CA2580650A1 - Novel aromatic and aliphatic sulfonates and properties and applications thereof - Google Patents

Abstract

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

Description

NOVEL AROMATIC AND ALIPHATIC SULFONATES
AND PROPERTIES AND APPLICATIONS THEREOF
This application is a division of copending Canadian Application Serial No. 2,228,430 filed May 27, 1997.

Both aromatic and aliphatic sulfates and sulfonates are an important group of anionic surface-active agents used extensively in a number of industrial applications. These include operations in drilling for and recovery of crude oil; emulsifiers for pesticides used in crop protection; in shampoos and creams for personal acre; laundry detergents; hard surface cleaners;
emulsifiers for emulsion polyme:=ization systems;
lubricants; wetting agents; and dispersants in a variety of specialized industrial applications. Sulfates, being susceptible to breakdown in acidic environments, are limited to formulations 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 sulfonat:es 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 usE:ful properties.

The present invention is directed to novel alkyl diglyceryl ether disulfonate conipositions (ADEDS), alkylphenol polyethoxy sulfate-sulfonates, and ethoxylated alkylphenol sulfonates, and their methods of preparation and uses.

In accordance with one embodiment of the present invention there is provided a sulfonate composition selected from the group consisting of (I) compositions of matter comprising a mixture of products of the formulae (I), (I-A) and (I-B) R-O-(CHyCHZO) CHZ-- i H---CH2SO3M ((~

R-O-(CH2CH20) CH2-HC-CH2S03M (I-A) I
0 CHZ-CH-CHZO H =

O RI

(I-B) R-O-(CH2CH2O) CHZ-HC-CH2S03M

0 -CH2-CH-CH2O CH=CH-CHy H

R~ 2 wherein i is an integer from 0 to 10 and R' is (ALK-O)pH or H, whereby R' is (ALK-0)PH when i=0, and M is selected from the group consisting of lithium, sodium, potassium and ammonium cations and mixtures thereof; p is an integer from 1 to 10, . .. .. .... . .. . .... .... .. .. .. ..._ ..:__. ,._ ... . ... .. . .. .i .
. _.. ..... ... ...... .. . ... .

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, 4 or 5, w:ierein the mole average value of d is 1.8 to 2.2 and (II) products of the formula ( I I I) 0~(CH2CH20)n A

SOgfV, ( I I I) 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.
In accordance with another embodiment of the present invention there is provided a method of preparing an alkyl glyceryl ether sulfonate composition which comprises a mixture of compounds of the formulae (I), (I-A) and (I-B), as noted above, the method comprising:
a) forming a mixture of alkyl glyceryl halides of formulae (II) and (II-B) R-O-(CH2CH20)i C}2- H= -CHZC1 (II) R

d (Il-B) R-O-(CH2CH2O)i CH2-HC-CH2C1 C{{ (CH (OR~ ) CH;O- (CH=CHCH2O) 2H
d wherein i, d, R and R' have the meaning as defined above, by reacting epichlorohydrin with an alcohol or alcohol ethoxylates of the formula R-O-(CH2CH2O)i-H to form the mixture of compounds of formulae (II) and (II-B);

and optionally subsequent alkoxylation of the pendent hydroxyl group on the compounds of formula (II), with the proviso that the subsequent alkoxylation is performed if i=O; and then b) replacing the chloro substituents on the compounds of formulae (II) and (II-B) with -S03M.

In accordance with another embodiment of the present invention there is provided a method of preparing an alkylphenol polyethoxy sulfate-sulfonate of the formula (III) defined above wherein A is -S03M comprising the steps of:

a) reacting an ethoxylated alky7. phenol of the formula R2-Ph-O(CHZCH2O)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):

0 -I(CH2N2O)n SO3H
SQ,H

((V) and b) reacting the product of formula (IV) formed in step (a) with a hydroxide of the formula M-OH under conditions wherein the product of formula (III) with A as -S03M is formed.
Yet another embodiment of the present invention provides a method of preparing an ethoxylated alkylphenol sulfonate of the formula (V) O,(CHyCHyO)~-H

I (V) wherein M is a lithium, sodium, potassium or ammonium cation, R 2 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- 0(CH2CH2O)nH wherein R 2 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) olo(CH2tHz0)n SOH
SO"H

(tv) 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 produce of formula (V) is formed.

-5a-The present invention further relates to alkyl diglyceryl ether disulfonate compositions (ADEDS) comprising compounds of formula (I). The invention also contemplates alkylphenol polyethoxy sulfate-sulfonates of formula (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 significant in the rnanufacture 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 irivention in the benefication of ores by froth flotation.

The present invention is also directed towards the use of compounds of the present irivention as emulsifiers in emulsion polymerization reactions.

The present invention is also directeci towards the use of compounds of the present invention in hard surface cleaners, laundry spot removers, and detergents; in dyeing of f=ibers, e.g. nylorr; and as brightening agents in metal electroplating baths.
The present invention is also directed towards Lhe use of compounds of the present invention in tlie deinking of waste paper.
Compounds and Synthesis The present invention is directed towards novel alkyl diglyceryl ether disulfonates (ADEDS), alkylphenol polyethoxy sulfate-sulfonates, and ethoxylated alkylphenol sulfonates, and to novel niethods of preparation of these compounds.
More particularly, the present inventioi7 is directed to a process for preparing an alkyl diglyceryl ether disulfonate coinposition (ADEDS) which comprises a mixture of compounds of formula (I):

