conditions normal to its application undergo : gelling and thus become an unusable product. The product may have a prohibitive slow rate of solution in water or have an undesirable cloud point, whereby the value of the surfactant is substantially diminishet.
The possession of such attributes as biodegradability, non-gelling tendencies, a rapid rate of solution in water, and a desir-able cloud point, are, in effect, conditions precedent to the bene-ficial utilization of a surfactant's basic functions.
Obviously, the worth of an alcohol-derived surfactant is .
heavily dependent on the characteristics of the alcohol. The basic character of the alcohol determines, to a large extent, whether the alcohol can be satisfactorily and conveniently converted to a sur-factant material and whether the surfactant will successfully demon-strate the aforementioned attributes. In summary, the alcohol must be biodegradable and exist in a convenient form, such as in the liquid state at room temperature, in order to enable successful utilization in a wider variety of applications.
-2-To these ends, and in view of recent ecology awareness,alcohols which are essentially linear in nature, such as those de-rived from natural gourceg, were necessarily desired by the deter-gent and related industries for their biodegradable nature.
For many practical reasons, incluting costs, product con-trol, and availability of such natural alcohol sources as fats, oils and waxes, manufacturers have turned to synthesizing alcohols, and their derivatives, which simulate the straight chain character of the naturally occurring products.
U. S. patent No. 3,598,747 is representative of such an endeavor Therein, Ziegler-type primary linear alcohols are prepared from trialkylaluminum mixtures made by way of ethylene polymeriza-tion, subsequent oxidation, and hydrolysis of the resultant aluminum alkoxides. U. S. patent No. 3,391,219 representatively describes the preparation of such trialkylaluminum mixtures and further exem-plifies the desire to prepare a highly pure linear alpha-olefin chain, such as one suitable for subsequent alcohol preparation.
The high linearity of the Ziegler-type alcohols is reported to result in a high degree of biodegradability. The unsuitability and the avoidance of the branched type alcohols, and their deriva-tives, in the surfactant area is additionally exemplified in U. S.
patent Nos. 3,488,384; 3,504,041 and 3,567,784. Notably, a ma~or application for the Ziegler-type alcohols has been in nonionic sur-factant production.
Another method now customarily employed for producing simi-lar alcohols is the process comprising reacting linear olefins with carbon monoxide and hydrogen under oxo reaction conditions. Hereto-fore, however, several companies were employing propylene tetramer feed~tocks in the named oxo reaction to produce tridecylalcohol but
For many practical reasons, incluting costs, product con-trol, and availability of such natural alcohol sources as fats, oils and waxes, manufacturers have turned to synthesizing alcohols, and their derivatives, which simulate the straight chain character of the naturally occurring products.
U. S. patent No. 3,598,747 is representative of such an endeavor Therein, Ziegler-type primary linear alcohols are prepared from trialkylaluminum mixtures made by way of ethylene polymeriza-tion, subsequent oxidation, and hydrolysis of the resultant aluminum alkoxides. U. S. patent No. 3,391,219 representatively describes the preparation of such trialkylaluminum mixtures and further exem-plifies the desire to prepare a highly pure linear alpha-olefin chain, such as one suitable for subsequent alcohol preparation.
The high linearity of the Ziegler-type alcohols is reported to result in a high degree of biodegradability. The unsuitability and the avoidance of the branched type alcohols, and their deriva-tives, in the surfactant area is additionally exemplified in U. S.
patent Nos. 3,488,384; 3,504,041 and 3,567,784. Notably, a ma~or application for the Ziegler-type alcohols has been in nonionic sur-factant production.
Another method now customarily employed for producing simi-lar alcohols is the process comprising reacting linear olefins with carbon monoxide and hydrogen under oxo reaction conditions. Hereto-fore, however, several companies were employing propylene tetramer feed~tocks in the named oxo reaction to produce tridecylalcohol but
-3--the branched nature of the alcohol virtually eliminated it as a serious candidate in the surfactant area.
In the present conventional oxo processes linear alpha-olefin feeds are used whereby a mixture of normal and 2-alkyl branched primary alcohols are produced. Because approximately 30 to 40 wt. %, and greater, of the alcohols have 2-alkyl branching, the conventional oxo alcohol method has been sub~ected to criticism.
More recently, however, efforts in improving the oxo process have resulted in oxo alcohols having congiderably less 2-alkyl branching.
U. S. patent Nos. 3,239,569 and 3,239,571 illustrate such facts.
It has been reported, such as by the Stanford Research Institute, Linear Hi~her Alcohols, Report No. 27, August 1967, at pages 3 and 133, that these more recent oxo alcohols having sub-stantially less 2-alkyl branching are biodegradable because of the occurrence of branching at the favorable 2-position, which type of branching has only a relatively small detrimental effect on the bio-degratability of its derivatives. It is evident, therefore, from the above-stated art that branched alcohols for surfactant production are to be otherwise avoided.
Other alcohol types have also been produced by the oxida-tion of normal paraffins but, unlike those alcohols produced by the ethylene polymerization process and those generally derived from natural origins, are secondary alcohols. The secondary alcohols, unlike the corresponding primary alcohols, in some surfactant appli-cations, such as in the sulfated alcohol area, do not demonstrate the same desired properties. The secondary alcohols have other reported disadvantages.
As will be hereinafter re fully presented, the known alcohols or their surfactant derivatives, lack in varying degrees _4--some of the heretofore detailed criteria that govern the overall suitability and/or acceptability of the alcohol and/or its surfactant derivatîves.
Accordingly, the heretofore known alcohols do not generally exist in a convenient liquid state and, except for those alcohols below undecanol, and the highly branched alcohols, such as prepared from propylene and butylene trimers, tetramers, and the like, they can be generally character-ized as solid or relatively solid materials at or near room temperature.
The latter named branched alcohols are unsuitable for surfactant application because of their resistence to biodegradation.
It is clearly evident that there is a definite and acute need for higher molecular weight alcohols that are liquid at room temperatures, biodegradable and able to meet the basic standards that regulate whether the useful attributes of the alcohol and its surfactant derivatives can be fully utilized.
Surprisingly, such alcohol compositions have now been discovered.
- We have fortuitously found novel alcohol compositions that are not only biodegradable but exist at room temperature in the liquid state. Accord-ingly, our novel alcohol compositions, when compared to the biodegradable prior art alcohols, possess freezing point (melting point) values far below anything heretofore known. Our alcohol compositions, in addition to being easily facilitated in a variety of applications, have effectively broadened the molecular weight range of surfactant suitable alcohols.
According to the present invention, there is provided a vinylidene alcohol composition indicating compounds of the formula:
,1 R2 C,--~CH2)Z (OC2H4)~1oH
(CH2)y wherein Rl is hydrogen, methyl, or a double bond with R2, R2 represents CH3(CH2)x- or R"-CH=, in which X is a integer from O to 17 and R" is a linear alkyl radical containing at least one carbon atom, ,~ ~
D ~ 5 c ~
~ ~ j . .. . .-........ .
.
y is a number from O to 17 and the sum of X and Y is an integer in the range 6 to 17, W is an integer in the range of 7 to 15, Z is an integer in the range of 1 to 18, with the proviso that when Rl is hydrogen, Z is an integer of 2 to 17.
Further, the novel biodegradable ethoxylated derivatives of our unusual alcohols possess distinguishingly unique characteristics. For instance, the ethoxylates of our alcohols are products having excellent detersive and surfactant activity over a broader molecular weight range of the alcohol. Comparison of our ethoxylated -5a--: .
: , ~ 049046 alcohols with other prior art biodegradable ethoxylateg is accurately and representatively portrayed at similar cloud polnts, the cloud point being the temperature at which a one wt. % aqueous solution of the surfactant turns from clear to cloudy as the temperature of the solution i9 raised. The particular cloud point of the surfac-tant is very important and the surfactant must obviously meet the cloud point specifications of the practitioner if the surfactant is to be commercially acceptable. For most general applications cloud point specifications are preferably between 55C and 65C. Recog-nizably, some specialized applications require a somewhat highercloud point.
The synthetic alcohol ethoxylate derivatives of this inven-tion exhibit outstanding qualities within said specifications.
Therefore, when a comparison is made of our synthetic alcohol ethoxy-- late compositions with the related alcohol derived products now in the art, our compositions demonstrate superior wetting ability and much faster rates of water solubility. Perhaps most exciting is the fact that our herein defined alcohol derived surfactant compositions have a reduced tendency to gel in water at room temperature, a con- -dition that has plagued the ethoxylates of the Ziegler and oxo-type alcohols previously mentioned. A further surprising advantage is that certain of our alcohol ethoxylate compositions are synergistic in wetting ability.
Therefore, in accordance with our invention, novel vinyli-dene alcohol compositions are provided which can be representatively depicted by the following Formulas I to V:
Formula I
CH3(cH2)x-cH(cH2)ycH3 , .
~ 049046 wherein, individually, x and y are numbers from 1 to 15 and the sum of x and y is in the range of 6 to 16.
Formula II
CH3(CH2)U-lc-(cH2)v C 3 wherein, individually, u and v are numbers from 0 to 16 and the sum of u and v is in the range of 6 to 16.
Formula III
CH3(CH2)n~CH(cH2)mcH2oH
wherein n is a number from 0 to 17, m is a number from 2 to 17 and the sum or n and m is in the range of 7 to 17.
Formula IV
fH3 CH3(CH2)r-CH-(cH2) 8 -1CH(CH2)t CH3 wherein, individually, r, 9 and t are numbers from 0 to 15 and the sum of r, s and t is in the range of 5 to 15.
Fonmula V
R"-CH - C-CH2CH2OH
R"' wherein, indivitually, R" is a linear alkyl radical containing at least one carbon atom ant R"' i9 a linear alkyl radical containing at least 2 carbon atoms and wherein the total carbon atoms of R"
and R"' are in the range of 7 to 17.
The alcohols of this invention are employed to provide novel alcohol ethoxylates by conventional ethoxylation processes and can be representatively depicted as follows:
1049()46 Fo mula VI
R''''-(OC2H4)W-OH
wherein R"" is an alkyl radical which corresponds to the alkyl portion of the above-represented vinylidene alcohols.
It should be noted that our novel compositions have been herein referred to as vinylidene alcohols and vinylidene ethoxylates.
The term "vinylidene" has been employed for convenience to describe our compositions because vinylidene olefins have herein been employed to provide these novel compositions. Accordingly, "vinylidene olefins" herein referred to are those corresponding to the following representative formula:
Formula VII
R-C = CH2 R' wherein R and R' are linear alkyl radicals having a total of 8 to 18 carbon atoms and wheréin R and R' taken individually represent a C2 to C14 alkyl radical, preferably a C4 to C10 alkyl radical.
Therefore, the term "vinylidene alcohol" as used through-out the specification and/or claim designates those alcohols rep-resented by Formulas I to V herein and, correspondingly, the term"vinylidene ethoxylate" is used herein to designate those ethoxy-lates represented by Formula VI herein.
The vinylidene alcohols of this invention can be prepared by the hydroformylation of the vinylidene olefins (Formula VII), whereby said vinylidene olefins are reacted with carbon monoxide and hydrogen. Said vinylidene olefins can also be reacted with formalde-hyde or formaldehyde-yielding components to also provide our vinyli-dene alcohols. The vinylidene alcoholæ prepared by either the hydroformylation or formaldehyde addition reactions contain one more carbon atom than the olefin starting material.
.:
The unsaturated vinylidene alcohols represented by Formula V can be prepared by employing said vinylidene olefins in the stated formaldehyde addition reaction. For some unexplained reason, the vinylidene olefins used in our invention are unusually reactive with formaldehyde and formaldehyde-yielding components.
Further, the formaldehyde addition process is so selective that when the vinylidene olefins of this invention are utilized in this process, the primary alcohol product contains 90 to 100 wt. %, usually 95 wt. % and greater, of the novel compositions representet by Formula V.
These alcohols, being unsaturated, can be hydrogenated by conventional means to form vinylidene alcohols such as represented by Formula I.
Use of the stated hydroformylation process for preparing our novel compositions provides vinylidene alcohols represented by Formulas I through IV, any or all of which can be coproduced in varying amounts. For example, when using the oxo process typically about 25 to 90 wt. % of the vinylitene alcohols produced will be of the Formula I type.
Our novel compositions include, therefore, mixtures of vinylidene alcohols, or mixtures of the corresponding vinylidene ethoxylates, such as a mixture of those representatively depicted in Formulas I and II or a mixture of compounds represented by Formulas I, II, III and IV, and the like. As herein noted, the vinylidene alcohols will have one re carbon atom than did the vinylidene olefin from which they can be obtained. Accordingly, if ; a particular vinylidene olefin, such as a C14, is employed in the hydroformylation or formaldehyde addition reaction, a C15 alcohol which corresponds to one or more of the represented Formulas I
_g_ through V is produced. In like manner, where mixtures of olefins, such as a mixture of C14 and C16 olefins, are employed, mixtures of C15 and C17 vinylidene alcohols are protuced which correspond to one or more of the representative formulas.
Our inventive compositions, as herein depicted by repre-sentative formulations, include, therefore, mixtures of vinylidene alcohols or correspondingly vinylidene ethoxylates, such as a mixture~
of C12 and C13 alcohols as well as covering mixtures of alcohols, such as a mixture of C14 vinylidene alcohols represented by two or more of the above formulas.
