Title of Invention


Abstract The present invention relates to a process for preparing detersive surfactants derived from mid-to-near-mid-chain branched alcohols. Alpha-olefin"s are dimerised to form vinylidene olefin"s, which are then isomerised and reacted with CO/H2 under OXO conditions or reacted directly with CO/H2 under OXO conditions to give mid- to near-mid chain branched alcohols. These brached-chain alcohols are feedstock for the production of alkyl sulphate, alkyl ethoxy sulphate, and alkyl carboxylate surfactants and other surfactants.
The present invention relates to processes for manufacturing detersive surfactants, especially those containing branched-chain hydrophobic units.
Conventional detersive surfactants comprise molecules having a water-solubilizing substtlucnt (hydrophilic group) and an oleophilic subslitucnt (hydrophobic group), Such surfactants typically comprise hydrophilic groups such as carboxylate, sulfatc, sulfonate, amine oxide, polyoxyethylene, and the like, attached to an alkyl, alkenyl or alkaryl hydrophobe usually containing from about 10 to about 20 carbon atoms. Accordingly, the manufacturer of such surfactants must have access to a source of hydrophobe groups to which the desired hydrophile can be attached by chemical means. The earliest source of hydrophobe groups comprised the natural fats and oils, which were converted' into soaps (i.e., carboxylate hydrophile) by saponification with base. Coconut oil and palm oil are still used to manufacture soap, as weli as to manufacture the alkyl sulfate ("AS") class of surfactants. Other hydrophobes arc available from petrochemicals, including alkylated benzene which is used to manufacture alkyl benzene sulfonate surfactants ("LAS").
The literature asserts that certain branched hydrophobes can be used to advantage in the manufacture of alkyl sulfatc detersive surfactants; sec, for example, U.S. 3,480,556 to dcWitt, et al., November 25, 1969. However, it has been determined that the beta-branched surfactants described in the '556 patent arc inferior with respect to certain solubility parameters, as evidenced by their Krafft temperatures. It has further been determined that surfactants having branching towards the center of carbon chain of the hydrophobe have much lower Krafft temperatures. »Sec: "The Aqueous Phase Behavior of Surfactants", R.G. Laughlin, Academic Press, N.Y. (1994) p. 347. Accordingly, it has now been determined that such surfactants are preferred for use especially under cool or cold water washing conditions (e.g., 20°C-5oC).
One problem associated with the manufacture qf detersive surfactants having hydrophobe groups with mid- or near-mid chain branching is the lack of a ready source of such hydrophobes. By the present invention, a process is described for manufacturing such branched hydrophobes and converting them into mid- or near-mid chain branched surfactants.
The present invention encompasses a process for preparing mid- to near mid-chain branched olefins (primarily, methyl branched at or near the mid-chain region). Such materials are then vised as the basic feedstock which provides the hydrophobic portion of branched-chain detersive surfactants.
The process herein is illustrated by the following reaction sequence.
1) Alpha-Olefin Dimerization
(Formula Removed) and
(Formula Removed)
wherein R and R1 may be the same or different linear alkyl, and wherein R is C3-C7, preferably C5 to C7 linear alkyl, and R' is C3-C7, preferably C5-C7 linear alkyl. For use in preparing surfactants in cleaning products such as laundry detergents, dishwashing liquids, and the like, R and R' are preferably the same or within one or two carbon atoms of each other in chain length. Some linear olcfins may also result from the dimcrization and these can optionally be removed using molecular sieves. Step 1 of the process herein is designed to provide branched olcfins which preferably contain from about 12 to about 18 (avg.) total carbon atoms.
2) Alcohol Production
In Step 2 (Route A), the olcfin mixture for Step 1 can be pre-randomized to enhance the ultimate formation of alcohols (i) and (ii) in subsequent Step 3. Alternatively (Step 2, Route B), this pre-randomization step can be deleted and the Oxo catalyst, itself, can randomize the final product among the three possible terminal positions.
Route A
(i) (1)/(11) (Equation Removed)Random Internal Olefin Mixture (R10M)
(ii) RIOM (Equation Removed)Branched Alcohol Mixture
or l
Route D
(1)/(I1(Equation Removed) Branched Alcohol Mixture
Oxo Catalyst
The Oxo process to make alcohols is described in detail in Kirk-Othmer Encyclopedia of Chemical Technology. 4th Edition, Volume 1, pp. 903-8 (1991), Jacqueline I. Kroschwitz, Executive Editor, Wiley-Interscience, N.Y. The catalyst for this step is, for example, cobalt-carbon monoxide-organophosphine.
The alcohol mixture of Step (2) of the present process comprises branched-chain primary alcohol compounds of the following formulae for use in Step (3), below.
i) (Formula Removed)and
ii) (Formula Removed) and
minor amounts of
iii) (Formula Removed)
It is to be understood that when CH2OH is substituted on R or R' it is primarily on their respective terminal carbons or to a lesser extent on their penultimate carbons. Desirably, minimal amounts of compounds of the formula (iii) are present in Step
3) Surfactant Production
Branched Alcohol Mixture >• Branched Alkyl Sulfate
Advantageously, the present process results in no geminal branching, i.e., no "quaternary" carbon substitution. Steric hindrance will block inverse addition to vinylidene carbon with cobalt-carbon monoxide-organophosphine which otherwise would form a non-biodegradable quaternary carbon. Moreover, little (less than about 3%) vicinal branching occurs. Of course, some of the overall feedstock may remain unbranched. Typically, and preferably from the standpoint of cleaning performance and biodegradability, the present process provides hydrophobes with one near-central methyl in the case of isomers i) and ii).
All percentages, ratios and proportions herein are by weight, unless otherwise specified. All documents cited herein are, in relevant part, incorporated

