CA2228430A1

CA2228430A1 - Novel aromatic and aliphatic sulfonates and properties and applications thereof

Info

Publication number: CA2228430A1
Application number: CA 2228430
Authority: CA
Inventors: Khalid Rasheed
Original assignee: Individual
Current assignee: Nouryon Surface Chemistry AB
Priority date: 1996-05-31
Filing date: 1997-05-27
Publication date: 1997-12-04
Also published as: EP0851783A4; US5919975A; EP0851783A1; US6133474A; ATE347923T1; AU3368997A; EP0851783B1; DE69737085D1; WO1997045186A1; DE69737085T2; JP2002516603A

Abstract

The present invention is directed to novel alkyl glyceryl ether disulfonate compositions (ADEDS), alkylphenol polyethoxy sulfate-sulfonates, and ethoxylated alkyphenol sulfonates, and novel methods of preparation and uses thereof.

Description

W O 97/45186 PCTAJS97tO8821 NO~nBL ~RO~L~TIC l~DD ~iLIPE~TIC SlnLF~r~T~-~
~DD PRO~Kll~S ~DD ~iPPLIC~TIONS ~.~F

Both aromatic and aliphatic sul~ates and sulfonates are an important group of anionic surface-active agents used extensively in a number of industrial applications. These include operations in drilling ~or and recovery of crude oil; emulsifiers for pesticides used in crop protection; in shampoos and creams for personal care; laundry detergents; hard ~ur~ace cleaners; emulsifiers ~or emulsion polymerization systems; lubricants; wetting agents;
and dispersants in a variety of specialized industrial applications. Sul~ates, being susceptible to breakdown in acidic environments, are limited to ~ormulations used in weakly acidic or basic systems.
Although sulfonates can be used under both acidic and basic conditions, they cannot be efficiently used in high electrolyte systems. In hard waters, for example, they tend to precipitate out as insoluble calcium and magnesium salts.
The present invention relates to the synthesis and properties of novel sulfonates that are not only electrolyte tolerant and thermally stable, and can be used in the applications mentioned above, but also have other interesting and commercially useful properties.
The present invention is directed to novel alkyl di~lyceryl ether disulfonate compositions (ADEDS), alkylphenol polyethoxy sulfate-sulfonates, and ethoxylated alkylphenol sulfonates, and their methods of preparation and uses.

W O97/45186 PCTrUS97/08821 More specifically, the pre~ent invention is directed to a method ~or preparing an alkyl glyceryl ether disulfonate composition (ADEDS) which comprises a mixture of compounds o~ formula (I):

R-O-(CH2CH20)itCH2-CH-cH2s03~ (I) ~ d--Rl wherein i is an integer from O to 10;
M is a cation selected from the group consisting of lithium, sodium, potassium, ammonium, and mixtures thereo~;
Rl is (A~K-O)pH or H, wherein p is an integer from 1 to 10 and each ALK is independently ethyl or propyl; and R is straight or branched alkyl or alkenyl containing 8 to 18 carbon atoms and O to 3 carbon-carbon double bonds, the mixture cont~;n~ng compounds of ~ormula ~I) wherein d is 1, 2, 3 and 4 and optionally 5, wherein the mole average value of d in the composition is 1.8 to 2.2, the method comprising:
a~ forming a mixture of alkyl glyceryl halides o~ formula (II~

~ / ~
R-O-(cH2cH2o~i-cH2-cH-cH2-cl (II) I

~ J d--R

by reacting epichlorohydrin with an alcohol or alcohol ethoxylate of the ~ormula R-O-(CH2CH20)i-H to ~orm said W O 97/4S186 PCT~US97/08821 ~ --3--mixture of compounds of formula (II) and then optionally al~oxylating the pendant hydroxyl group on ~aid compounds of formula (II)i and then b) replacing the chloro ~ubstituent~ on the compounds of formula (II) with -S03M.
The pre~ent invention i~ further directed to a method of preparing an alkylphenol polyethoxy sulfate-sul~onate of formula (III):

-(C~ C~ O)nS ~ M
~S 03 M
~ (III) wherein R2 is a straight or branched allcyl group containing 8-12 carbon atoms, M is lithium, sodium, potassium, or ammonium, and n i8 6-10 compri~ing:
a) reacting an ethoxylated alkyl phenol of the formula R~-Ph-O(CHzCH20)nH wherein R2 and n are a~
defined above and Ph denotes a phenyl ring and the ~ubstituents thereon are in the para-position, with ~ulfur trioxide to form an intermediate of formula (IV):

~(CH2 C~ ~)n S 03 H ( IV) ~503 H

R

W O 97/45186 PCTrUS97/08821 - _4_ and ~)reacting the sulfonated product (IV) of ~tep (a) with a hydroxide of the formula M-OH under conditions wherein said product of formula (III3 i8 formed.
The present inventlon is still further directed toward~ a method of preparing an ethoxylated alkylphenol sodium sulfonate of formula (V):

~ct~2 C~2 ~)" ~

~,S03M (V) wherein R2 i8 straight or hranched allcyl con~aining 8 to 12 carbon atoms, M i~ lithium, sodium, potassium, or ammonium and n is 6 to 10, comprising:
a3 reacting an ethoxylated allcylphenol of the formula R2-Ph-O(CH2CEIzO)nH wherein R2 and n are as defined above and Ph denotes a phenyl ring and the sub~tituents thereon are in the para-position, with sulfur trioxide to form a product of formula (IV):

o--(c~2~1~2~)n S~3~ V) n~

W O 97145186 PCTrUS97/08821 and then b) reacting the sulfonated product of step (a) with a hydroxide of the formula M-O~ under conditions wherein said product of formula (V) is formed.
The present invention further relates to alkyl diglyceryl ether disulfonate compositions (ADEDS) comprising compounds of formula (I). The invention also contemplates alkylphenol polyethoxy sul~ate-sulfonates of ~ormula (III); and ethoxylated alkyl phenol sodium sulfonates of formula (V).
The present invention is further directed towards the use of compounds of the present invention in the manufacture of paper, particularly in that they optimize the effectiveness of wet strength resin additives for paper, and they increase the wet strength/dry tensile strength ratio which is very signi~icant in the manufacture of paper products that may be creped or uncreped and paper that is through-dried or not, such as paper towels, paper napkins and similar paper products.
The present invention is also directed towards the use of compounds of the present invention in the beneficiation of ores by froth flotation.
The present invention is also directed towards the use of compounds of the present invention as emulsifiers in emulsion polymerization reactions.
The present invention is also directed towards the use o~ compounds of the present invention in hard surface cleaners, laundry spot removers, and W O 97/45186 PCT~US97/08821 detergents; in dyeing o:E fibers, e.g. nylon; and as brightening agents in metal electroplating baths.
The present invention is also directed towards the use of compounds of the present invention in the deinking of waste paper.
Compounds and SYnthesis The present invention is directed towards novel alkyl diglyceryl ether disul~onates (ADEDS), alkylphenol polyethoxy sulfate-sulfonates, and ethoxylated alkylphenol sulfonates, and to novel methods o~ preparation o~ these compounds.
More particularly, the present invention is directed to a process for preparing an alkyl diglyceryl ether disulfonate composition (ADEDS) which comprises a mixture of compounds o~ formula (I):