It should also be noted that the above representative formulas of our vinylidene alcohols, and correspondingly our vinyli-dene ethoxylates, individually include various stereo isomers, or mixtures thereof, whenever asymmetrical carbon atom is present.
Included, therefore, in our invention are such isomeric forms of the compositions depicted.
The particular vinylidene alcohols represented by Formula I
are generally preferred because they are very representative, or - highly illustrative of, the many unusual and unexpected characteris-tics of our novel compositions.
As previously indicated the vinylidene ethoxylate~ (For-mula VI) of our invention comprise an alkyl portion, i.e., R"", which corresponds to the alkyl moiety of the vinylidene alcohols, such that R"" in the representative formula Formula VI
R""-(OC2H4)wOH
is an alkyl radical containing 11 to 21 carbon atoms and is selected from the following radicals (a) to (d):
- .... -. ' : . .
a) H
CH3(CH2)X-f-cH2cH2-(CH2)yCH3 whereln, individually, x and y are lntegers from 1 to 15 and the sum of x and y is in the range of 6 to 16;
b) fH3 CH3-(CH2)U-f-cH2 2 v wherein, individually, u and v are integers from 0 to 16 and the s~m of u and v is in the range of 6 to 16;
c ) ICH3 CH3(CH2)n-C-(cH2)m-cH2 wherein n is an integer from 0 to 17, m is an integer from 2 to 17 and the sum of n and m is in the range of 7 to 17;
d) fH3 H (IcH2)8 CH3-(cH2)r-f-(cH2)t-H-cH2 . CH3 wherein, individually, r, 8 and t are integers from 0 to 15 and the sum of r, 8 and t is in the range of 5 to 15; or R"" is an unsatu-rated alkyl radical represented as .. e) R"-CH = f-CH2-CH2-.. j .
wherein, individually, R" is a linear alkyl radical containing at ~t least one carbon atom and R~" is a linear alkyl radical containing at least 2 carbon atoms and wherein the total carbon atoms of R" and R~" are in the range of 7 to 17; and admixtures of (a) to (e), and wherein w is a number in the range of 7 to 15, preferably 7 to 12.
.
r.. . .. . .
1049~46 It i~ understood that when a plurality of ethylene oxide units are condensed with a vinylidene alcohol, or mixture of alco-hols, that various oxyethylene chain lengths will result. Accord-ingly, as used herein, the value of w is an average number indicat-ing the average number of oxyethylene units present.
In order to further characterize a particularly surprising aspect of our invention, we have included in the above-mentioned formula the subscript z. Therefore, z in the following formula Formula VIII
Rz"'-(OC2H4)wOH
represents a number corresponding to the number of the carbon atoms contained in the alkyl radical R"" and z is within the range of 11 to 15. For example, when z is 15 and w is 11 the vinylidene ethoxy-late represented is the ll-mol ethoxylate adduct of the vinylidene alcohol, pentadecanol.
In this regard, we have surprisingly found that if the value of the ratio of w to z, in this formula, i8 within the range .685 to .755 the vinylidene ethoxylates not only will demonstrate the preferred surfactant requisites discussed throughout the speci-fication but they will, unlike the primary alcohols of the Zieglerand oxo process of the prior art, possess the significant advantage of having the particular cloud points that satisfy the general speci-; fications of the industry.
; Another startling aspect is the discovery that when z is 13 and w is in the range of 9 to 10, i.e., the 9 to 10-mol ethoxy-late of our Cl3 vinylidene alcohol, the vinylidene ethoxylate demon-strates synergistic wetting ability with other alcohol ethoxylates and particularly enhances the activity of the stated prior art alcohol ethoxylates.
. .-. .. -- : . :
--' ~
.- . ~
1~49046 In accordance with our invention the vinylidene olefin starting materials, i.e., those repregented by Formula VII, can be prepared by a conventional process such as by dimerizing alpha-olefins, e.g., Alkyl-CH = CH2, mixtureg thereof, and the like. For example, a mixture of C6 to Clo alpha-olefins can be used. A suit-able process to produce vinylidene olefins is representatively des-cribed in U. S. patent No. 2,695,327. Typical vinylidene olefins are 2-hexyldecene-1, 2-octyldecene-1, 2-octyldodecene-1, ant the like.
The alpha-olefins can be provided via the conventional conversion of ethylene by a combined growth-displacement reaction using Ziegler-type polymerization catalysts such as the trialkyl-aluminums. The resultant olefin fraction can be separated and the particular olefin fraction desired can be recovered for vinylidene olefin preparation such as by dimerization.
The vinylidene olefins are most readily converted to our novel alcohols by way of the stated formaldehyde addition process or by the hydroformylation (oxo) process.
Process conditions typical to a conventional oxo reaction can be employed. The conditions can be varied over broad ranges according to the desires of the practitioner and dictates of the particular catalyst used. Generally, temperatures in the range of about 25C to 250C and pressures in the range of about 15 to 10,000 psig can be employed. Conventional catalysts and conditions known to enhance alcohol production selectively over aldehydes can be employed. Catalysts such as those derived from cobalt and rhodium which are usually complexes of hydrogen, carbon monoxide, with or without other ligands, are also suitable. Catalyst complexes con-taining amines, phosphines, phosphites, pentavalent phosphorus, arsenic and antimony compound8, halides, carboxylate anions, ant the like, are exemplary. Repregentative catalysts, conditions and recovery techniques are exemplarily described in U. S. patent Nos.
3,594,425; 3,239,566; 3,239,571; 3,420,898 and in Carbon Monoxide in Or~anic SYnthesis, Jurgen Falbe, Springer-Verlag, New York, 1970.
As previously stated, the formaldehyde addition process can also be employed. Thig procesg provides high selectivity and unexpectedly rapid and complete conversions of vinylidene olefins to our vinylidene alcohols. mis process can be employed without a catalyst when temperatures are sufficiently high such as around 200C
Acidic catalysts can be employed, if desired, Catalysts are ~r ~
if temperatures less than 200C are employed to give better reaction rates. Exemplary catalysts suitable are BF3 and complexes thereof, acetic acid, tin halides, such as stannic chloride, and the like.
Temperatures up to that where decomposition begins can be employed.
Generally, temperatures in the range of about 50C to 300C are used.
Generally, pressures sufficient to maintain an essentially liquid phase sre used. Exemplary conditions, and the like, are further des-cribed in U. S. patent Nos. 2,235,027; 2,624,766 and in An~ewandte Chemie. International Edition, H. M. R. Hoffmann, 8, S56 (1969).
The vinylidene alcohols of this invention can be converted to our vinylidene ethoxylates by way of typical alkoxylation proce-dures, such as wherein an alcohol and ethylene oxide are condensed in the presence of alkaline catalysts, such as alkali metal hydroxide alkali metal alcoholates or phenolates or metallic sodium and potas-sium, and the like. Sodium and potassi~n hydroxide are exemplary catalysts.
Other methods for preparing the alkyl polyoxyethylene adducts of our alcohols can be employed such as by the conversion . '. ' ' of the alcohol to the corresponding alkyl halide, e.g., alkyl bromide, by means of, e.g., PBr3, followed by reaction with the appropriate glycol, i.e., HO(c2H4O)xH
ROH+PBr3--~RBr Na ~ RO(c2H4O)xH
Another method i8 by the gtepwise reaction of the alcohol with ethyl-ene chlorohydrin.
The base catalyzed addition of ethylene oxide to the alcohol is the preferred method and it readily enables the control of the number of oxyethylene units added to the alcohol. Usually in this process temperatures in the range of about 100C to 350C are em-ployed. Generally, pressures sufficient to maintain an essentially liquid phase are used. One representative process is described in U. S. patent No. 3,436,426. It should be noted that the ethoxylates of this invention have an advantage over the secondary alcohol ethoxy-lates, previously mentioned, in that they can be easily prepared in a one-step ethoxylation process.
The foregoing discussion and description is further illus-trated by the following examples which depict various of our alcohol ethoxylate compositions and demonstrate many of the distinguishing aspects of this invention. The examples are not to be interpreted as a limitation on the scope of the foregoing discussion and description or on the materials therein employed. The compositions prepared in the following examples were verified by nuclear magnetic resonance, infrared, chromatographic and hydroxyl number analysis.
EXAMPLE I
This example, as well as Examples II through V, demonstrate preparation of our novel primary alcohol compositions such as those corresponding to Formula 5 hereinabove.
To a one-gallon autoclave was charged 2,060 grams of a Clo vinylidene olefin fraction comprising a 50:50 weight mixture of 2-ethyl-1-octene and 2-butyl-1-hexene and 230 grams of paraformalde-hyde. The autoclave was flushed with nitrogen and heated at 250C
for one hour. The reactor effluent was washed twice with water and distilled to provide 690 grams of vinylidene Cll alcohols, b.p. 119 to 127C at 20 mm. Referring to Formula V, about 50 wt. % of the product comprised a composition wherein R" is propyl and R"' is butyl.
About 50% of the product comprised a mixture of (a) wherein R" is 10 pentyl and R"' is ethyl and (b) wherein R" is methyl and R"' is hexyl.
Accordingly, almost 100 wt. % of the products comprised a mixture of 3-ethyl-non-3-enol, 3-hexyl-pent-3-enol, and 3-butylhept-3-enol.
EXAMPLE II
A one-liter stirred autoclave was charged with 340 grams of a C12 vinylidene olefin fraction comprising 2-butyl-1-octene and 32 grams paraformaldehyde. The reactor was flushed with nitrogen and heated at 275C for one hour. The effluent was washed with successive 200 ml portions of an aqueous solution of 0.5 wt. % sulfuric acid and 5 wt. % sodium bicarbonate. The washed effluent was dried over anhy-20 drous sodium sulfate, filtered, and distilled to give 95 grams ofproduct, b.p. 105C to 110C at 3 mm. Over 90 wt. % of the product was identified as 3-butylnon-3-enol, 3-pentyloct-3-enol and their formate esters.
EXA~LE III
A one-gallon stirred autoclave was charged with 1,960 grams of a C14 vinylidene olefin fraction comprising a 50:50 weight mixture of 2-butyl-1-decene and 2-hexyl-1-octene and 110 grams paraformalde-hyde. The autoclave was flushed with nitrogen and heated at 250C
for one hour. The effluent was washed with water and distilled to ~.
give 1,434 grams unreacted C14 olefins ant 421 grsms C15 alcohols,b.p. 135 to 140C at 5 mm. The products were about 95 wt. % of a 50:50 mixture of 3-hexylnon-3-enol and a mixture of 3-butylundec-3-enol and 3-octylhept-3-enol.
EXAMPLE IV
A one-liter stirred autoclave was charged with 450 grams of a C16 vinylidene olefin fraction comprising 2-hexyl-1-decene and 33 grams of paraformaldehyde. me autoclave was flushed with nitro-gen and heated at 250C to 252C for one hour. The effluent was washed once with 200 ml water and distilled to give 356 grams unre-acted olefin and 90 grams of product, b.p. 150C to 157C at 5 mm.
The product fraction was identified as over 95 wt. % of a mixture of 3-hexylundec-3-enol and 3-octylnon-3-enol.
EXAMPLE V
A three-gallon autoclave was charged with 6,048 grams of a C18 vinylitene olefin fraction comprising a 50:50 wt. % mixture of 2-octyl-1-decene and 2-hexyl-1-dodecene and 396 grams of paraformal-dehyde. The autoclave was flushed with nitrogen and heated at 250C
to 254C for 1.5 hours. The temperature was reduced to 200C and 400 ml water was in~ected into the autoclave. The temperature was maintained at 185C to 190C for one hour. The reactor effluent was washed twice with water and distilled to give 1,585 grams Clg alco~ols b.p. 153C to 159C at 0.5-0.7 mm. me product alcohol comprised about 50 wt. % of 3-decylnon-3-enol and about 50 wt. % of a mixture of 3-octylundec-3-enol and 3-hexyltridec-3-enol EXAMPLE VI
This example, as well as Examples VII through X demonstrate the hydrogenation of unsaturated vinylidene alcohols to provide satu-rated alcohols corresponding pr;dominantly to the alcohols of , ~ .
;1~49046 Formula I. The unsaturated Cll vinylidene alcohols produced in Example I, above, were hydrogenated over a nickel-copper-chromium hydrogenation catalyst at 154C to 165C and 700 to 1,800 psig. Dis-tillation of the filtered effluent gave 353 grams of a saturated C
alcohol, b.p. 114C to 116C at 10 mm. The primary alcohol product was essentially a 100 wt. % mixture of 3-ethylnonanol and 3-butyl-heptanol.
EXAMPLE VII
A 400-ml sample of C13 unsaturated vinylidene alcohols pre-pared as in Example II was hydrogenated over a reduced nickel catalyst at 158C to 163C at 1,175 to 2,100 psig. me reactor effluent was filtered and a portion of it distilled to give 311 grams of C13 satu-rated vinylidene alcohols, b.p. 135C to 138C at 8 mm. The vinyli-dene alcohol was essentially 100 wt. % 3-butylnonanol.
EXAMPLE VIII
A 1,300-gram sample of unsaturated Cls vinylidene alcohol, prepared as in Example III, was hydrogenated over a nickel-copper-chromium hydrogenation catalyst at 138C to 164C at 650 to 1,050 psig. me hydrogenated material was distilled to give 1,240 grams of Cls vinylidene alcohols, b.p. 117C to 121C at 0.35 to 0.60 mm.
The saturated vinylidene alcohols were a mixture of 3-butylundecanol and 3-hexylnonanol.
