CA2159982A1 - Sulfonated ester oligomers suitable as dispersing agents in detergent compositions - Google Patents

Abstract

Fully and partially oligomerized anionic esters useful as dispersing agents in detergent compositions. The esters comprise terephthalate units, oxy-1,2-alkyleneoxy units (oxyethyleneoxy units preferred), and sulfoisophthalate units.

Description

SULFONATED ESTER OLIGOMERS SUITABLE AS
DISPERSING AGENTS IN DETERGENT COMPOSITIONS

TECHNICAL FIELD
The present invention relates to anionic ester compositions useful as soil dispersing agents in fabric care compositions, especially liquid and granular laundry detergent compositions and synthetic laundry bar detergents.
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of copending application Serial Number 08/044,995, filed April 7, 1993.
BACKGROUND OF THE INVENTION
It has long been known that a need exists for detergent compositions which provide superior cleaning benefits on heavily soiled textiles and fabrics and which disperse and suspend soils in the laundry liquor to prevent their redeposition onto the fabrics.
This is especially true for organic soils and stains, such as those formed by industrial pollution, body soils and/or automobile exhaust. Fabrics exposed to such heavy soiling can often have a dull gray or dingy look even after washing. In many instances the consumer re-uses the laundry liquor for several wash loads. During the wash cycle, the soils and stains that are removed from the fabrics become concentrated in the laundry liquor and redeposit onto the fabrics before they can be removed from the wash. The redeposited soils also contribute to the dull and dingy appearance.
The problem is compounded by the laundering methods used by many consumers wherein the fabrics are typically washed with the use of granular detergents or detergent bars in a low water to fabric ratio, i.e., wherein the ratio of water:fabric load is substantially less than in automatic laundry machines. This is especially true under hand-wash conditions, but also occurs in concentrated washing processes, such as those disclosed in U.S.
Patents 4,489,455 and 4,489,574, both issued to Spendel on Dec. 25, 1984.
A number of dispersing or antiredeposition compounds are known to be effective in detergent compositions, particularly for WO 94122937 2 t ~ 9 9 8 2 PCT/US94/03740 ~

inorganic particulates such as clay. However, to date, these compounds have not been found to be effective under conditions of heavy, organic soiling wherein the soils become highly concentrated in the laundry liquor.
Another component of modern conventional detergent composi-tions is soil release agents (s.r.a.'s). It is believed that s.r.a.'s deposit on the fabric surface, particularly polyester fabrics, during the laundry cycle. As the fa~rics are used or worn, soils collect on the treated fabric surface. When the fabric is re-laundered, the s.r.a.'s aid in the removal of these soils from the fabric's surface.
A wide variety of soil release agents for use in in-home fabric treatment processes are known in the art. Various s.r.a.'s have been commercialized and are currently used in detergent compositions and fabric softener/antistatic articles and composi-tions. Anionic s.r.a.'s typically comprise an oligoester backbone, which may itself optionally contain various anionic substituents, and will usually terminate with one or more end-capping units which are also anionic. For example, various oxyalkylene/terephtha-late/sulfoisophthaloyl oligomers end-capped with sulfoaroyl substi-tuents compr~se a known and important class of s.r.a.'s for use in laundry detergents.
One major difference between s.r.a.'s and the oligomer compositions of this invention is that s.r.a.'s require multi-cycle laundering to provide benefits. Through multiple launderings the s.r.a.'s are deposited onto the fabric surface. It is only after the s.r.a.'s have been deposited onto the fabric that the s.r.a.'s aid in the cleaning process. In contrast, the dispersing agents of this invention are not required to deposit on the fabric surface;
cleaning benefits are, therefore, provided even during the first laundry cycle before the fabrics have been previously contacted with the dispersing agent.
By the present invention, it has now been discovered that certain anionic oligomer compositions similar to those employed as s.r.a.'s, especially those of low molecular weight and incomplete oligomerization, can be employed as dispersing agents. Such dispersing agents have been found to be especially effective under conditions of heavy fabric soiling. Without wishing to be limited by theory, it is believed that the oligomer compositions disperse and suspend the soil in the laundry liquor and prevent the soil from redepositing onto the fabric surface. Accordingly, the laundered fabrics have a brighter, less dingy appearance, even after the first laundry cycle.
The present invention thus solves the long-standing need for an effective dispersing agent which provides a novel method of brightening fabrics by suspending organic soils in the laundry liquor and preventing their redeposition onto the fabric surface.
The dispersing agents are particularly effective in liquid or granular detergent compositions and synthetic detergent bars for use in hand-wash, or under other circumstances where low water to fabric ratios are used in a laundering operation.
These and other objects are secured herein as will be seen from the following disclosure.
BACKGROUND ART
U.S. Patent 4,702,857, Gosselink, issued October 27, 1987, discloses block polyester esters and mixtures thereof useful as soil release agents in detergent compositions. See also U.S.
Patent 4,861,512.
U.S. Patent 4,721,580, Gosselink, issued January 26, 1988, discloses end-capped oligomeric esters and mixtures thereof for use as soil release agents in detergent compositions. See also U.S.
Patent 4,968,451 and U.S. Patent 4,877,896.
Polyesters have also been disclosed for use in rinse-added consumer laundry products, in dryer-added products, and in certain bullt liquid detergents. $ee Canadian Patent 1,100,262, Becker et al, issued July 8, 1975; U.S. Patent 3,712,873, Zenk, issued January 23, 1973; U.S. Patent 4,238,531, Rudy et al, issued December 9, 1980; and British Patent Application 2,172,608, Crossin, published September 24, 1986.
Types of synthetic and analytical methods useful herein are well illustrated in European Patent Application 185,427, Gosselink, published June 25, 1986, and in Odian, PrinciDles of PolYmerization, Wiley, NY, 1981. Chapter 2.8 of the Odian reference, entitled "Process Conditions", pp 102-105, focuses on the synthesis of poly(ethylene terephthalate).