R-O-(CH2CH2O)i-CH2-CH-CH2SO3M (I) O / d--Rl wherein i is an integer from O to 10;
M is selected from the group consisting o~ lithium, sodium, potassium, ammonium, and mixtures thereof;
R1 is (ALK-O)pH or H, wherein p is an integer from 1 to 10, and R is straight or branched alkyl or alkenyl containing 8 to 18 carbon atoms and O to 3 carbon to carbon double bonds. The composition is a mixture of compounds wherein d is ~, 2, 3 and 4. Typically, compounds wherein d is 5 are also present, in trace amounts. Each ALK present can be ethyl or propyl; the preferred propyl group is isopropyl. Pre~erably, when WO 97/45186 PCTrUS97/08821 Rl is an alkoxylate group it is entirely ethoxylate or entirely propoxylate.
- The preparation of the compound of formula (I) comprises reacting epichlorohydrin with an alcohol or alcohol ethoxylate of the formula R-O-(CH2CH2O)i-H, wherein i and R are a~ defined above, under conditions wherein an intermediate compound of formula (II) is formed:

R-o-(cH2cH2o)i- CH2-CH-CH2-Cl (II) ~ J d--Rl It should be understood that the reaction with epichlorohydrin generally forms a mixture of adducts formed as epichlorohydrin reacts with the pendant hydroxyl group left by addition of a previous molecule of epichlorohydrin. Typically, the reaction mass formed in production of the mixture of compounds of formula (II), carrying out the reaction under the conditions disclosed herein, is a mixture containing on the order of about 35 to 45% monoadduct, about 35 to 45~ of diadduct, about 10 to 20% of triadduct, about 2 to 10~ of tetraadduct, and optionally traces of pentaadduct. According to gas chromatographic analysis of a typical such reaction mass, the mass is a mixture of about 40~ mono-adduct, about 40% of diaddict, about 15% of triadduct, about 5~ of tetraadduct, and traces of pentaadduct.
The reaction with the epichlorohydrin to form the mixture of compounds of formula (II) is believed to form byproducts having either or both of the structures (II-A) and (II-B):

R-O-(CH2CH2O)i~ CH2CH-CH2-Cl / \ (II-A) O / d~ CH2CHCH2Cl o J l 2R

R-O-(CH2 CH20 ) i ~CH2 CHCH2 C 1~ (II-R) ~ /d-- CH2CH (oRl) CH20- (CH=CHCEI20) 2H

Employing the reaction conditions described herein generally leads to a reaction mixture wherein the mixture of compounds of formula (II) constitutes on the order of about 60~ of the reaction mixture.
Preferably the reaction to form the product mixture of compounds of formula (II) involves an acid catalyzed addition of epichlorohydrin to the alcohol or alcohol ethoxylate in a 2:1 molar ratio of epichlorohydrin to alcohol or alcohol ethoxylate. The catalyst may be any protonic acid or Lewis acid suitable for acid catalyzed addition, preferably boron trifluoride.
At this point the pendant hydroxyl group of the intermediate compounds (II) wherein R1 is -H may optionally be alkoxylated with 1 to 10 ethoxy and/or propoxy units. Preferred alkoxylates contain 2 to 6 ethoxy units or 2 to 4 propoxy units. The reaction is a conventional acid-catalyzed alkoxylation with CA 02228430 l998-0l-30 W O 97/4~186 PCT~US97/08821 ethylene oxide and/or propylene oxide. Boron trifluoride is the preferred catalyst The resulting mixture of compounds of formula (II) contains chloro substituents which are then replaced with -SO3M. This reaction is performed under conditions suf~icient to replace all the chloro substituents in ~II) with -S03M. Preferably this reaction involves the reaction of the compounds of formula (II) and an aqueous solution of M2S03 at a temperature of 50~C to 300~C, preferably 150-160~C.
The reaction may embody the conditions of the well known Streckerization reaction. The preferred cation M is sodium.
Mass spectral analysis indicates that this mixture contains compounds corresponding to formulas (I), (I-A) and (I-B):

R-O-(cH2cH2o)itcH2-c~H-cH2so3M (I) ~ / 1-4-- Rl W O 97/45186 PCT~US97/08821 RO(CH~CH~O)l -- CH2-~CH-CH2SO3M
0 ~ 3 CH2C~H-cH2O

¦I-A) RO(CH~CH~O)l ~ CH2-CH-CH2SO3 ~
o / CH,CH-CH,OtcH~cH-cH~O~H

(I-B) wherein i i8 an integer from 0 to 10; and Rj Rl, and M
are as defined herein. Thi~ mixture is referred to collectively as alkyl diglyceryl ether disulfonates ~ADEDS).
Preferably R i~ straight or branched C~
(such as 2-ethylhexyl), C10, Cl2, Cl3, Cl4, or oleyl.
Mixtures of compounds of the foregoing formulas are also contemplated. A preferred mixture i8 that obtained from "~xxal 12", a commercially available mixture of methyl-branched nonanols. The R groups can be synthetic or can be derived from naturally occurring sources such as fatty alcohols, e.g. oleyl alcohol.
The present invention is also directed towards methods of preparing an alkylphenol polyethoxy sulfate-sulfonate of formula (III):

W O 97/45]L86 PCTrUS97/08821 (CH2C ~2 ~)nS ~ M (III) . ~SO3M

R~
wherein M is a lithium, sodium, potassium or ammonium cation, R2 i8 straight or branched alkyl containing 8-12 carbon atoms and n is 6-~0.
The process involves the sulfonation of an ethoxylated alkyl phenol of the formula R2-Ph-O(CH2CH20)nH, wherein R2 and n are as defined above and Ph denotes a phenyl ring and the substituents thereon are in the para-position, with sulfur trioxide under conditions effective to form an intermediate of formula (IV):

~(CH2 CH2 ~)n S03H
~ 03H (IV) Preferably this sulfonation reaction is performed with a 2:1 molar ratio of S03 to R2-Ph-0 (CH2CH20) nH using a continuous air/S03 thin film sulfonator.
The sulfonated intermediate (IV) is then neutralized with a hydroxide of the formula M-OH and preferably with sodium hydroxide, under conditions wherein said product of formula (III) is formed.

W O 97145186 PCT~US97/08821 Further, the present invention is directed toward6 the preparation of an ethoxylated alkylphenol ~ulfonate of formula (V):

~(C~2 C~2 ~)n H (v) ~SO3M
J
~.

wherein M i8 a lithium, sodium, potassium or ammonium cation, ~2 iS a straight or branched alkyl group containing 8 to 12 carbon atoms, and n is 6 to 10.
The ethoxylated alkylphenol sulfonate of ~ormula (V) is prepared from intermediate (IV) prepared as described above. Preferably, M is a sodium cation.
To prepare the alkylphenol sulfonate (V), the product (IV) is desulfated under conditions such that an ethoxylated sulfonated product is obtained.
Preferably, this de~ulfation is performed by heating an aqueous solution of intermediate (IV) and subsequently neutralizing the solution with an alkali, to obtain an ethoxylated sulfonate of formula (V).
This reaction generates a molar amount of sulfate which separates as a saturated aqueous phase.
The saturated aqueous phase can be separated leaving behind a compound of formula (V) containing low levels of alkali sulfate.

