WO1999036376A1

WO1999036376A1 - Anionic surfactants based on alkene sulfonic acid

Info

Publication number: WO1999036376A1
Application number: PCT/US1998/025414
Authority: WO
Inventors: Paul D. Berger; Christie H. Berger; Iris K. Hsu
Original assignee: Berger Paul D; Berger Christie H; Hsu Iris K
Priority date: 1998-01-20
Filing date: 1998-11-30
Publication date: 1999-07-22
Also published as: EP1056693A1; EP1056693B1; BR9813676A; AU1613999A; CN1221498C; CN1297427A; DE69835033D1; CA2319092A1; ES2268806T3; EP1056693A4; DE69835033T2; BR9813676B1; US6043391A; CA2319092C; MXPA00006614A

Abstract

New anionic surfactants and methods of preparation which are derived from aromatic or substituted aromatic molecules and alkene sulfonic acid. Wherein the aryl compound is alkylated and sulfonated in one-step with an alkene sulfonic acid prior to sulfonic acid neutralization. The methods allow the functional sulfonate group to be attached to the end of the alkyl chain rather than to the aromatic ring thus allowing for selective substituted groups, either branched, linear or alkoxylated or combinations thereof to be placed on the aryl compound prior to sulfonation and alkylation. The invention uses the alkene sulfonic acid produced from thin-film sulfonation of an alpha-olefin to alkylate benzene, mono-substituted aromatic, poly-substituted aromatic, alkylbenzene, alkoxylated benzene, polycyclic aromatic, mono-substituted polycyclic aromatic, poly-substituted polycyclic aromatic, naphthalene, alkylnaphthalene, phenol, alkylphenol, alkoxylated phenol, and alkoxylated alkylphenolalkyl substituted or polysubstituted cyclic or polycyclic compounds to produce the corresponding sulfonic acid having an additional alkyl group derived from the alpha-olefin used during the thin-film sulfonation which is either linear or branched.

Description

ANIONIC SURFACTANTS BASED ON ALKENE SULFONIC ACID

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to new anionic surfactants derived from

aromatic or substituted aromatic molecules and alkene sulfonic acid. More

particularly this invention relates to alkyl, dialkyl and higher substituted aromatic

sulfonates and methods for preparing the substituted aromatic sulfonates

wherein an aryl compound is alkyiated and sulfonated in one step with an alkene

sulfonic acid prior to neutralizing the acid.

The new surfactants and the new method to prepare them have the

following advantages over existing aromatic sulfonate type surfactants:

1. Dialkyl and higher substituted aromatic sulfonates can be produced easily

and in high yields.

2. Alkoxylated aromatic sulfonates can be produced easily and in high

yields.

3. Mixed linear and branched substituted di-alkylaromatics can be produced

easily and in high yields.

4. Alkyl benzene sulfonates can be produced without using, presently costly,

conventional alkylation processes.

5. Sulfonated alkyl phenol alkoxylates can be produced without using,

presently costly, conventional alkylation processes. 6. The new surfactants possess a unique structure where the sulfonate

group is attached to the end of one of the alkyl chains rather than to the aromatic

ring.

2. The Prior Art

Alkyl benzene sulfonates have been popular surfactants for a wide variety

of detergent and industrial use. Beginning just after World War II, synthetic

detergents based on the reaction of propylene tetramer and benzene using AICI₃

catalyst began to gain popularity and widespread use as laundry detergents.

During the 1960s alkylbenzene sulfonates based on branched alkyl groups were

found to be causing excessive foaming in sewage treatment plants and in rivers

and lakes due to their slow biodegradability. Linear alkylbenzenes based on the

reaction of linear olefins (US 3,585,253 issued to Huang on June 15,1971 ) or

linear chloroparaffins (US 3,355,508 issued to Moulden on Nov 28,1967) were

developed which gave acceptable detergency and were quickly biodegraded.

Even more recently, the AICI₃ process has been replaced by the HF process

and the Detal Process because of environmental objections to the AICI₃

process. Table 1 shows the typical yields obtained for detergent alkylates using

HF catalyst. Table 1 Typical Yields of Detergent Alkylate (values in tons) Branched Alkylate Linear Alkylate

Material Charged

Linear Paraffins - 82.9

Benzene 39.9 34.3

Propylene tetramer 86.7 -

Total charged 126.6 117.3

Materials Produced

Hydrogen - 1.1

Light ends - 3.8

HF regenerator bottoms 2.5 2.8

Light alkylate 8.0 -

Detergent alkylate 100.0 100.0

Heavy alkylate 16.1 9.6

Total produced 126.6 117.3

Detergent use is the predominant market for alkylbenzenes and

alkylbenzene sulfonates. These products; however; are also employed in

considerable quantities as lubricants, coolants, industrial surfactants,

dispersants, emulsifiers, corrosion inhibitors, demulsifiers and for many other

uses. They find widespread use in many industries among which are petroleum

recovery, refining, emulsion polymerization, textile dyeing, agriculture, industrial

and institutional cleaning, drilling fluids, paper processing, coatings, and

adhesives.