wo 94/22937 21~ 9 9 8 2 PcTruss4/03740 SUMMARY OF THE INVENTION
The present invention encompasses a method for cleaning fabrics, said method comprises contacting said fabrics in an aqueous liquor comprising conventional detergent ingredients and oligomeric, substantially linear ester compositions useful as dispersing agents. The detergent ingredients can optionally comprise detergent builders and other conventional detersive adjuncts in a liquid, granular or laundry bar detergent composi-tion.
The method also encompasses presoaking soiled fabrics before washing. The detergent compositions employed in the present invention may even be used for overnight soaking of the laundry.
Therefore, the preferred method of laundering involves contacting fabric or textiles with an aqueous laundry liquor comprising a detergent composition which comprises at least about 300 ppm, preferably from about 3~0 ppm to about 20,000 ppm, of conventional detersive ingredients and at least about 1 ppm, preferably from about 1 ppm to about 50 ppm, of said dispersing agent for about 5 minutes to about 15 hours. When the detersive ingredients comprise a detersive surfactant, the ratio of dispersing agent to surfactant should preferably be below about 1:10. The washing operation preferably employs agitating the fabrics with an aqueous liquor containing the compositions herein. The fabrics can then be rinsed with water and line or tumble dried. The dispersing agents are especially effective under typical hand-wash conditions or in low water to fabric load laundering situations wherein the ratio of fabric:water (kg:liters) ranges from about 1:15 to about 1:0.5, especially from about 1:7 to about 1:1. A typical ratio under hand-wash conditions is about 1:5.
The dispersing agents herein comprise ester compositions with relatively low Completion ~ndices and relatively low molecular weights (i.e., below the range of fiber-forming polyesters).
Typical dispersing agents of the present invention have a number average molecular weight ranging from about 400 to about 3,000.
Said ester compositions employed herein comprise oxyethyleneoxy or oxy-1,2-propyleneoxy units and terephthaloyl units. Preferred ester compositions additionally comprise sulfoisophthalate and sulfonated end-capping units. (Mixtures of such esters with reaction by-products and the like retain their utility as soil dispersing agents when they contain a minimum of doubly end-capped esters.) Taken in their broadest aspect, the ester compositions provided by this invention encompass a mixture of oligomeric esters comprising "backbones" which are optionally end-capped on one or both ends of the backbone by end-capping units. Preferably, the esters are not fully oligomerized, i.e., doubly end-capped. The relative ratio of fully oligomerized to partially oligomerized ester molecules in a given composition can be related to its Completion Index (defined hereinafter).
The end-capping units herein are anionic sulfonated hydro-philes and connected to the esters by an ester linkage. The pre-ferred end-capping units are selected from the group consisting of:
a) M03S(CH2Jm(CH2CH20)(RO)n-, wherein M is a salt-forming cation such as sodium or tetraalkylammonium, R is ethylene or propylene or a mixture thereof, m is O or 1, and n is from O to 4; b) sulfobenzoyl units of the formula (M03S)(C6H4)C(O)-, wherein M is a salt-forming cation; and c) mixtures of a) and b).
Certain noncharged, hydrophobic aryldicarbonyl units are essenttal in the backbone unit of the oligoesters herein.
Preferably, these are exclusively terephthaloyl units. Other noncharged, hydrophobic aryldicarbonyl units, such as isophthaloyl or the like, can also be present if desired, provided that the soil dispersing benefits of the esters are not significantly diminished.
It is also possible optionally to incorporate additional hydrophilic units into the esters. For example, anionic hydrophllic units capable of forming two ester bonds may be used.
Suitable anionic hydrophilic units of this specific type are well illustrated by sulfonated dicarbonyl units, such as sulfoisophthal-oyl, i.e., -(O)C(C6H3)(S03M)C(O)-, wherein M is a salt-forming cation such as an alkali metal or tetraalkylammonium ion.
Thus, preferred dispersing agents herein comprise mixtures of:
A) from OX to aboùt 95% of fully oligomerized (di-capped) esters of the formula:
(CAP)2(EG/pG)v(T)y(sI)z wherein wo 94l22937 21~ 9 9 8 2 PCTrUSs4/03740 i) (CAP) represents sulfonated end-capping units selected from the group consisting of:
(a) M03S(CH2)m(CH2CH20)(RO)n-, wherein M is a salt-forming cation, R is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is from 0 to 4;
(b) sulfobenzoyl units of the formula (M03S)(C6H4)C(0)-, wherein M is a salt-forming cation; and (c) mixtures of (a) and (b);
ii) (EG/PG) represents oxyethyleneoxy units, oxy-1,2-propyl-eneoxy units or mixtures thereof;
iii) (T) represents terephthaloyl units; and, optionally, iv) (SI) represents 5-sulfoisophthaloyl units of the formula -(O)C(C6H3)(S03M)C(0)-, wherein M is a salt-forming cation; v is from about 0.25 to about 50, y is from about 1.25 to about 30, preferably from about 1.5 to about 8, and z is determined by the formula y/(z+1) - about 1.25 to about 5; wherein, v, y and z represent the average number of moles of the corresponding units per mole of said ester; and B) from about 5% to 100% of partially oligomerized esters of A) with a number average molecular weight of no more than 70X
of the molecular weight of the fully oligomerized esters, A);
such that the number average molecular weight of the dispers~ng agent is from about 400 to about 3,000, preferably from about 500 to about 1,100, and most preferably from about 600 to about 900.
Preferably, when the (CAP) units are i)(a), v is determined by the formula v ~ y+z to y+z-l. When the (CAP) units are i)(b), v is determined by the formul2 v - y+z+1, and when the (CAP) units are ~)(c), v is determined by the formula v ~ y+z+1.
The preferred esters have a number average molecular weight of no more than 70%, preferably from about 10% to about 60Y., of the formula weight of the fully oligomerized or "targetN structure. In calculating the number average molecular weight of the compositions only the ester components are included and not any residual free glycols which may also be present. The degree of oligomerization necessary to achieve the desired percent of target formula weight can be related to a Completion Index. Ester compositions of the WO 94/22937 215 9 9 8 ~PCT/US94/03740 invention will comprise at least about 5%, preferably at least about 10% and most preferably at least about 50%, of partially oligomerized esters. A fully oligomerized ester will be doubly end-capped and will have a Completion Index of infinity.
The ester "backbone" of the present compositions, by defini-tion, comprises all the units other than the end-capping units. All the units incorporated into the esters being interconnected by means of ester bonds. Thus, in one simple embodiment the ester "backbones~ comprise only terephthaloyl units and oxyethyleneoxy units. In preferred embodiments incorporating oxy-1,2-propylene-oxy units, the ester "backbone" comprises terephthaloyl units, oxyethyleneoxy, and oxy-1,2-propyleneoxy units. In still other highly preferred embodiments, hydrophilic units such as 5-sulfo-isophthalate are present in the backbone wherein the preferred ratio of terephthaloyl to 5-sulfoisophthaloyl units is determined by the formula y/(z+1) - 2 to 4, wherein y and z are defined above.
The ester compositions herein comprise at least 50% by weight of said ester oligomers having a number average molecular weight ranging from about 400 to about 3,000.
The invention also encompasses the preparation of dispersing agents characterized in that they consist essentially of the oligomeric product of reacting dimethyl terephthalate or terephthalic acid, ethylene glycol, propylene glycol or a mixture thereof, a compound selected from the group consisting of monovalent cation salts of sulfonated end-capping monomers and, optionally, dimethyl sodiosulfoisophthalate or sulfoisophthalic acid, monosod1um salt. The resulting water-soluble oligomeric products are useful for dispersing soils in an aqueous laundry liquor.
A preferred dispersing agent is prepared by reacting 1 mole of monovalent cation salts of sulfonated end-capping monomers, 5 moles of dimethyl terephthalate, 1 mole of dimethyl sulfoisophthalate, and 12 moles of ethylene glycol, propylene glycol or mixtures thereof.
The conventional detergent ingredients used in the present invention comprise from about 1% to about 99.9%, preferably from about 5Z to about 80X, of a detersive surfactant. Optionally, the detergent ingredients comprise from about 5X to about 80% of a WO 94/22937 21~ 9 9 8 2 PCT/US94/03740 ~

detergent builder. Other optional detersive adjuncts can also be included in such compositions, at conventional usage levels. The dispersing agents will typically constitute from about 0.1% to about 10%, preferably from about 0.25% to about 5%, by weight of detergent composition.
All percentages, ratios, and proportions herein are on a weight basis unless otherwise indicated. All documents cited are incorporated herein by reference.
DETAILED OESCRIPTION OF THE INVENTION
The essential component of the compositions employed in the present invention is a dispersing agent comprising a mixture of fully and partially oligomerized esters characterized by certain essential backbone units and optional end-capping units, all in particular proportions and having structural arrangements as described hereinafter.
The following structures are illustrative, but by no means limiting, of preferred structures of ester molecules of the invention. The target structure of a fully oligomerized ester has the formula:
O O O
Il 11 r~ 11 NaO3S(C6H4)-C-O- CH2CH2-0-C ~ .~-C-O- - -CH2CH2-0--C ~ C-O- ;CH2CH2-O-C-(C6H4)S03Na S03Na The preferred partially oligomerized ester employed in the present invention will have about 50% of the formula weight of the above target ester and a Completion Index of about 6.
In another example, the target structure is:
O O O O
NaO3S(CH2CH20)2-C ~ C-O- -CH(CH3)CH2-0-C ~ -C-O -O O
-CH(CH3)CH2-0-C ~ C- ;(OCH2CH2)2S03Na S03Na -~WO 94/22937 215 9 9 8 2 PCT/US94/03740 g The preferred partially oligomerized ester employed in the present invention will have about 40X to 50~. of the formula weight of the S above target ester and a Completion Index of about 3.
In still another example, the target structure is:
O O ~ O O
NaO3S(CH2CH~0)2-C ~ -C-0- -CH2CH2-0-C- ~ -C-0-10 -- o O
-CH2CH2-0-C ~ C- -(OCH2CH2)2S03Na S03Na~
The preferred partially oligomerized ester employed in the present invention will have about 20% of the formula weight of the above target ester and a Completion Index of about 1.8.
The esters herein can be simply characterized as oligomers which comprise a su~stantially linear ester "backbone~ and, optionally, one or more kinds of end-capping units, especially 2-(2-oxyethoxy)ethanesulfonate or sulfobenzoyl.
Proper selection of the structural units which comprise the ester backbone, use of sufficient amounts of the sulfonated end-capping units, and control of the degree of oligomerization results in the desired soil dispersing benefits provided by these materials-Dearee of Oliqomerization - It is to be understood that the compositions herein are not resinous, high molecular weight, macromolecular or fiber-forming polyesters but, instead, are relatively low molecular weight and contain species more ap-propriately described as oligomers rather than as polymers. Estermolecules herein, including the end-capping units, can have number average molecular weights ranging from about 400 to about 3,000.
Relevant for purposes of comparison with glycol-terephthalate fibrous polyesters (typically averaging 15,000 or more in molecular weight) is the molecular weight range of from about 500 to about 1,100, within which preferred molecules of the esters of the invention which incorporate the essential units are generally found. Accordingly, the compositions of this invention are referred to as "oligomeric esters" rather than "polyester" in the colloquial sense of that term as commonly used to denote high polymers such as fibrous polyesters.
Molecular GeometrY - The esters of the invention are all "substantially linear" in the sense that they are not significantly branched or crosslinked by virtue of the incorporation into their structure of units having more than two ester-bond forming sites.
(By contrast, for a typical example of polyester branching or 0 crosslinking of the type excluded in defining esters of the present invention, see Sinker et al, U.S. Patent 4,554,328, issued November 19, 1985.) Furthermore, no cyclic esters are essential for the purposes of the invention but may be present in the compositions of the invention at low levels as a result of side-reactions during ester synthesis. Preferably, cyclic esters will not exceed about 2% by weight of the compositions; most preferably, they will be entirely absent from the compositions.
Contrasting with the above, the term "substantially linear" as applied to the esters herein does, however, expressly encompasses materials which contain side-chains which are unreactive in ester-forming or transesterification reactions. Thus, oxy-1,2-propyleneoxy units are of an unsymmetrically substituted type;
their methyl groups do not constitute what is conventionally regarded as "branching~ in polymer technology (see Odian, Principles of Polymerizat~on, Wiley, N.Y., 1981, pages 18-19, with which the present definitions are fully consistent) and are unreactive in ester-forming reactions. Optional units in the esters of the invention can likewise have side-chains, provided that they conform with the same nonreactivity criterion.
Molecular Units - The esters of this invention comprise end-capping units and repeating backbone units. To briefly illustrate an embodiment of the invention, molecules of the ester are comprised of three kinds of units, namely:
i) sulfonated end-capping units selected from the group consisting of:
(a) MO3S(CH2)m(CH2CH20)(R0)n-, wherein M is a salt-forming cation, R is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is from O to 4; (b) sulfobenzoyl units of the formula (MO3S)(C6H4)C(O)-, wherein M is a salt-forming cation; and (c) mixtures of (a) and (b);