herein by reference.
According to the present invention there is provided a process for preparing detersive surfactants derived from mid-to-near-mid-chain branched hydrophobic units, comprising the steps of:
(a) dimerizing alpha olefins of the formula RCH=CH2 and R'CH=CH2, to form olefins of
the formula in a conventional manner
(Formula Removed) and
(Formula Removed)
wherein in the above formulas R and R' may be the same or different C3 to C7 linear alkyl substituents
(b) followed by either isomerizing the olefins from Step (a) and the subsequent reaction of
said isomerized olefins with CO/H2 under Oxo conditions; or directly reacting the olefins
from Step (a) with CO/H2 under Oxo conditions;
to obtain the desired branched alcohols of the formula:
(Formula Removed) and (Formula Removed)
followed by either
(i) preparing branched alkyl sulphate surfactants by sulphating the alcohols;
(ii) preparing branched alkyl ethoxy sulphates, comprising first ethoxylating, then
sulphating, the alcohols;
or (iii) preparing branched alkyl carboxylate surfactants by oxidising the alcohols or
their aldehyde intermediates.
i) Olefin dimerization:
The present invention encompasses, in a process for preparing surfactant precursor hydrophobes from dimerization of two same or near same chain length alpha-olcfins to form a detergent range vinylidcnc olefin. These alpha olcfins C5 to C10, preferably C7 to C9 are dimerized to give C10 to C20, preferably C14 to C18 vinylidene olefins which upon Oxo reaction give C11 to C21, preferably C15 to C19 alcohols. There are a number of processes for accomplishing said dimerization; sec US Application 9,200,398, US 4,658,078, US 4,973,788; O. S. Vostrikova, A. G. Ibragimov, G. A. Tolslikov, L.M.Zelenova and U. M. Dzhemilev, Izv. Akad. Nauk ' SSSR, Ser. Khini, (1980), (10), 2330-2 [Chem. Abstr, 94:65032]; Jpn. Kokai Tokkyo Koho, 06228016 A2 [Chcm. Abstr. 122:186930]. 2) Alcohol Production Route A
part a) The carbon-carbon double bond of the vinylidcnc olefin is pre-isomerized using a method such as Shell uses to isomcrizc alpha-olefins in their SHOP process; sec Kirk-Otluner Eneyclopedia of Chemical Technology, 4th Edition, Volume ) 7, pp. 848-50 (1996), Jacqueline I. Kroschwitz, Executive Editor, Wiley-Interscience, N. Y. and Chemical Economics Handbook, pp. 681.5030K-L, Stanford Research Institute, Menlo Park, CA 94025, Oct. 1993.
part b) Oxo chemistry is used to convert the pre-isomerized vinylidene olefin (now largely internal olefin) to a primary alcohol mixture. For this an Oxo catalyst which isomerizes the double bond to alpha positions prior to carbonylation is desired as is the case using cobalt-carbonyl-phosphinc catalysts in the one step process, see Kirk-; Othmer Encyclopedia of Chemical Technology. 4th Edition, Volume 1, pp, 903-8 (1991). Route A, (that is including pre-isomerization) is undertaken to assure relatively high yields of alcohols i and ii versus alcohol iii. Note alcohol sulfatcs of i and ii are desired surfactants whereas that of iii may be deficient. Route B
This step utilizes the same Oxo catalyst on the vinylidene olefin directly without its pre-isomerization. This relics upon the catalyst to completely isomerize the carbon-carbon double bond of the vinylidene olefin prior to carbonylation, The object is to obtain as much i and ii relative to iii as is obtained in Route A.
Other fatty alcohol-derived surfactants can also be made, e.g., alkyl ethoxyl sulfatcs (AES), alkyl polyglucosides (APG), etc. Note that surfactants other than alcohol sulfates or AES may be made by oxidizing said alcohol or its aldehyde intermediate into a carboxylatc (i.e., a branched-chain soap). This soap can be an excellent surfactant and/or detergent builder in and of itself. This carboxylatc can also be used as a feedstock and converted to branched acyl-taurates, -isethionates, -