R-O- (CH,CH1O) ; CHl-CH-C112SO,M ( I ) wherein i is an integer from 0 to 10;
M is selected froni the group consisting of lithium, sodium, potassium, ammonium, and mixtures thereof;
R' is (ALK-O)PH 'or H, wherein p is an integer froni 1 to 10, and R is straight or branched alkyl or alkenyl containing 8 to 18 carbon atoms and 0 to 3 carbon to carbon double lionds. The composit:ion is a mixture of compounds wherein d is 1', 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. Preferably, when R1 is an alkoxylate group it is entirely ethoxylate or entirely propoxylate.
The preparation of the conipound of formula (I) comprises reacting epichlorohydrin with an alcohol or alcohol ethoxylate of the formula R-O- (CH2CH2O);-H, wherein i and R are as defined above, under conditions wherein an intermediate coinpound of formula (II) is f ormed :

I2-0- (CHZCH,O); CH2-CH-CH2-C1 (II) 0 R ' It should be understood that the reaction with epichlorohydrin generally forms a mixture of adducts fortned as epichlorohydrin reacts with the pendant hydroxyl group left by addition of a previous niolecule 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 45o monoadduct, about 35 to 45% of diadducL, about 10 to 200 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 ainixture of about 409.- mono-adduct, about 40% of diaddict, about 15% of triadduct, about 5a.of tetraadduct, and traces of pentaadduct.
The reaction with the epichlorohydrin to f-orm the mixture qf compounds of formula (II) is believed to form byproducts having either or both of the structures (II-A) and (II-B):

R-O- (CHzCH,O) i CHzCH-CH2-Cl (II-A) I
O d CH2CHCH2C1 i 0 1_ZR

R-O- (CH,CH,O); CHzCHCH,Cl (II-B) O d-CH2CH (OR') CH7O- ( CH-CHCHzO ),H
Employing the reaction conditions described lierein 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 niixture of compounds of formula (II) involves an acid catalyzed addition of epicsllorohydrin to the alcohol or alcohol ethoxylate in a 2:1 molar ratio of epichiorohydrin to alcohol or alcohol ethoxylate. The catalyst cnay 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 R' 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 etliylene oxide and/or propylene oxide. Boron trifluoride is the preferred catalyst.
The resulting mixture of conipounds of formula (II) contains chloro substituents which are then replaced with -SOM. 'This reaction is perfornied under conditions sufficient to.replace all the chloro substituents in (II) with -SO3M. Preferably this reaction involves the reactibn of the compounds of formula ( I I) and an aqueous solution of MZSO, at a tenlperature of 50 C to 300 C, preferably 150-160 C.
The reaction may embody the conditions of the well known Streckerization reactiori. The preferred cation M is sodium.
Mass spectral analysis indicates that this mixture contains compounds corresponding to forinulas (I), (I-A) and '(I-B) :

R-O- (CHZCHZO); (CH2-CFI-CH2SO3M (I) I ' O 1 _4- R

RO (CH2CH2O) 1 CI-12-CH-CII2SO3M
O ~CII2CHCII2)_.H
O R
~-z (I-A) RO (CH2CH.O) i CHz-CH-CH2S03M
0 CHZCH-CHzO CIi=CH-CHZO Ii (I-B) wherein i is an integer from 0 to 10; and R; R', and M
are as defined herein. This mixture is referred to collectively as alkyl diglyceryl ether disulfonates (ADEDS).
Preferably R is straight or branched Co (such as 2-ethylhexyl), Clo, C121 C13, C14, or oleyl.
Mixtures of compounds of the foregoing formulas are also contemplated. A preferred mixture is that obtained from "*Exxal 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 allcylphenol polyethoxy sulfate-sulfonate of formula (III):

*Trade-mark O-(CHiCHIO)-6S03 M (IIZ) RZ
wherein M is a lithium, sodium, potassium or aminonium cation, RZ is straight or branched alkyl containing 8-12 carbon atoms and n is 6-10.
The process involves the sulfonation of an ethoxylated alkyl phenol of the formula R2-Ph-O(CH;.CH,O) õH, wherein RZ 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) :

0---(CH2(;H2O)nSO3H

~ ~ (IV) I

R2, Preferably this sulfonation reaction is performed wit}i a 2:1 molar ratio of SO3 to Rl-Ph-O (CIiZCH1O) õH using a continuous air/SO3 thin "film-sulfonator.
The sulfonated intermediate (IV) is then neutralized with a hydroxide of the formula M-OH and preferably with sodium hydroxide, under condit'ions wherein said product of formula (III) is formed.

Further, the present invention is directed towards the preparation of an ethoxylated alkylphenol sulfonate of formula (V) :.

o-(cHzcHzo)n H (V) wherein M is a lithium, sodium, potassiuni or amnionium cation, RZ is a straight or branched alkyl group containing 8 to 12 carbon atoms, and n is G to 10.
The ethoxylated alkylphenol sulfonate of formula (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 desulfation 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.

In a preferred method, the intermediate (IV) is reacted with 3 moles of concentrated sodium hydroxide, and heated to about 20 C to 1500C, preferably about 60 C, under conditions wherein said product of formula (V) is formed.
The present invention further contemplates mixtures of alkyl glyceryl ether sulfonate compounds of forniulas (I), (I-A) and (I-B) :

R-O- (CH2CH2O);. CHz-CH-CII,SO3M (I) ~ R1 RO ( CH2CH2O ); CHZ - CH - CHZSO,M
O 1_3 (CH2CH2oH
\

(I-A) RO (CH2CH2O) ; CH2-CH-CH2SO3M
0 CH2CH-CH2O H=CH-CH2O H
,_, ORi z (I-B) wherein i is an integer from 0 to 10; and R, R', and M
are as defined above.
The present invention further contemplates an alkylphenol polyethoxy sulfate-sulfonate compound of formula (III) :
O-(CH2CH1 O)nSO3 M
SO9M (III) wlierein Rz is straight or branched alkyl of 8 to 12 carbon atoiiis, and= n and M are as defined above.
The present invention is still further directed towards an ethoxylated alkylphenol sulfonate coinpound of formula (V) :

O--(CH2 CH2 O)~ H (V) \ I
RZ
wherein R2 is straight or branched allcyl 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 co-npounds, 1.0 mole of a nonylphenol 10-mole ethoxylate was treated with 2.0 moles of SO3 in a laboratory air/SO, 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 RZ=C9 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.a NaOH, which yielded the disodiuin product of forinula III with R'=C, and n=10, as a light tan liquid.