ii) oxyethyleneoxy backbone units, i.e., -OCH2CH20-, oxy-1,2-propyleneoxy units, i.e., -OCH(CH3)CH20- or -OCH2CH(CH3)0-or mixtures thereof; and iii) terephthaloyl backbone units, i.e., -(O)CC6H4C(O)-.
Optionally but preferably, the esters herein also contain anionic hydrophilic units in the backbone. These units most preferably are:
iv) 5-sulfoisophthaloyl backbone units of the formula -(O)C(C6H3)(SO3M)C(O)-, wherein M is a salt-forming cation.
~he following structures are illustrative of structures of ester molecules falling within the foregoing embodiments and demonstrate how the units are connected:
a) doubly end-capped ester molecule comprised of the units i), ii) and iii);
O O O O
NaO3SCH2CH20CH2CH2-0-C- ~ -C-O-CH2CH2-O-C- ~ -C-O--CH2CH2-0-C-<~C-O-CH2CH2 -o-c-~?-c-o-cH2cH2ocH2cH2so3Na b) sing~ end-capped ester ecule comprised of units i), ii) and iii);
O O O O .
NaO3SCH2CH20CH2CH2-0-C-<~Y-0-CH2CH2-0-C-<~-C-O O
-O-CH2CH2-O-C ~ -C-O-CH2CH2-OH
c) singly end-capped ester molecule, (termed a "hybrid backbone~ ester molecule herein) comprised of units i), ii) and 1ii). Units ii) are a mixture of oxyethyleneoxy and oxy-1,2-propyleneoxy units, in the example shown below at a 3:1 mole ratio;
O O o o NaO3SCH2CH20CH2CH2-O-C ~ -C-OCH2CH20-C-~ ~ C-O O O O
-OCH2CH20-C- ~ -C-O-CH2CH(CH3)-0-C-', ~ C-OCH2CH20H

21~ 9 9 8 2 PCT/US94/03740 d) singly end-capped ester molecule comprised of units i), ii), iii) and iv);
S o o ~ O
NaO3SCH2CH20CH2CH2-0-C- ~ -Y-O-CH2CH(CH3)-O-C- ~ -C-O--CH(CH3)CH2-0-C ~ -~-O-CH2CH2-0-C-< ~ )-C-O-CH2CH2-0-o o o o o o -C-( ~ -C-O-CH2CH2-0-C ~ -C-O-CHZcH2 S03Na CH2CH(CH3)-OH
In the context of the structures of ester molecules disclosed herein it should be recognized that the present invention encompasses not only the arrangement of units at the molecular level, but also the gross mixtures of esters which result from the reaction schemes herein and which have the desired range of composition and properties. Accordingly, when the number of monomer units or ratios of units are given, the numbers refer to an average quantity of monomer units present in oligomers of the composition.
Ester Backbone - As illustrated in the structures shown above, in the esters employed herein, the backbone is formed by oxyethyleneoxy and/or oxypropyleneoxy and terephthaloyl units connected in alternation. Optionally, the backbone is formed by 5-sulfoisophthaloyl units, terephthaloyl units, oxyethyleneoxy and/or oxypropyleneoxy units connected with alternation of the aryldicarbonyl and oxyalkyleneoxy units. It should be recognized that polyoxyethyleneoxy units, especially di(oxyethylene)oxy units, formed during synthesis of the esters, can be present in trace amounts in the backbone.
GrouDs at the Termini of the Ester Backbone - Likewise, the nesters employed herein" is a term which encompasses the doubly and singly end-capped compounds disclosed herein, mixtures thereof, and mixtures of said end-capped materials with non-capped species.
Thus, when referring simply to an "ester" herein it is intended to refer, by definition, collectively to the mixture of sulfonated capped and uncapped ester molecules resulting from any single preparation.
Any ester molecules which are present in compositions of the invention which are not fully, i.e., doubly, end-capped by the end-capping units must terminate with units which are not sulfonated - end-capping units. These termini will typically be hydroxyl groups or other groups attributable to the unit-forming reactant. For example in the structure b) above, a chain terminal position to which is attached -H forms a hydroxyl group. In other structures which may be constructed, units such as -(O)CC6H4C(0)-OCH3 and -(O)CC6H4C(0)-OH may be found in terminal positions.
Anionic End-CaPDinq Units - The end-capping units used in the esters of the present invention are anionic sulfonated groups.
These end-cap units provide anionic charged sites when the esters are dispersed in aqueous media, such as a laundry liquor. The end-caps serve to assist transport in aqueous media and to provide hydrophilic sites on the ester molecules.
It is not intended to exclude the acid form, but most generally the esters herein are used as sodium salts, as salts of other alkali metals, as salts with nitrogen-containing cations (especially tetraalkylammonium), or as the disassociated ions in an aqueous environment.
Examples of anionic end-capping group monomers include sodium isethionate, sodium 2-(2-hydroxyethoxy)ethanesulfonate, sodium 2-[2-(2-hydroxyethoxy)ethoxy]ethanesulfonate, sodium 5-hydroxy-4-methyl-3-oxapentanesulfonate, sodium alpha-3-sulfopropyl-omega-hydroxy-poly(oxy-1,2-ethanediyl), sodium 5-hydroxy-3-oxa-hexanesul-fonate, sodium 3-hydroxy-1-propanesulfonate, sulfobenzoyl and mixtures thereof.
SvmmetrY - It is to be appreciated that in esters in which oxy-1,2-propyleneoxy units are also present, the oxy-1,2-propyl-eneoxy units can have their methyl groups randomly alternating with one of the adjacent -CH2- hydrogen atoms, thereby lowering the symmetry of the ester chain. Thus, the oxy-1,2-propyleneoxy unit can be depicted as having either the -OCH2CH(CH3)0- orientation or as having the opposite -OCH(CH3)CH20- orientation. Carbon atoms in the oxy-1,2-propylene units to which the methyl groups are attached WO 94/22937 215 9 9 ~ PCT/US94/03740 ~

are, furthermore, asymmetric, i.e., chiral; they have four nonequivalent chemical entities attached.
Preferably, various optional units of a hydrophilicity-enhancing and nonpolyester substantive type can be incorporated into the esters. The pattern of such incorporation will generally be random. Preferred optional units are anionic hydrophiles, such as 5-sulfoisophthaloyl or similar units.
It should also be noted that the essential non-charged aryldicarbonyl units herein need not exclusively be terephthaloyl units. Thus, for example, minor amounts of isomeric non-charged dicarbonyl units, such as isophthaloyl or the like, are acceptable for incorporation into the esters.
Method for Makinq Sulfonated End-CaDDed Esters - The ester compositions of the present invention can be prepared using any one or combination of several alternative general reaction types, each being well-known in the art. Many different starting materials and diverse, well-known experimental and analytical techniques are useful for the syntheses.
Mechanistically, the suitable general reaction types for preparing esters of the invention include those classifiable as:
1. alcoholysis of acyl halides;
2. esterification of organic acids;

3. alcoholysis of esters (transesterification);
and 4. reaction of alkylene carbonates with organic acids.
Of the above, reaction types 2-~ are highly preferred since they render unnecessary the use of expensive solvents and halogenated reactants. Reaction types 2 and 3 are especially preferred as being the most economical.
Suitable starting materials or reactants for making the esters of this invention are any reactants (especially esterifiable or transesterifiable reactants) that are capable of combining in accordance with the reaction types 1-4, or combinations thereof, to provide esters having the correct proportions of all the above-specified units (i) to (iv) of the esters. Such reactants can be categorized as ~simple reactants, i.e., those that are singly capable of providing only one kind of unit necessary for ~o 94/22937 215 g 9 8 2 PCT/US94/03740 making the esters, or as derivatives of the simple reactants which singly contain two or more different types of unit necessary for making the esters. Illustrative of the simple kind of reactant is dimethyl terephthalate which can provide only terephthaloyl units.
In contrast, bis(2-hydroxypropyl)-terephthalate is a reactant that can be prepared from dimethyl terephthalate and 1,2-propylene glycol and which can desirably be used to provide two kinds of unit, viz. oxy-1,2-propyleneoxy and terephthaloyl, for making the esters herein.
In principle it is also possible to use oligoesters, or polyesters such as poly(ethylene terephthalate), as reactants herein and to conduct transesterification with a view to incorporation of end-capping units while decreasing molecular weight. Nonetheless, the more highly preferred procedure is to make the esters from the simplest reactants in a process involving molecular weight increase (to the limited extent provided for by the invention) and end-capping.
Since "simple" reactants are those which will most preferably and conveniently be used, it is useful to illustrate this kind of reactant in more detail. Thus, 2-(2-hydroxyethoxy)ethanesulfonate can be used as the source of the end-capping units herein. Note that the metal cation can be replaced by potassium or a nitrogen-contain~ng cation provided that the latter does not overly promotecrystallization of the oligomer and is unreactive during the synthesis, e.g. tetraalkylammonium. It is, of course, possible to subject any of the esters of the invention to cation exchange after the synthesis and, thereby, afford a means of introducing more esoteric or reactive cations into the ester compositions.
Appropriate glycols or cyclic carbonate derivatives thereof can be used to provide oxy-1,2-alkyleneoxy units; thus, 1,2-propyléne glycol or (where the starting carboxyl groups are present in an acidic form) the cyclic carbonate C
o are suitable sources of oxy-1,2-propyleneoxy units for use herein.
Oxyethyleneoxy units are most conveniently provided by ethylene WO 94/22937 215 9 9 8 2 PCT/US94/03740 ~