Present processes are designed to optimize the yields of detergent

alkylate (predominantly monoalkylbenzene). The yields of heavy alkylate

(predominantly dialkylbenzene) are therefore low. These heavy alkylates

however find considerable demand as oil soluble surfactants and specialty

chemicals. Dialkylbenzene sulfonates (US 4,004,638 issued to Burdyn, Chang and Cook on Jan. 25,1977, US 4536301 issued to Malloy and Swedo on Aug.

20,1985), alkyl xylene sulfonates (EP121964) and dialkyl phenol polyethoxy

alkyl sulfonates (US 4,220,204 issued to Hughes, Kudchadker and Dunn on

Sept. 2, 1980) have all been used to increase the productivity of crude oil;

however; the availability of these materials has been limited until this invention

because of the low yields of heavy alkylates available for conversion to their

corresponding sulfonates. In addition no commercially feasible process is

available, until this invention, for producing di- and tri- alkylbenzenes where both

linear and branched alkyl groups are present on the same benzene ring.

Alkoxylated Alkyl Substituted Phenol Sulfonates have been produced and

found to be useful as surfactants in numerous applications. US 5,049,311 issued

to Rasheed, Cravey, Berger and O'Brien on Sept 17,1991 , lists many uses for

these compounds including surfactants for Enhanced Oil Recovery, corrosion

inhibitors, hydrotropes, foaming agents in concrete formation, surfactants for dye

carriers, surfactants for fiber lubricants, surfactants for emulsion polymerization ,

textile detergents, foaming agents for drilling fluids, and agricultural emulsifiers.

SUMMARY OF INVENTION

The present invention resides in an improved process for producing novel

sulfonated alkylaromatic compounds in which the aromatic group is sulfonated

and alkyiated in one step. The invention uses alkene sulfonic acid produced by the thin film sulfonation of an alpha-olefin to alkylate an aromatic compound such as benzene or naphthalene or a substituted aromatic compound such as alkylbenzene or aikylnaphthalene or phenol or alkoxylated phenol or alkoxylated alkylphenol to produce the corresponding sulfonic acid having an additional alkyl group derived from the alpha-olefin used during the reaction. The subsequent sulfonic acid may be used "as is" or neutralized with a variety of cations such as Na, K, Ca, Mg, Ba, NH₄, MEA, DEA, TEA, iso-Propanol Amine.and other amines, etc. to form anionic surface active agents.

Thus a benzene or a substituted aromatic compound of the formulation shown below is used. Naphthalene and any other polycyclic aromatic may be substituted for benzene with similar results and offer the additional advantage of forming di- and higher sulfonate derivatives.

R=none,alkyl (branched or linear Ci to C₃₀+) or alkoxylate (EO, PO, BO or mixtures)

R-none,alkyl(branched or linear Cj to C₃₀+) R'-none,alkyl(branched or linear C_\ to C₃₀+) The benzene or substituted aromatic compound is reacted with the

alkenesulfonic acid produced from the sulfonation of an alpha-olefin. The

sulfonation of an alpha-olefin produces a mixture of alkene sulfonic acid and

sultone whose composition is shown below. Alkene sulfonic acid is the

precursor to alpha-olefin sulfonate or AOS which is a widely used surfactant with

many applications for foaming, cleaning, emulsifying, and wetting. Alkene

sulfonic acid is produced through the reaction of SO₃ with mono-olefinic

hydrocarbon as known in the art (US 2,061 ,617; 2,572,605 issued to Fincke on

Oct. 23,1951 ; 3,444,191 issued to Nelson on May 13, 1969). A process for

producing high yields of alkene sulfonic acids is revealed by Weil, Stirton and

Smith in JAOCS Vol. 41 , Oct. 1965, pp 873-875.

CH₃(CH₂)nCH-CHCH₂SO₃H alkene sulfonic acid

CH3(CH2)mCHCH2CH2

sultone

The ratio of alkene sulfonic acid to sultone is from 1 :1 to about 1 :4

depending on manufacturing temperature, pressure, flow rates and other

parameters known to those skilled in the art. The position of the double bond of the alkene sulfonic acid and the number of carbons in the sultone ring can also vary depending on these same parameters.

The alpha olefin sulfonic acid is reacted with benzene or substituted aromatic compounds at elevated temperature up to just under the decomposition temperature of the reactants and in the presence of a limited amount of water. A catalysts has been found useful to reduce the reaction temperature, the reaction times and improve yields. Useful catalysts include H₂SO₄, methane sulfonic acid, sulfosuccinic acid, and other strong acid catalysts generally used for alkylation. Higher temperatures, up to the decomposition temperatures of the reactants are preferred. Pressure may be necessary to reach the desired higher temperatures when using low boiling starting materials such as benzene and to prevent water from escaping during the early stages of the reaction. The alkali or alkaline metal salts of various carboxylic acids such as acetic, propionic or carbonates such as sodium or potassium carbonate may be used as catalysts if the corresponding alkali or alkaline earth sulfonate salt is desired rather than the free sulfonic acid. The reaction results in the product shown below. The free acid may be further reacted with any of a number of cations such as Na, K, NH4, Ca, Mg, Ba, Amines, etc. to form anionic surface active salts. Naphthalene and any other polycyclic aromatic may be substituted for benzene with similar results.

