AU740032B2 - Branched surfactant manufacture - Google Patents

Description

AUSTRALIA

Patents Act COMPLETE SPECIFICATION

(ORIGINAL)

Class Int. Class Application Number: Lodged:

C

t CC

S

C.

Complete Specification Lodged: Accepted: Published: Priority Related Art:

C.

Name of Applicant: The Procter Gamble Company Actual Inventor(s): Daniel Stedman Connor Address for Service: PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Invention Title: BRANCHED SURFACTANT MANUFACTURE Our Ref: 630399 POF Code: 44135/44135 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): -1- 1A BRANCHED SURFACTANT

MANUFACTURE

"The present appliction is a divisional application from Australian application number 29910/97 the entire disclosure of which is incorporated herein by reference".

FIELD OF THE INVENTION The present invention relates to processes for manufacturing detersive surfactants, especially those containing branched-chain hydrophobic units.

BACKGROUND OF THE INVENTION Conventional detersive surfactants comprise molecules having a watersolubilizing substituent (hydrophilic group) and an oleophilic substituent (hydrophobic group). Such surfactants typically comprise hydrophilic groups such as carboxylate, sulfate, sulfonate, amine oxide, polyoxyethylene, and the like, attached to an alkyl, alkenyl or alkaryl hydrophobe usually containing from about 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 15 be attached by chemical means. The earliest source of hydrophobe groups comprised the natural fats and oils, which were converted into soaps carboxylate hydrophile) by saponification with base. Coconut oil and palm oil are still used to manufacture soap, as well as to manufacture the alkyl sulfate class of surfactants. Other hydrophobes are available from petrochemicals, 20 including alkylated benzene which is used to manufacture alkyl benzene sulfonate surfactants The literature asserts that certain branched hydrophobes can be used to advantage in the manufacture of alkyl sulfate detersive surfactants; see, for example, U.S. 3,480,556 to deWitt, et al., November 25, 1969. However, it has been determined that the beta-branched surfactants described in the '556 patent are 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. See: "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 20*C-5°C).

One problem associated with the manufacture of 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 nearmid chain branched surfactants.

SUMMARY OF THE INVENTION The present invention encompasses a process for preparing mid- to near midchain branched olefins (primarily, methyl branched at or near the mid-chain region).

Such materials are then used 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

CH

2

RCH=CH

2

R'CH=CH

2

R-CH

2

CH

2 and

CH

2

II

R'CH

2

CH

2 -C-R (II) wherein R and R' may be the same or different linear alkyl, and 10 wherein R is C 3

-C

7 preferably C 5 to C 7 linear alkyl, and R' is C 3

-C

7 preferably C 5

-C

7 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 olefins may also result from the dimerization and 15 these can optionally be removed using molecular sieves. Step 1 of the process herein is designed to provide branched olefins which preferably contain from about 12 to about 18 (avg.) total carbon atoms.

2) Alcohol Production In Step 2 (Route the olefin mixture for Step 1 can be pre-randomized to 20 enhance the ultimate formation of alcohols and (ii) in subsequent Step 3.

Alternatively (Step 2, Route 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 Isoneriation (iy(I) Catal Random Intenal Olefin Mixture (RIOM) Catalyst CO/H2 (hi) RIOM Branched Alcohol Mixture Oxo Catalyst or Route B

CO/H,

CO t 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-lnterscience, N.Y. The catalyst for this step is, for example, cobalt-carbon monoxide-organophosphine.

The alcohol mixture of Step of the present process comprises branched-chain primary alcohol compounds of the following formulae for use in Step below.

CH

3 S R CH 2

C

C

CH R' -CHOH and i) and

**CHCH

2 0H (iii) R-CH2CH 2 CH- R' It is to be understood that when CH 2 OH 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 3) Surfactant Production Branched Alcohol Mixture SO, Branched Alkyl Sulfate Thus, the present invention provides a process for preparing mid-to nearmid chain branched alcohols, comprising the steps of: dimerizing alpha olefins of the formula RCH=CH 2 AND R'CH 2

=CH

2 to form Aolefins of the formula:

CH

2

R-CH

2

CH

2 and

CH

2

R'CH

2

CH

2

R

wherein in the above formulas R and R' may be the same or different C 3 to

C

7 linear alkyl substituents; followed by either isomerizing the olefins from Step and the subsequent reaction of said .isomerized olefins with CO/H 2 under Oxo conditions; or directly reacting the olefins from Step with CO/H 2 under Oxo conditions; and 10 recovering the desired branched alcohols of the formula

CH

3 R CH 2

CH

2 CH R' CH 2 OH and CH3 "HOCH2--

CCH

2 CH-- R 0 Advantageously, the present process results in no geminal branching, i.e., 15 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 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 other documents cited herein are, in relevant part, incorporated herein by reference.