Example 2 Preparation of Alkylphenol polvethoxy sodium sulfonates Employing 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=C9) which was formed 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 IV 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 nlixture 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 Na2SO4, was withdrawn and discarded. The upper phase, a tan solution, contained 55-60 wt. o of a compound of formula V with R2=C 9 and n=10.

. . . . . . . .. .. . . ... ........ .. . _... ...... i . . . -... ....- ., ..._ . . . .. . ..... . . .. .. ..._.

Example 3 Preparation of Allcyl Diglyceryl Ether Disulfonates (ADEDS) Employing the typical procedure for making these mixtures of compounds, 800 g of lauryl alcohol (containing a ininor proportion of C14 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 50 C, aiid 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/C,4, 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. T'his formed product of forniula II in which R=C12/C14, i=0, and -(ALK-O)PH =
- (CH2CI-I1O)4H.
For conversion to the mixture of sulfonates, the product of formula II (1,530 g), 4,600 ml of water and 1,000 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.

. . ... . . .. _.. . . _.. .. . . ..... . . . .. i ..... ....,,. , ....,.... .
... .. . . . ... ... ., _ . . . . . . . . .. , 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 for-nula I wherein R=C12/C14 i=0, and R1=H, as a hazy mixture.

Properties and Applications The alkyl glyceryl ether sulfonate inixtures of formula (I), the alkylphenol polyethoxy sulfate-sulfonates of formula (III), and the ethoxylated alkylphenol sulforiates of formula (V), have a number of useful properties and applications which also coniprise aspects of the present invention.
Electrolyte Tolerance/EmulsionPolymerization 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 styrerie includi,ng acrylonitrile-butadiene-styrene, styrene-butadiene and st.yrene-acrylonitrile;
acrylamide; acrylates, methacrylates, and derivatives sucli as 2-dimethylaminoethyl niethacrylate and 2-diethylaminoethyl methacry.late, acrylic acid, methacrylic acid, 2-hydroxyethyl methacrylate and 2-lzydroxyetllyl acrylate; vinyl chloride, vinyl acetate, vinyl sulfonate, and the like.

Emulsion polymerization is 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 calciuni chloride is added to mediate precipitation of the polymer particle fro-n the aqueous phase. With surfactants conventionally eniployed 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 contaminant and can adversely affect the polymer's properties and its usefulness for certain applications.
The compounds of the present invention (e.g.
conlpounds of formulas (I), ( I I I) 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 exhibit. The . .. . . . . . . ... ... .. . . . . . .. __.._ :. _ .. ,.... . ... i ... ..
... .............. .. ... ... . ....._ . .. ... , . .._. . . . . . . . .. ..

following example deinonstrates electrolyte tolerance of compounds of this invention, and thereby indicates that the compounds of this invention exhibit superior performance in other contexts fteeding 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.o surfactant in water, were prepared. To each stirred sample was added either a 1 wt.o or a 5 wt.a 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 indicate.s a higher degree of electrolyte tolerance.

Table 1 Electrolyte Tolerance ml of Electrolyte Added to Cloudy End Point Saniple Surfactant Aluminuni Sulfate Calcium Chloride No. 1 wt.% 5 wt.o 1 wt.o 5 wt.o 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 R'=nonyl 3 Formula, >250 >250 >250 >250 (V), M=Na n= 9 R'=
dodecyl 4 Formula >250 >250 >250 >250 (III), n=6, M=Na RZ=nonyl Formula >250 >250 >250 >250 (III) , M=Na n=5 , RZ=
dodecyl (1) "Dowfax 2A1", a commercial surfactant . . ... ._ ...,.... ...... .._ ._.._.... ... i 6 Forinula >250 >250 >2=50 >250 (III), n=9, RZ=
dodecyl 7 Formula' >150 >150 >150 >150 (I)2, i=0, R1=H
R=Ciz/Cin 8 Formula >150 >150 >150 >150 (I)i=0, R'=
( CH2CH,O ) ,f:
R=C1z/CI4 9 Formula <30 <10 <15 <4 (I) Z, i=0 R1=
(C3H6O) ,,1I
R=Ci2/Cin Formula >150 >150 >150 >150 (I)2, i=4, R1=H
R=Ciz/Ci4 11 Formula >150 >150 >150 >150 (I)2 , i=0, R1=
(CHZCH2O)8H
R=Ci2./Cin 12 Formula >150 >150 >150 >150 (I)2, i=0 R'=H
R=1, 3, 5-tri-methyl-nonyl' 13 Formula >150 >150 >150 >150 (I)z, i=0, R1=H R=2-ethyl-hexyl . . . . _ . . . .. . .. .._. . ....... . ... ..... .. . ... .. .. .. . i ....... ..,........ ..... . , _. . . . . . .,, ... : . . . _ . . . . . . . . .
.. . ... . .