glycol. Although, as an alternative, ethylene carbonate could be used when free carboxylic acid groups are to be esterified.
Aryldicarboxylic acids or their lower alkyl esters can be used to provide the essential aryldicarbonyl units; thus, terephthalic acid or dimethyl terephthalate are suitable sources of terephthal-oyl units. In general, it is preferred herein to use ester rather than acid forms of reactants to provide the aryldicarbonyl units.
Other units of the esters will be provided by well-known and readily identifiable reagents; for example, dimethyl 5-sulfoiso-phthalate is an example of a reagent capable of providing 5-sulfo-isophthaloyl units for optional incorporation into the esters of the invention. It is generally preferred that all units of the type (iv) as defined hereinabove should be provided by reactants in ester or carboxylic acid forms.
When starting with the simplest reactants as illustrated above, the overall synthesis is usually multi-step and involves at least two stages, such as an initial esterification or trans-esterification (also known as ester interchange) stage followed byan oligomerization stage in which molecular weights of the esters are increased, but only to a limited extent as provided for by the invention.
Formation of ester-bonds in reaction types 2 and 3 involves eliminat~on of low molecular weight by-products such as water (reaction 2) or simple alcohols (reaction 3). Complete removal of the latter from reaction mixtures is generally somewhat easier than removal of the former. However, since the ester-bond forming reactions are generally reversible, it is necessary to "drive" the reactions forward in both instances by removing these by-products.
In practical terms, in the first stage (ester interchange) the reactants are mixed in appropriate proportions and are heated to provide a melt at atmospheric or slightly superatmospheric pressures (preferably of an inert gas such as nitrogen or argon).
Water and/or low molecular weight alcohol is liberated and is distilled from the reactor at temperatures up to about 200C. (A
temperature range of from about 150-200C is generally preferred for this stage).
In the second (i.e., oligomerization) stage, vacuum and temperatures somewhat higher than in the first stage are applied;

o 94/22937 - 17 - 2 1 ~ 9 9 8 ~cT~uss4/03740 removal of volatile by-products and excess reactants continues until the reaction is at the desired stage of completion, as monitored by conventional spectroscopic techniques. Continuously applied vacuum, typically of about 50 mm Hg or lower can be used.
In both of the above-described reaction stages, it is neces-- sary to balance on one hand the desire for rapid reaction (higher temperatures and shorter times preferred), against the need to avoid thermal degradation (which undesirably might result in off-colors and by-products). It is possible to use generally higher reaction temperatures especially when reactor design minimizes super-heating or "hot spots"; also, ester-forming reactions in which ethylene glycol is present are more tolerant of higher temperatures. Thus, a suitable temperature for oligomerization lies most preferably in the range of from about 150C to about 260C when higher ratios of EG/PG are present and in the range of from about 150C to about 240C when lower ratios of EG/PG are present (assuming that no special precautions, such as of reactor design, are otherwise taken to limit thermolysis). When tetraalkylammonium cations are present, condensation temperatures are preferably 150-240C.
It is very important in the above-described procedure to use continuous mixing so that the reactants are always in good contact;
highly preferred procedures involve formation of a well-stirred homogeneous melt of the reactants in the temperature ranges given above. It is also highly preferred to maximize the surface area of reaction mixture which is exposed to vacuum or inert gas to facilitate the removal of volatiles, especially in the oligomeri-zation step; mixing equipment of a high-shear vortex-forming type giving good gas-liquid contact are best suited for this purpose.
Catalysts and catalyst levels appropriate for esterification, transesterification, oligomerization, and for combinations thereof are all well-known in polyester chemistry, and will ~enerally be used herein; as noted above, a single catalyst will suffice.
Suitably catalytic metals are reported in Chemical Abstracts, CA83:178505v, which states that the catalytic activity of transition metal ions during direct esterification of K and Na carboxybenzenesulfonates by ethylene glycol decreases in the order Sn (best), Ti, Pb, Zn, Mn, Co (worst).

WO 94/22937 2 l ~ g ~ 8 2 PCT/US94/03740 ~

The reactions can be continued over periods of time sufficient to reach the desired level of oligomerization, or various conventional analytical monitoring techniques can be employed to monitor progress of the forward reaction. Such monitoring makes it possible to speed up the procedures somewhat and to stop the reaction as soon as a product having the minimum acceptable composition is formed. In general when tetraalkylammonium cations are present, is is preferred to stop the reaction at less than full completion, relative to the sodium cation form, to reduce the possibility of thermal instability.
Appropriate monitoring techniques include measurement of relative and intrinsic viscosities, hydroxyl numbers, 1H and 13C
nuclear magnetic resonance (n.m.r) spectra, and liquid chroma-tograms.
Most conveniently, when using a combination of volatile reactants (such as a glycol) and relatively involatile reactants (such as dimethyl terephthalate), the reaction will be initiated with excess glycol being present. As in the case of ester interchange reactions reported by Odian (op. cit.), "stoichiometric balance is inherently achieved in the last stages of the second step of the process~. Excess glycol can be removed from the reaction mixture by distillation; thus, the exact amount used is not critical.
Inasmuch as the final stoichiometry of the ester compositions depends on the relat~ve proportions of reactants retained in the react~on mixtures and incorporated into the esters, it is desirable to conduct the condensations in a way which effectively retains the non-glycol eactants and prevents them from distilling or subliming. Dimethyl terephthalate and to a lesser extent the simple glycol esters of terephthalic acid have sufficient volatility to show on occasion "sublimation~ to cooler parts of the reaction apparatus. To ensure achieving the desired stoichiometry, it is desirable that this sublimate be returned to the reaction mixture or, alternatively, that sublimation losses be compensated by use of a small excess of terephthalate. In general, sublimation-type losses, such as of dimethyl terephthalate, may be minimized 1) by apparatus design; 2) by raising the reaction temperature slowly enough to allow a large proportion of dimethyl terephthalate to be converted to less volatile glycol esters before reaching the upper reaction temperatures; 3) by conducting the early phase of the transesterification under low to moderate pressure (especially effective is a procedure allowing sufficient reaction time to evolve at least about 90% of the theoretical yield of methanol before applying vacuum). On the other hand, the "volatile" glycol components used herein must be truly volatile if an excess is to be used. In general, lower glycols or mixtures thereof having boiling points below about 350C at atmospheric pressure are used herein; these are volatile enough to be practically removable under typical reaction conditions.
Typically herein, when calculating the relative molar pro-portions and the target Completion Index for a polymer synthesis, the following routine is followed as illustrated for a combination of reactants sodium 2-(2hydroxyethoxy)ethanesulfonate (A), ethylene glycol (B), propylene glycol (C), dimethyl terephthalate (D), and dimethyl 5-sulfoisophthalate (E):
1. The generalized target structure is selected for a fully dicapped polymer consisting of units derived from the desired monomeric reactants. In this example, the generalized target structure is: (CAP)2(EG/PG)X(T)y(SI)z, where the CAP units are derived from (A), the EG/PG units from (B) and (C), the T
units from (D), and the SI units from (E);
2. The average number of terephthalate units desired for the target structure is selected; for the present example, the value of 5 is selected for y, which falls in the range of most highly preferred values according to the invention, is used;
3. The average number of sulfoisophthalate units desired for the target structure is selected; for the present example, the value of 1 is selected for z, which falls in the range of the most highly preferred values according to the invention, is used;
4. The mole ratio of (A) to (D) to (E) should thus be 2:5:1;
amounts of the reactants (A), (D), and (E) are taken accordingly;

5. An appropriate excess of the glycols is selected; typically 2 to 10 times the sum of the number of moles of dimethyl terephthalate plus dimethyl 5-sulfoisophthalate is suitable;

WO 94122937 r 2 ~ 9 8 2 PCT/US94/03740 in this example, the glycols are ethylene glycol, (B) and propylene glycol, (C);

6. The target ratio of incorporated ethylene glycol:propylene glycol (EG/PG ratio is selected; for the present example, the ratio of 2:1 is selected which is in the most highly preferred range according to the invention; typically, the EG/PG ratio incorporated is higher than the initial (B):(C) reactant ratio because of volatility and reactivity differences; for this reason the initial (B):(C) ratio of about 1.5:1 is selected for this example to give a 2:1 EG/PG ratio in the final oliogomer.