sarcosinates, -N-methylglucamide or other acyl-dcrivcd surfactants using art-disclosed techniques.
Branched-chain surfactants of the type resulting from the present process can be used in all manner of cleaning compositions. Such compositions include, but are not limited to: granular, bar-form and liquid laundry detergents; liquid hand dishwashing compositions; liquid, gel and bar-form personal cleansing products; shampoos; dentifrices; hard surface cleaners, and the like. Such compositions can contain a variety of conventional detersive ingredients. The following listing of such ingredients is for the convenience of the formulator, and not by way of limitation of the types of ingredients which can be used with the branched-chain surfactants herein.
The branched-chain surfactants herein can be used in combination with detergency builders, Such builders include, for example, 1-10 micrometer zeolite A, polycarboxylatc builders such as citrate, layered silicate builders such as "SKS-6" (Hoechsl) and phosphate materials, especially sodium tripolyphosphate ("STPP"). Most laundry detergents typically comprise at least about 1% builder, more typically from about 5% to about 80% builder or mixtures of builders,
Enzymes, such as proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof, can be employed in detergent compositions containing the branched-chain surfactants. Typical detergent compositions comprise from-about 0.001 % to about 5% of commercial enzymes.
Detergent compositions can also contain polymeric soil release agents (SRA's). Such materials include, for example, anionic, cationic and non-charged monomer units, especially polyester materials, Preferred materials of this type include oligomerie terephthalate esters, sulfonated substantially linear ester oligomers comprising a backbone of tcrcphthaloy] and oxyalkyleneoxy repeat units and phthalolyl-derived sulfonated terminal moieties. A variety of SRA's arc described, for example, in U.S. 4,968,451; 4,711,730; 4,721,580; 4,702,857; 4,877,896; 5,415,807; and in other literature references. Such soil release materials typically comprise from about 0.01% to about 10% of finished detergent compositions.
Detergent compositions may also optionally contain bleaching compositions comprising a bleaching agent and one or more bleach activators. If present, bleaching agents such as pcrcarbonate or perborate (especially perborate monohydratc "PBl") typically are used at levels from about 1% to about 30% of finished detergent compositions. Bleach activators such as nonanoyloxy-benzene
sulfonatc ("NOBS") and telraacetyl ethylcncdiamine ("TAED"), and mixtures thereof, can be vised to enhance the bleaching activity of materials such as pcrboralc and perearbonate. If present, the amount of bleach activator will typically be from about 0.1% to about 60% of a bleaching composition comprising a bleaching agent-plus-blcach activator. Other bleaching agents such as the so-called "photoactivated" bleaches (see U.S. 4,033,718) can also be used. Sulfonated zinc phthalocyanine is an especially preferred photoactivated bleaching agent.
Detergent compositions can also contain clay soil removal/antiredeposition agents such as ethoxylated tetraethylene pentamine; see U.S. 4,597,898, Such materials typically comprise from about 0.01% to aboul 10% of fully-formulated laundry detergents.
Detergent compositions can also contain from about 0.1% to about 7% of polymeric dispersing agents, which are especially useful in the presence of zeolite and/or layered silicate builders. Such materials are known in the art (see U.S. 3,308,067). Such materials include acrylate/malic-based copolymers, such as described in EP ) 93,360, as well as polyethylene glycol ("PEG").