EXAMPLE IX
A 920-gram sample of unsaturated C17 vinylidene alcohol, prepared as in Example IV, was hydrogenated over a nickel-copper-chromium hydrogenation catalyst at 163C to 173C at 550 to 1,100 psig. me hydrogenation effluent wa~ filtered and distilled to give 804 grams of C17 saturated vinylidene alcohols, b.p. 155C to 157C
at 3.0 mm. me vinylidene alcohol product contained greater than 90 wt. % 3-hexylundecanol.
EXAMPLE X
A l,000-gram sample of Clg ungaturated vinylitene alcohol that was prepared in previous Example V was hydrogenated over a nickel-copper-chromium hydrogenation catalyst at 153C to 165C at 725 to 1,100 psig. The hydrogenated material was distilled to give 839 grams of Clg saturated vinylidene alcohols, b.p. 156C to 161C
at 0.7 mm. The vinylidene alcohol product was over 95 wt. % of a mixture of 3-hexyltridecanol and 3-octylundecanol.
EXAMPLE XI
This example, as well as Examples XII through XVI, demon-strates the preparation of our vinylitene alcohols by way of the hydroformylation process. The vinylidene alcohol compositions pro-duced corresponded to the above Formulas I through IV.
A 1,400-ml rocking autoclave was charged with 500 grams of Clo vinylidene olefin fraction comprising a 50:50 wt. % mixture of 2-ethyl-1-octene and 2-butyl-1-hexene, 17 grams of a cobalt octoate solution ~12 wt. % cobalt), and 14 grams of tributylphosphine. The reaction mixture was contacted with a 1:1 mixture of hydrogen and carbon monoxide at 180C to 187C and 1,500 to 3,000 psig for four hours. The reactor effluent was distilled to give 219 grams of a mixture of Cll aldehyde and Cll vinylidene alcohol, b.p. 105C to 125C at 15 mm. A portion of the mixture, i.e., the Cll oxo product, was hydrogenated over a reduced cobalt catalyst at 160C at 1,000 to 1,300 psig for one hour. The reaction mixture was filtered and dis-tilled to provide 156 grams of Cll primary vinylidene alcohol, b.p.
of 112C to 117C at 10 mm.
EXAMPLE XII
A 1,400-ml rocking autoclave was charged with 400 grams of a C12 vinylidene olefin comprising 2-butyl-1-octene, 7 grams of a ... .
1~49i~46 solution of cobalt linoresinate (6 wt. % cobalt) and 10 grams of tris(nonylphenyl)phosphate. The autoclave was fluched with synthesis gas (1:1 weight mixture of hydrogen and carbon monoxide) and heated to 160C. Synthesis gas was introduced at a constant pressure of 3,000 psig and the temperature held at 160C for one hour. The reactor effluent was flashed in a wiped film evaporator at 220C and 1.5 mm pressure to give 401 grams overhead material and 53 grams bottoms.
The overhead fraction was hydrogenated over a reduced cobalt catalyst at 180C at 400 to 1,000 psig hydrogen pressure.
Distillation of 340 grams of the hydrogenated material provided 242 grams of C13 vinylidene primary alcohols, b.p. 120C to 130C at 5 mm. About 53 wt. % of the vinylidene alcohols confonmed to Formula I
e.g., 3-butyl-1-nonanol, and the remainder was a mixture of alcohols corresponding to Formulas II to IV.
EXAMPLE XIII
A mixture of 50 wt. % 2-butyl-1-octene, 25 wt. % 2-butyl-l-decene and 25 wt. % 2-hexyl-1-octene containing 0.1 wt. % cobalt (as cobalt linoresinate) and 1.5 mols tris(nonylphenyl)phosphate per gram atom of cobalt was fed to a continuous tubular reactor with an excess of 1:1 mixture of hydrogen and carbon monoxide. me reaction was conducted at a temperature in the range of 140C to 160C at 3,000 psig and at a liquid hourly space velocity of 1 gram/hour/ml.
The reactor effluent was passed through a wiped film evaporator to separate the unreacted olefins and product aldehydes and alcohols as overhead material from the catalyst.
me flashed material was hydrogenated in a continuous fixed bed reactor over a reduced cobalt catalyst at 1,500 psig, and 165C
to 190C temperature and at a liquid hourly space velocity of .
10490461 gram/hour/ml. Distillation of the hydrogenation reactor effluent provided C13 primary vinylidene alcohols, b.p. 125C at 5 mm and C15 primary vinylidene alcohols, b.p. 150C to 157C at 5 mm. The C13 alcohols were essentially identical to those produced in Example XII.
The product boiling at 150C to 157C was a mixture of isomers of Cls primary vinylidene alcohols as representatively shown in Formulas I to IV as demonstrated by chromatographic, spectral and wet analysis methods.
EXAMPLE XIV
A 1,400-ml rocking autoclave was charged with 500 grams of C16 vinylidene olefin comprising 2-hexyl-1-decene and 75 grams of a heptane solution of cobalt octacarbonyl containing 3.6 grams cobalt.
This mixture was treated with synthesis gas, as in the previous ex-amples, at 130C to 133C and 2,000 to 3,000 psig for 2.5 hours. The reactor effluent was decobalted by stirring with 300 ml of an aqueous solution containing 7 wt. % acetic acid and 3 wt. % sodium acetate ^for one hour at 60C to 65C. The mixture was cooled and the aqueous layer separated to give 596 grams material. The recovered material was hydrogenated over a cobalt catalyst at 160C to 190C and 200 to 2,000 psig for 75 minutes. me catalyst was removed by filtration and the product distilled to provide 349 grams of C17 primary vinyli-dene alcohol, b.p. 150C to 170C at 3 to 4 mm.
EXAMPLE XV
A 1,400-ml rocking autoclave was charged with 530 grams of a 50:50 weight mixture of a Clg vinylidene olefin fraction comprising 2-hexyl-1-dodecene and 2-octyl-1-decene, and 12 grams of a rhodium heptanoate solution containing 3 wt. % rhodium. m is solution was - treated with a 1:1 mixture of hydrogen and carbon monoxide at 124C
to 130C and 750 to 3,000 psig for two hours. me autoclave was ~ 049046 cooled and vented and 50 grams of a reduced cobalt hydrogenation catalyst was added. The reaction mixture was treated with hydrogen at 160C and 975 to 1,300 psig for 3.25 hours. The reactor effluent was filtered and distilled to provide 442 grams of Clg primary vinyli-tene alcohols, b.p. 153C to 158C at 1 mm.
EXAMPLE XVI
A 1,400-ml rocking autoclave was charged with 500 grams of a C20 vinylidene olefin comprising 2-octyl-1-dodecene and 75 grams of cobalt octacarbonyl solution in heptane containing 3.6 grams of cobalt. This mixture was contacted with synthesis gas as in the previous examples at 130C to 140C and 1,200 to 3,000 psig for three hours. The autoclave was cooled and vented and 40 grams of a reduced cobalt hydrogenation catalyst was added. This mixture was treated with hydrogen at 170C and 1,375 to 2,000 psig for 1.5 hours. The reactor effluent was filtered and distilled to give 224 grams of C
primary vinylidene alcohol, b.p. 168C to 172C at 0.3 to 0.5 mm.
EXAMPLE XVII
In a stainless steel autoclave was placed 100 grams of C13 primary vinylidene alcohol prepared as in Example XIII. The olefin feed for the vinylidene alcohol preparation was made using a vinyli-dene olefin product prepared from hexene-l dimerization. Flaked potassium hydroxide (0.5 gram) was added, and the contents of the autoclave were heated to 140C. Ethylene oxide was added at such a rate that the pressure was maintained at about 50 psig and the~p~-ture at about 140C. When 220 grams of ethylene oxide had been added the catalyst was neutralized with 0.54 gram of oxalic acid. Filter aid was added and the product filtered to provide a vinylidenealcoho¦
ethoxylate having a cloud point of 62C and a pour point of 16C.
. : ., . ... . ... ~ - ..
. .: . ~: : . . . , ~
- .
- ~
A small amount of this product was poured into water at approximately 25C and the vinylidene alcohol ethoxylate dissolved readily without forming a gel. Contrarily, an ethoxylate made from a C13 alcohol prepared by the hydroformylation of dodecene-l gelled immediately when added to water and was dissolved only with great difficulty.
EXAMPLE XVIII
The novel vinylidene alcohols of this invention are herein further compared with corresponding prior art alcohols. Type A
primary vinylidene alcohols represent those vinylidene alcohols pre-pared according to Examples I through V. Type B primary vinylidene alcohols represent those vinylidene alcohols prepared according to Examples VI through X. Type C primary vinylidene alcohols represent those prepared by Examples XI through XVI. Type D prior art primary alcohols are those oxo alcohols made from the hydroformylation of linear alpha-olefins. Type E prior art primary alcohols represent those normal primary alcohols prepàred from trialkylaluminum.
Certain novel and unique characteristics of our primary vinylidene alcohols are demonstrated by the following data reported in Table 1. It is evident that with the sole exception of the C
vinylidene alcohol prepared by the hydroformylation of 2-octyl-1-dodecene our vinylidene alcohols do not freeze above -50C. It is particularly noteworthy and surprising that our vinylidene alcohols exhibit significantly lower freezing points than the prior art alcohols that contain 2-monoalkyl branching.
.
~3~
o o o o ~.c o o o o o ~ o ,~ o ~ ~ ~ o ~ ~ o ~ oo _I N ~ t~ ~ u~ 1/'l u~
~ _~
¢ O
o ~0 U o oO ~ ~~ u~
~¢
X
O S
~-_~ o oO o O
P Qu~
rl .C I ~ V
~ ~ 8 v V v \/ v ,~, ~~ o¢ ~3 ~ ~ ~ q, z c~ 3 8 P.
_~ U~
3~ 1 o oo o oo o 3a~
~ ~ 9~ U~
v J V V j ~ !! A
¢ o oO o o ;; ~ E
~ ~ V v v v v 8 :, 3~ 8 8 8 ".
Z~
... . .
`.. , ,, . . . . :, '; ` .,. ~. . : ,, :
,, ~ ~ . , EXAMPLE XIX
The novel vinylidene alcohols of this invention are herein compared to the prior art liquid primary alcohols, e.g., tridecyl alcohol prepared by the hydroformylation of propylene tetramer.
Contrary to expectations from the known teachings, the data reported in Table 2 clearly demonstrate the biodegradability of our vinyli-dene alcohols.
The tests were run in a Hach Manometric BOD apparatus, Model 2173. Each test used 100 mg of the subject alcohol and 157 ml of BOD dilution water containing 10% or 20% by volume of bacterial seed. The bacterial seed was either raw domestic sewage from a sew-age treatment plant which had been settled for 24 hours at 20C and filtered through glass wool or an acclimated seed. The acclimated bacterial seed was obtained by aerating raw sewage with daily settl-ing and siphoning off of two-thirds of the liquid and feed increas-ing increments of test alcohols along with fresh sewage for a one-week period.
1~)49046 a~ o~ c~
C~ OD C~ ¢
I
,, ~ P- .
~ ~ ~ ,, ¢ _, C~
:
~ ~ .
,_ .,, g ~ ~
u~ ~n ~ oo o ~ :: ~
~ ~ U~
~ 5~ o ~
~ ~ _i C ~
z ~ s~
, 0 ~ ~ z ~ 9 ~ o ~ ~o c~
~ ~ ~ CJ ~ ~ 0~
~ O ~ 0 ID ~ ~ ~
~ ¢ C~ ¢ ~ ¢ E~ ,5 ~ C~
~ ,, 3 ~ .
zl ~ ,~ c 3 C _, 0 D U~
_ ___ EXAMPLE XX
Using the procedure of Example XVII, many different carbon numbered alcohols from Cll to C21 were converted to ethylene oxite adducts. The alcohols were made from the vinylidene olefins either by the oxo reaction or by the formaldehyde addition process. The vinylidene alcohols from the formaldehyde reaction were employed both as the unsaturated alcohol or as the hydrogenated (saturated) alcohol where indicated. The e~hylene oxide adducts have been characterized by their cloud point of a one wt. % aqueous solution. The novel vinylidene alcohol ethoxylates of this invention are herein compared with corresponding prior art alcohol ethoxylates. As previously demonstrated in Example XVII, most of the prior art primary alcohol ethoxylates which are generally employed for surfactant application undergo gel formation when the nonionic ethoxylate is added to water.
Accordingly, aqueous solutions are prepared often with great diffi-culty. As previously stated the vinylidene alcohol ethoxylates of this invention show a significantly less tendency to form such gels.
mi8 example, therefore, demonstrates the comparative rapidity at which our vinylidene alcohol ethoxylates are dissolved in water at 25C. Obviously, the rate of solution in water at room temperature is important for many utilizations of the alcohol ethoxylates. This characteristic further permits convenient room temperature mixing, reacting, and the like.
This example was conducted by placing 60 ml of-deionized water at 25C in a 150 ml beaker in which a magnetic stirrer was employed. Ten drops of the liquid alcohol ethoxylate to be tested -~:
was rapidly added to the water while stirring the solution at a con-stant rate by means of the magnetic stirrer. An electric timer, trig~
gered when the first drop was added, measured the elapsed time for i~ . . ~ , , .`: . . :, "
1049046complete dissolution of the added surfactant. Three duplicate runs were made for each sample tested and the average elapsed time was calculated. These average times in seconds for the various alcohol ethoxylates are reported in Table 3.
, ~ .