R=none,alkyl (branched or linear C_j to C₃₀+) or alkoxylate (EO, PO, BO or mixtures)

R'=none,alkyl(branched or linear C] to C₃₀+)

R'-none,alkyl(branched or linear Ci to C₃₀+) R =CH₃(CH₂)nCH(CH)₂mSO₃H

Thus it is an object of the present invention to provide a one-step method of producing useful anionic surfactants which are derived from mono-substituted, and poly-substituted aromatic sulfonates. We define poly-substituted as having two or more substituents on an aromatic compound. More particularly the object of the present invention is to provide novel compounds and their methods of production wherein an aromatic compound is alkyiated and sulfonated in one- step with an alkene sulfonic acid prior to neutralizing the acid. The alkene sulfonic acid may include an alkyl group which is either linear or branched, while the sulfonation leads to the formation of a product which has the functional sulfonate group attached to the alkyl group rather than the aromatic ring.

Furthermore, it is an object of the present invention to provide methods of producing mono-, and poly- substituted alkylaromatic compounds where both linear and branched alkyl groups may or may not be present on the same cyclic ring.

Additionally, it is an object of the present invention to provide a one-step method of producing mono-substituted, and poly-substituted alkylaromatic sulfonates whereby a alkene sulfonic acid is used to alkylate benzene, naphthalene, a monosubstituted aromatic compound, and a poly substitiuted aromatic compound , prior to neutralization of the sulfonic acid, to produce the corresponding sulfonic acid having the additional alkyl group derived from the alpha-olefin used in the sulfonation and wherein the method includes recycling water and unreacted aromatic to increase the yield of the alkylaromatic sulfonic acid.

DETAILED DESCRIPTION OF THE INVENTION

Alpha-Olefin sulfonates are widely used as surfactants for personal care, emulsion polymerization, fire-fighting foam and a wide variety of other uses.

These materials are produced by the sulfonation of an alpha-olefin using a thin film SO₃ reactor. Weil, Stirton and Smith (JOACS Vol 42, Oct 1965, pp 873-875) describe the reaction of hexadecene-1 and octadecene-1 with SO3 followed by neutralization with NaOH to form the corresponding hexadecene sulfonates. The inventors note that the final product is not a single component but

predominantly a mixture of two materials. These are the alkene sulfonate and the hydroxyalkane sulfonate. The hydroxyalkane sulfonate is present due to the

formation of an intermediate sultone when SO₃ reacts with the alpha olefin.

Neutralization with NaOH not only neutralizes the acid formed from this reaction

but also opens the sultone ring forming additional alkene sulfonate and

hydroxyalkane sulfonate. This results in a final product having approximately the

following composition shown in Table 2:

Table 2 Typical Products of Alpha-Olefin/SOs/NaOH Reaction

Component Approximate Amount by Weight

Alkene Sulfonate 60-70%

3-Hydroxy Sulfonate + 4-Hydroxy Sulfonate 30%

Disulfonates 0-10%

U.S. 3,845,114 issued to Sweeney and House on Oct. 29, 1974, teaches

that the addition of limited amounts of water to AOS acid and the subsequent

heating to 150°C converts the sultone to alkene sulfonic acid and hydroxyalkane

sulfonic acid. The presence of water during the ring-opening prevents

dimerization of the alkene sulfonic acid. Removal of the water dehydrates the

hydroxyalkane sulfonic acid back to sultone but leaves the alkene sulfonic acid

intact. Repeating the process of adding limited amounts of water, heating to

150°C and removing the water reduces the hydroxyalkane sulfonic acid content

and increases the alkene sulfonic acid content. This process is shown below. CH3(CH2)nCHOHCH2CH2CH2S03H hydroxyalkane sulfonic add

sultone

In another early study, Ault and Eisner (JOACS Vol 39, Feb 1962, pp 132-

133), describe the acid catalyzed addition of phenols and phenyl ethers to oleic

acid. They discovered that by using an acid catalyst, such as polyphosphoric

acid or methane sulfonic acid, they could produce aryl substituted stearic acids as shown below. CH₃(CH₂)xCH=CH(CH₂)yCOOH + C^OH