W O97/45186 PCT~US97108821 In a preferred method, the intermediate (IV) is reacted with 3 moles of concentrated ~odium hydroxide, and heated to about 20~C to 150~C, pre~erably about 60~C, under conditions wherein said product of formula (V) is formed The present invention further contemplates mixtures o~ alkyl glyceryl ether sulfonate compounds of formulas (I), (I-A) and (I-B):

R~o-(cH2cH2o)i~cH2-clH-cH2so3M) (I) RO(CH2CH2O)i ~ CH2-CH-CH2SO3~
~ 1-3 ~CH2C~H-CH2O - H

(I-A) RO(CH2CH2O)i ~ CH2-CH-CH2SO3M~ ~
O J CH2CH-CH2O ~H=CH-CH2O-H
1-3 OR \ ~2 (I-B) wherein i is an integer from 0 to 10; and R, Rl, and M
are as defined above.
The present invention further contemplates an alkylphenol polyethoxy sulfate-sulfonate compound W O 97145186 PCTrUS97/08821 of ~ormula (III):

~(CH2 cH2 ~)n SO3M
SOgM (III) ~2 wherein R2 is straight or branched alkyl of 8 to 12 carbon atom~, and n and M are as defined above.
The pre~ent invention is still further directed towards an ethoxylated alkylphenol sul~onate compound o~ ~ormula (V):

~--(CH2 C~ ~)n H (v) ~b~S03M

wherein R2 is straight or branched alkyl containing 8 to 12 carbon atoms, and n and M are as defined above.

Example 1 Preparation of Alkylphenol polyethoxy sulfate-sulfonates Employing the typical procedure for making these compounds, 1.0 mole of a nonylphenol 10-mole ethoxylate was treated with 2.0 moles of S03 in a laboratory air/S03 falling-film sulfonating apparatus.
The ethoxylate, at about 60~C., was fed to this sulfonator at 8-10 grams per minute, and contacted there with a stream of air/S03 at about 35~C. The reaction zone was maintained at 70-75~C. A sulfate-sulfonic acid corresponding to formula IV, with R2=Cg and n=10 (having an acid number of 135-140) was obtained as a dark viscous liquid. This product was then neutralized by addition to a stirred aqueous solution of about 10 wt.~ NaOH, which yielded the disodium product of formula III with R2=Cg and n=10, as a Iight tan liquid.

CA 02228430 l998-0l-30 W O 97/45186 PCT~US97/08821 Example 2 PreParation of ~lkylphenol PolYethoxy sodium sulfonates Employin~ the typical procedure for making these mixtures of compounds, to a stirred aqueous solution of 50 wt.~ sodium hydroxide (3 moles) was added 1.0 mole of the acid of formula IV (R2=Cg) which was ~ormed in Example 1. The heat of neutralization was allowed to raise the temperature of the mixture to 75-80~C. After addition of the acid I~ was complete, the mixture was heated to maintain its temperature at 75-80~C. for 2 hours. Heating was then discontinued, and about 1,000 ml of water was added to the mixture which was then stirred for an additional 30 minutes.
The mixture was then allowed to cool to 30-40~C
without agitation, and it formed into two distinct aqueous phases. The lower phase (about 650 grams), a saturated aqueous solution of Na2S04, was withdrawn and discarded. The upper phase, a tan solution, contained 55-60 wt.~ of a compound of formula V with R2=Cg and n=10.

W O 97/45186 PCTrU~97/08821 .

Example 3 Preparation of Alkyl DiqlYceryl Ether Disulfonates (ADEDS) Employing the typical procedure for making these mixtures of compounds, 800 g of lauryl alcohol (containing a minor proportion of Cl4 alcohol) and 8.5g of boron trifloride etherate were charged to and mixed in a 1-gallon Parr pressure reactor. The reactor was evacuated and pressurized with nitrogen to 60 psi, and vented. The stirred mixture was heated to 50OC, and then 724 g of epichlorohydrin was added slowly to maintain the reaction temperature at 60-70~C. After addition of epichlorohydrin was complete, the mixture was held at 60-70~C for 60 minutes. The product was a mixture of compounds corresponding to formula II with R=C12/Cl4, i=0, and mono-, di-, tri- and tetra-adducts present wherein the average value of n in the mixture was about 2.
For conversion to the ethoxylate, the mixture was heated to 100~C., and 176 g of ethylene oxide was added over 60 minutes. This formed product of formula II in which R=Cl2/Cl4, i=0, and -(ALK-O)pH =
~(CH2CH2O)4H
For conversion to the mixture of sulfonates, the product of formula II (1,530 g), 4,600 ml of water and l,000 g of sodium sulfite were charged to a Parr reactor. The reactor contents were stirred and heated to 160-170~C (correspondingly the pressure reached 80-100 psi) until the reaction was complete (requiring 10-12 hours) as monitored by assaying for sulfite.

W O97/45186 PCT~US97/08821 The reaction mixture was cooled to 50~C. and sufficient hydrogen peroxide was added to convert residual sulfite to sulfate. This yielded a mixture of sulfonates of formula I wherein R=Cl2/C14, i=0, and R1=H, as a hazy mixture.

Properties and Applications The alkyl glyceryl ether sulfonate mixtures of formula (I), the alkylphenol polyethoxy sulfate-sulfonates of formula (III), and the ethoxylated alkylphenol sulfonates of formula (V), have a number of useful properties and applications which also comprise aspects of the present invention.

Electrolyte Tolerance/Emulsion Polymerization One example is in emulsion polymerization.
This method of polymerization, which is well known in general, is useful in the production of a wide variety of polymers and copolymers, including but not limited to polymerization of: styrene and copolymers of styrene including acrylonitrile-butadiene-styrene, styrene-butadiene and styrene-acrylonitrile;
acrylamide; acrylates, methacrylates, and derivatives ~uch as 2-dimethylaminoethyl methacrylate and 2-diethylaminoethyl methacrylate, acrylic acid, methacrylic acid, 2-hydroxyethyl methacrylate and 2-hydroxyethyl acrylate; vinyl chloride, vinyl acetate, vinyl sulfonate, and the like.

W ~ 97/45186 PCTAUS97/08821 --lg--Emul~ion polymerization i8 typically carried out starting from an aqueous system containing the monomer(s~, one or more surfactants, an initiator system for the polymerization, and optionally other conventional additives. The concentration of the surfactant is generally in the order of 10 to 100 grams per liter, depending chiefly on identity, concentration, and solubility of the monomer(s).
Conventional emulsion polymerization methods often include a step in which an electrolyte such as aluminum sulfate or calcium chloride is added to mediate precipitation o~ the polymer particle ~rom the a~ueous phase. With surfactants conventionally employed heretofore in emulsion polymerization, anionic surfactants are usually found to coprecipitate with the precipitated polymer as the insoluble calcium or aluminum salts. The surfactant which coprecipitates with the polymer is effectively a cont~m;n~nt and can adversely affect the polymer's properties and its usefulness for certain applications.
The compounds of the present invention (e.g.
compounds of formulas (I), (III) and (V)) are useful as surfactants in emulsion polymerization systems. In that application they exhibit the surprising and useful property that they have a significantly reduced tendency to coprecipitate with polymers which are formed via emulsion polymerization.
This reduced tendency to coprecipitate is reflected in the degree of electrolyte tolerance which the compounds of the present invention exhi~it. The CA 02228430 l998-0l-30 W O 97/45186 PCTAU~97/08821 following example demonstrates electrolyte tolerance of compounds of this invention, and thereby indicates that the compounds of this invention exhibit superior performance in other contexts needing high electrolyte tolerance, such as in emulsion polymerization wherein low coprecipitation of surfactant is an advantage.