7. The target Completion Index is calculated which will correspond to the desired molecular we~ght range for the desired, partially polymerized ester; this calculation is based on the simplifying assumptions: first that the 13C-NMR
peak heights accurately reflect the ratios of the different kinds of species present and second, that although the measurements are made only for ethylene glycol esters, the same ratio of di:monoesters exists for both ethylene and propylene glycols. The calculation is also based on a formalism in which a fully polymerized sample is reacted with glycol by transesterification such that one free glycol reacts with one diester of glycol in the polymer to produce two monoesters of glycol as end groups of polymer fragments. The number of such cleavages needed to reduce the average molecular weight to the desired range is then determined and the ratio of glycol diesters:monoesters at that degree of cleavage is determined. From this, the ratio of 13C-NMR peaks for monoester and diesters of ethylene glycol at the desired level of cleavage is determined and converted to a Completion Index; For simpl~city, the cleavages are assumed to occur only at glycol diester linkages and the contribution of attacking glycol to the molecular weight of the cleaved polymer is ignored. For the present example, the calculation is as follows:
a. Average MW of fully polymerized target 1594 b. Average MW for desired ester 640 c. Fraction of target MW desired (640/1594) 1/2.5 215 9 9 8 2 PcT~s94/03740 d. ~ of cleavages ~PcP~C~ry by glycol LL~ L~Lifications to get average MW
reduced by 1/2.5 1.5 e. Mbles of glyool to cleave target 1.5 tImes ~;5 f. Moles of glyool in average, fully polymerized target 5 g. Total moles glycol aft~r 1.5 cleavages 6.5 h. I~ Lers of glycol after 1.5 cleavages 3 i. ~iPctDrs of glycol after 1.5 cleavages 3.5 j. Diester ~o~L~ at -63 ~ " in 13C-NMR
after 1.5 cleavages (3.5 diesters X 2 ~aLL~ per ester) 7 (assarlLng all ethylene glycol) ~ L~ L~ at -60 ppm in 3C-NMR after 1.5 cleavages (3 nh~r~L ~s X 1 r~r~on per ester) 3 (as~cing all ethylene glyool) 1. CA1~1A~JP~ 63/60 peak ~Pi~ht ratio (7/3) 2.3 m. ~A~ t*~ CompletiQn $ndex fQr desired ester 2.3 Oligomeric ~t~rC useful as dispers ~ agents as ~ic~lnFA~ in this invP~tis~ may AlcO be ~.~t~la~ frcm an oligomeric ester oomprising tbe desired monomer ~ ts but with a higher Com~l~t;~
Index than dbsired. The oli~n~eric ester is mixed with ethylene glycol, or a m~bIre of ethylene glyool and ~ ylene glycol, under heat to ~ ~ the polymerization of the oligomer. The glycol acts to cleave the oligomeF and, L~u~L~, provi~oc a mixture of oligomeric ~c~rs with a lcwer average Ch~rle~jn~ In~ex.
F~ bly, if a mixture of ethylene glycol and prcpylene glycol is used, the ratio of ethylene glycol to propylene glycol will be about the same as the ratio of the two glycols ~e~f~lL in the oligomeric ester. The amount of glycol to be mixed with the oligomeric ester is d~A~ ~ nt upon the final Completion Index APcired. Generally, a lower Completion Index will be achieved by using more glycol.
ni~rp~cin~ agents which contain end-cap units having from 1 to 3 cLhylene or propylene groups and a ratio of oxyethyleneoxy to WO 94/22937 21~ 9 9 8 2 PCT/US94/03740 ~cy-1,2-prcpyleneoxy ur~its of a~ove A~t 0.5:1, may ~u~u un~e5irable cry~A~ Ation durin~ synthesis or when introduc~l to the laun~ry liquar. A c -l fo~ate--type hy~L-JLL~e or 51-Ahi 1; 7~r~
such as alk~l~llfanate, cL~ulfonate or toluen~ulfor~te, S may be mix ~ with the L~ ~æUlL~; ~uring synt~h~:; C of the ester to reduce the cry~Alli7Atin~ proh1em. Typically 0.5~ to a_out 20%, ky w-ight of the ecter compo6ition, of 5~hili7~r is added to the compo6ition.
In light of the t~A~hi~g of the ~LL5X~lL invention (insofar as 10 the identity an~ ~lutu~Lions of ~ ~ _a~ying an~ e units are ~Y~ nucer~us S~n~ PC of ester cn~rositions according to the inv~n~i~n follow strai~l~fuLwardly from the above ~;C~ln~tne.
The fo~ g, mLre ~Ai1~ ~Y~-~rlPc are ~ rative.
FX~ME~ I
S~ ic of ~ ium 2-(2-hydroxyethoxy)~U~ lf~ate A 1 liter, 3-neck, rc~u~ l-lL~ flask q~;rpF~ with m3gnetic stirring bar, pH prcbe, thcrmoreter ~ dYl to a Inu~ WatchIM
(I ~), an~ an inert gas inlet throu3h a c~ is ~ d with 400g of t~ct;llo~ wa~ . Thi_ is deOx~y~laLe~ by hlhhli~g inert ZO ~p c ~ h the water fo~ 30 minutes while stirring vigorously. To ~h;.c ic added sr~il~ ~ ide (40.0g, 1.00 mol, Malli~ udL).
When the cnlt~;n~ is homL~ s, a glAcc tube is placed into the ~ll~;n~ thrcugh a rlAc;~n head while maintaining the inert atmrk~ in the system. The p~ is above 11. Sulfur tlinY;~P gas (Air P,~h~ ~ Co.) is hlhhlF~ into the basic ~ol-~isn at ca. 0.02 mol per minute. When the pH of the sol~ n drcpc to 4.0 in ca. 1 hr, the 92 AA~it;n~ is ~ ~1. The L ~ aL~re of the cnl~rt;n~
is r~ioP~ to ca. 85 & and held there. Inert gas ic used to flush the delivery tuke free of rpc;~Al 92 Ethylene oxide (Wright DLC~ Corp.) is then hlhh~P~ through the hc~t, pale yellow ~UY~C cQl-~inn at a rate of ca. 0.02-0.03 mol per minute.
C~ t~ion of the sulfite to icethio~ate is manitored by iodometric titration of 0.50ml aliquots of the rPA~inn. The pH of the ~oll~inn slc~wly ricPc as the sulfite reacts. Only after ca. 98~ of th~ ~llfi~e is ccnsumed dc~es the rPA~ti~n mixture ~C~A~I~ mildly 1inP. At the very end, when the titration indicates that ~ lly no sulfite remains, the pH rises to 9. At this point, the addition of ethylene oxide is ~Luy~ed. The pH of the clear W O 94/22937 - 215 9 9 8 2 PCTrUS94/03740 ,sol ~lt i~n is adjusted ~ack down to ca. pH 5 by the addition of a small amcunt of 5M sulfuric acid. This adju~ .L of pH is ~_~P~(e~ as needed until the pH StAhi 1; 7~C (tl~lAlly after a few minutes). At this point any tiny r~Ci~lAl of sulfite may ~P
~ by adding a ~ ng nt of 30% H202 to o~ e it to ~llfA~e. (Alternatively, any sulfite r~ l may be oxidiz-ed after c~ tL~ion to cn~;um 2-(2-hydroxyethoxy) ~U~ lfonate.) The resulting iCP~hin~ate sQlt~;on may ke used directly for conver-sion to m~l;fi P~ ; CP~h;~rAtes.
~a~ in~ of the iC~h;nnRte C~lt~;~n into sodium 2-t2-hydroxyethoxy)t~u ~ ~lfonate is ~rrn~rl;chPA by adding sodium hydroxide (4.00g, O.lO mol, Malli~ L) and ethylene glycol (260g, 5.9 mol, Baker Chemical Co.). While maintaining the inert at~c~Le, the pH probe is remLved and r~rlAr~ by a modified rlA;cP~ head to distill out the water. The L~.~Ldl~.e is A~tAl ly ralsed to ca. lss& as water ~;ctil1 C and then is held for ca. 20 hr as dditional water of rPA~ti~n ~ict;llC out. Th_ r~Ar~ mixture is neutrAli 7F~ to pH 7 with m~U~lfonic acid.
This yields 407.gg of stock ~oll~jnn which partially Cryc~Alli7~c at room temp~ e. Th i may be used directly for oligomer u~ c or if it is decired to isolate the 2-~2-hydroxy-ethoxy)~l~f~lfonate, a tra oe of l,~,~h~cic pa~q5i~
(~ç}nllcLD~tely 1 mole % of the 2-(2-hydroxyethoxy _U~ f~nate salt) is AAAC~ as a ~ffer and the eXcecs ethylene glycol is stripped off on a K~gelrbhr ~nl~L5 un~er vacuum.
The s~ ic of modified icP~hin~ate, par~ rly ~ ylated iCp~h;rr~te~ is preferably ooY~ctP~ with an eXrqC of polyol ~Z ~A~ to iC~pth;n~ate. A mole ratio of at least 2:1 polyol to iCp~hin~ate i~s preferred. In still other more ~.ef~
en~xyl~l3TtD~ a mole ratio of at least 5:1, most preferred fLa., about 5:1 to akout lO:1, is used. Even higher ratios of polyol to icP~hi~r~te can be used to Lnsure predominate mono sulfonate ~L~U~. Wit~x~lt wis~L~ng to be limited by theory, it is believed that the ~YrYx~s polyol L~z_1~u.L provides the ~cired mono sulfonate product. t~se of a 1:1 or lower ratio may lead to p~d~.~nately 1f~t~ p~-W O 94l22937 215 9 9 8 2 PCTrUS94/03740 Ihe preferred polyols include volatile diols, triols, and mixtures U~eof, including ethylene glyccl, 1,2-prcpylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5 ~ .k~ ~
diol, 1,G hks~uf3~iol, 2,2~dimethyl-1,3-propanRdiol, 2-methyl-1,3-~,c~xu~sliol,glycerin, diethylene glycol, triethylene glycol, andmL~ u~r.
The ro~inn m2y be ooY~rt*~ at any pressure, typicdlly from about at~n~ ic to about 300 psig. ~he L~l~ dL~re of the roAr~inn ~p-l~ be helow the temperature in which the polyol will ~ict~ll off under the r~A~tin~ conditions, and high encugh to allcw removal of the water formed, typically from about 150 & to abcut 250 & .
The re~;~n is preferably oon~l~t~ in the ~Lt~*~ of a hACP
catalyst. T~he ~ase is ~4es~,L in _n amount equal to fL~. about 1 to about 25 mole ~._ w .L of the iSp~hi~ate ~L 1~u.L. In pla oe of the ~ase catalyst, one or mDre of the hydroxyl substituents of the polyol can be ~A~ _l~1 into an alk3xide. Suitable L~
u ~ to fcrm the ~ Y;~ of the polyol in~lude alkali metals, alkali oxides, alkali hydrcxides. Part~ rly ~L~Led ~ tcu~L
20 inrllYl~ sodium metal and sodium h ~ ide.
The completion of the rP~c~;nn is dt~æ~Y~.L on the ~ase used and the temperature at which the reaction is ooY~lr~o~. Typically the r~r~;rn is run until most of the U~tical wa er is ~;c-tilled from the r~Ao~;n~ ves_el. If a mixture of i~thin~ate and m~ifio~ ;~o~hin~ate is ~cired~ the reA~in~ can be oo~lr~P~
until the desired fr~ n of U~3u.~Lical mcdified iCp~hi~ate is ,.b~l, This can be estLmated based on the fraction of U~ ical water Aic~;llP~ from the roArtio~ vessel.
pA~ti~nally, if it is desirad to isolate the modified ;c~th;n~A~ ccr~xamd, the exoess polyol ~h~ fe~bly ~e vnlAt;l~ to aid in its removal. Prior to removal of P~xcess polyol ~y v~lAt;l;7Aff nn~ it is prefP~rable to neutralize the basic catAlyst so that the pH of the system during the stripping be m~;r~A;np~ near neutrality. T~ this P~nd, it is often helpful to add a low le~el of a buffer, such as an aLkali ~,G~h~Le, to the system. Removal of excess polyol is preferably con~rte~ under a vacuum of less than akout 100 mm Hg.