where x + y =14 and a+ b = 15

US 3,502,716 issued to Kite on March 24, 1970, uses alkali or alkaline earth metal carboxylates reacted at high temperature with hydroxy sulfonic acid anhydrides to produce the corresponding alkali or alkaline earth alkene sulfonate salts. This work does demonstrate that AOS acids can be predominantly converted to salts of alkene sulfonic acids at high temperatures. US 3,951 ,823 issued to Straus, Sweeney, House and Sharman on April 20, 1976, teaches the reaction of AOS acid with itself and other sulfonated monomers to produce disulfonated dimers having good foaming properties for use in foam well cleanout applications. This reference specifically requires that both monomers contain a sulfonate group. This reference teaches that suitable starting materials must contain at least about 5 nonaromatic carbon atoms per molecule, a sulfonate functional group, i.e., -SO₃-, and one of the following: (1) a carbon-carbon double bond, i.e., -CH=CH-; (2) an alkanol hydroxy group, or a sulfonate ester group of which the above sulfonate group is a component, i.e., a

sultone, and the functional groups must be substituents attached to non-

aromatic carbon atoms with the balance being carbon and/or hydrogen.

Despite the prior innovations, and probably because di-substitute and

higher substituted aromatic sulfonates were considered undesirable by-products,

those skilled in the art have never attempted to use the AOS acid from the

reaction of an alpha-olefin and SO₃, before neutralization, to simultaneously

alkylate and sulfonate an aryl compound such as benzene, naphthalene, or

substituted benzene, and naphthalenes.

The present invention forms new sulfonic acid and sulfonate derivatives

by the simultaneous alkylation and sulfonation of aromatic compounds resulting

in the formation of sulfonic acids and sulfonate derivatives which are useful as

anionic surface active agents. The acid from the reaction of an alpha-olefin and

SO₃, and the subsequent repeated hydrolysis and dehydration with water results

in the formation of alkene sulfonic acid as taught by US 3,845,114 We have

found that this strong acid can be used to alkylate aromatic compounds. An

additional strong acid catalyst is beneficial to obtain useful yields of final

product. In contrast to US 3,951 ,823, our invention does not require that the

reactants both contain at least about 5 nonaromatic carbon atoms per molecule,

a sulfonate functional group, i.e., -SO₃-, and one of the following: (1 ) a carbon-

carbon double bond, i.e.,-CH=CH-; (2) an alkanol hydroxy group, or a sulfonate ester group of which the above sulfonate group is a component, i.e., a sultone,

and the functional groups must be substituents attached to non-aromatic carbon

atoms with the balance being carbon and/or hydrogen. In fact the most

preferred starting materials such as benzene, naphthalene, alkylbenzenes and

alkylnaphthalenes do not meet any of the criteria mentioned in US 3,951 ,823.

EXAMPLE 1

78.0g Benzene (1.00 Mole) was added to a five necked, 2000 ml round-

bottom flask equipped with blade stirrer, thermometer, and water condenser.

The two empty fittings were closed with ground glass stoppers. Table 3 list the

charge for Example 1. While stirring, 240 g (0.839 Mole) of AOS acid

(EW=286), having the analysis shown in Table 4 below, was added at 21 °C. The

temperature was gradually raised to 110°C over a 3 hour period. A collection

tube was added to recover any unreacted benzene that distilled over. The

mixture was held at 110°C until no benzene was observed distilling off. The

recovered benzene was weighed and the activity of the alkylbenzene sulfonic

acid was determined from the acid value and CID activity (2-phase titration) of

the material remaining in the flask. 48.9g of benzene were recovered. 266.3g of

product remained in the flask. The percent conversion was calculated as follows:

100 x ((78.0g-48.9g)/(0.8x78g)) = 46.6% Activity of the product, determined by CID titration was found to be

44.4%. As is known to those skilled in the art, CID titration using Hyamine 1622

is a method of determining surfactant activity of anionic materials. The surface

tension at 22° for a 0.10 % solution neutralized to pH 7.0 with NaOH was found

to be 42.9 mN/m and the critical micelle concentration (CMC) was found to be

0.05%.

Table 3 Material Charge for Example 1

MATERIAL MW AMOUNT.g MOLE RATIO

Benzene 78.0 78.0 1.00 AOS Acid 286.0 240.0 0.839

Table 4 Analysis of AOS Acid

PROPERTY ANALYSIS

Acid Value, meq/g 1.55

CID Activity , meq/g 1.53

Average Molecular Weight, Calc 286

C-14,% 65

C16% 35

EXAMPLE 2

78.0g Benzene (1.00 Mole) was added to a stainless steel 2 liter Parr

Bomb reactor equipped with stirring, heat control, cooling cool and 300 PSI

rupture disk. 28.3g (0.100 Mole) of 70% sulfosuccinic acid catalyst which

contained 8.49 g H₂O was added. While stirring, 301 g (1.05 Mole) of AOS acid

(EW=286), having the analysis shown in Table 4 above, was added at 21 °C. The charge for Example 2 is listed in Table 5. The temperature was gradually

raised to 150°C and held at temperature for 4 hours. After 4 hours the

temperature was lowered to below 110°C and all the unreacted benzene and

water was allowed to distill off and was collected, measured and reintroduced to

the reaction flask. The flask was again heated to 150°C and held at temperature

for 4 hours. After 4 hours the temperature was lowered to below 110°C and all

the unreacted benzene and water was allowed to distill off and was collected,

measured and reintroduced to the reaction flask. This process of reintroducing

the water and benzene, heating to 150°C for 4 hours, cooling to below 110°C

and distilling off the benzene and water was repeated a third time. Analysis of

the final product after the third sequence of reacting and distilling indicated

92.6% conversion of the AOS acid to C14-16 alkylbenzene sulfonic acid.