ExamPle 4 Electrolyte Tolerance Samples, each 50 ml of 1 wt.~ surfactant in water, were prepared. To each stirred ~ample was added either a 1 wt.~ or a 5 wt.~ aqueous solution of either aluminum sulfate or calcium chloride The amount of solution that could be added before the sample became cloudy was recorded, and is set forth in the following Table 1. A higher number for a given electrolyte indicates that more of that electrolyte could be present before the cloudy end point was reached, and thus indicates a higher degree of electrolyte tolerance.

W O 97/45186 PCTrUS97/08821 Table 1 Electrolyte Tolerance ml o~ Electrolyte Added to Cloudy End Point Sample Surfactant Aluminum Sulfate Calcium Chloride No. 1 wt.~ 5 wt.~ 1 wt.~ 5 wt.
- Sodium 11 --- 50 ---dodecyl diphenyl oxide disulfon-atel 1 Formula >250 >250 >250 >250 (III), M=Na n= 10 R2=nonyl 2 Formula >250 >250 >250 >250 (V), M=Na n= 10 R2=nonyl 3 Formula >250 >250 >250 >250 (V), M=Na n= 9 R2=
dodecyl 4 Formula >250 >250 >250 >250 (III), n=6, M-Na R2=nonyl Formula >250 >250 >250 >250 (III), M=Na n=5,R2=
dodecyl (1) "Dowfax 2A1", a commercial surfactant W O 97/4S186 PCT~US97/08821 6 Formula >250 >250 >250 >250 (III), n=g, R2=
dodecyl 7 Formula >150 >150 ~150 >150 (I) 2, i=o, Rl=H
R=C12/Cl4 8 Formula >150 >150 >150 >150 (I)2, i=o, Rl=
(CH2CH2O)4H
R=C12/Cl4 9 Formula c30 clO c15 c4 (I) 2~ i=o, Rl=
(c3H6o)4H
R=Cl2/Cl4 Formula >150 >150 >150 >150 (I)2, i=4, Rl=H
R=Cl2 / C14 11 Formula >150 ,150 >150 >150 (I) 2 , i=o, Rl=
(CH2CH20) 8H
R=Cl2/Cl4 12 Formula >150 >150 >150 >150 (I) 2, i=o Rl=H
R=1,3,5-tri-methyl-nonyl 3 13 Formula >150 >150 >150 >150 (I)2, i=o, Rl=H R=2-ethyl-hexyl W O g7/4S186 PCT~US97/08821 14 Formula >150 ~150 >150 ~150 (I)2, i=o, ~ Rl=H
R=oleyl Formula >150 >150 >150 ~150 (I) 2~ i=o, Rl=H
R=C,3/Clo (2) = a mixture of mono-, di-, tri-, tetra-and possibly trace amounts of penta-adducts, wherein the mole average value of d is about 2; and M=Na.
(3) = deri~ed from "Exxal 12"

W O 97/4~186 PCTAUS97/08821 -2~-Example 5 As further demonstration of the utility of the products of the present invention in emulsion polymerization, styrene was polymerized in emulsions containing as the surfactant either a mixture of mono-, di-, tri- and tetra-adduct compounds of formula (I), wherein R is 1,3,5-trimeth~l nonyl (derived from "Exxal 12"), i=0, M is Na, and the mole average value o~ n is about 2 and R1 is H (product "DS" in Table 2), or a commercially available sodium Cl4/C16 alpha-olefin sulfonate (compound "AOS" in Table 2).
The polymerizations were run batchwise.
Since product DS contained about 5 wt.~ of salt, salt was added to the AOS so that each surfactant had the same amount of salt. The batch polymerizations were run at 70~C. for 6 hours with either 1.5 wt.~ or 3.0 wt.~ surfactant present, and with 0.5 wt.~ sodium persulfate as initiator. All weight percentages are expressed herein as % b~ weight of the initial monomer weight.
The properties of the latexes obtained are set forth in Table 2:

CA 02228430 l998-0l-30 W O 9714~86 PCT~US97/08821 Table 2 Surfactant/ Product yield, Particle size, concentration ~ nm AOS/l~ 92.7 116/48 AOS/3~ 95.9 77/22 DS/1% 79.4 98/31 DS/3~ 97.g 73/23 The data in Table 2 show that the product "DS" is an ef~ective surfactant for emulsion polymerization. At 1~ concentration, product ~DS~
gave subs~antial coagulum. At 3% concentration, the coagulum was very low and even better than AOS. The stability of the latex emulsion was found to be excellent.

Wettinq The compounds of the present invention are also useful as wetting agents. A particularly valuable application of this property is in the formation of pulp from which paper is made. The pulp comprises water, feedstock, a surfactant component, and optional conventional additives. The feedstock can be recycled material such as paper, paperboard, cardboard, and the like; and can be pulpwood directly from trees, having been suitably processed if desired e.g. by kraft processing, sulfite bleaching, or otherwise; or a mixture of recycled material and pulpwood.

W O 971~5186 PCT~US97/08821 It is desirable to include a surfactant component to increase the rate of wetting, and to increase the extent of wetting, by which the aqueous medium wets the external and interstitial surfaces of the feedstock. Increasing the rate and the extent of wetting are associated with formation of improved pulp, at a faster rate and with a more desirable consistency and ~uality to the pulp and the paper obtained from it.
In general, wetting is provided by adding 0.1 to 20.0 pounds of surfactant per ton of feedstock, to the pulp. Preferred amounts are 1.0 - 10 pounds per ton.
The ability to enhance the wetting of the feedstock can be characterized by absorbency rates (rate of water absorption by the feedstock) and by increases in the absorbency rate (as ~ absorbency rate change, compared to standard). The advantages of using compounds according to the present invention are demonstrated in this way in the following example.

Exam~le 6 The determination of wetting was assessed as ~ absorbency rate change, using standard methods employed in the paper industry.
The compounds tested for ~ change in the rate of water absorption, and the identities of those compounds, are shown in Table 3.

W O 97145186 PCTrUS97/08821 The ethoxylated alkylphenol sulfonate compounds showed good water absorbency in several feedstocks.

CA 02228430 lsss-0l-30 W O97/45186 PCT~US97/08821 Table 3 Absorbency Rates Feedstock = Recycled cardboard cartons:
Dose (lbs.
surfactant/
ton of ~Absorbency Rate Chanqe Surfactant feedstock) 0-5sec. 6-12 sec. 20 sec.
Formula 0. 5 +7.7 +56.0 +31.3 (III), n=
10, R2=nonyl 1.0 +20.5 +68.0 +43.4 3.0 +17.9 +48.0 +34.5 5.0 +12.8 +60.0 +37.5 Formula 0. 5 +20.5 +44.0 +27.4 (V), n=
10, R2=nonyl 1.0 +23.1 +32.0 +28.6 3.0 +30.8 +36.0 +32.7 5.0 +33.3 +44.0 +34.3 W O 97/45186 PCT~US97/08821 Feedstock=Northern softwood (kraft):
Formula 0.5 +18.5 -9.4 +5.3 ~ (III), n=
1 o , R2 =nonyl 1.0 +9.3 -5.6 +5.0 3.0 +13.3 -13.2 +3.5 5.0 +22.2 -9.4 +10.5 Formula 0.5 +35.2 +1.9 +14.6 (V), n=
1 0 , R2=nonyl 1.0 +31.5 -7.5 +9.9 3.0 +40.7 -5.6 +14.7 5.0 +57.4 +3.6 +30.2 Exam~le 7 Compounds of the present invention were also tested for their effect on dry tensile strength, and on absorbency (as % change of absorbency rate) of tissue handsheets produced from unbleached recycled ~iber (Freeness #303) to which a surfactant of the present invention had been added in the pulp. The results are set forth in Table 4. They show very useful and significant improvement in the properties of the paper product.