14 Formula >150 >150 >150 >150 (I)', i=0, R'=H
R=oleyl 15 Fornlula >150 >150 >150 >150 (I) 2, i=0, R'=H
R=Ce/Cio (2) = a mixture of mono-, di-, tri-, tetra-and possibly trace aniounts of penta-adducts, wherein the mole average value of d is about 2; and M=Na.
( 3 ) = derived troni "Exxal 12"

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 niixture of mono-, di-, tri- and tetra-adduct conipounds of forniula (1), wherein R is 1,3,5-trimethyl nonyl (derived from "Exxal 12"), i=O, M is Na, and the mole average value of n is about 2 and R' is H (product "DS" in Table 2), or a commercially available sodium C14/C,,, alpha-olefin sulfonate (compound "AOS" in Table 2).
The pol'ymerizations were run batchwise.
Since product DS contained about 5 wt.o of salt, salL-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.o or 3.0 wt.o surfactant present, and with 0.5 wt.% sodium persulfate as initiator. All weight percentages are expressed herein as o by weight of the initial monomer weight.
The properties of the latexes obtained are set forth in Table 2:

. . . . _._. ...._ ...... .. ..... . ~...... .:,.:. .._.. ,..... ..._ .....
... ., .. . .... .

Table 2 Surfactant/ Product yield, Particle size, concentration nm AOS/1% 92.7 116/48 AOS/3o 95.9 77/22 DS/106 79.4 98/31 DS/3o 97.9 73/23 The data in Table 2 show that the product "DS" is an effective surfactant for emulsion polymerization. At 1% concentration, product "DS"
gave substantial coagulum. At 3% concentration, the coaguluni was very low and even better than AOS. The stability of the latex enlulsion was found to be excellent.

Wetting 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, feedstoclc, 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.

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 inedium wets the external and interstitial surfaces of the feedstock. Increasing the rate and the extent of wetting are associated with formation of inlproved pulp, at a faster rate and with a tnore desirable consistency and quality 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 o 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.

Example 6 The determination of wetting was assessed as o absorbency ra,te change, using standard methods einployed in the paper industry.
The compounds tested for % change in the rate of water absorption, and the identities of those conlpounds, are shown in Table 3.

. .. . .. .... _...... ._.... ... i. . .... ...... .. ...... .. .... ._ ......
... . . . . .. . .. ... .

The ethoxylated allcylpheriol sulfonate cocnpounds showed good water absorbency in several feedstocks.

. . . .. .... ... ....._ ...... . i... .._.. . .. .. .,. . .... . . ........ .
.. . . ..... . .. . .. .... . .

Table 3 Absorbency Rates;
Feedstock = Recycled cardboard cartons:

Dose (lbs.
surfactant/
ton of %Absorbency Rate Change Surfactant feedstock) 0-5 sec. 6-12 sec. 20 sec.
Formula 0.5 +7.7 .+56.0 +31.3 (III), n=
10, R2=nonyl 1.0 +20.5 +G8.0 +43.4 3.0 +17.9 +48.0 +34.5 5.0 +12.8 +G0.0 +37.5 Formula 0.5 +20.5 +44.0 +27.4 (V) , n=
10, Rz=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 FFedstock=Northern softwood (kraft):
Forniula 0.5 +18.5 -9.4 +5.3 (III), n=
10, I2z=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 Forniula 0.5 +35.2 +1.9 +14.6 (V), n=
10, R'=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 Example 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 fiber (Freeness #303) to which a surfactant of the present invention had been added in the pulp. The results are set fprth in Table 4. They show very useful and significant improvement in the properties of the paper product.

Table 4 Dose ( lbs .
surf . /
ton of % Dry Surfactant feed- Tensile Absorbency Rate Change stock) change 0-5 sec. 6-12 sec. 20 sec.
Formula 0.5 +11.0 +18.5 0 +11.0 (V), n= 10, R'=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, R'=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=0 R=C,,/C14, R1=
(CH2OCII20) 4H
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 ...... . . . . . . . . . .._. ._.. ... . .. .. .... ...... . i .. ..... , ..._... .. ..... . ._... . . ... . .. . .

Formula 1.25 +46.4 -6.2 -5.6 -7.6 (I), i=0, R'=I-I, 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 0 +0.3 Forniula 1.25 +42.3 +4.6 0 +6.0 (I), i=0, R'=H, R=Ci2/CIa 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 effe,ctive wetting agents.
Significantly, they increase the wet/dry tensile ratio when used with a known wet strength resin like "ICymene 557H". The conipounds tested had little or no effect 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 al)cyl moiety. Arocnatic sulfonates, (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 denlonstrate ouLstanding 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 coinpounds can be further enhanced by formulating them with other surface-active materials including nonionic wetting agents. Preferred materials include alkoxylated Co-C20 , alcohols, and C2-C2U 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.