Activity of the product remaining in the flask, determined by CID titration, was

found to be 92.5% assuming an equivalent weight of the product of 364. The

surface tension at 22° for a 0.10 % solution neutralized to pH 7.0 with NaOH was

found to be 32.2 mN/m and the CMC was found to be 0.65%. The surface

tension at the CMC was 29.5 mN/m and the Draves Wetting time for 0.10%

sodium salt of the product was 4.2 seconds. These values indicate the product

is an excellent surfactant. Table 5 Material Charge for Example 2

MATERIAL MW AMOUNT.g MOLE RATIO

Benzene 78.0 78.0 1.00

Water 18.0 8.5 0.47

Suifosuccinic Acid 198.1 19.8 0.10

AOS Acid 286.0 301.0 1.05

Table 6 Analysis of Product from Example 2

STEP BENZENE % g H₂0 ACID, CID, me/g %,ACTIVITY GRAMS CONVERSION me/g

Before 78.0 0.0 8.5 1.83 1.09

Heating After 1^st 17.9 77.0 8.5 2.84 2.10 76.4

Cycle After 2^nd 10.2 86.9 8.5 3.12 2.38 86.4

Cycle After 3^ra 5.8 92.6 8.5 3.28 2.54 92.5

Cycle

EXAMPLE 3

253.5g alkylbenzene (1.00 Mole) obtained by the HF alkylation of

benzene using linear C10-C14 paraffin and having the analysis shown in Table

7 was added to a five necked, 2000 ml round-bottom flask equipped as Example

1. 10.Og of reagent grade H₂SO₄ was added and the stirrer was turned on.

301.0g (1.05 Mole) AOS acid having the analysis shown in Table 4 above was

added and the mixture heated to 140°C over a two hour period. The charge for

Example 3 is shown in Table 8. The mixture was held at 140°C and periodically

analyzed for increasing acid value (AV) until the value remained constant. After

the AV remained constant the sample was cooled and the unreacted H₂SO₄ was

recovered by extracting the sample with an equal volume of deionized water. The amount of H₂SO₄ recovered was 9.59g or 95.9% of the amount added to the

reaction. 529.1g of product were recovered after extracting the H₂SO₄ out with

water. Analysis of this material gave 96.2% dialkyl benzene sulfonic acid

assuming MW of 539. IR curves of the starting materials, AOS (Figure 1 ) and

Linear Alkylbenzene (Figure 2) and the final product (Figure 3) show the loss of

sultone bands at 1330-1360, 940, 895 and alkene groups at 1700, 1165, 1040,

965 and 910 indicating the conversion of AOS acid into alkyiated, alkylbenzene

sulfonate.

Table 7 Analysis of Linear Alkylbenzene

PROPERTY ANALYSIS

Appearance Water white liquid

Bromine Index, | ppm 47

Color, Pt-Co <3

2-phenyl isomer ^•, Wt % 15.6

Average Molecular Weight 253.5

Homologue Distribution, Wt %

<C10 0.0

C10 1.6

C11 7.8

C12+C13 82.2

C14 7.6

>C14 0.8

Table 8 Material Charge for Example 3

MATERIAL MW AMOUNT.g MOLE RATIO

Linear Alkyl Benzene 253.5 253.5 1.00

Sulfuric Acid 98.0 10.0 0.10

AOS Acid 286.0 301.0 1.05 EXAMPLE 4

229g alkylbenzene (1.00 Mole) obtained by the HF alkylation of benzene

using propylene tetramer and having the analysis shown in Table 9 was added

to a five necked, 2000 ml round-bottom flask equipped as Example 1. 49.0g of

reagent grade H₂SO₄ (0.500 Mole) was added and the stirrer was turned on.

301.0g AOS (1.05 Mole) acid having the analysis shown in Table 4 above was

added and the mixture heated to 150°C over a two hour period. The charge for

Example 4 is listed in Table 10. The mixture was held at 150°C and periodically

the AV remained constant the sample was cooled and the unreacted H₂SO₄was

recovered by extracting the sample with an equal volume of deionized water.

The amount of H₂SO₄ recovered was 47.3g or 96.5% of the amount added to the

reaction. 528.5g of product were recovered after extracting the H₂SO₄ out with

water. Analysis of this material gave 56.8% dialkyl benzene sulfonate assuming

MW of 515.