W O 97/45186 PCT~US97/08821 Table 4 Dose (lbs.
surf./
ton of % Dry Surfactant feed- Tensile ~ Absorbency Rate Chanqe etock) change 0-5 sec. 6-12 sec. 20 eec.

Formula 0.5 +11.0 +18.5 0 +ll.0 (V), n= 10, R2=nonyl, M=Na 1.0 +5.2 +21.5 +12.2 +16.3 3.0 +3.1 +26.2 -5.6 +12.2 5.0 +6.7 +29.2 +11.1 +24.3 Formula 0.5 +14.1 +32.3 +19.4 29.0 (III), n=
10, R2 =nonyl, M=Na 1.0 +7.6 +30.8 +27.8 +34.9 3.0 +20.8 +10.8 +2.8 +9.9 5.0 +20.0 +3.1 0 +0.7 Formula 1.25 +41.0 -13.8 +11.1 -10.4 (I), i=o R=Cl2/Cl4 /
Rl=
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M=Na 2.50 +48.4 +18.5 +19.4 +16.4 7.50 +34.8 +10.8 +11.1 +7.3 12.50 +46.6 +16.9 +12.2 +16.6 W O97/45186 PCT~US97/08821 Formula 1.25 +46.4 -6.2 -5.6 -7.6 (I), i=0, Rl=H, R=1,3,5-trimethyl-nonyl, M=Na 2.50 +48.2 +7.7 +12.2 +10.1 7.50 +36.1 +10.8 +16.7 +12.4 12.50 +52.7 +3.1 o +0.3 Formula 1.25 +42.3 +4.6 0 +6.0 (I), i=o, Rl=H, ~=Cl2/
M=Na 2.50 +45.1 +12 3 +12.2 +11.9 7.50 +33.8 +24.6 +22.2 +23.6 12.50 +28.6 +29.2 +30.6 +30.2 Example 8 Compounds of this invention were also tested by standard procedures to determine and correlate the percentage changes in dry and wet tensile strengths, the percentage changes in absorbency rate, and the percentage change in capacity index, in the production of paper tissue and towels from several different feedstocks. The results are set forth in Tables 5-8.
The data demonstrate that the inventive compounds are effective wetting agents.
Significantly, they increase the wet/dry tensile ratio when used with a known wet strength resin like "Kymene 557Hn. The compounds tested had little or no effect W O 97/45186 PCT~US97/08821 on dry tensile (debonding) or density (bulk enhancement). This results in an economic savings because a paper manufacturer would be able to use less wet strength resin.
The data also indicate that absorbance rates, capacities and uptake of the wet strength resin are not significantly changed by alkoxylation or modification of the alkyl moiety. Aromatic ~ulfonates, (III) and (V), and ADEDS, (I), show excellent performance at dosages of, for example, 1.25-1.5 lbs. per ton.
The compounds of the present invention demonstrate outstanding performance for the production of a range of paper products such as toilet tissue, paper towels, paper napkins, facial tissue, and fine paper. The paper may be creped and pressed, uncreped, and unpressed, including processing wherein the sheet is through dried. The utility of these unique compounds can be further enhanced by formulating them with other surface-active materials including nonionic wetting agents. Preferred materials include alkoxylated C8-C20 alcohols, and C2-C20 alkylphenols, as well as silicone based surfactants.
In the tests reported in Tables 5-8, each indicated dose size of surfactant was added to the pulp together with 20 pounds per ton of the wet strength resin "Kymene 557H". The tables show however only the dose sizes and the identities of the surfactants used.

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W O 97/45186 PCTrUS97/08821 DYe Levelinq During dyeing of a fiber it iB important that the dye is evenly distributed throughout the fiber. This is known as dye-leveling. The alkyl diglyceryl ether disulfonate (I), alkylphenol polyethoxy sulfate-sulfonate (III), and ethoxylated alkylphenol sulfonate (V) compounds of the present invention are useful in that when a fiber is being dyed, such as a nylon fiber, they assist attaining uniform distribution of dye throughout the ~iber being dyed. This property is useful for instance in the carpet industry. In general, one can use effective amounts ranging generally ~orm 0.5~ to 5~ by weight o~
surfactant based on the weight of dye.

Exam~le 9 The compounds of the present invention were tested as dye-levelers and compared to "Dowfax 2A1", a commercially important dye-leveling additive.

Preparation of DYe Stock A trichromic dye stock solution was prepared by mixing 21.0 grams o~ 0.5~ Ciba Tectilon orange 3G200, 10.5 grams of 0.5~ Ciba Tectilon blue 4RS KWL
200, 10.5 grams of 0.5~ Ciba Tectilon red 2KWL 200N
with 2.0 grams o~ Ammo~;um sulfate. The mixture was diluted to 4000 grams with tap water and mixed well.

W O 97/4~186 PCT~US97108821 NYlon DYe Levelinq 400 gram aliquots of the dye ~tock ~olution were poured into stainless steel cylinders, and the surfactant to be tested was added, 0.1 grams to 1.0 gram of 10% active. "Dow~ax 2A1" was used for comparison. The material was mixed and adju~ted to pH
5.8-6.0 with 10~ acetic acid. A 10 gram swatch of Nylon 6 Barre (tiger) cloth, from Monsanto Co., was added along with 3-4 stainless steel balls. The cylinder was sealed and placed in an Atlas Laundrometer at 20~C. The cylinders were heated to 80~C, at an average rate of 1~C/minute, for 60 minutes. The cylinders were cooled to 30~C, the swatch removed, rinsed with tap water and allowed to air dry overnight. The dried swatches were analyzed on the Hunter Lab D25M/L colorimeter and the L values (whiteness and brightness) recorded. The data obtained on the two ends, lengthwise, of each swatch is expressed as ~ leveling.
The results are shown in Table 9. The compounds o~ the present invention performed as well as or better than "Dowfax 2A1".

W O 97/45186 PCT~US97/08821 Table 9 Dye Levelinq Concentration Suractant (wt.~) ~ Dye Leveling "Dowfax 2A1" 0.015 83.8 0.0075 97.7 Formula (I), 0.015 96.8 i=o, Rl=H, R=1,3,5-trimethyl-nonyl 0.0075 94.6 Formula (I), 0.0075 95.8 i = o , Rl=(C3H6O)4H
R=Cl2/Cl4 Formula (I), 0.0075 99.4 i=o, Rl= (CH2CH20) 8H
R=Cl2 - C14 Formula (V), n= 0.015 98.6 10 R2=nonyl Formula (III), 0.015 97.0 n= 10 RZ=nonyl WO 97/45~86 PCT~US97/08821 Froth Flotation The compounds of the present invention are also useful as frothers in the froth flotation beneficiation of ores. A particular example is the froth flotation of phosphate ore to separate impurities present in the ore as it naturally occurs.
In general, flotation can be carried out by slurrying water and the finely divided ore in a cell with the surfactant of the present invention in amounts of about 0.02 to 2.0 pounds of surfactant per ton of ore (preferably, 0.025 to 1.0 pounds of surfactant per ton of ore). Other additives can also be present, such as tall oil fatty acids (TOFA) as auxiliary frother;
other possible additives can include collectors and depressants, as needed in the amounts useful to achieve those functions.
Air is then circulated into the cell at its bottom and upwards through the slurry, at a flow rate effective to form a froth in the slurry. The froth containing the impurities is skimmed off continuously, or otherwise removed, all in accordance with known techniques.