Detergent compositions herein can also include various brighteners, dye transfer inhibiting agents (especially polymers of N-vinylpyrrolidone and N-vinylimidazole), suds suppressors (especially silicones), chelating agents such, as nitrilotriacetate, ethylenediamine disueeinate, and the like. Such materials will typically comprise from about 0.5% to about 10%, by weight, of fully-formulated cleaning compositions.
Moreover, it is to be understood that the branchcd-chain surfactants prepared in the manner of the present invention may be used singly in cleaning compositions or in combination with other detersive surfactants. Typically, fully-formulnted cleaning compositions will contain a mixture of surfactant types in order to obtain broad-scale cleaning performance over a variety of soils and stains and under a variety of usage conditions. One advantage of the branched-chain surfactants herein is their ability to be readily formulated in combination with other known surfactant types. Nonlimiting examples of additional surfactants which may be used herein typically at levels from about 1% to about 55%, by weight, include the unsaturated sulfatcs such as olcyl sulfatc, the C10-C18 alky] alkoxy sulfates ("AExS"; especially EO 1-7 ethoxy sulfates), C10-C18 alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the C10-18 glycerol ethers, the C10-C18 alkyl polyglyeosides and their corresponding sulfated polyglycosides, and C12-C18 alpha-sulfonated fatty acid esters. Nonionic. surfactants such as the ethoxylated C10-C18 alcohols nnd alkyl phenols, (e.g., C10-C18 EO (1-10) can also be used. If desired, other
conventional surfactants such as the C12-C18 bctaines and sulfobetaines ("sultaines"), C10-C18 amine oxides, and the like, can also be included in the overall compositions. The C10-C18 N-alky) polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyI) glucamide. The N-propyl through N-hcxyl C12-C18 glucamidcs can be used for low sudsing, C10-C18 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. C10C14 alkyl benzene sulfonates (LAS), which are often used in laundry detergent compositions, can also be used with the branched surfactants herein.
The following Examples illustrate the use of branched-chain surfactants prepared according to the present invention in various cleaning compositions, but is not intended to be limiting thereof.
EXAMPLE.! Granular laundry detergents are prepared as follows.
Blown Powder
Zeolite A .30.0 22.0 6.0
Sodium sulfatc 19.0 5,0 7.0
LAS 13.0 11.0 21.0
Branched AS* 9,0 8.0 , 8.0
Silicate, Na - 1.0 S.O
Soap - - 2.0
Carbonate, Na 8.0 16,0 20.0
Spray On
C14-15EO7 1.0 1.0 1.0
Dry additives
Protease 1.0 1.0 1.0
Lipase 0,4 0.4 0.4
Amylase 0,1 0.1 0.1
Cellulasc 0.1 0.1 0,1
NOBS - 6.1 4.5
PB1 1.0 5.0 6.0
Sodium sulfatc - 6.0
Moisture &. Miscellaneous - Balance—-—
C12-C14 methyl branched alkyl sulfate, prepared as disclosed above.
A bleach-containing nonaqueous liquid laundry detergent is prepared as
Component Wt, % Range (%
Liquid Phase
Branched AS* 25.3 18-35
C12-14, EO5 alcohol ethoxylate 13.6 10-20
llexylene glycol 27.3 20-30
Perfume 0.4 0-1.0
Protease enzyme 0,4 0-1.0
Na3 Citrate, anhydrous 4.3 3-6
Sodium perborate (PB-1) 3.4 2-7
Sodium nonanoyloxybcnzene sulfonate (NOBS) 8.0 2-12
Sodium carbonate 13.9 5-20
Diethyl triamine pcntaacctic acid (DTPA) 0.9 0-1.5
Brightener 0.4 0-0.6
Suds Suppressor 0.1 0-0.3
Minors Balance
*C12-C16 methyl branched alkyl sulfate, Na salt, prepared as disclosed above,
A hand dishwashing liquid is as follows.
Ingredient % (wt) Range (% wt.)
Branched AS* 13.0 5-15 .
Ammonium C12-13 alkyl
cthoxy sulfate 15.0 10-35
Coconut amine oxide 2,6 2-5
Bctaine**/Tetronic 704® 0.87-0.10 0-2 (mix)
Alcohol Ethoxylatc C8E11 5.0 2-10
Ammonium xylene sulfonatc 4.0 1-6
Ethanol 4.0 0-7
Ammonium citrate 0,06 0-1.0
Magnesium chloride 3.3 0-4.0
Calcium chloride 2.5 0-4.0
Ammonium sulfatc 0.08 0-4.0
Hydrogen peroxide 200 ppm 0-300 ppm
Perfume 0.18 0-0.5
Maxatase® protease 0.50 0-1.0
Water and minors —Balance
*C12C14 methyl branched alkyl sulfate, triethanolammonium salt, prepared as disclosed above.
**Cocoalky) betainc.