W O 94/22937 215 9 9 8 2 PCT~US94/03740 ExamPle II
Synth~cic of cn~i~ 2-(4-Hydroxybutox~)ethanesulfonate Using a StainlPcc Steel Kettle A IL stainl~cc steel kettle is fitted with a three neck glass oover which is clEmped in place. ~hrough one neck of the lid is ~ Le~ a glass rcd with a teflon stir paddle at one end. The gla~c rod ic cx~ ted to a mctar for stirring pu~oses. The other nÆckc of the lid are ~-irpP~ with a U~ ~le and temperature control devi oe (ThermrO ~L~-TM I2R), and a mcdified rlAicPn head and cx~ set for distillation. To this rPA~ n flask ic added the ice~hi~nic acid, ~c~ m salt (Aldrich, 50.2g, 0.339 molec) and an equal weight of water. The mixture is All~ to stir until the jCP~hin~iC acid, co~;ltm salt is fully ~i!ccnlvad.
Cne drcp of h~d~. peroxide (Aldrich, 30 wt~ SQl~inn in water, to ~Yi~i7~ any tra oe s of sulfite) is added to the r ~ lt*inn~ and the c~lt*inn is At~ to stir for abcut one hour-At this ti~e the ~nll*i~n tests waakly positive for the ~les~ ~ ofpercxide with an ir~i~At~r strip. ffl e 1,4-butancd1ol (Aldrich, 213.6g, 2.37 moles) and the ~it~ h ~ ide (Mallinkrodt, 1.36g, 0.034 moles) are ad~ed to the flask. ffl e rPAr~i~n is heated at 225C under an arg~n environment for 4 hcurs as water ~ictillc f.~u the r~Arti~ vessel. 'nhe ~3.~aL~re of the visoous product mixture is lowered to 90C. At this ~ aL~re, the p~ of the ~nltttin~ is Z~ L3d to neutral with m~U~ lfonic acid (Aldrich). Ihe ~LU~ mixture is now dissolved in deionized water to form a 30~ ~olllti~. The solution is LLal~f~LLa~ ,to a lL, ci~gl~ neck, round bottom flask. To the flask is ~Aed a small amcunt of l~ ~ilnn ~ Le, monnh~ci~ (Aldrich, 2.6g, 0.019 moles, 6 mole% relative to amount of isethicnic acid, sodium salt) in crder to ~uLE~ against pH shifts during the stripping operation. At ~ point, the pH of the ~;n~ ~e~sures -5.5.
The pH is l~a~ju~Led to 7 using lN NaOH ~ol-~i n~ and a pH meter.
The majority of t]he water is sLLipped on the RDkavapor (Buchi) under aspiratcr vacuum at 65 & . Next, the flask is plA~Y~ in a Kugelrbhr ~yolaLus (Aldrich) Un~OE a 2mm Hg vacuum. The temperature of ~he Kugelrohr is maintained at 170C for 1.5 hours to L~ the excess 1,4-butanediol and the last L~ces of watOE.
Tlhe Erxx~lct is a light yellow, brittle solid.

WO 94/22937 215 9 9 ~ 2 PCTrUS94/03740 --A 13C-NMR (in D20) shows characteristic resonances at -25 ppm (-CH2CH20H), -28 ppm (-OCH2CH2CH2CH20H), ~50ppm (NaS03CH2-), -61.5 ppm (-CH2CH20H), -65 ppm (NaS03CH2CH20CH2-), an~ -70.6 ppm (NaS03CH2Cff20-). Likewise, a ~-NMR (in D20) shows resonances at -1.7 ppm for 4 ~ OCH2CH2CH2CH20H), -3.3 ppm for 2 protons (Na9O3CH2-), -3-7 pFm for 4 ~L~B (-OCH2CH2CH2CH20H), and -3.9 ppm for 2 ~ c (NbS03CH2CH20-). Integrals are consistent with the complete removal of excess ~utanediol.
FX~MPLE III
An ester cLu~Dition made f m m sodium 2-(2-hydroxyethoxy)-~U ~, ~ ~lfonate, ~ ~rli~ salt, ethylene glycol, 1,2-propylene glycol, an~ dimethyl ~- ~ ,U ~late. The ~YA~ illu~L-~L~s an ester composition accordinq to the invention wherein the ~L~
ccntains a mixture of essential ethylene glycol and ~ s~,lLial 1,2-prcpy1ene glycol.
A IL, three neck, round boktam flask is ~;rF~ with a ~A~;t' St~ a ~lifi~ t~lAi~:Prs head~ a the= ~ , a t ~ ~ e control dÆvi oe (IbY~ Watch~M, 12R), and a cu.~
set for ~ic~illA~inn To the r~Artinr, fl~Ck are added the Leay~lLs sodium 2-(2-hydroxyethoxy)eU~uea~lfonate (~ d as in Example I, 40.1g, 0.209 moles), dImethyl ~ te (Aldrich, 80.8g, 0.416 moles), ethylene glycol (Baker, 105.0g, 1.69 moles), propylene glycol (BakQr, 120.3g, 1.58 moles), and catalyst ti~anium (IV~ ;A~ (Aldrich, 0.058g, 0.02~ of tLtal r~Ar~inn w-igh~).
Also ad~ed are the h~d~ yyes cn~ium c~PnP~lfonate, c~
~nll~rYx3llfnr~ and sa~ium xylenesulfonate (all from ~-~1-J~
Nease, 4.8g each, each is 4% of final polymer weight). The r~r~inll mixture is h~A~ed at a ~ ~L~ t~ re of 180 & under an argon environrlnt for a period of one day as methanol and water ~ic~ll from the r~Ar~;~n vecsel to give a prepolymer rpAr~iffn product. An 81.7g portion of this prepolymer col~ n is poured in a lL, .einqlP neck, round ~ottam flask and plaoe d in a KLgelrohr ~r al lc (Aldrich) under a 2 m~Hg vacuum. The tempera~re of the K~gelrohr is r~ced to 240 & and maintained at this tempera ~re for 6 minutes. At this time, the heatLnq element is switched off, and the flask is ~ to cool to room t~~ dl~re under continuous vacuum for thirty minNtes. m e yield of the desired oligomer is - 37.6,g of opzgue, light yellow glassy material. A 13C-NMR (in W 0 94l22937 ~ ~ 5 9 9 8 2 PcTrus94/03740 .