Table 5 (Southern Softwood, Freeness 14-734) o Absorb. % Absorb. Capacity o Dry o Wet Rate Rate Change Dose Tensile Tensile Change Change Index Surfactant (lb/ton) Change Change 0-5 Sec. 6-12 Sec. 20 Sec.
Formula 1 -3.0 +3.6 +18.8 +8.7 +9.8 (V) , n= 10, RZ=nonyl, M=Na = N
'T' o 3 -8.8 -17.4 +21.9 +4.3 +12.1 -1.3 +7.7 +31.3 +17.4 +20.3 = o ' o -2.2 +13.3 +40.6 +21.7 +19.5 .3 w Formula 1.25 +8.6 +28.6 +2.2 0 +0.5 ~1-(I)1, R'= L' ( CH2CH20 ) ,,H
R=Ciz/Cia i=0, M=Na 2.5 +10.2 +12.5 +8.7 0 +5.2 7.5 +17.6 +22.0 +8.7 0 +4.1 12.5 -0.7 +5.0 +15.2 -3.6 +5.9 Formula 1.25 +16.1 +22.5 +8.7 0 +5.9 (I) 1, R'=H, i=0, R=1,3,5-tri-methyl nonyl, M=Na 2.5 +6.5 +8.5 +13.0 0 _ +9.7 7.5 +7.4 +8.0 +10.9 +7.1 +8.6.
12.5 -5.9 +7.0 +13.0 +7.1 +11.2 Formula 1.25 -1.3 +13.5 +10.9 0 +5.8 0 (I) 1, R'=H, i=0, . w N
Ln R=C12/C14 = ~ o M=Na Ln 2.5 -0.9 +2.5 +15.2 .+3.6 +8.0 7.5 +0.9 +8.5 +13.0 +3.6 +6.2 0 w 12'.5 -12.6 +26.5 +19.6 +14.3 +15.0 ~
Formula 1.25 +4.1 -1.5 +21.8 0 +12.3 (I) 1, R1=H, i=0, R=2-ethylhexyl M=Na 2.5 +9.1 +5.0 +21.8 0 +11.5 7.5 +6.4 -8.0 +21.8 +3.6 +13.6 12.5 +14.1 +20.0 +26.1 -3.6 +12.2 Formula 1.25 +16.1 +19.5 +6.5 -3.6 +2.1 (I) ', P.'=H, i=0, R=oleyl M=Na 2.5 +9.4 -8.5 +6.5 -3.6 +1.7 7.5 +4.0 +11.5 +8.7 -3.6 +4.6 12.5 +3.4 -1.5 +19.6 +7.1 +14.5 Formula 1.2_5 +1.6 +37.4 +13.0 +7.1 +8.2 (I) 1, 1=0, R1=
( CH,CHzO ) aH
R=C12/C14 = ~ ~
M=Na Ln 2.5 +2.2 +16.7 +8.7 +3.6 +6.4 cn 7.5 +5.9 +21.2 +21.8 0 +12.5 12.5 -13.1 +1.5 +28.3 +10.7 +17.1 - ' .3 Formula 1.25 -2.2 +21.2 +21.8 0 +14.1 W
~, (I)1, z-4, R'-=H
R=Cl2?~C14 M=Na 2.5 -7.7 +16.7 +23.9 0 +12.8 7.5 -9.9 +25.1 +30.4 0 +16.1 12.5 -13.1 +3.0 +23.9 0 +12.4 (1): A mixture of compounds in which n was each of 1-5 and its mole average value was about 2.

Table 6 TISSUE - HANDSHEET DATA
(Northern Softwood Kraft, Freeness #681) Dry % Wet o Rate of o Rate of Rate of Dose Tensile Tensile Absorb. Chg. Absorb. Chg. Absorb. Chg.
Surfactant (lb/ton) Change Change 0-5 sec. 6-12 sec. 20 sec.
Formula (V), 1.0 +4.1 +44.2 +14.3 +7.8 +11.2 n= 10, RZ=nonyl M=Na 3.0 -3.2 +7.2 +9.5 -7.8 -5.5 Ln co 5.0 0 +25.7 +9.5 0 +4.9 = I o 10.0 -13.0 -9.4 +9.5 +7.8 +4.4 Formula (I) 1, 1.25 +3.4 +21.0 +4.5 -9.9 +0.8 R1= (CH2CHz0) ,aH W
R=Cia/Caa ~1-i=0 'n M=Na 2.50 -2.7 +4.9 -9.1 -26.8 -13.6 7.50 -4.3 +12.8 -11.8 -25.4 -13.8 12.50 -13.5 +18.7 +9.1 -5.6 +5.7 Formula (I)1, 1.25 +5.4 +27.4 +18.2 -8.5 +7.9 R1=H, i=0, R=C12/C14 M=Na 2.50 +8.8 +20.2 +13.6 -9.9 +4.4 7.50 +6.7 . +15.8 +9.1 -4.2 +5.7 .12.50 +8.1 +31.7 +22.7 +5.6 +16.4 Formula (I)1, 1.25 +5.5 +20.3 +14.3 0 +8.0 i=0, R1= (CH2CH2O) BH
R=C12/C14 N '.
M=Na cn 2.50 +5.7 +8.1 +4.8 0 +2.4 Ln 7.50 +0.9 +8.9 +9.5 -5.9 +6.7 = o 12.50 -1.2 +25.8 +28.6 0 +17.5 0 w Formula (I)1, 1.25 +2.3 +20.3 +19.0 -1.5 +13.7 i=0, R1=(C3H50)4H
R=C12/C14 M=Na 2.50 +4.1 +13.7 +9.5 -5.9 +6.4 7.50 +1.1 +20.3 +14.3 -5.9 +9.6 12.50 +2.5 +11.4 +14.3 +7.4 +11.6 Formula (I)1, 1.25 +8.2 +34.3 +4.8 -2.9 +3.0 R1=H, i=0, R=2-ethylhexyl M=Na .

2.50 -1.6 +5.9 +4.8 -2.9 - .+2.0 7.50 -1.1 +36.9 +9.5 0 +5.2 12.50 -2.0 +14.8 +19.0 +7.4 +12.8 w Formula (I)1, 1.25 +1.8 +49.4 +14.3 +8.8. +12.9 ;o Ln R'=H, i=0, 00 R=oleyl M=Na 2.50 -3.0 +12.5 +14.3 +8.8 +12.8 0 7.50 +0.6 +23.2 +19.1 +13.2 +16.1 ~' 12.50 -7.2 +12.5 +19.0 +11.8 +16.3 Ln (1): A mixture of compounds in which n was each of 1-5 and its mole average value was about 2.