Example 10 The effectiveness of the compounds of the present invention in froth flotation for the beneficiation of ores was measured using known standard methods. The results for phosphate ore flotation using compounds of this invention in ~ combination with tall oil fatty acids are shown in W O97/45186 PCTrUS97/08821 Table 10. The beneficiation observed for phosphate rock even at 0.04 lbs/ton using the lauryl alcohol based ADEDS mixtures is noteworthy.

Table 10 Surfactant Amt. (lb. TOFA1 ~Phosphate /ton of ore) (lb./ton) Recovery (None) -- 1.0 11.0 (None) -- 2.0 64.0 Formula 0.75 l.O 86.0 (I) 2, i=o~
Rl=H, M=Na R=Cl2/Cl4 Formula 0.04 1.0 48.0 (I) 2, i=o, Rl=H, M=Na R=Cl2 / C14 Formula 0.75 1.0 89.0 ,(I) 2, l=o, M=Na Rl=
(CEI2CH20) 8H
R=Cl2 / C14 (l)= TOFA i8 tall oil fatty acids.
(2)= A mixture of compounds in which n i8 each 1-5 and its mole average value is about 2.
Hard Surface Cleaners, Stain Removers, and Laundry Deterqents The compounds of the present in~ention are also useful in cleaning substrates ranging from fabrics and carpeting, to hard surfaces such as floors, porcelain fixtures, countertop~, and the like.

They can be formulated into cleaning products contA; n; ng 0.1 to 20 wt.~ or more, of one or more compoundR of the present invention. Several compounds of the present invention were tested as laundry detergents using test methods well known in the industry. The results are shown in Example 11 and Table 11.
~ he low molecular weight and branched compounds of formula (I) were found to be good compatibility agents and good lime-soap dispersants even at low pH. The ADEDS were also found to be efficient spot removers for laundry applications.

CA 02228430 l998-0l-30 WO 97/45186 PCT~US97/08821 Example 11 Swatches of fabric which were soiled or stained were prepared and washed using various compound~ of the present invention as the soil removal/stain removal surfactant. The degree of effectiveness, as ~ removal, was then determined. The washing was carried out in 100 ppm hardness water at 700~., in 1-liter o~ wash water containing 1 gram of surfactant (=1 gpl). The wash cycle was 10 minutes, the rinse cycle was 5 minutes, agitation was at 100 rpm, and the rinsed swatche~ were air dried overnight.
The results were:

W O 97145186 PCTnUS97/08821 Table 11 ~ Soil/Stain Removal Surfactants:
Fabric Soil/Stain A B C
Cotton Clay 71.6 72.7 79.9 Cotton Olive oil 79.8 84.6 93.4 Cotton/ Co~fee 79.9 85.7 87.1 polyester Cotton/ Grape 81.6 92.0 93.6 polyester juice Surfactant A: Formula (I), i=o, Rl=H, R=1,3,5-trimethyl-nonyl, M=Na B: Formula (I), i=O Rl=(CH2CH20)4H, R=Cl2/Cl4, M=Na C: Dodecylbenzene sulfonic acid, sodium salt WO 97/45186 PCTrUS97/08821 PaPer Deinkinq The compositions of the present invention are also useful in deinking of waste paper. While paper deinking is known, it is summarized here.
In general, effective deinking is provided by intimately contacting the waste paper with any of the compositions of the present invention, preferably in an aqueous or other liquid medium to provide desired fluidity and penetration of the sur~actant components to the paper/ink interface. Preferably, the waste paper is first shredded or otherwise converted to small pieces so as to improve the contact o~ the paper and ink with the liquid medium bearing the surfactants. Of course, appropriate agitation can be provided to enhance the desired contact between the sur~actant components and the paper/ink interface.
It is preferred to utilize the compositions of the present invention in connection with the froth flotation of ink from the waste paper. The general conditions of froth flotation deinking techniques are known in this ~ield. The waste paper is pulped in an aqueous bath, which has preferably been rendered alkaline by appropriate adjustment of the pH via the addition of a base such as sodium hydroxide.
Preferably, the pH is about 9 to 11. The desired composition or compounds o~ the present invention are added at amounts calculated to provide the desired ratio between amounts of the respective compounds.
The overall amount o~ product to use is selected with respect to the quantity o~ the paper in the cell and CA 02228430 l998-0l-30 W O 97/45186 PCTnUS97/08821 with respect to the general amount of ink product on the paper. Generally, the total amount of product comprises about 0.05-0.1 wt.~ to about 5.0 wt.% and preferably up to about 1.0 wt.~ based on the amount of waste paper present. Lesser amounts risk reducing the efficiency of the deinking, whereas higher amounts may assist in the deinking of waste paper but not necessarily enhance the efficiency of the deinking in proportion to the additional amounts of product used.
The flow of gas, typically air, through the flotation cell agitates the liquid medium and the waste paper, provides enhanced contact with the product, and propels ink particles removed ~rom the waste paper to the top surface where a froth rich in removed ink is establi~hed. The froth can be removed or continuously or intermittently. After a period of time appropriate for the volume of the cell and the quantity of waste paper and its ink content, the pulp of deinked waste paper is removed from the cell for further processing toward the recovery and reuse in regenerated paper products.
The present invention has been found to provide improved effectiveness and efficiency in the deinking of waste paper, particularly waste paper comprising mixtures of different types of paper.

Example 12 To demonstrate the effectiveness in paper deinking of compositions containing compounds of W O 97145186 PCT~US97108821 formula (I), the following comparative tests were carried out.

EXPERIMENTAL PROCEDURE
RepulPinq A furnish of mixed office waste consisting of 70~ laser-printed paper and 30~ ledger paper was repulped in a Modern Laboratory Slush-Maker at 2900 rpm, and 6~ consistenc~. Initially water (28.4 liters) was added, then steam was injected to increase the temperature to 120~F. Four pound (O.D.) batches were added over 5 minutes to maintain stock circulation in the Slush-Maker. The pH was adjusted to 10 with 5~ NaOH. The repulping was performed at the followin~ conditions:

Consistency - 6~
Temperature - 120~F
pH - 10 Repulping time - 30 minutes After repulping the stock from the Slush-Maker was diluted to approximately 0.75-0.08~ consistency to make a ~master batchn. The temperature of the master batch was adjusted to 100~F before it was fed to the flotation cell.

Flotation CA 02228430 l998-0l-30 W O 97/45186 PCTrUS97/08821 Flotation was performed in a laboratory-scale flotation cell. The furnish was added manually at approximately 0.8~ consistency to the flotation cell which has a 7.7 gallon capacity. The furnish was recirculated in the flotation cell at 15 gal/minute for mixing. The surfactants as identified in Table 12 were allowed to mix five minutes prior to starting the compressed air flow to cell. The air flow was fed at 8ft3/minute. All the surfactants were diluted to 68.1 gms/liter and added at o.3, 0.6 and o.g~, based on dry solids. Inky foam formed on the surface is rejected out the center of the cell while accepts remain in the cell. The ~lotation cell was operated for ten minutes while collecting rejects. Six flotation runs were performed at different surfactant addition levels with one master batch. Samples o~ feed and accepts were collected for brightness pads. Rejects were collected and weighted for yield calculation.