Run Alcoho~ Carbon No. Cloud Point, C. Solution Time No. TYPe a) Alcohol Alcohol EthoxYlate _ Seconds 3 C 13 70 ao
In the present conventional oxo processes linear alpha-olefin feeds are used whereby a mixture of normal and 2-alkyl branched primary alcohols are produced. Because approximately 30 to 40 wt. %, and greater, of the alcohols have 2-alkyl branching, the conventional oxo alcohol method has been sub~ected to criticism.
More recently, however, efforts in improving the oxo process have resulted in oxo alcohols having congiderably less 2-alkyl branching.
U. S. patent Nos. 3,239,569 and 3,239,571 illustrate such facts.
It has been reported, such as by the Stanford Research Institute, Linear Hi~her Alcohols, Report No. 27, August 1967, at pages 3 and 133, that these more recent oxo alcohols having sub-stantially less 2-alkyl branching are biodegradable because of the occurrence of branching at the favorable 2-position, which type of branching has only a relatively small detrimental effect on the bio-degratability of its derivatives. It is evident, therefore, from the above-stated art that branched alcohols for surfactant production are to be otherwise avoided.
Other alcohol types have also been produced by the oxida-tion of normal paraffins but, unlike those alcohols produced by the ethylene polymerization process and those generally derived from natural origins, are secondary alcohols. The secondary alcohols, unlike the corresponding primary alcohols, in some surfactant appli-cations, such as in the sulfated alcohol area, do not demonstrate the same desired properties. The secondary alcohols have other reported disadvantages.
As will be hereinafter re fully presented, the known alcohols or their surfactant derivatives, lack in varying degrees _4--some of the heretofore detailed criteria that govern the overall suitability and/or acceptability of the alcohol and/or its surfactant derivatîves.
Accordingly, the heretofore known alcohols do not generally exist in a convenient liquid state and, except for those alcohols below undecanol, and the highly branched alcohols, such as prepared from propylene and butylene trimers, tetramers, and the like, they can be generally character-ized as solid or relatively solid materials at or near room temperature.
The latter named branched alcohols are unsuitable for surfactant application because of their resistence to biodegradation.
It is clearly evident that there is a definite and acute need for higher molecular weight alcohols that are liquid at room temperatures, biodegradable and able to meet the basic standards that regulate whether the useful attributes of the alcohol and its surfactant derivatives can be fully utilized.
Surprisingly, such alcohol compositions have now been discovered.
- We have fortuitously found novel alcohol compositions that are not only biodegradable but exist at room temperature in the liquid state. Accord-ingly, our novel alcohol compositions, when compared to the biodegradable prior art alcohols, possess freezing point (melting point) values far below anything heretofore known. Our alcohol compositions, in addition to being easily facilitated in a variety of applications, have effectively broadened the molecular weight range of surfactant suitable alcohols.
According to the present invention, there is provided a vinylidene alcohol composition indicating compounds of the formula:
,1 R2 C,--~CH2)Z (OC2H4)~1oH
(CH2)y wherein Rl is hydrogen, methyl, or a double bond with R2, R2 represents CH3(CH2)x- or R"-CH=, in which X is a integer from O to 17 and R" is a linear alkyl radical containing at least one carbon atom, ,~ ~
D ~ 5 c ~
~ ~ j . .. . .-........ .
.
y is a number from O to 17 and the sum of X and Y is an integer in the range 6 to 17, W is an integer in the range of 7 to 15, Z is an integer in the range of 1 to 18, with the proviso that when Rl is hydrogen, Z is an integer of 2 to 17.
Further, the novel biodegradable ethoxylated derivatives of our unusual alcohols possess distinguishingly unique characteristics. For instance, the ethoxylates of our alcohols are products having excellent detersive and surfactant activity over a broader molecular weight range of the alcohol. Comparison of our ethoxylated -5a--: .
: , ~ 049046 alcohols with other prior art biodegradable ethoxylateg is accurately and representatively portrayed at similar cloud polnts, the cloud point being the temperature at which a one wt. % aqueous solution of the surfactant turns from clear to cloudy as the temperature of the solution i9 raised. The particular cloud point of the surfac-tant is very important and the surfactant must obviously meet the cloud point specifications of the practitioner if the surfactant is to be commercially acceptable. For most general applications cloud point specifications are preferably between 55C and 65C. Recog-nizably, some specialized applications require a somewhat highercloud point.
The synthetic alcohol ethoxylate derivatives of this inven-tion exhibit outstanding qualities within said specifications.
Therefore, when a comparison is made of our synthetic alcohol ethoxy-- late compositions with the related alcohol derived products now in the art, our compositions demonstrate superior wetting ability and much faster rates of water solubility. Perhaps most exciting is the fact that our herein defined alcohol derived surfactant compositions have a reduced tendency to gel in water at room temperature, a con- -dition that has plagued the ethoxylates of the Ziegler and oxo-type alcohols previously mentioned. A further surprising advantage is that certain of our alcohol ethoxylate compositions are synergistic in wetting ability.
Therefore, in accordance with our invention, novel vinyli-dene alcohol compositions are provided which can be representatively depicted by the following Formulas I to V:
Formula I
CH3(cH2)x-cH(cH2)ycH3 , .
~ 049046 wherein, individually, x and y are numbers from 1 to 15 and the sum of x and y is in the range of 6 to 16.
Formula II
CH3(CH2)U-lc-(cH2)v C 3 wherein, individually, u and v are numbers from 0 to 16 and the sum of u and v is in the range of 6 to 16.
Formula III
CH3(CH2)n~CH(cH2)mcH2oH
wherein n is a number from 0 to 17, m is a number from 2 to 17 and the sum or n and m is in the range of 7 to 17.
Formula IV
fH3 CH3(CH2)r-CH-(cH2) 8 -1CH(CH2)t CH3 wherein, individually, r, 9 and t are numbers from 0 to 15 and the sum of r, s and t is in the range of 5 to 15.
Fonmula V
R"-CH - C-CH2CH2OH
R"' wherein, indivitually, R" is a linear alkyl radical containing at least one carbon atom ant R"' i9 a linear alkyl radical containing at least 2 carbon atoms and wherein the total carbon atoms of R"
and R"' are in the range of 7 to 17.
The alcohols of this invention are employed to provide novel alcohol ethoxylates by conventional ethoxylation processes and can be representatively depicted as follows:
1049()46 Fo mula VI
R''''-(OC2H4)W-OH
wherein R"" is an alkyl radical which corresponds to the alkyl portion of the above-represented vinylidene alcohols.
It should be noted that our novel compositions have been herein referred to as vinylidene alcohols and vinylidene ethoxylates.
The term "vinylidene" has been employed for convenience to describe our compositions because vinylidene olefins have herein been employed to provide these novel compositions. Accordingly, "vinylidene olefins" herein referred to are those corresponding to the following representative formula:
Formula VII
R-C = CH2 R' wherein R and R' are linear alkyl radicals having a total of 8 to 18 carbon atoms and wheréin R and R' taken individually represent a C2 to C14 alkyl radical, preferably a C4 to C10 alkyl radical.
Therefore, the term "vinylidene alcohol" as used through-out the specification and/or claim designates those alcohols rep-resented by Formulas I to V herein and, correspondingly, the term"vinylidene ethoxylate" is used herein to designate those ethoxy-lates represented by Formula VI herein.
The vinylidene alcohols of this invention can be prepared by the hydroformylation of the vinylidene olefins (Formula VII), whereby said vinylidene olefins are reacted with carbon monoxide and hydrogen. Said vinylidene olefins can also be reacted with formalde-hyde or formaldehyde-yielding components to also provide our vinyli-dene alcohols. The vinylidene alcoholæ prepared by either the hydroformylation or formaldehyde addition reactions contain one more carbon atom than the olefin starting material.
.:
The unsaturated vinylidene alcohols represented by Formula V can be prepared by employing said vinylidene olefins in the stated formaldehyde addition reaction. For some unexplained reason, the vinylidene olefins used in our invention are unusually reactive with formaldehyde and formaldehyde-yielding components.
Further, the formaldehyde addition process is so selective that when the vinylidene olefins of this invention are utilized in this process, the primary alcohol product contains 90 to 100 wt. %, usually 95 wt. % and greater, of the novel compositions representet by Formula V.
These alcohols, being unsaturated, can be hydrogenated by conventional means to form vinylidene alcohols such as represented by Formula I.
Use of the stated hydroformylation process for preparing our novel compositions provides vinylidene alcohols represented by Formulas I through IV, any or all of which can be coproduced in varying amounts. For example, when using the oxo process typically about 25 to 90 wt. % of the vinylitene alcohols produced will be of the Formula I type.
Our novel compositions include, therefore, mixtures of vinylidene alcohols, or mixtures of the corresponding vinylidene ethoxylates, such as a mixture of those representatively depicted in Formulas I and II or a mixture of compounds represented by Formulas I, II, III and IV, and the like. As herein noted, the vinylidene alcohols will have one re carbon atom than did the vinylidene olefin from which they can be obtained. Accordingly, if ; a particular vinylidene olefin, such as a C14, is employed in the hydroformylation or formaldehyde addition reaction, a C15 alcohol which corresponds to one or more of the represented Formulas I
_g_ through V is produced. In like manner, where mixtures of olefins, such as a mixture of C14 and C16 olefins, are employed, mixtures of C15 and C17 vinylidene alcohols are protuced which correspond to one or more of the representative formulas.
Our inventive compositions, as herein depicted by repre-sentative formulations, include, therefore, mixtures of vinylidene alcohols or correspondingly vinylidene ethoxylates, such as a mixture~
of C12 and C13 alcohols as well as covering mixtures of alcohols, such as a mixture of C14 vinylidene alcohols represented by two or more of the above formulas.
It should also be noted that the above representative formulas of our vinylidene alcohols, and correspondingly our vinyli-dene ethoxylates, individually include various stereo isomers, or mixtures thereof, whenever asymmetrical carbon atom is present.
Included, therefore, in our invention are such isomeric forms of the compositions depicted.
The particular vinylidene alcohols represented by Formula I
are generally preferred because they are very representative, or - highly illustrative of, the many unusual and unexpected characteris-tics of our novel compositions.
As previously indicated the vinylidene ethoxylate~ (For-mula VI) of our invention comprise an alkyl portion, i.e., R"", which corresponds to the alkyl moiety of the vinylidene alcohols, such that R"" in the representative formula Formula VI
R""-(OC2H4)wOH
is an alkyl radical containing 11 to 21 carbon atoms and is selected from the following radicals (a) to (d):
- .... -. ' : . .
a) H
CH3(CH2)X-f-cH2cH2-(CH2)yCH3 whereln, individually, x and y are lntegers from 1 to 15 and the sum of x and y is in the range of 6 to 16;
b) fH3 CH3-(CH2)U-f-cH2 2 v wherein, individually, u and v are integers from 0 to 16 and the s~m of u and v is in the range of 6 to 16;
c ) ICH3 CH3(CH2)n-C-(cH2)m-cH2 wherein n is an integer from 0 to 17, m is an integer from 2 to 17 and the sum of n and m is in the range of 7 to 17;
d) fH3 H (IcH2)8 CH3-(cH2)r-f-(cH2)t-H-cH2 . CH3 wherein, individually, r, 8 and t are integers from 0 to 15 and the sum of r, 8 and t is in the range of 5 to 15; or R"" is an unsatu-rated alkyl radical represented as .. e) R"-CH = f-CH2-CH2-.. j .
wherein, individually, R" is a linear alkyl radical containing at ~t least one carbon atom and R~" is a linear alkyl radical containing at least 2 carbon atoms and wherein the total carbon atoms of R" and R~" are in the range of 7 to 17; and admixtures of (a) to (e), and wherein w is a number in the range of 7 to 15, preferably 7 to 12.
.
r.. . .. . .
1049~46 It i~ understood that when a plurality of ethylene oxide units are condensed with a vinylidene alcohol, or mixture of alco-hols, that various oxyethylene chain lengths will result. Accord-ingly, as used herein, the value of w is an average number indicat-ing the average number of oxyethylene units present.
In order to further characterize a particularly surprising aspect of our invention, we have included in the above-mentioned formula the subscript z. Therefore, z in the following formula Formula VIII
Rz"'-(OC2H4)wOH
represents a number corresponding to the number of the carbon atoms contained in the alkyl radical R"" and z is within the range of 11 to 15. For example, when z is 15 and w is 11 the vinylidene ethoxy-late represented is the ll-mol ethoxylate adduct of the vinylidene alcohol, pentadecanol.
In this regard, we have surprisingly found that if the value of the ratio of w to z, in this formula, i8 within the range .685 to .755 the vinylidene ethoxylates not only will demonstrate the preferred surfactant requisites discussed throughout the speci-fication but they will, unlike the primary alcohols of the Zieglerand oxo process of the prior art, possess the significant advantage of having the particular cloud points that satisfy the general speci-; fications of the industry.
; Another startling aspect is the discovery that when z is 13 and w is in the range of 9 to 10, i.e., the 9 to 10-mol ethoxy-late of our Cl3 vinylidene alcohol, the vinylidene ethoxylate demon-strates synergistic wetting ability with other alcohol ethoxylates and particularly enhances the activity of the stated prior art alcohol ethoxylates.