Table 7 (Recycled Cartons, Freeness #440) Absorb. % Absorb. % Absorb.
Rate Rate Rate o Dry Wet Change Change Change Dose Tensile Tensile 0-5 6-12 20 Surfactant (lb/ton) Change Change sec. sec. sec. , N
Ln Formula 1 +11.3 +24.6 +19.5 +16.2 +19.0 ~
(V) Ln n= 10, Rz=nonyl M=Na ' w 3.0 +8.8 +0.6 +18.2 +13.5 +15.8 5.0 +7.0 +15.0 +22.1 +13.5 +20.7 10.0 +6.1 +1.8 1+23.4 +10.8 +20.7 Formula 1.25 +2.7 +21.0 +5.2 +8.1 +7.2 (I) l, i=o, R1=
( CHZ CH~O ) 8H
R=C12/Cis M=Na 2.50 +5.5 +0.3 +2.6 +8.1 +6.5 7.50 +4.3 +15.3 +2.6 +8.*1 +4.8 12.50 +5.4 +6.0 +9.1 +13.5 +11.2 Formula 1.25 +7.8 +13.5 0 +13.5 +5.3 (I)1, i-4, R1=H, o R=C12/C1, M=Na o 2.50 +4.8 0 -2.6 +2.7 +1.0 o 7.50 +9.6 +15.6 +11.7 +10.8 +12.7 w ~
12.50 +2.6 +3.0 +9.1 +13.5 +10.2 L"
Formula 1.25 +8.4 +2.4 -1.3 -2.7 -2.0 (I) 1, R'=H, i=0, R=2-ethylhexyl M=Na 2.50 1 +4.3 0 +13.0 1 +2.7 +11.7 7.50 +10.3 +21.6 1+15.6 1+13.5 +14.0 12.50 f+2.7 +1.5 [+16.9 [~13.5 +15.0 Formula 1.25 +2.7 +21.6 +15.6 +5.4 +13.5 (I)1, R1=H, i=0, R=oleyl M=Na -2.50 +2.0 -3.0 +10.4 +2.7 +7.4 7.50 -6.7 +19.8 +7.8 0 +4.8 12.50 -8.4 +9.3 +18.2 +13.5 . +17.8 .F.ormula 1.25 +8.6 +24.9 +5.5 +10.3 +8.1 Ln (I)1, R1= 00 ( CH2CHzO ) SH
cn R=C1z/C19 i=O
M=Na .3 2.50 +4.2 +8.4 -5.5 -7.7 -5.1 '' cn 7.50 +7.3 +19.7 -4.1 -12.8 -5.2 12.50 +1.0 +15.4 +13.7 +5.2 +14.0 Formula 1.25 +14.4 +19.1 +1.4 -2.6 -0.2 (I) 1, i=0 R1=H
R=1,3,5-tri-methyl-nonyl M=Na 2.50 +6.0 +7.0 -1.4 -5.1 -0.6 7.50 +7.9 +27.8 +4.1 0 +2.8 ~ N .
Ln 12.50 +13.0 +10..7 +5.5 +10.3 +7,0 cn 1.25 9.5 +27.0 +16.4 +10.3 +17.4 Formula o (I)=, R==H, i=0, w R=Ciz/C

r M=Na 'n 2.50 +11.8 +9.0 +8.2 +10.3 +10.0 7.50 +10.2 +22.6 +1.4 +5.2 +3.9 12.50 +8.4 +12.8 +5.5 +10.3 +6.6 (1): A mixture of compounds in which n was each of 1-5 and its mole average value was about 2.

Table 8 TOWEL - HANDSHEET DATA
Feedstock = Screened Recycled Fiber (Freeness #437) -% Absorb. % Absorb. Capacity o Dry o Wet Rate Rate Index Dose Tensile Tensile Change Change Change Surfactant (lb/ton) Change Change 0-5 sec. 6-12 sec. 20 sec.
Formula (V), 1 +6.4 +48.8 -5.7 -8.7 -6.0 n= 10, R2= nonyl 0 0) M=Na L' 3 +4.6 -3.3 -34.3 -43.5 -40.7 +8.2 +12.5 -31.4 -39.1 -34.7 0 =
w +2.2 -5.0 -14.3 -17.4 -15.1 v~, Feedstock = CTMP (Freeness #582) Formula (V), 1 +0.5 +31.1 +10.3 +14.3 +6.1 n= 10, R2= nonyl .
M=Na 3 -5.0 -2.7 +28.2 +35.8 +15.9 +13.5 +14.2 +35.9 +32.1 +12.7 -14.1 -12.8 +33.3 +28.6 +12.7 cn ao Feedstock = Blend NOC (Freeness # 585) Ln Formula (V), 1 +11.6 +10.5 +10.0 +16.7 _ +11.3 n= 10, 1 .3 Rz= nonyl W
M=Na cn 3 +9.3 -15.7 -5.0 0 -4.0 5 +14.9 +15.7 +5.0 +16.7 +5.0 10 +2.2 -16.9 +10.0 +16.7 +12.6 Feedstock = Sulfite (Freeness #707) Formula (V), 1 +5.6 +11.5 0 -6.1 -4.9 n= 10, Rz= nonyl M=Na 3 -14.2 - -19.1 +27.1 - +15.2 +42.9 -9.5 - -13.7 -12.5 - -3.0 -9.0 -9.4 +1.6 +66.7 +93.4 +82.6 = ~

Feedstock = Softwood/CTMP (50:50)(Freeness #654) LTI
co Formula (V), 1 +0.8 -7.9 -14.6 -6.7 -13.0 ~
n= 10, R2= nonyl 3 +4.0 +9.0 -9.8 -13.3 -7.9 0 w 5 -3.3 +17.4 0 -20.0 -6.4 Ln 10 -1.2 -11.2 +22.0 -20.0 +3.7 Dye Leveling During dyeing of a fiber it is 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 fiber being dyed. This property is useful for instance in the carpet industry. In general,"one can use effective amounts ranging generally form 0.506 to 5% by weight of surfactant based on the weight of dye.
Example 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 solutioii was prepared by mixing 21.0 grams of 0.501 Ciba Tectilon orange 3G200, 10.5 grams of 0.5% Ciba Tectilon blue 4RS KWL
200, 10.5 grams of 0.5o Ciba Tectilon red 2KWL 200N
with 2.0 grams of ammonium sulfate. The mixture was diluted to 4000 grams with tap water and mixed well.