CMS0-d6) shows a resonance for diesters of ethylene glycol (-C(0) ~ CH20C(0)-) at -63.2 ppm, and a L~C~r~ for ~ Lers of ethylene glycol (-C(0)0- ~ CH20~) at -59.2 ppm. The ratio of the hPjght of the diester peak to the height of the ,.~l~e~Ler peak is foun~ to be 2.8:1.0 for a Ch~rl~tinn Index (CI) of 2.8. A ~-NMR
(in nMS0-d6) shows a ~ Y~ ~ at -7.9 ppm for the aromatic ~LU~
in the I ~ grcups, and a L~5~U~ at -2.8 ppm for the . adjacent to the sulfur (-C~2S03Na) in the capping groups ~ived from 2-(2-hydroxyethoxy)~U~u~ _alfonate. The ratio of the area of the peak for ~ull~ in the methylene grcup of diesters of ethylene glycol at -4.7 ppm to the area of peak for the methyne a~l. of ~iPS~rS of prapylene glycol at -5.4 p~m is measured.
From this, the molar ratio of irx~JL~u~Lad ethylene/propylene glyools (EG/PG ratio) is cAl~lAted to be 1.6. A small sample of the finichA~ polymer is placed into a screw cap vial, and crushed into fine particles. Encugh deionized water is added to make 2%
cnl-Jt;n~ by w~;~ht. The polymer initially dissolves to furm a clear ~oll~in~ but becomes a clcudy, miIky white color over the ~n~cP of two hLurs.
An ester compoRi~inn made from m-sulfol~oic acid, monosodium salt, ethylene glycol, prcpylene glycol, dimethyl 5-sulfoi~ }A-late, sodium salt, and dimethyl Lt~ AlAte~ The example illus-LL~Le~ an ester .~u4~ acc~rdlnq to the invention wherein the ester mo~ lPc have a ~ Lul~ il ~ L~ul~Ling ~llfona~ units.
To a lL, three neck, round ~ottom flask e~ pp~ with a m~rF~;~ stirring ~ar, mcdified ClA;cPn head, OUI~ fi~ (set for ~;~n), tbY4~lometer, and t~.~L~re controller (ThermrO IL~ M, I2R) is added m~sulfobenzoic acid, r~Jx~i31ium salt (50.0g, 0.223 mol), dimethyl ttL~~ AlAte (237.9g, 1.22 mol), dimethyl g~ fQi~ 1~ 1A~e~ SC~;~ salt (Aldrich, 66.0g, 0.223 mol), ethylene glycol (Baker, 103.7g, 1.67 mol), propylene glycol (Fisher, 127.1g, 1.67 mol), titanium (IV) pr~YxY;~ (Aldrich, O.lOg, 0.02% of tDtal reArtin~ weight), s~i-~ a oe tate (Baker, 0.73g, 2 mol% of dimethyl 5-su1foisophthalate, cn~il~ salt and mrsulfo~ oic acid, m~rr~o~i-~ salt), s~ ~ cumencsulfonat.
~ tJ~ J~ , 14g, 4% of final polymer wt.), ~n~il~
xylenesulfonate (~~ ~a3e, 14g, 4% of final polymer wt.) and WO 94/22937 21~ 9 9 8 2 PCTrUS94/03740 ~ ~ toluenesulfonate (~l~J~.S N~a~c, 14g,4% of fLnal polymer wt.). This mixture is heated to 180C an~ maintained at that temperature for 2 nights under argon as methanol an~ water distill from the rP~ n vessel. A -224g portion of the material (pr~p~lymer) is ~L~ ~ft~ ~i to a lL, single neck, roun~ bottom flask an~ hP~e~ gradually over about 20 minutes to 240C in a Kugelrohr ~ c (Aldrich) at akcut 2mm Hg and maintained there far 10 min. The rPAr~ flask is then ;~11~ to air ocol quite rapidly to near roa~ te~perature under vacwm (-30 min. ) The r~ion affc~l~ 13~g of the desired oliga~r ~c a yellch~ crunchy gl ;~cc .
A 13C_~R(~d6) sh~fi a L~ X for -C(O)OC~2C~I20(0)C- at -63.2 ~n (~ 'r) and a ~ar,æ for -C(O)OÇH2~2Cfl at 59.4 pF~n (D~l ). The ratio of the diester peak to the l.~LtL peak is ~-~ad to be 1.4:1.0 for a ~l~inrl ~c tC.1.(63/60)] Of 1.4.
A lH~(~d6) shaws a .~-x at -8.4 ppm ~ .Ling the ~11 foi ~ ~ ~ t t ~1 A~e aranatic h~ , a ~a~ uaa~ at -8.3 ppm Lq~L~C~ one of the sulfo ~ ~o~Le aromatic h~uy~ ~, and a ~ Yuaa~ at -7.9 p~u ~c~e~*~.Ling L ~ ~lAt~ aromatic h~L~ ~. Ihe ratio of the peak for the methylene group6 of ~iPc~or~ of ethylene qlycol at -4.7 ppm to the area of the peak for the me*hyne ~t~a~ of ~iact~rs of propylene glycol at -5.4 ppm is mYL_~la~. E~u thi_, the molar ratio of i~ GLe~ ethylene/
propylene glycols (EG/PG ratio) is c~ Ated to ~e 1.5:1. The ~ lhility is ~al~l by wni~hti~g a small amount of material into a vial, ad~ing ~Tr~Y~h ~i ct; ~ water to make a 35% by weight cn11~in~ an~ agitating t~e vial vigorcusly. The material is mcctly sQ1llhlP under these csn~itions. The milky ~ ~in~ whic~
fcrms gP~c after a few hours.
Heating a 194g sample of the above prepolymer on a Kugelrohr ~o~a~S at 240 & for 20 min. at 2mm Hg, affords 150g of yellow Ll~a~l~ glass with an EG/PG = l.4 and CI(63/60) = 2.3. This matP~rial iS ~olllhl~ under the a~ove conditions. It makes a cl~
c~ which becomes cloudy after appro ~ tely 1 day.
A4{I~Iclrately lOOg of each of the above o1;~nm~rs is retained.
The remaining material is combined in a lL round bottom flask and heated on a K~gelrchr o4ya~aL~5 at 240 & for 15 min. at -2mm Hg to W O 94l22937 215 9 9 8 2 PcT~us94lo374o afford 67.2g of yellow crunchy glass with an EG/PG = 1.4 an~
CI(63/60) = 4.9. m is material is soluble under the above oonditions. It makes a clear solution which ~o~ clou~y aft~r approximately 3 days.
~he oli~mors l~t~e~*~,Ling a ~nrrlet;~n Index range of 1.4 to - 4.9 are used directly ~c soil suspension agents.
E)~E V
lh~ ester composition made from m~sulfo~t~oic acid ~
salt, ethylene glycol, dimethyl 5-sulfo;~oF~thAlAte, sodium salt, and dimethyl l~r~ ~lAte. m e ~Y~rl~ ill~LLaL~s an ester cr~pn~itian aOc~rd m g to the invention with low completion index.
To a 250ml, three neck, round bottam fla~k ~ ~l with a magnetic stirring bar, ~m~dified ~ Pn head, ~UI~ ~r (set for ~ictillAtinn)~ thLal~ometer, and tem.~_rature controller (ISY~=-{~-WbtchTM, I2R) is added 3-sulfcL~oic acid, mcrr~n~
salt (Eastman Kodak, 30.3q, 0.135 mol), dim~thyl t~L~ ~lAt-e (Aldrich, 65.6g, 0.338 mol), ~i~ot~yl 5-sulfoiG~ lAtp~ sodium t (Aldric]h, 20.0g, 0.0675 m~l), ethylene glycol (Baker, 41.9g, 0.675 mol), h~d1aL~ monokutyltin oxide (M~T ~PmirAlc~ 0.32g, 0.2%
of tctal r~Artisn w-i~ht), and ca~ilm AretAte (MK~3, 0.33g, 2 mol%
of sum of ~-l~ J~ oir acid, 1~ lium salt and dimethyl s_~.lfQic ~ A~e, sodium salt). Ihis m ~ is heated to 180 &
and main~Airp~ at that temperature overnight under argon as n~ .~l and water distill form the rP~rt; 9n vessel. A 13C-NMR
t~ken at the ro~r~ir~ mixture at this po m t shcws some rPc;~ ~l methyl ester. About 20g more ethylene glycol is added and heating is Cn~t;~YY~ for ~a~ 18 hours to give a m terial with no ci~1 methyl ester. The material is tran~cf~rred to a lOOOml, ~in~l~ neck, rcund bott~m flask and heated gradually over about 20 D~rbes to 240C in a Xugelrohr c4yal~Llc (Aldrich) at about 0.5mm Hg and maintained there for 2.5 hours. me rP~t;nn flask ic then ~ to air cool quite rapidly to near room temperat~re under vacuum (-30 min.) The r~ ion affords about llOg of the desired oligomer ~c an orange glass. A
13C-NMR(DMsO-d6) shows a resonance for -C(O)O ~ CH20(0)C- at -63.2 ppm (~i~ctPr) and a ~x~u~ for -C(O)O~H2CH20H at -59.4 ppm (m~ ,). Ihe ratio of the heights of the diester to ~ #~ er peaks is n~*~1lred to be 6.8:1 for a Completion Index of 6.8. A