We claim:

I. A process for preparing detersive surihetants derived from mid-to-near-mid-chain branched hydrophobic units, comprising the steps of:

(a) dimerizing alpha olefins of the formula RCH=CH, and k'CI—I=CH,, to form oletins of the formula, in a conventional manner

wherein in the above formulas R and k' may be the same or different Q to C7 linear alkyl substituents

(b) followed by either isomerizing the olefins from Step (a) and the subsequent reaction of said isomerized oletins with CO/U, under Oxo conditions~ or directly reacting the olefins from Step (a) with CO/H2 under Oxo conditions;

to obtain the desired branched alcohols of the formula:

followed by either

(i) preparing branched alkyl sulphate surfactants by sulphating the alcohols;

(ii) preparing branched alkyl ethoxy sulphates. comprising tirst ethox~ lating, then su Iphating, the alcohols:

or (iii) prepar'ing branched alkyl carboxylate surfhctants by oxidising the alcohols or their aldehyde intermediates.

2. A process for preparing detersive surfactants derived [Porn mid—to-near-mid— chain branched hydrophobic units substantially as herinbefore described in any of the Examples.






955-del-1997-description (complete).pdf









Patent Number 214529
Indian Patent Application Number 955/DEL/1997
PG Journal Number 08/2008
Publication Date 22-Feb-2008
Grant Date 12-Feb-2008
Date of Filing 15-Apr-1997
# Inventor's Name Inventor's Address
PCT International Classification Number C07C 309/05
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 60/015,521 1996-04-16 U.S.A.