Table 9 Analysis of Branched Alkylbenzene

PROPERTY ANALYSIS

Appearance Water white liquid

Bromine Index, ppm 30

Color, Pt-Co <3

Average Molecular Weight 229

Homologue Distribution, Wt %

C9 3.7

C10 2.8

C11 9.3

C12 65.8

C13 15.5

C14 2.3

C15 0.6

Table 10 Material Charge for Example 4

MATERIAL MW AMOUNT.g MOLE RATIO

Branched Alkylbenzene 229.0 229.0 1.00

Sulfuric Acid 98.0 49.0 0.50

AOS Acid 286.0 301.0 1.05

EXAMPLE 5

226.0g phenol with 3 mole EO (1.00 Mole) obtained by the alkylation of

phenol using ethylene oxide was added to a five necked, 1000 ml round-bottom

flask equipped as Example 1. 295. Og C16 AOS acid (1.00 Mole) was added

and the mixture heated to 150°C over a two hour period. The charge for

Example 5 is Listed in Table 11. The mixture was held at 150°C and periodically

analyzed for increasing acid value (AV) until the value remained constant. These values are shown in Table 12. After the AV remained constant the sample was

cooled. 520.7g of product were recovered. Analysis of this material gave 70.0%

alkylphenolethoxy sulfonate assuming MW of 521.

Table 11 Material Charge for Example 5

MATERIAL MW AMOUNT.g MOLE RATIO

Phenol + 3 EO 226.0 226.0 1.00 AOS Acid 295.0 295.0 1.00

Table 12 Analysis of Reaction Mixture

TIME @ 150°C ACID VALUE

0 Hours 59.9

1 Hours 62.8

2 Hours 73.6 8 Hours 75.4

EXAMPLE 6

94.0g phenol (1.00 Mole) was added to a five necked, 1000 ml round-

bottom flask equipped as Example 1. 306g C16 AOS acid (1.04 Mole) was

added and the mixture heated to 120°C over a two hour period. The charge for

Example 6 is shown in Table 13. The mixture was held at 120°C and

periodically analyzed for increasing acid value (AV) until the value remained

constant (Table 14). After the AV remained constant the sample was cooled and

400g of product were recovered. Analysis of this material gave 147.8 AV(100%

alkyl phenolsulfonate assuming MW of 389). CID titration gave 2.47 meq/g or

405 EW. Table 13 Material Charge for Example 6

MATERIAL MW AMOUNT.g MOLE RATIO Phenol 94.0 94.0 1.00

AOS Acid 295 306 1.04

Table 14 Analysis of Reaction Mixture from Example 6

TIME @ 120°C ACID VALUE

0 Hours 70.0

2 Hours 146

3 Hours 147

Theoretical 147

EXAMPLE 7

Mixtures of natural and synthetic alkylarylsulfonates are used to provide

ultra-low interfacial tensions (<1.0 x 10^"2 mN/m) when used in combination with

various alkali materials such as NaOH or Na₂CO₃and contacted with crude oil.

For example, US 4,536,301 issued to Malloy and Swedo on Aug. 20, 1985 uses

mixtures of mono and dialkylbenzene sulfonates to obtain ultra-low interfacial

tensions against crude oil, US 4,004,638 issued to Burdyn, Chang and Cook on

Jan. 25,1977 uses similar mixtures along with alkali agent to obtain ultra-low IFT

and GB 2,232,428 filed by Muijs, Beers, and Roefs on June 6, 1989, uses

mixtures of dialkylbenzene alkali sulfonates and polyalkoxyphenyl-ether alkali

sulfonates also to obtain low IFT values. All these references claim increased

oil recovery by injection of the sulfonate mixtures into subterranean crude oil

reservoirs. The utility of the products of the invention as surfactants for Alkaline

Surfactant Polymer Flooding was evaluated in this example using surfactant compositions as formulated below.

FORMULATION A 17.0 g lsopropanol

5.0 g Ethylene Glycol 16.4 g Deionized Water 11.6 g NaOH(50% aqueous)

30.0 g Dialkyl Benzene Sulfonate from Example 3 above 20.0 g Branched Monoalkylbenzene Sulfonic Acid (98% active, E.W. = 309) ^*

* Prepared by thin falling film sulfonation using Air/SO₃ of alkylbenzene from the HF alkylation of benzene with propylene tetramer.

FORMULATION B 17.0 g lsopropanol

5.0 g Ethylene Glycol

16.4 g Deionized Water

11.6 g NaOH(50% aqueous)

30.0 g Dialkyl Benzene Sulfonate, Commercial Source (94.6% active, E.W. = 429)

20.0 g Branched Monoalkylbenzene Sulfonic Acid (98% active, E.W. = 309) *

Each of the two surfactant formulations above was diluted to 0.3 wt % with

simulated field brine of the composition shown in Table 15. The alkalinity of

each sample was adjusted to 0.6 to 1.40 wt% NaOH and the IFT of each sample

against a Chinese crude oil at 45°C was measured using a Model 500 Interfacial

Tensiometer from the University of Texas, Austin, TX.