. .-. .. -- : . :
--' ~
.- . ~
1~49046 In accordance with our invention the vinylidene olefin starting materials, i.e., those repregented by Formula VII, can be prepared by a conventional process such as by dimerizing alpha-olefins, e.g., Alkyl-CH = CH2, mixtureg thereof, and the like. For example, a mixture of C6 to Clo alpha-olefins can be used. A suit-able process to produce vinylidene olefins is representatively des-cribed in U. S. patent No. 2,695,327. Typical vinylidene olefins are 2-hexyldecene-1, 2-octyldecene-1, 2-octyldodecene-1, ant the like.
The alpha-olefins can be provided via the conventional conversion of ethylene by a combined growth-displacement reaction using Ziegler-type polymerization catalysts such as the trialkyl-aluminums. The resultant olefin fraction can be separated and the particular olefin fraction desired can be recovered for vinylidene olefin preparation such as by dimerization.
The vinylidene olefins are most readily converted to our novel alcohols by way of the stated formaldehyde addition process or by the hydroformylation (oxo) process.
Process conditions typical to a conventional oxo reaction can be employed. The conditions can be varied over broad ranges according to the desires of the practitioner and dictates of the particular catalyst used. Generally, temperatures in the range of about 25C to 250C and pressures in the range of about 15 to 10,000 psig can be employed. Conventional catalysts and conditions known to enhance alcohol production selectively over aldehydes can be employed. Catalysts such as those derived from cobalt and rhodium which are usually complexes of hydrogen, carbon monoxide, with or without other ligands, are also suitable. Catalyst complexes con-taining amines, phosphines, phosphites, pentavalent phosphorus, arsenic and antimony compound8, halides, carboxylate anions, ant the like, are exemplary. Repregentative catalysts, conditions and recovery techniques are exemplarily described in U. S. patent Nos.
3,594,425; 3,239,566; 3,239,571; 3,420,898 and in Carbon Monoxide in Or~anic SYnthesis, Jurgen Falbe, Springer-Verlag, New York, 1970.
As previously stated, the formaldehyde addition process can also be employed. Thig procesg provides high selectivity and unexpectedly rapid and complete conversions of vinylidene olefins to our vinylidene alcohols. mis process can be employed without a catalyst when temperatures are sufficiently high such as around 200C
Acidic catalysts can be employed, if desired, Catalysts are ~r ~
if temperatures less than 200C are employed to give better reaction rates. Exemplary catalysts suitable are BF3 and complexes thereof, acetic acid, tin halides, such as stannic chloride, and the like.
Temperatures up to that where decomposition begins can be employed.
Generally, temperatures in the range of about 50C to 300C are used.
Generally, pressures sufficient to maintain an essentially liquid phase sre used. Exemplary conditions, and the like, are further des-cribed in U. S. patent Nos. 2,235,027; 2,624,766 and in An~ewandte Chemie. International Edition, H. M. R. Hoffmann, 8, S56 (1969).
The vinylidene alcohols of this invention can be converted to our vinylidene ethoxylates by way of typical alkoxylation proce-dures, such as wherein an alcohol and ethylene oxide are condensed in the presence of alkaline catalysts, such as alkali metal hydroxide alkali metal alcoholates or phenolates or metallic sodium and potas-sium, and the like. Sodium and potassi~n hydroxide are exemplary catalysts.
Other methods for preparing the alkyl polyoxyethylene adducts of our alcohols can be employed such as by the conversion . '. ' ' of the alcohol to the corresponding alkyl halide, e.g., alkyl bromide, by means of, e.g., PBr3, followed by reaction with the appropriate glycol, i.e., HO(c2H4O)xH
ROH+PBr3--~RBr Na ~ RO(c2H4O)xH
Another method i8 by the gtepwise reaction of the alcohol with ethyl-ene chlorohydrin.
The base catalyzed addition of ethylene oxide to the alcohol is the preferred method and it readily enables the control of the number of oxyethylene units added to the alcohol. Usually in this process temperatures in the range of about 100C to 350C are em-ployed. Generally, pressures sufficient to maintain an essentially liquid phase are used. One representative process is described in U. S. patent No. 3,436,426. It should be noted that the ethoxylates of this invention have an advantage over the secondary alcohol ethoxy-lates, previously mentioned, in that they can be easily prepared in a one-step ethoxylation process.
The foregoing discussion and description is further illus-trated by the following examples which depict various of our alcohol ethoxylate compositions and demonstrate many of the distinguishing aspects of this invention. The examples are not to be interpreted as a limitation on the scope of the foregoing discussion and description or on the materials therein employed. The compositions prepared in the following examples were verified by nuclear magnetic resonance, infrared, chromatographic and hydroxyl number analysis.
EXAMPLE I
This example, as well as Examples II through V, demonstrate preparation of our novel primary alcohol compositions such as those corresponding to Formula 5 hereinabove.
To a one-gallon autoclave was charged 2,060 grams of a Clo vinylidene olefin fraction comprising a 50:50 weight mixture of 2-ethyl-1-octene and 2-butyl-1-hexene and 230 grams of paraformalde-hyde. The autoclave was flushed with nitrogen and heated at 250C
for one hour. The reactor effluent was washed twice with water and distilled to provide 690 grams of vinylidene Cll alcohols, b.p. 119 to 127C at 20 mm. Referring to Formula V, about 50 wt. % of the product comprised a composition wherein R" is propyl and R"' is butyl.
About 50% of the product comprised a mixture of (a) wherein R" is 10 pentyl and R"' is ethyl and (b) wherein R" is methyl and R"' is hexyl.
Accordingly, almost 100 wt. % of the products comprised a mixture of 3-ethyl-non-3-enol, 3-hexyl-pent-3-enol, and 3-butylhept-3-enol.
EXAMPLE II
A one-liter stirred autoclave was charged with 340 grams of a C12 vinylidene olefin fraction comprising 2-butyl-1-octene and 32 grams paraformaldehyde. The reactor was flushed with nitrogen and heated at 275C for one hour. The effluent was washed with successive 200 ml portions of an aqueous solution of 0.5 wt. % sulfuric acid and 5 wt. % sodium bicarbonate. The washed effluent was dried over anhy-20 drous sodium sulfate, filtered, and distilled to give 95 grams ofproduct, b.p. 105C to 110C at 3 mm. Over 90 wt. % of the product was identified as 3-butylnon-3-enol, 3-pentyloct-3-enol and their formate esters.
EXA~LE III
A one-gallon stirred autoclave was charged with 1,960 grams of a C14 vinylidene olefin fraction comprising a 50:50 weight mixture of 2-butyl-1-decene and 2-hexyl-1-octene and 110 grams paraformalde-hyde. The autoclave was flushed with nitrogen and heated at 250C
for one hour. The effluent was washed with water and distilled to ~.
give 1,434 grams unreacted C14 olefins ant 421 grsms C15 alcohols,b.p. 135 to 140C at 5 mm. The products were about 95 wt. % of a 50:50 mixture of 3-hexylnon-3-enol and a mixture of 3-butylundec-3-enol and 3-octylhept-3-enol.
EXAMPLE IV
A one-liter stirred autoclave was charged with 450 grams of a C16 vinylidene olefin fraction comprising 2-hexyl-1-decene and 33 grams of paraformaldehyde. me autoclave was flushed with nitro-gen and heated at 250C to 252C for one hour. The effluent was washed once with 200 ml water and distilled to give 356 grams unre-acted olefin and 90 grams of product, b.p. 150C to 157C at 5 mm.
The product fraction was identified as over 95 wt. % of a mixture of 3-hexylundec-3-enol and 3-octylnon-3-enol.
EXAMPLE V
A three-gallon autoclave was charged with 6,048 grams of a C18 vinylitene olefin fraction comprising a 50:50 wt. % mixture of 2-octyl-1-decene and 2-hexyl-1-dodecene and 396 grams of paraformal-dehyde. The autoclave was flushed with nitrogen and heated at 250C
to 254C for 1.5 hours. The temperature was reduced to 200C and 400 ml water was in~ected into the autoclave. The temperature was maintained at 185C to 190C for one hour. The reactor effluent was washed twice with water and distilled to give 1,585 grams Clg alco~ols b.p. 153C to 159C at 0.5-0.7 mm. me product alcohol comprised about 50 wt. % of 3-decylnon-3-enol and about 50 wt. % of a mixture of 3-octylundec-3-enol and 3-hexyltridec-3-enol EXAMPLE VI
This example, as well as Examples VII through X demonstrate the hydrogenation of unsaturated vinylidene alcohols to provide satu-rated alcohols corresponding pr;dominantly to the alcohols of , ~ .
;1~49046 Formula I. The unsaturated Cll vinylidene alcohols produced in Example I, above, were hydrogenated over a nickel-copper-chromium hydrogenation catalyst at 154C to 165C and 700 to 1,800 psig. Dis-tillation of the filtered effluent gave 353 grams of a saturated C
alcohol, b.p. 114C to 116C at 10 mm. The primary alcohol product was essentially a 100 wt. % mixture of 3-ethylnonanol and 3-butyl-heptanol.
EXAMPLE VII
A 400-ml sample of C13 unsaturated vinylidene alcohols pre-pared as in Example II was hydrogenated over a reduced nickel catalyst at 158C to 163C at 1,175 to 2,100 psig. me reactor effluent was filtered and a portion of it distilled to give 311 grams of C13 satu-rated vinylidene alcohols, b.p. 135C to 138C at 8 mm. The vinyli-dene alcohol was essentially 100 wt. % 3-butylnonanol.
EXAMPLE VIII
A 1,300-gram sample of unsaturated Cls vinylidene alcohol, prepared as in Example III, was hydrogenated over a nickel-copper-chromium hydrogenation catalyst at 138C to 164C at 650 to 1,050 psig. me hydrogenated material was distilled to give 1,240 grams of Cls vinylidene alcohols, b.p. 117C to 121C at 0.35 to 0.60 mm.
The saturated vinylidene alcohols were a mixture of 3-butylundecanol and 3-hexylnonanol.
EXAMPLE IX
A 920-gram sample of unsaturated C17 vinylidene alcohol, prepared as in Example IV, was hydrogenated over a nickel-copper-chromium hydrogenation catalyst at 163C to 173C at 550 to 1,100 psig. me hydrogenation effluent wa~ filtered and distilled to give 804 grams of C17 saturated vinylidene alcohols, b.p. 155C to 157C
at 3.0 mm. me vinylidene alcohol product contained greater than 90 wt. % 3-hexylundecanol.
EXAMPLE X
A l,000-gram sample of Clg ungaturated vinylitene alcohol that was prepared in previous Example V was hydrogenated over a nickel-copper-chromium hydrogenation catalyst at 153C to 165C at 725 to 1,100 psig. The hydrogenated material was distilled to give 839 grams of Clg saturated vinylidene alcohols, b.p. 156C to 161C
at 0.7 mm. The vinylidene alcohol product was over 95 wt. % of a mixture of 3-hexyltridecanol and 3-octylundecanol.
EXAMPLE XI
This example, as well as Examples XII through XVI, demon-strates the preparation of our vinylitene alcohols by way of the hydroformylation process. The vinylidene alcohol compositions pro-duced corresponded to the above Formulas I through IV.
A 1,400-ml rocking autoclave was charged with 500 grams of Clo vinylidene olefin fraction comprising a 50:50 wt. % mixture of 2-ethyl-1-octene and 2-butyl-1-hexene, 17 grams of a cobalt octoate solution ~12 wt. % cobalt), and 14 grams of tributylphosphine. The reaction mixture was contacted with a 1:1 mixture of hydrogen and carbon monoxide at 180C to 187C and 1,500 to 3,000 psig for four hours. The reactor effluent was distilled to give 219 grams of a mixture of Cll aldehyde and Cll vinylidene alcohol, b.p. 105C to 125C at 15 mm. A portion of the mixture, i.e., the Cll oxo product, was hydrogenated over a reduced cobalt catalyst at 160C at 1,000 to 1,300 psig for one hour. The reaction mixture was filtered and dis-tilled to provide 156 grams of Cll primary vinylidene alcohol, b.p.
of 112C to 117C at 10 mm.
EXAMPLE XII
A 1,400-ml rocking autoclave was charged with 400 grams of a C12 vinylidene olefin comprising 2-butyl-1-octene, 7 grams of a ... .
1~49i~46 solution of cobalt linoresinate (6 wt. % cobalt) and 10 grams of tris(nonylphenyl)phosphate. The autoclave was fluched with synthesis gas (1:1 weight mixture of hydrogen and carbon monoxide) and heated to 160C. Synthesis gas was introduced at a constant pressure of 3,000 psig and the temperature held at 160C for one hour. The reactor effluent was flashed in a wiped film evaporator at 220C and 1.5 mm pressure to give 401 grams overhead material and 53 grams bottoms.
The overhead fraction was hydrogenated over a reduced cobalt catalyst at 180C at 400 to 1,000 psig hydrogen pressure.
Distillation of 340 grams of the hydrogenated material provided 242 grams of C13 vinylidene primary alcohols, b.p. 120C to 130C at 5 mm. About 53 wt. % of the vinylidene alcohols confonmed to Formula I
e.g., 3-butyl-1-nonanol, and the remainder was a mixture of alcohols corresponding to Formulas II to IV.
EXAMPLE XIII
A mixture of 50 wt. % 2-butyl-1-octene, 25 wt. % 2-butyl-l-decene and 25 wt. % 2-hexyl-1-octene containing 0.1 wt. % cobalt (as cobalt linoresinate) and 1.5 mols tris(nonylphenyl)phosphate per gram atom of cobalt was fed to a continuous tubular reactor with an excess of 1:1 mixture of hydrogen and carbon monoxide. me reaction was conducted at a temperature in the range of 140C to 160C at 3,000 psig and at a liquid hourly space velocity of 1 gram/hour/ml.