SC:\WIMORD\NNAINODELETE\SPECIES\2g1O0-g7.DOC 3B Throughout the description and claims of the specification the word "comprise" and variations of the word, such as "comprising" and "comprises", is not intended to exclude other additives, components, integers or steps.

DETAILED DESCRIPTION OF THE INVENTION 1) Olefin dimerization:

S'*

o *0

*S

o o C ONWORDIANNANODELETESPECIE S2910-97 DOC The present invention encompasses, in a process for preparing surfactant precursor hydrophobes from dimerization of two same or near same chain length alpha-olefins to form a detergent range vinylidene olefin. These alpha olefins C 5 to

C

1 0 preferably

C

7 to C 9 are dimerized to give C 10 to C 20 preferably

C

14 to C 1 8 vinylidene olefins which upon Oxo reaction give C 1 1 to C21, preferably

C

15 to C 19 alcohols. There are a number of processes for accomplishing said dimerization; see US Application 9,200,398, US 4,658,078, US 4,973,788; 0. S. Vostrikova, A. G.

Ibragimov, G. A. Tolstikov, L. M. Zelenova and U. M. Dzhemilev, Izv. Akad. Nauk SSSR, Ser. Khim. (1980), 2330-2 [Chem. Abstr. 94:65032]; Jpn. Kokai Tokkyo Koho, 06228016 A2 [Chem. Abstr. 122:186930].

2) Alcohol Production Route A part a) The carbon-carbon double bond of the vinylidene olefin is pre-isomerized using a method such as Shell uses to isomerize alpha-olefins in their SHOP process; 15 see Kirk-Othmer Encyclopedia of Chemical Technology 4th Edition, Volume 17, pp. 848-50 (1996), Jacqueline I. Kroschwitz, Executive Editor, Wiley-Interscience, SN. 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-phosphine catalysts in the one step process, see Kirk- Othmer Encyclopedia of Chemical Technology 4th Edition, Volume 1, pp. 903-8 S(1991). Route A, (that is including pre-isomerization) is undertaken to assure 25 relatively high yields of alcohols i and ii versus alcohol iii. Note alcohol sulfates 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 relies upon the catalyst to completely isomerize the carboncarbon 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, alkyl ethoxyl sulfates (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 carboxylate a branched-chain soap). This soap can be an excellent surfactant and/or detergent builder in and of itself. This carboxylate can also be used as a feedstock and converted to branched acyl-taurates, -isethionates, sarcosinates. -N-methylglucamide or other acyl-derved surfactants using artdisclosed techniques.

INDUSTRIAL

APPLICABILITY

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, polycarboxylate builders such as citrate, layered silicate builders such as "SKS-6" (Hoechst) 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 25 monomer units, especially polyester materials. Preferred materials of this type include oligomeric terephthalate esters, sulfonated substantially linear ester oligomers comprising a backbone of terephthaloyl and oxyalkyleneoxy repeat units and phthalolyl-derived sulfonated terminal moieties. A variety of SRA's are 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 percarbonate or perborate (especially perborate monohydrate "PBI") typically are used at levels from about 1% to about 30% of finished detergent compositions. Bleach activators such as nonanoyloxy-benzene sulfonate ("NOBS") and tetraacetyl ethylenediamine and mixtures thereof, can be used to enhance the bleaching activity of materials such as perborate and percarbonate. If present, the amount of bleach activator will typically be from about 0.1% to about 60% of a bleaching composition comprising a bleaching agentplus-bleach 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 about 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.

15 3,308,067). Such materials include acrylate/malic-based copolymers, such as described in EP 193,360, as well as polyethylene glycol Detergent compositions herein can also include various brighteners, dye transfer inhibiting agents (especially polymers of N-vinylpyrrolidone and Nvinylimidazole), suds suppressors (especially silicones), chelating agents such as nitrilotriacetate, ethylenediamine disuccinate, 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 branched-chain surfactants prepared in the manner of the present invention may be used singly in cleaning compositions 25 or in combination with other detersive surfactants. Typically, fully-formulated 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 sulfates such as oleyl sulfate, the C 10

-C

18 alkyl alkoxy sulfates ("AExS"; especially EO 1-7 ethoxy sulfates), C 0-C 18 alkyl alkoxy carboxylates (especially the EO ethoxycarboxylates), the C10-18 glycerol ethers, the C 0-C1g alkyl polyglycosides and their corresponding sulfated polyglycosides, and C 12

-C

18 alpha-sulfonated fatty acid esters. Nonionic surfactants such as the ethoxylated C10-C 1 8 alcohols and alkyl phenols, C 10

-C

18 EO (1-10) can also be used. If desired, other conventional surfactants such as the C 1 2 -C18 betaines and sulfobetaines ("sultaines"),

C

10 -C18 amine oxides, and the like, can also be included in the overall compositions. The C 10

-C

1 8 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C 12

-C

18 N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C 10

-C

18

N-(

3 -methoxypropyl) glucamide. The N-propyl through N-hexyl

C

1 2

-C

1 8 glucamides can be used for low sudsing.