Nylon Dye Leveling 400 gram aliquots of the dye stock solution were poured into stainless steel cylinders, and the surfactant to be tested was added, 0.1 grams to 1.0 gram of 10% active. "Dowfax 2A1" was used for comparison. The material was mixed and adjusted 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 o leveling.
The results are shown in Table 9. The compounds of the present invention performed as well as or better than "Dowfax 2A1".

Table 9 Dye=Leveling Concentration Suractant (wt.%) % Dye Leveling "Dowfax 2A1" 0.015 83.8 0.0075 97.7 Formula (I), 0.015 96.8 i=0, R1=H, R=1,3,5-trimethyl-nonyl 0.0075 94.6 Formula (I), 0.0075 95.8 i=0, R1=(C311G0)4H
R=C12/Ci4 Formula (I), 0.0075 99.4 i=0, R'= (CHZCHZO) BH
R=C12-C,,, Formula (V), n= 0.015 98.6 Rz=nonyl Formula (III), 0.015 97.0 n= 10 Rz=nonyl 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 dan 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 botto-n 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 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. TOFA' oPhosphate /ton of ore) (lb./ton) Recovery (None) 1.0 11.0 (None) -- 2.0 64.0 Formula 0.75 1.0 86.0 (I) 2, i=0, R'=II, M=Na R=Ci2/Ci4 Formula 0.04 1.0 48.0 (I)', i=0, R'=H, M=Na R=Ci2/Cia Formula 0.75 1.0 89.0 (I)', i=0, M=Na R'=
( CHzCH,O ) 8H
R=C12/CI4 (1)= TOFA is tall oil fatty acids.
(2)= A mixture of compounds in which n is each 1-5 and its mole average value is about 2.

Hard Surface Cleaners, Stain Removers, and Laundry Detergents The compounds of the present invention are also useful in cleaning substrates ranging from fabrics and carpeting, to hard surfaces such as floors, porcelain fixtures, countertops, and the like.

They can be formulated into cleaning products containing 0.1 to 20 wtA or more, of one or more compounds 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.
The low niolecular 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.

Example 11 Swatches of fabric which were soiled or stained were prepared and washed using various compounds of the present invention as the soil removal/stain removal surfactant. The degree of effectiveness, as o removal, was then determined. The washing was carried out in 100 ppm hardness water at 70 F., in 1-liter of 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 rpni, and the rinsed swatches were air dried overnight.
The results were:

Table 11 o Soil/Stain Removal Surfactants:
Fabric Soil/Stain A B C
Cotton Clay 71.6 72.7 79.9 Cotton 01ive oil 79.8 84.6 93.4 Cotton/ Coffee 79.9 85.7 87.1 polyester Cotton/ Grape 81.6 92.0 93.6 polyester juice Surfactant A: Formula ( I), i=0 , Rl=I-I, R=1, 3, 5-trimethyl-nonyl, M=Na B: Formula (I), i=0 R1= (CHzCH20) 4H, R=C12/C14, M=Na C: Dodecylbenzene sulfonic acid, sodium salt Paper Deinking The compositions of the present invention are also useful in deinlcing of waste paper. While paper deinking is known, it is sumtnarized 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 surfactant 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 of 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 surfactant components and the paper/ink interface.
It is preferred to utilize the compositions of the present invention in connection wi=th the froth flotation of ink from the waste paper. The general conditions of froth flotation deinking techniques are known in this field. The waste paper is pulped in ari 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 coniposition or compounds of the present invention are added at amounts calculated to provide the desired ratio between amounts of the respective compounds.
The overall amount of product to use is selected with respect to the quantity of the paper in the cell and with respect to the general amount of ink product on the paper. Gen.erally, the total aniount of product cocnprises about 0.05-0.1 wt.o to about 5.0 wt.o and preferably up to about 1.0 wt.o.based on the amount of waste paper present. Lesser amounts rislc reducing the efficiency of the deinking, whereas higher amounts inay 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 from the waste paper to the top surface'where a froth rich in removed ink is established. The froth can be removed or continuously or iiitermittently. After a period of ticne appropriate for the volume uf 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 forniula (I), the following comparative tests were carried out.

EXPERIMENTAL PROCEDURE
Repulping 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% consistency. Initially water (28.4 liters) was added, then steam was injected to increase the teniperature to 120 F. Four pound (O.D.) batches were added over 5 ininutes to maintain stock circulation in Lhe Slush-Maker. The pH was adjusted to 10 with 5% NaOH. The=repulping was performed at the following conditions:

Consistency - 60 Temperature - 120 F
pH - 10 Repulping time - 30 minutes After repulping the stock from the Slush-Maker was diluted to approximately 0.75-0.0801 consistency to make a "master batch". The temperature of the master batch was adjusted to 100 F before it was fed to the flotation cell.

Flotation 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 8ft'/minute. All the surfactants were diluted to G8.1 gms/liter and added at 0.3, 0.6 and 0.9%, 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 flotation cell was operated for ten minutes while collecting rejects. Six flotation runs were perfornied at different surfactant addition levels with one niaster batch. Samples of feed and accepts were collected for brightness pads.' Rejects were collected and weighted for yield calculation.

Brightness 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 airt count. Brightness was measured (two readings on each side of five sheets) on the pad surface using S4-M a brightmeter.