The reactor effluent was passed through a wiped film evaporator to separate the unreacted olefins and product aldehydes and alcohols as overhead material from the catalyst.
me flashed material was hydrogenated in a continuous fixed bed reactor over a reduced cobalt catalyst at 1,500 psig, and 165C
to 190C temperature and at a liquid hourly space velocity of .
10490461 gram/hour/ml. Distillation of the hydrogenation reactor effluent provided C13 primary vinylidene alcohols, b.p. 125C at 5 mm and C15 primary vinylidene alcohols, b.p. 150C to 157C at 5 mm. The C13 alcohols were essentially identical to those produced in Example XII.
The product boiling at 150C to 157C was a mixture of isomers of Cls primary vinylidene alcohols as representatively shown in Formulas I to IV as demonstrated by chromatographic, spectral and wet analysis methods.
EXAMPLE XIV
A 1,400-ml rocking autoclave was charged with 500 grams of C16 vinylidene olefin comprising 2-hexyl-1-decene and 75 grams of a heptane solution of cobalt octacarbonyl containing 3.6 grams cobalt.
This mixture was treated with synthesis gas, as in the previous ex-amples, at 130C to 133C and 2,000 to 3,000 psig for 2.5 hours. The reactor effluent was decobalted by stirring with 300 ml of an aqueous solution containing 7 wt. % acetic acid and 3 wt. % sodium acetate ^for one hour at 60C to 65C. The mixture was cooled and the aqueous layer separated to give 596 grams material. The recovered material was hydrogenated over a cobalt catalyst at 160C to 190C and 200 to 2,000 psig for 75 minutes. me catalyst was removed by filtration and the product distilled to provide 349 grams of C17 primary vinyli-dene alcohol, b.p. 150C to 170C at 3 to 4 mm.
EXAMPLE XV
A 1,400-ml rocking autoclave was charged with 530 grams of a 50:50 weight mixture of a Clg vinylidene olefin fraction comprising 2-hexyl-1-dodecene and 2-octyl-1-decene, and 12 grams of a rhodium heptanoate solution containing 3 wt. % rhodium. m is solution was - treated with a 1:1 mixture of hydrogen and carbon monoxide at 124C
to 130C and 750 to 3,000 psig for two hours. me autoclave was ~ 049046 cooled and vented and 50 grams of a reduced cobalt hydrogenation catalyst was added. The reaction mixture was treated with hydrogen at 160C and 975 to 1,300 psig for 3.25 hours. The reactor effluent was filtered and distilled to provide 442 grams of Clg primary vinyli-tene alcohols, b.p. 153C to 158C at 1 mm.
EXAMPLE XVI
A 1,400-ml rocking autoclave was charged with 500 grams of a C20 vinylidene olefin comprising 2-octyl-1-dodecene and 75 grams of cobalt octacarbonyl solution in heptane containing 3.6 grams of cobalt. This mixture was contacted with synthesis gas as in the previous examples at 130C to 140C and 1,200 to 3,000 psig for three hours. The autoclave was cooled and vented and 40 grams of a reduced cobalt hydrogenation catalyst was added. This mixture was treated with hydrogen at 170C and 1,375 to 2,000 psig for 1.5 hours. The reactor effluent was filtered and distilled to give 224 grams of C
primary vinylidene alcohol, b.p. 168C to 172C at 0.3 to 0.5 mm.
EXAMPLE XVII
In a stainless steel autoclave was placed 100 grams of C13 primary vinylidene alcohol prepared as in Example XIII. The olefin feed for the vinylidene alcohol preparation was made using a vinyli-dene olefin product prepared from hexene-l dimerization. Flaked potassium hydroxide (0.5 gram) was added, and the contents of the autoclave were heated to 140C. Ethylene oxide was added at such a rate that the pressure was maintained at about 50 psig and the~p~-ture at about 140C. When 220 grams of ethylene oxide had been added the catalyst was neutralized with 0.54 gram of oxalic acid. Filter aid was added and the product filtered to provide a vinylidenealcoho¦
ethoxylate having a cloud point of 62C and a pour point of 16C.
. : ., . ... . ... ~ - ..
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- ~
A small amount of this product was poured into water at approximately 25C and the vinylidene alcohol ethoxylate dissolved readily without forming a gel. Contrarily, an ethoxylate made from a C13 alcohol prepared by the hydroformylation of dodecene-l gelled immediately when added to water and was dissolved only with great difficulty.
EXAMPLE XVIII
The novel vinylidene alcohols of this invention are herein further compared with corresponding prior art alcohols. Type A
primary vinylidene alcohols represent those vinylidene alcohols pre-pared according to Examples I through V. Type B primary vinylidene alcohols represent those vinylidene alcohols prepared according to Examples VI through X. Type C primary vinylidene alcohols represent those prepared by Examples XI through XVI. Type D prior art primary alcohols are those oxo alcohols made from the hydroformylation of linear alpha-olefins. Type E prior art primary alcohols represent those normal primary alcohols prepàred from trialkylaluminum.
Certain novel and unique characteristics of our primary vinylidene alcohols are demonstrated by the following data reported in Table 1. It is evident that with the sole exception of the C
vinylidene alcohol prepared by the hydroformylation of 2-octyl-1-dodecene our vinylidene alcohols do not freeze above -50C. It is particularly noteworthy and surprising that our vinylidene alcohols exhibit significantly lower freezing points than the prior art alcohols that contain 2-monoalkyl branching.
.
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The novel vinylidene alcohols of this invention are herein compared to the prior art liquid primary alcohols, e.g., tridecyl alcohol prepared by the hydroformylation of propylene tetramer.
Contrary to expectations from the known teachings, the data reported in Table 2 clearly demonstrate the biodegradability of our vinyli-dene alcohols.
The tests were run in a Hach Manometric BOD apparatus, Model 2173. Each test used 100 mg of the subject alcohol and 157 ml of BOD dilution water containing 10% or 20% by volume of bacterial seed. The bacterial seed was either raw domestic sewage from a sew-age treatment plant which had been settled for 24 hours at 20C and filtered through glass wool or an acclimated seed. The acclimated bacterial seed was obtained by aerating raw sewage with daily settl-ing and siphoning off of two-thirds of the liquid and feed increas-ing increments of test alcohols along with fresh sewage for a one-week period.
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_ ___ EXAMPLE XX
Using the procedure of Example XVII, many different carbon numbered alcohols from Cll to C21 were converted to ethylene oxite adducts. The alcohols were made from the vinylidene olefins either by the oxo reaction or by the formaldehyde addition process. The vinylidene alcohols from the formaldehyde reaction were employed both as the unsaturated alcohol or as the hydrogenated (saturated) alcohol where indicated. The e~hylene oxide adducts have been characterized by their cloud point of a one wt. % aqueous solution. The novel vinylidene alcohol ethoxylates of this invention are herein compared with corresponding prior art alcohol ethoxylates. As previously demonstrated in Example XVII, most of the prior art primary alcohol ethoxylates which are generally employed for surfactant application undergo gel formation when the nonionic ethoxylate is added to water.
Accordingly, aqueous solutions are prepared often with great diffi-culty. As previously stated the vinylidene alcohol ethoxylates of this invention show a significantly less tendency to form such gels.
mi8 example, therefore, demonstrates the comparative rapidity at which our vinylidene alcohol ethoxylates are dissolved in water at 25C. Obviously, the rate of solution in water at room temperature is important for many utilizations of the alcohol ethoxylates. This characteristic further permits convenient room temperature mixing, reacting, and the like.
This example was conducted by placing 60 ml of-deionized water at 25C in a 150 ml beaker in which a magnetic stirrer was employed. Ten drops of the liquid alcohol ethoxylate to be tested -~:
was rapidly added to the water while stirring the solution at a con-stant rate by means of the magnetic stirrer. An electric timer, trig~
gered when the first drop was added, measured the elapsed time for i~ . . ~ , , .`: . . :, "
1049046complete dissolution of the added surfactant. Three duplicate runs were made for each sample tested and the average elapsed time was calculated. These average times in seconds for the various alcohol ethoxylates are reported in Table 3.
, ~ .
Run Alcoho~ Carbon No. Cloud Point, C. Solution Time No. TYPe a) Alcohol Alcohol EthoxYlate _ Seconds 3 C 13 70 ao
4 A 13 56 <10 6Tridecyl 13 39.5 30 7 D 15 53.5 400 11 D 17 52 > 400 12 B 17 51.3 60 13 D 11/13(b) 60 101 14 C 11/13(b) 61 70 D 13/15(C) 59 292 16 C 13/15(d) 50 28 17 C 13/15(d) 65 20 18 C 13/15(d) 88 131 19 ~ 11/13/15(e) 61 198 20D/C/C(f) 11/13/15(f) 63 ao 21D/D/C/C(g) 11/13/13/15(g) 49 19 22 D 12-15(h) 50 343 23 D 12-15(i) 90 175 24 D 12-13(~) 45 171 E 12-18(k) 59 298 26 E 12-14(1) 55 263 27 E 12(m) 62 > 400 (a) The alcohol composition is the same as that reported in Table 1.
(b) 25:75 wt. % mixture (c) 60:40 wt. % mixture (d) 57:43 wt. % mixture (e) 25:50:25 wt. % mixture (f) 40:40:20 wt. % mixture of Type E/C/C alcohol as reported in Table 1.
(g) 35:30:20:15 wt. % mixture of Type E/E/C/C/ alcohols as reported in Table 1. ~ `
(h) 20:30:30:20 wt. % mixture of C12- C13, C14, Cls oxo alcohols, e.g., NEODOL~ 25 (7-mol ethylene oxide adduct).
See footnote (2) Table 1.
-TABLE 3 (cont'd.) (i) Same as (h) except 12 mol ethylene oxide adduct.
(;) 6.5 Ethylene oxide adduct of NEODOL~ 23 alcohol (40:60 wt. % Cl2-cl3).
(k) Ethylene oxide adduct of ALFOL~ 1218 alcohol (40:30:20:10 wt. % Cl2~ C14, C16, C18)-(1) Ethylene oxide adduct of ALFOL~ 1214 alcohol (55:45 wt. %
C12-C14 ) -(m) Ethylene oxide adduct of ALFOL~ 12 alcohol.
.
.
It is evident from the data reported in Table 3 that the vinylidene ethoxylates of this invention, e.g., from alcohols of Type A, B and C, are vastly superior to the linear alcohol ethoxy-lates prepared from either Ziegler alcohols, e.g., Type E alcohols, or from alcohols prepared by the hydroformylation of alpha-olefins, e.g., Type D alcohols. The advantage of incorporating the vinyli-dene ethoxylates of this invention with prior art products is demon-strated in Runs 20 and 21. Comparison of Runs 3, 8 and 17 demon-strates that when the C13 vinylidene ethoxylate is incorporated with other vinylidene ethoxylates that the time to solution in seconds is much faster than would be predicted from the solution time in seconds of the individual components alone. The synergistic effects of the C13 vinylidene alcohol ethoxylates of this invention will be further demonstrated herein.
EXAMPLE XXI
The novel vinylidene alcohol ethoxylates of this invention are herein compared with corresponding prior art alcohols as to wet-tin8 times. The alcohol types are the same as reported in Example XVIII and Table 1. Wetting times are measured by the Draves method (American Association for Textile Chemists and Colorists), Method No. 17-1952, at 25C. The cloud point of the alcohol ethoxylates and the wetting time in seconds are reported in Table 4. The wetting times reported are for a 1.5 gm hook at 0.10 wt. % concentration.
The following data demonstratively show the clear superiority of the ` vinylidene alcohol ethoxylates of this invention over the linear primary alcohol ethoxylates of the prior art in wetting performance.
The data also effectively demonstrates the surprising superiority of the products of this invention over presently available commercial primary alcohol ethoxylates.
~.,,~ . .. .. .. . . . .. .
Run Alcohol Carbon No. Cloud Point, C Wetting Time, No. TYPe Alcohol Alcohol EthoxYlate Secont~
1 D 11 60 8.0 2 C 11 60 7.5 3 B 11 58.4 6.8 4 D 13 61 10.0 A 13 56 4.8 6 B 13 44 5.0 7 C 13 49 6.0 8 D 15 53.5 26 9 A 15 61 8.0 B 15 55 9.0 11 C 15 64 10.0 12 D 17 52 70 ~-C 17 51. 3 30 17 D 11/13(a) 57 10.5 18 D 13/15(b) 57.5 17.0 j 19 C 13/15(C) 65 9.8 D 11/13/15(d~ 59 14.0 21D/C/C(e) 11/13/15(e) 63 8.8 22D/D/C/C(f) 11/13/13/15(f) 49 8.0 23D(g) 12/13 45 7.8 24D(h) 12-15 71 21.8 25E(i) 12-18 59 26.7 26Secondar~
Alcohol ~) 60 8.3 . . , (a) 50:50 wt. X mixture (b) 65:35 wt. Z mixture (c) 57:43 wt. X mixture ` (d) 25:50:25 wt. % mixture (e) 40:40:20 wt. Z mixture (f) 35:30:20:15 wt. % mixture (g) Alcohol ~ame as reported footnote (~), Table 3.
(h) 9 mol ethylene oxide adduct of alcohol reported in ~ footnote (h), Table 3. 40 (i) Alcohol B~me as reported footnote (k), Table 3.
(~) TERGrTOL~ 15-S-9.