The results shown in Table 16 below indicate that the dialkylbenzene

sulfonate produced by the invention gives ultralow interfacial tensions comparable to and somewhat superior to the heavy alkylbenzene sulfonate produce by the HF process.

Table 15 Synthetic Brine Solution

INGREDIENT CONC. mg/L

CO₃ ^"2 37 5

HCO₃ ^" 1342

Total Dissolved Solids 3648

Table 16 Interfacial Tensions Against Crude Oil, 45° C

NaOH, WT % INTERFACIAL TENSION, mN/m INTERFACIAL TENSION, mN/m FORMULATION A FORMULATION B

0.6 0.7 x IO³

0.8 1.05 x 10-2 6.5 x ισ³

1.0 4.6 x IO-³ 1.6 x 10-²

1.4 7.4 x 10-³

The surface properties of the new compounds including low CMCs, low surface and interfacial tensions, and fast wetting times, make them ideal for a wide variety of surfactant applications including emulsifiers, wetting agents, dispersants, foaming agents, hydrotropes, detergents, and cleaners for industries and products such as oil field, agricultural, textile, corrosion inhibition, dye carriers, drilling fluids, lubricants, concrete, and cement.

Claims

1. An anionic compound comprising: a sulfonated alkylaromatic compound

formed by the reaction of an aromatic compound with the acid formed by the

sulfonation of an alkene, wherein:

a) the aromatic compound is selected from the group consisting of

benzene, mono-substituted aromatic, poly-substituted aromatic, alkylbenzene,

alkoxylated benzene, polycyclic aromatic, mono-substituted polycyclic aromatic,

poly-substituted polycyclic aromatic, naphthalene, aikylnaphthalene, phenol,

alkylphenol, alkoxylated phenol, and alkoxylated alkylphenol, and

b) wherein the alkene used to form the alkene sulfonic acid comprises an

alkyl group selected from the group consisting of linear and branched alkyl

groups of 3 to 30 carbon atoms.

2. The sulfonated alkylaromatic compound as set forth in claim 1 wherein the

group attached to the mono-substituted aromatic compound is selected from the

group consisting of linear and branched chain alkyl groups of 1 to 30 carbon

atoms.

3. The sulfonated alkylaromatic compound as set forth in claim 1 wherein the

poly-substituted aromatic compound comprises alkyl groups each selected from the group consisting of linear and branched alkyl groups of 1 to 30 carbon

atoms.

4. The sulfonated alkylaromatic compound as set forth in claim 1 wherein said

alkoxy group substituted on said aromatic compound is selected from the group

consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations

of two or more where the number of alkoxylate groups range from 1 to 100.

5. The alkene as set forth in claim 1 where the alkene is an alpha-olefin

containing 3 to 30 carbon atoms.

6. A method of preparing a sulfonated alkylaromatic compound wherein the sulfonate group is attached to the alkyl group comprising the steps: reacting an aromatic compound with an alkene sulfonic acid, to form an alkyaromatic sulfonic acid, wherein: a) said aromatic compound is selected from the group consisting of benzene, mono-substituted aromatic, poly-substituted aromatic, alkylbenzene, alkoxylated benzene, polycyclic aromatic, mono-substituted polycyclic aromatic, poly-substituted polycyclic aromatic, naphthalene, aikylnaphthalene, phenol, alkylphenol, alkoxylated phenol, and alkoxylated alkylphenol and b) wherein the alkene used to form the alkene sulfonic acid comprises an alkyl group selected from the group consisting of linear and branched alkyl groups of 3 to 30 carbon atoms.

7. The method as set forth in claim 6 wherein the mono-substituted aromatic compound comprises an alkyl group selected from the group consisting of linear and branched chain alkyl groups of 1 to 30 carbon atoms.

8. The method as set forth in claim 6 wherein the poly-substituted aromatic compound comprises alkyl groups each selected from the group consisting of linear and branched alkyl groups of 1 to 30 carbon atoms.

9. The method as set forth in claim 6 wherein said alkoxy group substituted on said aromatic compound is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations of two or more where the number of alkoxylate groups range from 1 to 100.

10. The method as set forth in claim 6 wherein the alkene is an alpha-olefin containing 3 to 30 carbon atoms.

11. The method as set forth in claim 6 wherein said reaction further comprises the step: adding a catalyst to the reaction mixture of the aromatic compound and the alkene sulfonic acid.

12. The method as set forth in claim 11 wherein said catalyst is selected from the group consisting of sulfuric acid, methane sulfonic acid, and sulfosuccinic acid.

13. The method as set forth in claim 6 wherein the method of preparation for the alkyaromatic sulfonic acid further combines the step: neutralizing the alkylaromatic sulfonic acid prior to use with one of the following: alkali, alkaline earth and amines.