Yield The flotation yield was calculated using the equation below.
Capacity of flotation cell =7.69 gallon Mass of flotation cell =29121 grains CF =Consistency of Feed CR =Consistency of Reject WR =Weight of reject Yield = 100 X((25121 X CF) -(WR X CR) (29121 X CF
Image 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 irich, that is, it can detect dirt and/or ink specks as stnall as 0.032 in-n in diameter or about 0.001 =z 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:

Table 12 Furnish: Old Newsprint (ONP.) / Old MacLazine (OMG) (70o ONP, 30% OMG) % IIrightneaa Surfact-ant- % Addition Increase '6 riber 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 Legend: 1: "Lionsurf 727", a commercial standard.
2: "DI-600", a commercial standard.
3: Mixture of compounds of Formula I, R'=I-I, i=o, R=trimethyl nonyl 4: #3 (60%) + "Witconol. NS500 LQ" (400) "Witconol NS 500 LQ" is a commercial alkoxylated alcohol Furnish: Mixed Office Waste (MOW) (70% laser, 30% ledger) I t Visible TAPPI Dirt Dirt count llecreases decreases l3rightnees Fiber (>0.005 (> 0.04 Surfactant %7 Addition Increase Yield imn') 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 0.9 24.41 94.88 99.70 98.95 Legend: 1: "Lionsurf 72711, a commercial standard.
2: "DI-600", a conimercial standard.
3: Mixture of compounds of Formula I, R'=H, i=o, R=trimethyl nonyl.
4: #3 (60%) + "Witconol NS 500LQ" (400) ("Witconol NS500 LQ" is an alkoxylated alcohol.

Table 12 con't Delta Surfactant Addition Accepts Briq_ht Increase Iteference I Pced ~ % %- %- Yield :
1 0.3 35.21 31.86 3.35 9.51 90.98 0.6 35.21 31.94 3.21 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 0.9 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 Legend: 1: "Lionsurf 727", a commercial standard.
2: "DI-600", a commercial standard.
3: Mixture of compounds of Forniula I, R'=H, i=o, R=trimethyl noiiyl.
4: 43 (600-) + "Witconol NS 500LQ" (40%) ("W.itconol NS500 LQ" is an alkoxylated alcohol.

Claims (22)

1. A sulfonate composition selected from the group consisting of (I) compositions of matter comprising a mixture of products of the formulae (I), (I-A) and (I-B) wherein i is an integer from 0 to 10 and R1 is (ALK-O),H or H, whereby R1 is (ALK-O)p H when i=0, and M is selected from the group consisting of lithium, sodium, potassium and ammonium cations and mixtures thereof; 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, 4 or 5, wherein the mole average value of d is 1.8 to 2.2; and (II) products of the formula (III) 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.

2. The composition according to claim 1 wherein i is 0.

3. The composition according to claim 1 wherein each ALK group is ethyl.

4. The composition according to claim 1 wherein each ALK group is propyl.

5. The composition according to claim 1 wherein M is sodium.

6. The composition according to claim 1 wherein the mixture additionally contains compounds wherein d is 5.

7. A method of preparing an alkyl glyceryl ether sulfonate composition which comprises a mixture of compounds of the formulae (I), (I-A), and (I-B) as presented in claim 1, the method comprising:
a) forming a mixture of alkyl glyceryl halides of formulae (II) and (II-B) wherein i, d, R and R1 have the meaning as defined in claim 1, by reacting epichlorohydrin with an alcohol or alcohol ethoxylates of the formula R-O-(CH2CH2O)i-H to form said mixture of compounds of formulae (II) and (II-B);
and optionally subsequent alkoxylation of the pendant hydroxyl group on said compounds of formula (II), with the proviso that said subsequent alkoxylation is performed if i=0; and then b) replacing the chloro substituents on the compounds of formulae (II) and (II-B) with -SO3M.

8. A method of preparing an alkylphenol polyethoxy sulfate-sulfonate of the formula (III) of claim 1 wherein A is -SO3M comprising the steps of:

a) reacting an ethoxylated alkyl phenol of the formula R2-Ph-O(CH2CH2O)n H wherein R2, and n are as defined in claim 1 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) with A as -SO3M is formed.

9. 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)n H 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.

10. The method according to claim 7 wherein i = 0.

11. The method according to claim 7 wherein each ALK
group is ethyl.

12. The method according to claim 7 wherein each ALK
group is propyl.

13. The method according to claim 7 wherein in step (a) the pendant hydroxyl group on said compounds of formulae (II) and (II-B) is alkoxylated such that R1 is (ALK-O)p H.

14. The method according to claim 7, 8 or 9 wherein M is sodium.

15. The method according to claim 8 or 9 wherein R2 is nonyl.

16. Use of the sulfonate according to claim 1 as wetting agent in a process of forming a pulp from which paper can be produced, which process comprises admixing together water, feedstock selected from the group consisting of recycled paper, wood pulp, and mixtures thereof.

17. Use of the sulfonate according to claim 1 as a dye leveling agent in a process of dyeing nylon which process comprises contacting nylon, the sulfonate and a dye.

18. Use of the sulfonate according to claim 1 as a surfactant in a process of emulsion polymerization, said process comprising polymerizing a monomer in an aqueous emulsion comprising the sulfonate.

19. Use of the sulfonate according to claim 1 in a process for beneficiating ore, comprising subjecting a finely divided mixture of ore and impurities to froth flotation in an aqueous medium which comprises said sulfonate.

20. Use of the sulfonate according to claim 1 as a surfactant in a hard surface cleaner.

21. Use of the sulfonate according to claim 1 as a surfactant in a composition which is effective to remove soil and stains from fabric.

22. Use of the sulfonate according to claim 1 as a surfactant in a method of deinking waste paper comprising subjecting said waste paper to froth flotation in an aqueous medium comprising said sulfonate.