~ . . . . .
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EXAMPLE XXII
To further exemplify the nongelling tendencies of the vinylidene alcohol ethoxylates of this invention, the following runs are presented. The type of alcohol employed to prepare the various ethoxylates reported in Table 5 are the same as those previously reported in Example XVIII and Table 1. The indicated alcohol ethoxy-lates were admixed with water in the reported concentrations. The viscosity of the aqueous mixture was measured in centipoises on a Brookfield viscometer at 25C. The generally lower viscosities and the significant tendency of our compositions not to gel are clearly evident from the following data reported in Table 5. :
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EXAMPLE XXIII -~
The instant example de nstrates another significant aspect of our invention and further exemplifies the vast differences between our novel alcohol ethoxylates from those of the prior art.
As heretofore d~scussed, preferred vinylidene alcohol ethoxylates conform to the following formula:
R~ z-(0C2H4)wOH
wherein the ratio of w/z is in the range of .685 to .755 and w and z are as previously defined. Accordingly, vinylidene ethoxylate compositions corresponding to the above formula were compared to ethoxylates of various other prior art alcohols. Comparison with other vinylidene ethoxylates where the ratio of w/z is outside said range was also made. It is evident from the comparisons reported in Table 6 that only the vinylidene alcohol ethoxylates, as above represented, have a cloud point temperature within the heretofore described cloud point range of 55C to 65C. The importance of this particular cloud point range was hereinbefore discussed.
Accordingly, the ethoxylated Cll to C15 vinylidene alcohols~
of this invention which correspond to the above formula, wherein the ratio of w/z is in the range of about .685 to .755, demonstrate more rapid rate of solution in water, high detersive and surfactant pro-perties, and the like, and provide cloud points within the particu-larly desired range. Thus, our alcohols and ethoxylate compositions are clearly distinguishable over those heretofore known. The alcohol types reported in Table 6 are those heretofore referred to in Example~
XVIII and Table 1.
-- . .
, , Carbon No. Alcohol RatioCloud Point Alcohol TyPe (~ w w/z (C.
C ~1 8.2 .745 57 D 11 8.2 .745 74 C 11 9 .818 77 D 11 9 .818 82 C 13 9.8 .754 63 D 13 9.8 .754 80 C 13 10.6 .815 75 13 10.6 .815 87 C 15 10.6 .706 64 - D 15 10.6 .706 78 C 15 13 .866 87 C 15 13 .866 95 .,.. - ,- . .. - -. -- :
. , , .,. :
EXAMPLE XXIV
To further exemplify the significance of the cloud point ranges as presented in Example XXIII, the following table lists the wetting times of the vinylidene alcohol ethoxylates of this inventlon compared with alcohol ethoxylates of the prior art midway between said preferred range, i.e., at a 60C cloud point. The wetting times were performed according to the AATCC-17-1952, at 25C as con-ducted in Example XXI. The alcnhol types reported are the same as previously reported.
Run Alcohol Carbon No. Cloud Point, C Wetting Time, No. TYpe AlcoholEthoxylate Seconds : 1 D 11 60 9.4 2 C 11 60 8.5 4 C 13 60 8.4 EXAMPLE XXV
This example further demonstrates the superior wetting ability of our vinylidene alcohol ethoxylates. In particular, the following runs evidence the synergistic wetting ability of our pre-ferred composition, i.e., the 9 to 10 mol ethylene oxide adduct of our C13 vinylidene alcohols. Part 1 of Table 8 reports the wetting times of various prior art alcohols and of our inventive composit;ons -~
. .
~ 049046 at cloud points ranging from 50C to 70C. Part 2 of Table 8 reports the wetting times of various mixtures of alcohol ethoxylates as well as the wetting times that would be predicted from the wetting times of the individual components, alone, as reported in Part 1 of the table. The expected and actual wetting times for the various mix-tures are reported. The wetting time procedure and the type alcohols employed are those as previously reported. The following runsc~rly demonstrate that as little as 20 wt. % of our preferred 9 to 10 mol adduct of the C13 vinylidene alcohols enhance the wetting ability of related vinylidene alcohols and of the prior art alcohols synergisti-cally. A preferred composition, therefore, contains 20 to 90 wt. %
of the 9 to 10 mol adduct of the C13 vinylidene alcohol, the remain-der other vinylidene ethoxylates or 5 to 15 mol ethoxylate adducts of linear primary alcohols or mixture thereof containing about 11 to 18 carbon atoms in the alcohol (alkyl) moiety. The linear primary alcohol or mixture thereof includes herein such alcohols prepared by the hydroformylation of alpha-olefins which includes about 10 to 50 wt. % alcohols having 2-lower alkyl branching. At the various reported cloud points the mols of ethylene oxide employed with our C13 vinylidene alcohols are as follows: the 50C cloud point ethoxylate repre8ents an 8.5-mol adduct; the 55C a 9.1-mol adduct;
the 60C a 9.5-mol adduct; the 65C a 10-mol adduct; and the 70C a 10.2-mol adduct.
. .
. ' .
~049046 Part 1 Wetting Times, seconds Cloud Point, C. of Alcohol Ethoxylate Run Alcohol Carbon No.
No. Type Alcohol 50 55 60 65 70 _ 1 D 11 5.06.25 8.5 8.75 8.5 2 D 13 10 10.6 12 12.1 11.5 3 C 13 6.558.0 8 9.0 8.5 4 C 15 13.712.5 11.2 11.25 12.5 Part 2 Wetting Times. Seconds ______ExE~ted/Actual ~ime Cloud Point, 'C. of Alcohol Ethoxylate Run Alcohol Carbon No.
No. Type Alcohol 50 55 60 65 70 1 D 11/13 (a~ 10.1/11.3 2 C 13/15 (b) 9.4/ 9.3 3 D/C 11/15 (c) 9 /10 4 D/C 11/15 (d) 9.6/10.6 D/C 11/15 (e) 10.1/11.7 6 DtC 11/15 (f) 9.7/12.5 7 D/C 13 (g) 11.2/ 9.6 8 D/C 13 (h) 10.4/ 8.7 g D/C 13 (i) 9.6/ 9.4 D/C 13 (~) 9.0/ 8.1 11 D/C/C(k) 11/13/15(k) ~ i 8.84/8 _~7_ 19-3 12 ~tD/~C(l) 11/13~3/15(1) 8.11 8.84 9.76/9.3 10.18 10.0 8.1 8.7 10 ~ 5 (a) 54:46 wt.% mixture (b) 57:43 wt.% mixture (c) 80:20 wt.Z mixture (d) 60:40 wt.% mixture ; (e) 40:60 wt.% mixture (f) 20:80 wt.% mixture (g) 80:20 wt.% mixture (h) 60:40 wt.% mixture (i) 40:60 wt.% mixture (~) 20:80 wt.% mixture (k) 40:40:20 wt.X mixture (1) 35:30:20:15 wt.% mixture EXAMPLE XXVI
The alcohol ethoxylates of this invention were tested and compared for detersive performance against prior art material.
Generally, the prior art material and our compositions performed comparably. However, with the ethoxylates of the higher carbon alcohols, i.e., C17 and above, the compositions of this invention were decidedly superior. Ross Miles Foam Tests (ASTM D-1173-53) at .1% concentrations, conducted at 125F likewise demonstrated that our compositions were comparable with prior art materials.
The preceding examples can be repeated with similar success by substituting the generically and specifically described reactants and conditions of this invention for those employed in the preceding examples. Various modifications of this invention can be made or followed in light of this disclosure and the discussion herein set forth without departing from the spirit or the scope thereof.
.`
~ , ': ', '
(b) 25:75 wt. % mixture (c) 60:40 wt. % mixture (d) 57:43 wt. % mixture (e) 25:50:25 wt. % mixture (f) 40:40:20 wt. % mixture of Type E/C/C alcohol as reported in Table 1.
(g) 35:30:20:15 wt. % mixture of Type E/E/C/C/ alcohols as reported in Table 1. ~ `
(h) 20:30:30:20 wt. % mixture of C12- C13, C14, Cls oxo alcohols, e.g., NEODOL~ 25 (7-mol ethylene oxide adduct).
See footnote (2) Table 1.
-TABLE 3 (cont'd.) (i) Same as (h) except 12 mol ethylene oxide adduct.
(;) 6.5 Ethylene oxide adduct of NEODOL~ 23 alcohol (40:60 wt. % Cl2-cl3).
(k) Ethylene oxide adduct of ALFOL~ 1218 alcohol (40:30:20:10 wt. % Cl2~ C14, C16, C18)-(1) Ethylene oxide adduct of ALFOL~ 1214 alcohol (55:45 wt. %
C12-C14 ) -(m) Ethylene oxide adduct of ALFOL~ 12 alcohol.
.
.
It is evident from the data reported in Table 3 that the vinylidene ethoxylates of this invention, e.g., from alcohols of Type A, B and C, are vastly superior to the linear alcohol ethoxy-lates prepared from either Ziegler alcohols, e.g., Type E alcohols, or from alcohols prepared by the hydroformylation of alpha-olefins, e.g., Type D alcohols. The advantage of incorporating the vinyli-dene ethoxylates of this invention with prior art products is demon-strated in Runs 20 and 21. Comparison of Runs 3, 8 and 17 demon-strates that when the C13 vinylidene ethoxylate is incorporated with other vinylidene ethoxylates that the time to solution in seconds is much faster than would be predicted from the solution time in seconds of the individual components alone. The synergistic effects of the C13 vinylidene alcohol ethoxylates of this invention will be further demonstrated herein.
EXAMPLE XXI
The novel vinylidene alcohol ethoxylates of this invention are herein compared with corresponding prior art alcohols as to wet-tin8 times. The alcohol types are the same as reported in Example XVIII and Table 1. Wetting times are measured by the Draves method (American Association for Textile Chemists and Colorists), Method No. 17-1952, at 25C. The cloud point of the alcohol ethoxylates and the wetting time in seconds are reported in Table 4. The wetting times reported are for a 1.5 gm hook at 0.10 wt. % concentration.
The following data demonstratively show the clear superiority of the ` vinylidene alcohol ethoxylates of this invention over the linear primary alcohol ethoxylates of the prior art in wetting performance.
The data also effectively demonstrates the surprising superiority of the products of this invention over presently available commercial primary alcohol ethoxylates.
~.,,~ . .. .. .. . . . .. .
Run Alcohol Carbon No. Cloud Point, C Wetting Time, No. TYPe Alcohol Alcohol EthoxYlate Secont~
1 D 11 60 8.0 2 C 11 60 7.5 3 B 11 58.4 6.8 4 D 13 61 10.0 A 13 56 4.8 6 B 13 44 5.0 7 C 13 49 6.0 8 D 15 53.5 26 9 A 15 61 8.0 B 15 55 9.0 11 C 15 64 10.0 12 D 17 52 70 ~-C 17 51. 3 30 17 D 11/13(a) 57 10.5 18 D 13/15(b) 57.5 17.0 j 19 C 13/15(C) 65 9.8 D 11/13/15(d~ 59 14.0 21D/C/C(e) 11/13/15(e) 63 8.8 22D/D/C/C(f) 11/13/13/15(f) 49 8.0 23D(g) 12/13 45 7.8 24D(h) 12-15 71 21.8 25E(i) 12-18 59 26.7 26Secondar~
Alcohol ~) 60 8.3 . . , (a) 50:50 wt. X mixture (b) 65:35 wt. Z mixture (c) 57:43 wt. X mixture ` (d) 25:50:25 wt. % mixture (e) 40:40:20 wt. Z mixture (f) 35:30:20:15 wt. % mixture (g) Alcohol ~ame as reported footnote (~), Table 3.
(h) 9 mol ethylene oxide adduct of alcohol reported in ~ footnote (h), Table 3. 40 (i) Alcohol B~me as reported footnote (k), Table 3.
(~) TERGrTOL~ 15-S-9.
~ . . . . .
. ' ~ ' .
EXAMPLE XXII
To further exemplify the nongelling tendencies of the vinylidene alcohol ethoxylates of this invention, the following runs are presented. The type of alcohol employed to prepare the various ethoxylates reported in Table 5 are the same as those previously reported in Example XVIII and Table 1. The indicated alcohol ethoxy-lates were admixed with water in the reported concentrations. The viscosity of the aqueous mixture was measured in centipoises on a Brookfield viscometer at 25C. The generally lower viscosities and the significant tendency of our compositions not to gel are clearly evident from the following data reported in Table 5. :
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EXAMPLE XXIII -~
The instant example de nstrates another significant aspect of our invention and further exemplifies the vast differences between our novel alcohol ethoxylates from those of the prior art.
As heretofore d~scussed, preferred vinylidene alcohol ethoxylates conform to the following formula:
R~ z-(0C2H4)wOH
wherein the ratio of w/z is in the range of .685 to .755 and w and z are as previously defined. Accordingly, vinylidene ethoxylate compositions corresponding to the above formula were compared to ethoxylates of various other prior art alcohols. Comparison with other vinylidene ethoxylates where the ratio of w/z is outside said range was also made. It is evident from the comparisons reported in Table 6 that only the vinylidene alcohol ethoxylates, as above represented, have a cloud point temperature within the heretofore described cloud point range of 55C to 65C. The importance of this particular cloud point range was hereinbefore discussed.