14. The method as set forth in claim 6 wherein neutralization, and alkylation of the aromatic compound is accomplished simultaneously by adding a catalyst in the form of a salt bearing a cation to the reaction mixture of the aromatic and the alkene sulfonic acid, wherein said cation is selected from a group consisting of Na, K, NH4, Ca, Mg, Ba, and Amines.

15. The method as set forth in claim 14 wherein the catalyst is selected from the group consisting of the alkali salts of weak acids; acetic acid, propionic acid, and carbonic acid.

16. The method as set forth in claim 6 wherein the reaction further comprises a means for converting a higher percentage of the aromatic compound to the alkylaromatic sulfonic acid, wherein the means comprises the additional steps: adding water to the reaction mixture, raising the temperature of the reaction mixture to about 150┬░C for about 4 hours, reducing the temperature to about 100┬░C, distilling essentially all the unreacted aromatic and water from the reaction mixture and repeating the heating to about 150┬░C for about 4 hours, reducing the temperature to about 100┬░C,and distilling off the unreacted aromatic and water until essentially all the aromatic compound is converted to the alkylaromatic sulfonic acid.

17. The method as set forth in claim 16 wherein the method of preparation for the alkyaromatic sulfonic acid comprises the step: neutralizing the alkylaromatic sulfonic acid prior to use with one of the following: alkali, alkaline earth and amines.

18. The use of alkylaromatic sulfonic acids and their salts as surfactants for enhanced oil recovery, cleaners, detergents, emulsion polymerization, foaming agents, concrete and drilling fluid emulsions, textile, components of lubricants, or corrosion inhibitors wherein said surfactants comprise: a) the salt of an alkylaromatic sulfonic acid formed by the reaction of an aromatic compound with an alkene sulfonic acid, wherein the aromatic compound is selected from the group consisting of benzene, mono-substituted aromatic, polysubstituted aromatic, alkylbenzene, alkoxylated benzene, polycyclic aromatic, mono-substituted polycyclic aromatic, poly-substituted polycyclic aromatic, naphthalene, aikylnaphthalene, phenol, alkylphenol, alkoxylated phenol, and alkoxylated alkylphenol and

b) wherein the alkene used to form the alkene sulfonic acid comprises an alkyl group selected from the group consisting of linear and branched alkyl groups of 3 to 30 carbon atoms.

19. The use as set forth in claim 18 wherein the mono-substituted aromatic compound comprises an alkyl group selected from the group consisting of linear and branched chain alkyl groups of 1 to 30 carbon atoms.

20. The use as set forth in claim 18 wherein the poly-substituted aromatic compound comprises alkyl groups each selected from the group consisting of linear and branched alkyl groups of 1 to 30 carbon atoms.

21. The use as set forth in claim 18 wherein said alkoxy group substituted on said aromatic compound is selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, and combinations of two or more where the number of alkoxylate groups range from 1 to 100.

22. The use as set forth in claim 18 wherein said alkene is an alpha-olefin containing 3 to 30 carbon atoms.

23. The use as set forth in claim 18 wherein said reaction further comprises the step: adding a catalyst to the reaction mixture of the aromatic compound and the alkene sulfonic acid.

24. The use as set forth in claim 23 wherein said catalyst is selected from the group consisting of sulfuric acid, methane sulfonic acid, and sulfosuccinic acid.

25. The use as set forth in claim 18 wherein the preparation of the alkyaromatic

sulfonic acid further comprises the step: neutralizing the alkylaromatic sulfonic

acid prior to use with one of the following: alkali, alkaline earth and amines.

26. The use as set forth in claim 18 wherein neutralization, and alkylation of the

aromatic compound is accomplished simultaneously by adding a catalyst in the

form of a salt bearing a cation to the reaction mixture of the aromatic and the

alkene sulfonic acid, wherein said cation is selected from a group consisting of

Na, K, NH4, Ca, Mg, Ba, and Amines.

27. The use as set forth in claim 26 wherein the catalyst is selected from the group consisting of the alkali salts of weak acids; acetic acid, propionic acid, and carbonic acid.

28. The use as set forth in claim 18 wherein the reaction further comprises a means for converting a higher percentage of the aromatic compound to the alkylaromatic sulfonic acid, wherein the means comprises the additional steps: adding water to the reaction mixture, raising the temperature of the reaction mixture to about 150┬░C for about 4 hours, reducing the temperature to about 100┬░C, distilling essentially all the unreacted aromatic and water from the

reaction mixture and repeating the heating to about 150┬░C for about 4 hours, reducing the temperature to about 100┬░C,and distilling off the unreacted aromatic and water until essentially all the aromatic compound is converted to the alkylaromatic sulfonic acid.

29. The use as set forth in claim 28 wherein the preparation of the alkyaromatic sulfonic acid further comprises the step: neutralizing the alkylaromatic sulfonic acid prior to use with one of the following: alkali, alkaline earth and amines.