Briqhtness Pads After repulping and flotation, portions of the furnish were taken to make brightness pads (TAPPI
Standard T-218). Five air dried brightness pads were made for brightness and dirt count. Brightness was measured (two readings on each side of five sheets) on the pad surface using S~-M a brightmeter.

Yield W O 97/45186 PCT~US97/08821 The flotation yield was calculated using the equation below.
Capacity of flotation cell =7.69 gallon Mass of flotation cell =29121 grams Cp =Consistency of Feed C~ =Consistency of Reject WR =Weight of reject Yield = 100 x ((29121 x CF)_(WP X CP)) (29121 x CF

Imaqe analysis Particle count measurements were performed on a Spec "Scan" image analyzer. It uses a HP Scan Jet scanner to digitize the image of the paper samples at resolutions up to 800 dots per inch, that is, it can detect dirt and/or ink specks as small as 0.032 mm in diameter or about 0.001 mm2 and counts and categorizes the specks size. Scanning was performed only for the MOW furnish. Ten four inch round circles were scanned for each samples. The total area scanned for each sample was 0.042 m2. The scanner settings are the following:

Resolution: 600 dots/inch Threshold: 80 manual The results obtained are set forth in Table 12:

W O 97/45186 PCTrUS97/08821 Table 12 Furnish: Old New~print (ONP)/ Old Maqazine (OMG) (70~ ONP, 30~ OMG) % Bri~htn~
S~rf~t~n~ % Addition Increase % Fiber Yield 1 0.3 14.55 95.87 0.6 13.90 91.33 0.9 13.82 89.90 2 0.3 12.21 94.05 0.6 10.68 90.86 0.9 10.59 87.49 3 0.3 7.24 98.48 0.6 6.64 98.38 0.9 5.51 98.52 4 0.3 9.17 97.37 0.6 8.72 95.67 0.9 8.61 93.82 Leqend: 1: "Lionsurf 727", a commercial standard.
2: "DI-600", a commercial st~n~d.
3: Mixture of compounds of For~ula I, Rl=H, i=o, R=trimethyl nonyl 4: #3 (60~) + ~Witconol NS500 LQ~ (40~) "Witconol NS 500 LQn is a commercial alkoxylated alcohol W 097/45186 PCT~US97/0882 Furnish: Mixed Of~ice Waste (MOW) (70% laser, 30% ledger) Vi~ible TAPPI Dirt Dirt count ~ ~ Decrea~e~ decreases Bri~htn~ Fiber (>0.005 (> 0-04 Surf~t~nt ~ Addition Increase Yield mm2) mm2) 1 0.3 17.49 95.29 98.64 94.03 0.6 15.74 92.88 94.94 87.08 0.9 14.80 91.96 91.89 79.24 2 0.3 18.53 95.84 99.13 97.18 0.6 18.75 94.54 97.22 91.81 0.9 17.03 94.44 94.82 89.70 3 0.3 28.54 98.11 99.49 98.79 0.6 25.34 97.54 99.51 98.98 0.9 26.02 96.41 99.43 99.39 4 0.3 25.24 98.00 99.72 99.04 0.6 25.40 95.58 99.90 99.78 o.9 24.41 94.88 99.70 98.95 Leqend: 1: "Lionsurf 727", a commercial standard.
2: "DI-600", a commercial standard.
3: Mixture of compound~ o~ Formula I, R1=H, i=o, R=trimethyl nonyl.
4: #3(60~) + "Witconol NS 500LQ" (40%) ("Witconol NS500 LQ" is an alkoxylated alcohol.

CA 02228430 l998-0l-30 W O 97/45186 PCT~US97/08821 Table 12 con't Delta Surfactant Addition Accepts Bright Increa3e Re~erence % Feed ~ % % % Yield 1 0.3 35.21 31.86 3.35 9.51 90.98 0.6 35.21 31.94 3.27 9.29 88.89 0.9 35.21 32.44 2.77 7.87 88.95 2 0.3 36.02 31.86 4.16 11.55 90.77 0.6 36.02 31.53 4.49 12.47 91.56 o.9 36.02 33.21 2.81 7.80 91.56 3 0.3 34.52 32.43 2.09 6.05 98.95 0.6 34.52 32.23 2.29 6.63 98.53 0.9 34.52 33.23 1.29 3.74 94.27 4 0.3 33.4 30.14 3.26 9.76 92.55 0.6 33.4 28.86 4.54 13.59 91.61 0.9 33.4 28.52 3.88 11.62 91.54 Leqend: 1: "Lionsurf 727", a commercial standard.
2: "DI-600", a commercial standard.
3: Mixture of compounds o~ Formula I, Rl=H, i=o, R=trimethyl nonyl.
4: #3(60g~) ~ "Witconol NS 500LQ" (40~) ("~itconol NS500 LQ/' is an alkoxylated alcohol.

Claims

WHAT IS CLAIMED IS:

1. A method of preparing an alkyl glyceryl ether sulfonate composition which comprises a mixture of compounds of the formula (I) wherein i is an integer from 0 to 10;
M is selected from the group consisting of lithium, sodium, potassium and ammonium cations and mixtures thereof;
R1 is (ALK-O)pH or H, wherein p is an integer from 1 to 10, each ALK is independently ethyl or propyl; and R
is straight or branched alkyl or alkenyl containing 8 to 18 carbon atoms and 0 to 3 carbon-carbon double bonds, wherein the mixture contains compounds of formula (I) wherein d is 1, 2, 3 and 4 and optionally 5, wherein the mole average value of d in the mixture is 1.8 to 2.2, the method comprising:
a) forming a mixture of alkyl glyceryl halides of formula (II) by reacting epichlorohydrin with an alcohol or alcohol ethoxylate of the formula R-O-(CH2CH2O)i-H to form said mixture of compounds of formula (II) and optionally alkoxylating the pendant hydroxyl group on said compounds of formula (II); and then b) replacing the chloro substituents on the compounds of formula (II) with -SO3M.

2. A method of preparing an alkylphenol polyethoxy sulfate-sulfonate of the formula (III) wherein M is lithium, sodium, potassium or ammonium cation, R2 is straight or branched alkyl containing 8 to 12 carbon atoms and n is 6-10 comprising:
a) reacting an ethoxylated alkyl phenol of the formula R2-Ph-O(CH2CH2O)nH wherein R2 and n are as defined above and Ph denotes a phenyl ring and the substituents thereon are in the para-position, with sulfur trioxide to form an intermediate of formula (IV):
and b)reacting the product of formula (IV) formed in step (a) with a hydroxide of the formula M-OH under conditions wherein said product of formula (III) is formed.

3. A method of preparing an ethoxylated alkylphenol sulfonate of the formula (V) wherein M is a lithium, sodium, potassium or ammonium cation, R2 is straight or branched alkyl containing 8 to 12 carbon atoms, and n is 6 to 10, comprising:
a) reacting an ethoxylated alkylphenol of the formula R2-Ph-O(CH2CH2O)nH wherein R2 and n are as defined above and Ph denotes a phenyl ring and the substituents thereon are in the para-position, with sulfur trioxide to form a product of formula (IV) and then b) reacting the product of formula (IV) formed in step (a) with a hydroxide of the formula M-OH under conditions wherein said product of formula (V) is formed.

4. A method according to Claim 1 wherein i is zero.

5. A method according to Claim 1 wherein each ALK group is ethyl.

6. A method according to Claim 1 wherein each ALK group is propyl.

7. A method according to Claim 1 wherein in step (a) the pendant hydroxyl group on said compounds of formula (II) is alkoxylated such that R1 is (ALK-O)pH.