C

1 0

-C

2 0 conventional soaps may also be used. If high sudsing is desired, the branched-chain

C

1 0

-C

1 6 soaps may be used. C 10

C

1 4 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 I Granular laundry detergents are prepared as follows.

A B

C

Blown Powder Zeolite A 30.0 22.0 Sodium sulfate 19.0 5.0 Polyacrylate LAS 13.0 11.0 21.0 Branched AS* 9.0 8.0 Silicate, Na 1.0 25 Soap Carbonate, Na 8.0 16.0 20.0 Spray On

C

1 4- 15 EO7 1.0 1.0 Dry additives Protease 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 NOBS -6.1 PB1 1.0 5.0 Sodium sulfate Moisture Miscellaneous R in,-.

*C

12 -C14 methyl branched alkyl sulfate, prepared as disclosed above.

A bleach-containing nonaqueous liquid laundry detergent is prepared as follows.

EXAMPLE II Component Wt% Range wt.) Liquid Phase Branched AS* 25.3 18-35 C12-14, E05 alcohol ethoxylate 13.6 10-20 10 Hexylene glycol 27.3 20-30 Perfume 0.4 0-1.0 Solids 0.4 0-1.0 Protease enzyme 0.4 0-1.0 Na3 Citrate, anhydrous 4.3 3-6 15 Sodium perborate (PB-1) 3.4 2-7 Sodium nonanoyloxybenzene sulfonate (NOBS) 8.0 2-12 Sodium carbonate 13.9 5-20 Diethyl triamine pentaacetic acid (DTPA) 0.9 0-1.5 Brightener 0.4 0-.6 20 Suds Suppressor 0.1 0-0.3 Minors C12-C 1 6 methyl branched alkyl sulfate, Na salt, prepared as disclosed above.

A hand dishwashing liquid is as follows.

EXAMPLE III Ingredient Range wt.)~ Branched AS* 13.0 5-15 Ammonium C 12 13 alkyl ethoxy sulfate 15.0 10-35 Coconut amine oxide 2.6 Betaine**/Tetronic 7040 0.87-0.10 0-2 (mix) Alcohol Ethoxylate C8E 1 1 5.0 2-10 Ammonium xylene sulfonate 4.0 1-6 Ethanol 4.0 0-7 Ammoniunm citrate 0.06 0-1.0 Magnesium chloride 3.3 0-4.0 Calcium chloride 2.5 0-4.0 Amnmonium sulfate 0.08 0-4.0 Hydrogen peroxide 200 ppmn 0-300 ppm *Perfume 0.18 0-0.5 Maxatase®D protease 0.50 0-1.0 Water and minors Balance *Cl 2

CI

4 methyl branched alkyl sulfate, triethanolammonium salt, prepared as disclosed above.

**Cocoalkyl betaine.

Claims (8)

1. A process for preparing mid- to near-mid chain branched alcohols, comprising the steps of: dimerizing alpha olefins of the formula RCH=CH 2 and R'CH 2 =CH2, to form olefins of the formula: CH 2 R-CH 2 CH 2 and CH 2 R'CH 2 CH 2 R, I wherein in the above formulas R and R' may be the same or different C 3 to C 7 linear alkyl substituents; followed by either isomerizing the olefins from Step and the subsequent reaction of said isomerized olefins with CO/H 2 under Oxo conditions; or directly reacting the olefins from Step with CO/H 2 under Oxo conditions; and recovering the desired branched alcohols of the formula: CH3 R-CH 2 CH 2 CH--R'-C H 2 0 H and o CH3 HOCH 2 -R-CH 2 CH 2 CH-R'

2. A process for preparing branched alkyl sulfate surfactants by sulfating the alcohols prepared according to Claim 1.

3. A process for preparing branched alkyl ethoxy sulfates, comprising first ethoxylating, then sulfating, the alcohols prepared according to Claim 1.

4. A process for preparing branched alkyl carboxylate surfactants by oxidizing the alcohols prepared according to Claim 1, or their aldehyde intermediates.

I, 11 A process for preparing branched acyl taurate, branched acyl isethionate, branched acyl sarcosinate, or branched acyl N-methylglucamine surfactants, or the like, using the branched carboxylates prepared according to Claim 4 as a feedstock.

6. A branched chain alcohol when prepared according to the process of any one of.Claims 1 to

7. A process according to Claim 1, substantially as hereinbefore described with reference to any one of the examples.

8. A branched chain alcohol, according to Claim 5, substantially as hereinbefore described with reference to any one of the examples. S *0* DATED: 23 August, 2001 PHILLIPS ORMONDE FITZPATRICK Attorneys for: THE PROCTER GAMBLE COMPANY I\U S C \ONWORDNNA\ODELETE\SPECIES\29 10-97-DOC I