Accordingly, the ethoxylated Cll to C15 vinylidene alcohols~
of this invention which correspond to the above formula, wherein the ratio of w/z is in the range of about .685 to .755, demonstrate more rapid rate of solution in water, high detersive and surfactant pro-perties, and the like, and provide cloud points within the particu-larly desired range. Thus, our alcohols and ethoxylate compositions are clearly distinguishable over those heretofore known. The alcohol types reported in Table 6 are those heretofore referred to in Example~
XVIII and Table 1.
-- . .
, , Carbon No. Alcohol RatioCloud Point Alcohol TyPe (~ w w/z (C.
C ~1 8.2 .745 57 D 11 8.2 .745 74 C 11 9 .818 77 D 11 9 .818 82 C 13 9.8 .754 63 D 13 9.8 .754 80 C 13 10.6 .815 75 13 10.6 .815 87 C 15 10.6 .706 64 - D 15 10.6 .706 78 C 15 13 .866 87 C 15 13 .866 95 .,.. - ,- . .. - -. -- :
. , , .,. :
EXAMPLE XXIV
To further exemplify the significance of the cloud point ranges as presented in Example XXIII, the following table lists the wetting times of the vinylidene alcohol ethoxylates of this inventlon compared with alcohol ethoxylates of the prior art midway between said preferred range, i.e., at a 60C cloud point. The wetting times were performed according to the AATCC-17-1952, at 25C as con-ducted in Example XXI. The alcnhol types reported are the same as previously reported.
Run Alcohol Carbon No. Cloud Point, C Wetting Time, No. TYpe AlcoholEthoxylate Seconds : 1 D 11 60 9.4 2 C 11 60 8.5 4 C 13 60 8.4 EXAMPLE XXV
This example further demonstrates the superior wetting ability of our vinylidene alcohol ethoxylates. In particular, the following runs evidence the synergistic wetting ability of our pre-ferred composition, i.e., the 9 to 10 mol ethylene oxide adduct of our C13 vinylidene alcohols. Part 1 of Table 8 reports the wetting times of various prior art alcohols and of our inventive composit;ons -~
. .
~ 049046 at cloud points ranging from 50C to 70C. Part 2 of Table 8 reports the wetting times of various mixtures of alcohol ethoxylates as well as the wetting times that would be predicted from the wetting times of the individual components, alone, as reported in Part 1 of the table. The expected and actual wetting times for the various mix-tures are reported. The wetting time procedure and the type alcohols employed are those as previously reported. The following runsc~rly demonstrate that as little as 20 wt. % of our preferred 9 to 10 mol adduct of the C13 vinylidene alcohols enhance the wetting ability of related vinylidene alcohols and of the prior art alcohols synergisti-cally. A preferred composition, therefore, contains 20 to 90 wt. %
of the 9 to 10 mol adduct of the C13 vinylidene alcohol, the remain-der other vinylidene ethoxylates or 5 to 15 mol ethoxylate adducts of linear primary alcohols or mixture thereof containing about 11 to 18 carbon atoms in the alcohol (alkyl) moiety. The linear primary alcohol or mixture thereof includes herein such alcohols prepared by the hydroformylation of alpha-olefins which includes about 10 to 50 wt. % alcohols having 2-lower alkyl branching. At the various reported cloud points the mols of ethylene oxide employed with our C13 vinylidene alcohols are as follows: the 50C cloud point ethoxylate repre8ents an 8.5-mol adduct; the 55C a 9.1-mol adduct;
the 60C a 9.5-mol adduct; the 65C a 10-mol adduct; and the 70C a 10.2-mol adduct.
. .
. ' .
~049046 Part 1 Wetting Times, seconds Cloud Point, C. of Alcohol Ethoxylate Run Alcohol Carbon No.
No. Type Alcohol 50 55 60 65 70 _ 1 D 11 5.06.25 8.5 8.75 8.5 2 D 13 10 10.6 12 12.1 11.5 3 C 13 6.558.0 8 9.0 8.5 4 C 15 13.712.5 11.2 11.25 12.5 Part 2 Wetting Times. Seconds ______ExE~ted/Actual ~ime Cloud Point, 'C. of Alcohol Ethoxylate Run Alcohol Carbon No.
No. Type Alcohol 50 55 60 65 70 1 D 11/13 (a~ 10.1/11.3 2 C 13/15 (b) 9.4/ 9.3 3 D/C 11/15 (c) 9 /10 4 D/C 11/15 (d) 9.6/10.6 D/C 11/15 (e) 10.1/11.7 6 DtC 11/15 (f) 9.7/12.5 7 D/C 13 (g) 11.2/ 9.6 8 D/C 13 (h) 10.4/ 8.7 g D/C 13 (i) 9.6/ 9.4 D/C 13 (~) 9.0/ 8.1 11 D/C/C(k) 11/13/15(k) ~ i 8.84/8 _~7_ 19-3 12 ~tD/~C(l) 11/13~3/15(1) 8.11 8.84 9.76/9.3 10.18 10.0 8.1 8.7 10 ~ 5 (a) 54:46 wt.% mixture (b) 57:43 wt.% mixture (c) 80:20 wt.Z mixture (d) 60:40 wt.% mixture ; (e) 40:60 wt.% mixture (f) 20:80 wt.% mixture (g) 80:20 wt.% mixture (h) 60:40 wt.% mixture (i) 40:60 wt.% mixture (~) 20:80 wt.% mixture (k) 40:40:20 wt.X mixture (1) 35:30:20:15 wt.% mixture EXAMPLE XXVI
The alcohol ethoxylates of this invention were tested and compared for detersive performance against prior art material.
Generally, the prior art material and our compositions performed comparably. However, with the ethoxylates of the higher carbon alcohols, i.e., C17 and above, the compositions of this invention were decidedly superior. Ross Miles Foam Tests (ASTM D-1173-53) at .1% concentrations, conducted at 125F likewise demonstrated that our compositions were comparable with prior art materials.
The preceding examples can be repeated with similar success by substituting the generically and specifically described reactants and conditions of this invention for those employed in the preceding examples. Various modifications of this invention can be made or followed in light of this disclosure and the discussion herein set forth without departing from the spirit or the scope thereof.
.`
~ , ': ', '
Claims (20)
PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A vinylidene alcohol composition indicating compounds of the formula:
wherein R1 is hydrogen, methyl, or a double bond with R2, R2 represents CH3(CH2)X- or R"-CH=, in which X is a integer from 0 to 17 and R" is a linear alkyl radical containing at least one carbon atom, y is a number from 0 to 17 and the sum of X and Y is an integer in the range 6 to 17, W is an integer in the range of 7 to 15 , Z is an integer in the range of 1 to 18, with the proviso that when R1 is hydrogen, Z is an integer of 2 to 17.
wherein R1 is hydrogen, methyl, or a double bond with R2, R2 represents CH3(CH2)X- or R"-CH=, in which X is a integer from 0 to 17 and R" is a linear alkyl radical containing at least one carbon atom, y is a number from 0 to 17 and the sum of X and Y is an integer in the range 6 to 17, W is an integer in the range of 7 to 15 , Z is an integer in the range of 1 to 18, with the proviso that when R1 is hydrogen, Z is an integer of 2 to 17.
2. A vinylidene alcohol ethoxylate composition according to claim 1 represented by the formula:
wherein, individually, x and y are integers from 1 to 15 and the sum of x and y is an integer in the range of 6 to 16 and wherein w is an integer in the range of 7 to 15.
wherein, individually, x and y are integers from 1 to 15 and the sum of x and y is an integer in the range of 6 to 16 and wherein w is an integer in the range of 7 to 15.
3. The composition of claim 2 wherein w is an integer in the range of 7 to 12.
4. The composition of claim 2 corresponding to the following formula:
R''''-(OC2H4)wOH
wherein R'''' is the alkyl radical as represented in claim 2 and having 11 to 15 carbon atoms, w is as previously defined and wherein the ratio of w to the number of carbon atoms in the R'''' radical is in the range of .685 to .755.
R''''-(OC2H4)wOH
wherein R'''' is the alkyl radical as represented in claim 2 and having 11 to 15 carbon atoms, w is as previously defined and wherein the ratio of w to the number of carbon atoms in the R'''' radical is in the range of .685 to .755.
5. The composition of claim 3 wherein w is an integer in the range of 9 to 10 and wherein the sum of x and y is the integer 8.
6. A composition comprising 20 to 90 wt. % of the composition of claim 5 and 80 to 10 wt. % of a 5 to 15 mol ethylene oxide adduct of a C11 to C18 linear primary alcohol.
7. A vinylidene alcohol ethoxylate composition according to claim 1 represented by the formula:
wherein, individually, u and v are integers from 0 to 16 and the sum of u and v is an integer in the range of 6 to 16 and wherein w is an integer in the range of 7 to 15.
wherein, individually, u and v are integers from 0 to 16 and the sum of u and v is an integer in the range of 6 to 16 and wherein w is an integer in the range of 7 to 15.
8. The composition of claim 7 wherein w is an integer in the range of 7 to 12.
9. The composition of claim 7 corresponding to the following formula:
R''''-(OCH2H4)wOH
wherein R'''' is the alkyl radical as represented in claim 7, and having 11 to 15 carbon atoms, w is as previously defined and wherein the ratio of w to the number of carbon atoms in the R'''' radical is in the range of .685 to .755.
R''''-(OCH2H4)wOH
wherein R'''' is the alkyl radical as represented in claim 7, and having 11 to 15 carbon atoms, w is as previously defined and wherein the ratio of w to the number of carbon atoms in the R'''' radical is in the range of .685 to .755.
10. The composition of claim 8 wherein w is an integer in the range of 9 to 10 and wherein the sum of u and v is the integer 8.
11. A composition comprising 20 to 90 wt. % of the composition of claim 10 and 80 to 10 wt. % of a 5 to 15 mol ethylene oxide adduct of a C11 to C18 linear primary alcohol.
12. A vinylidene alcohol ethoxylate composition according to claim 1 represented by the formula:
wherein n is an integer from 0 to 17, m is an integer from 2 to 17 and the sum of n and m is an integer in the range of 7 to 17 and wherein W is an integer in the range of 7 to 15.
wherein n is an integer from 0 to 17, m is an integer from 2 to 17 and the sum of n and m is an integer in the range of 7 to 17 and wherein W is an integer in the range of 7 to 15.
13. The composition of claim 12 wherein w is an integer in the range of 7 to 12.
14. The composition of claim 12 corresponding to the following formula:
R''''-(OC2H4)wOH
wherein R'''' is the alkyl radical as represented in claim 12 and having 11 to 15 carbon atoms, w is as previously defined and wherein the ratio of w to the number of carbon atoms in the R'''' radical is in the range of .685 to .755.
R''''-(OC2H4)wOH
wherein R'''' is the alkyl radical as represented in claim 12 and having 11 to 15 carbon atoms, w is as previously defined and wherein the ratio of w to the number of carbon atoms in the R'''' radical is in the range of .685 to .755.
15. The composition of claim 13 wherein w is an integer in the range of 9 to 10 and wherein the sum of n and m is the integer 9.
16. A composition comprising 20 to 90 wt. % of the composition of claim 15 and 80 to 10 wt. % of a 5 to 15 mol ethylene oxide adduct of a C11 to C18 linear primary alcohol.
17. A vinylidene alcohol ethoxylate composition according to claim 1 represented by the formula:
wherein, individually, R" is a linear alkyl radical containing at least one carbon atom and R''' is a linear alkyl radical containing at least two carbon atoms and wherein the total carbon atoms contained in R" and R''' is in the range of 7 to 17 carbon atoms.
wherein, individually, R" is a linear alkyl radical containing at least one carbon atom and R''' is a linear alkyl radical containing at least two carbon atoms and wherein the total carbon atoms contained in R" and R''' is in the range of 7 to 17 carbon atoms.
18. The composition of claim 17 wherein w is an integer in the range of 7 to 12.
19. The composition of claim 17 corresponding to the following formula R''''-(OC2H4)wOH
wherein R'''' is the unsaturated alkyl radical as represented in claim 17, and having 11 to 15 carbon atoms, w is as previously defined and wherein the ratio of w to the number of carbon atoms in the R'''' radical is in the range of .685 to .755.
wherein R'''' is the unsaturated alkyl radical as represented in claim 17, and having 11 to 15 carbon atoms, w is as previously defined and wherein the ratio of w to the number of carbon atoms in the R'''' radical is in the range of .685 to .755.
20. The composition of claim 18 wherein w is a number in the range of 9 to 10 and wherein the total carbon atoms contained in said R" and R''' radicals is 9.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US260545A US3887624A (en) | 1972-06-07 | 1972-06-07 | Vinylidene alcohol compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1049046A true CA1049046A (en) | 1979-02-20 |
Family
ID=22989598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA73170589A Expired CA1049046A (en) | 1972-06-07 | 1973-05-07 | Vinylidene alcohol compositions |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPS5136244B2 (en) |
| CA (1) | CA1049046A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6237074Y2 (en) * | 1979-04-23 | 1987-09-21 | ||
| TR199901159T2 (en) * | 1996-11-26 | 1999-08-23 | The Procter & Gamble Company | Polyoxyalkylen s�rfaktanlar�. |
| JP2005298443A (en) * | 2004-04-15 | 2005-10-27 | Idemitsu Kosan Co Ltd | Long-chain branched alcohol and its production method |
-
1973
- 1973-05-07 CA CA73170589A patent/CA1049046A/en not_active Expired
- 1973-06-07 JP JP6430873A patent/JPS5136244B2/ja not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS4954308A (en) | 1974-05-27 |
| JPS5136244B2 (en) | 1976-10-07 |
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