8. A method according to Claim 1, 2 or 3 wherein M is sodium.

9. A method according to Claim 2 or 3 wherein R2 is nonyl.

10. A composition of compounds of formula (I) produced by the process of Claim 1.

11. A product produced by the process of claim 2 or 3.

12. A composition of matter comprising a mixture of products of the formula wherein i is an integer from 0 to 10;
M is selected from the group consisting of lithium, sodium, potassium and ammonium cations and mixtures thereof;
R1 is (ALK-O)pH or H, wherein p is an integer from 1 to 10, each ALK is independently ethyl or propyl, and R
is straight or branched alkyl or alkenyl containing 8 to 18 carbon atoms and 0 to 3 carbon-carbon double bonds, wherein the mixture contains compounds of formula (I) wherein d is 1, 2, 3 and 4 and optionally 5, wherein the mole average value of n is 1.8 to 2.2.

13. A composition according to Claim 12 wherein i is zero.

14. A composition according to Claim 12 wherein each ALK group is ethyl.

15. A composition according to Claim 12 wherein each ALK group is propyl.

16. A composition according to Claim 12 wherein M is sodium.

17. A product of the formula wherein M is a lithium, sodium, potassium or ammonium cation, R2 is straight or branched alkyl containing 8 to 12 carbon atoms, n is 6-10 and A is -SO3M or H.

18. A product according to Claim 17 wherein M is sodium.

19. The method of forming a pulp from which paper can be produced, comprising admixing together water; feedstock selected from the group consisting of recycled paper, wood pulp, and mixtures thereof; and a wetting agent selected from the group consisting of (i) compositions comprising compounds of the formula wherein i is an integer from 0 to 10;
M is selected from the group consisting of lithium, sodium, potassium and ammonium cations and mixtures thereof;
R1 is (ALK-O)pH or H, wherein p is an integer from 1 to 10, each ALK is independently ethyl or propyl, R is straight or branched alkyl or alkenyl containing 8 to 18 carbon atoms and 0 to 3 carbon-carbon double bonds, wherein d is each of 1, 2, 3 and 4 and optionally 5, and the mole average value of d is 1.8 to 2.2; (ii) compounds of the formula wherein R2 is straight or branched alkyl containing 8 to 12 carbon atoms, n is 6-10 and A is -SO3M or H; and mixtures thereof.

20. A process for dyeing nylon comprising contacting nylon with a composition comprising dye and a dye leveling agent selected from the group consisting of (i) compositions comprising compounds of the formula wherein i is an integer from 0 to 10;
M is selected from the group consisting of lithium, sodium, potassium and ammonium cations and mixtures thereof;
R1 is (ALK-O)pH or H, wherein p is an integer from 1 to 10, each ALK is independently ethyl or propyl, R is straight or branched alkyl or alkenyl containing 8 to 18 carbon atoms and 0 to 3 carbon-carbon double bonds, wherein d is each of 1, 2, 3 and 4 and optionally 5, and the mole average value of d is 1.8 to 2.2; (ii) compounds of the formula wherein R2 is straight or branched alkyl containing 8 to 12 carbon atoms, n is 6-10 and A is -SO3M or H; and mixtures thereof.

21. A process of emulsion polymerization comprising polymerizing a monomer in an aqueous emulsion which comprises a compound selected from the group consisting of (i) compositions comprising compounds of the formula wherein i is an integer from 0 to 10;
M is selected from the group consisting of lithium, sodium, potassium and ammonium cations and mixtures thereof;
R1 is (ALK-O)pH or H, wherein p is an integer from 1 to 10, each ALK is independently ethyl or propyl, R is straight or branched alkyl or alkenyl containing 8 to 18 carbon atoms and 0 to 3 carbon-carbon double bonds, wherein d is each of 1, 2, 3 and 4 and optionally 5, and the mole average value of d is 1.8 to 2.2; (ii) compounds of the formula wherein R2 is straight or branched alkyl containing 8 to 12 carbon atoms, n is 6-10 and A is -SO3M or H; and mixtures thereof.

22. A process for beneficiating ore, comprising subjecting a finely divided mixture of ore and impurities to froth flotation in an aqueous medium which comprises a compound selected from the group consisting of (i) compositions comprising compounds of the formula wherein i is an integer from 0 to 10;
M is selected from the group consisting of lithium, sodium, potassium and ammonium cations and mixtures thereof;
R1 is (ALK-O)pH or H, wherein p is an integer from 1 to 10, each ALK is independently ethyl or propyl, R is straight or branched alkyl or alkenyl containing 8 to 18 carbon atoms and 0-3 carbon-carbon double bonds, wherein d is each of 1, 2, 3 and 4 and optionally 5, and the mole average value of d is 1.8 to 2.2; (ii) compounds of the formula wherein R2 is straight or branched alkyl containing 8 to 12 carbon atoms, n is 6-10 and A is -SO3M or H; and mixtures thereof.

23. A hard surface cleaner comprising a product selected from the group consisting of (i) compositions comprising compounds of the formula wherein i is an integer from 0 to 10;
M is selected from the group consisting of lithium, sodium, potassium and ammonium cations and mixtures thereof;
R1 is (ALK-O)pH or H, wherein p is an integer from 1 to 10, each ALK is independently ethyl or propyl, R is straight or branched alkyl or alkenyl containing 8 to 18 carbon atoms and 0 to 3 carbon-carbon double bonds, wherein d is each of 1, 2, 3 and 4 and optionally 5, and the mole average value of d is 1.8 to 2.2; (ii) compounds of the formula wherein R2 is straight or branched alkyl containing 8 to 12 carbon atoms, n is 6-10 and A is -SO3M or H; and mixtures thereof.

24. A composition which is effective to remove soil and stains from fabric, comprising a product selected from the group consisting of (i) compositions comprising compounds of the formula wherein i is an integer from 0 to 10;
M is selected from the group consisting of lithium, sodium, potassium and ammonium cations and mixtures thereof;
R1 is (ALK-O)pH or H, wherein p is an integer from 1 to 10, each ALK is independently ethyl or propyl, R is straight or branched alkyl or alkenyl containing 8 to 18 carbon atoms and 0 to 3 carbon-carbon double bond~, d is each of 1, 2, 3 and 4 and optionally 5, and the mole average value of d is 1.8 to 2.2; (ii) compounds of the formula wherein R2 is straight or branched alkyl containing 8 to 12 carbon atoms, n is 6-10 and A is -SO3M or H; and mixtures thereof.

25. The method of deinking waste paper comprising subjecting said waste paper to froth flotation in an aqueous medium comprising a product selected from the group consisting of (i) compositions comprising compounds of the formula wherein i is an integer from 0 to 10;
M is selected from the group consisting of lithium, sodium, potassium and ammonium cations and mixtures thereof;
R1 is (ALK-O)pH or H, wherein p is an integer from 1 to 10, each ALK is independently ethyl or propyl, R is straight or branched alkyl or alkenyl containing 8 to 18 carbon atoms and 0-3 carbon-carbon double bonds, wherein d is each of 1,2,3 and 4 and optionally 5, and the mole average value of d is 1.8 to 2.2; (ii) compounds of the formula wherein R2 is straight or branched alkyl containing 8 to 12 carbon atoms, n is 6-10 and A is -SO3M or H; and mixtures thereof.