W O 94l22937 215 9 9 8 2 PCTrUS94/03740 _ ~-NMR(DMSO-d6) shows a resonance at -8.4 ppm representing the sulfo;cnr~thAlAte aromatic h~d~ ~ and a resonance at -7.9 ppm ~ L;~g l~ ~late aromatic h~dLuy~ ~. m e solllh;lity is tested by weighing small amcunts of mat~rial into 2 vials, crushin~
it, ad~ing ~ h distilled water to make 5~ an~ 10% by weight 5~ 5~ an~ agitating the vials vigorously. m e material dissolves under these conditions.
F~E VI
An ester ~.y~ition made frcm ~o~ m 2-(2-hydroxyethoxy)-10 e~ forate, d~rethyl ~ .l hA1Ate, dimethyl 5-sulfoiso-~thA1A~e~ ~ salt, ethylene glycol, and pr~ylene glycol with mixed h~dL~ L~Je ~hi 1 i 7~r. The exa~ple ill~LLal ~ an ester ;tion acoording to the invention with a low o~1Pti~rl ~c.
A lL, three n~k, r~Kl bott~m flask is ~iE~ with a 15 m~r~iC stir ~ar, a m ~ifi ~ ~1A;~P71 head, a l~ , a ten~erature w~lL.~ ller (Tn~WatchTM, I2R), and a w,~ t for ~;~;1 lAt~ . To thic r~A~i~n flask is added the s~illm 2-(2-hy ~ yet ~ )~U.~ fcnate (~JL~Lal as in Exanple I), 75.Cg, 0.390 moles), ~ir^~hy~ h~lAte (Aldrich, 189.3g, 0.975 moles), dimethyl 5-sulfoic ~ Ate~ cn~ium salt, (Aldrich, 57.8g, 0.195 moles), ethylene glycol (Baker, 193.7g, 3.12 moles), and prqpylene glycol (Baker, 237.4g, 3.12 moles). Also added is sodium ~ J? (Baker, 0.320g, 2 moleS uf dimethyl 5-sulfoic~rhthAlAt~, cr~;um c~lt), catalyst titanium(IV) prornYi~ (Aldrich, 0.126g, 0.02% of total rPAr~ weight), and h~dLo~Lu~ts ~O~il~ cumenesNl-fonate, sodium toluenesulfonate, and cr~ium xylenesulfonate (all from P~J ~ , 12.9 g each, each is 4% of final polymer w~l~ht). The rPA~i~n mix~re is heated at a C~ 180C under an argon environment for a period of two days as m~ ~l and water 30 ~ic~ fmm the rp~rt;nn vessel to give a prepolymer r~Arti At th;c time, an 80.5g portion of the prepolymer cnlt~i~n is poured inko a lL, sinqle neck, round bottom flask and placed in a Kugelrchr ~t~ c (Aldrich) under a 2mm Hg vacuum. m e temp~a~uLe of the Kugelrohr is raiCP~ to 240 & and maintained for 20 minLtes. The heatinq element is switched off, an~ the flask cnr~;ni~ the polymer is All~ r~ to 1 - 1 under continuous vacuum for thirty minutes. m e yield of the desired oligomer is 36.6g of W 0 94l22937 . 2 I 5 9 9 8 2 PCT/USg4/03740 translu oe nt, light yellow, glassy material. A 13C-NMR (in DMSO-d6) shows a t ~UI~Ux~ for diesters of ethylene glycol (-C(O)O ~ Cff20C(O)-) at -63.2 ppm, and a rl#;~YLn~e for mcnesters of ethylene glycol at -59.2 ppm. The ratio of the height of the diester peak to the height of the ~ ,Ler peak is foun~ to be 3.9:1 for a Completion Index (CI) of 3.9.
A ~-NMR (in DMSO-d6) shows a r~UlYU~ at -8.4 ppm for the aromatic ~ ~ in the sulfo;~or~hAlAte group, a r~L~i~ at -7.9 ppm for the arcmatic ~LULUII~ in the l~t~ lAte grcuFs, and a ~5~ua~ at -2.8 ppm for the ~LU~ adjacent to the sulfur ( g 2SO3Na) in the capping groups derived frcm the ~o~
2-(2-hydroxyethcxy)~ fonate. The ratio of the area of the peak for ~LO~Ull- in the methylene group of diesters of ethylene glyool at -4.7 ppm to the area of t~he peak for the methyne ~LU~
of ~ tPrs of propylene glycol at -5.4 ppm is moosurcd and fund to be 1.7:1. From this, the ~molar ratio of i.~LL~aLe~ ethylene/pro-pylene glyoolc (EG/PG ratio) is c~ to be 1.7.
A cm~ll sample of the finished polymer is plaoed into a screw cap, glas~ vial for col~hility testing. It is crushed, and encugh ~ein~i7~ water is added to make a 35% ~nl~isn by w-ight. The polymer m itially ~iC~olves to form a clear ~Plutirn~ but after 3 hcurs the c~lt~;n~ iS milky white Ln color. The s~ gelc after tw~ days.
A second portion of the prepoly~ r (80.5q) is added to a lL, single neck, rcund LuL~.I. flask and is plAr~ on the Kugelrohr under vacuum as above. ~ cr, this ~.u~, is hPAte~ for only five minutes at 240 &. The NMR ~ t~ ~m t~ken of the resulting polymer in DMEO-d6 yields -~I = 1.3 and EG/PG ~ -1.7 by the same Dk~ ls Aocrribed a~ove. An 18.5g portion of this polymer is added to a 50nmr., single neck, rcund bottom flask and is pla oe d back on the Kugelrchr ~ aLls under vacuum. Again, the temperature of the Kugelrohr is ~ to rise to 240 & , and is maLntained at this temç~ .e for only 30 se~ l,. m e NMR ~e~t~um at this point reveals the CI = 2.0 and EG/PG 5 -1 .7. m e yield of this desired polymer is 17.5q of translu oe nt, light yellow, glassy material. A 35% by w~i~ht solution of this polymer is made up in ~inni7~ water. The ~ol~inn is initially clear, but hP~ c cloudy within an hour, and gels within 5 hcurs.

WO 94/22937 215 9 9 8 2 PCT~US94/03740 A third portion of prepolymer (81.3g) is added to a lL, single neck, roun~ bcttom flask, and is heated under the same t~ aL~re and F:}~R3rre conditions as above. m e 240C L~ aL~re is maintalned for 3 minutes an~ 30 seLu~s. The NMR ~e~L~ u~y data gi~es CI = 1.4 and EG/PG = -1.7. Part of this polymer (17.lg) is put into a SOOmL, single neck, round bottcm flask an~ heated on the Kugelrohr under the same conditions as descrihc~ abov~. m e 240 &
L_.r~aL~re is maintained for 1 minute. m e ~euLLAl data gives a CI = 2.3 an~ EG/PG ~ -1.7. m e yield of this polymer is 16.4g of trz~ c~ , light yellow, glassy mat~rial. A 35% by weight sollrt;~n of this polymer is made up in deionized w~Ater in the same manner as with the previaus polymers. The ~ol~;nn is initially clear, but turns cloudy after 1 hour, and gels hPt~E^n 6 and 24 haurs.
The samples which caver a range of ChrrlPtin~ Indi~cc hPt~ n 1.3 an~ 3.9 re used directly AS soil suspension agents.
Test Method Ihe extent of oligamerization can be est;~-tP~ fram the Completion Index which is ~Luy.~Lional to the ~ipctpr:DL~y~(~
ratio for ethylene glyools i~ uLaLed into the oligomeric ~LL~ ~le. An oligomer with a low Completion Index will have a relatively law ~LuyuL Lion of diesters of ethylene glycol and U~ ~f~Le have a law d~ee of ol iq~-ization. An oliga~r with a high Co~lP~;nr~ ex will have a relatively high EJL~LLion of ~ rs of ethylene glyool and U~ fuLe have a high degree of oliga~ri7~ As a U~Lical liDlit, a fully ~;r;~A oligomer will have ~ i ~ Prs and no ~ a of ethylene glyool and will have an ;nfini~ Cc~plëtion Index.
~e follanng te-ct method can be used to APt~i r~e the 'lC~l~tiffrl Indeoc" of the dispersing agents of the invention.
1. I~e ~i~:ir~g agent is well mixed aas a melt to ensure ~L~Live ~1 ing and is oooled rapidly frc~n a te~aLu~t: above the melting-point to well kelch~ the vitrificatian te~perature, e.g., 45& or lawer.
2. A solid saIlple of the h ~k ~ ;ng agent is taken.
3. A 10% s~ll~inn of the dispersing agent in (methyl sulfoxide)-d6 containing 1~ v/v teLlal.~UI~lsilane (Aldrich rh~mir~l co.~ is made up. If ,~cc~ry, warming W O 94/22937 21~ 9 9 8 2 PCTrUS94/03740 to 90-100 C is used to achieve ~lh~L~,Lially complete ~ic~o~ ;nn of the dispersing agent.
4. The ~n~ n is placad in a 180X5 mm NMR ~lk~ (Wilmad Scientific Gl~CC, 507-pp-7 RDyal Imperial thin w~ 5mm NMR sample tL~es, 8".) The 13C NMR ~ t~m is obkained under the followLng cQnditions:
a. General Electric QE-300 NMR instrument b. probe temperature = 25 &
C. cr~e E~ll.c~ ~,p~
d. pulse width = 6.00 mi.~ose~C
~ 30 degree e. ~ ition time = 819.20 msec f. recycle time = 1.00 cP~
g. no. of A~ citions = 5000 h. data size = 32768 i. line L~Yu~ n~ = 3.00 Hz ;. spin rate ~ 13 rps k. ~ ~--v~:
freguency ~ 75.480824 MHz cp~ width = 20,000 Hz gain = 60*8 r:
~k~ d br~ad ~and, 64 mLdulation fr~YrY~Y~y - 4.000 pFm power - 2785/3000 m. plot scale:
510.64-Hz/cm 6.7652 ~k~ll/cm from 225.00 to -4.99 ~all 6. ~he hPi~h~ of the tallest r~5ul~u ~ observed in the 63.0-63.8 ppm region (referred to as "the 63 peak" and with diesters of ethylene glycol) is me2sured.
(Ihis is often observed as a single peak under the srec;f~P~ conditions ~ut may appear as a poorly r~cnlved multiplet).
7. ~he hpi~ht of the tallest ~sw~e okserved Ln the 59-59.7 ppm region (referred to as "the 60 peak") and W O 94/22937 21~ 9 9 8 ~ PCT/US94/03740 A~Or; Ated with ~ x~e~Lers of ethylene glycol is me2sured. (When this is large enough to distinguish from the h~CPl ine~ it normRlly ~ed~ to be a single peak un~er the ~p~ified conlitions.) 8. The ~nmrlPt;~n Index is c~ te~ ~c the height ratio for the "63 peak" over the "60 peak".
In the ,cpe~; Al ~CP where the disper_ing agent comprises oxy-1,2-cxypropylenecKy units but very little or no oxyethyleneoxy units, the nYY#~D~3/ent of Ccmpletion Index kased on di- and nY~.~c~L~s of ethylene glycol is not fPACihlP. In thpcp cases, the Completion Index can be e_tLmated k~ using proton NMR (pmr) rt~ , far prcpylene glycol ~;PC~Pr5 (at a ~ t 1.4 ppm) and for prcpylene glycol ~ ers (in the range of akout 1.1 to 1.3 ppm).
These Le~ uaa~ are illL~La ed, and the ratio taken. The resulting ratio i_ then ~ti~ ky a factor of 2 to convert it to the same ~sis a_ the Çn~rl~tin~ Index derived f m m carkon NMR
. Ihis may be ~ s~l as the ~ ;n~
(pmr peak area at 1.4 ppm)(2)/(pmr peak area at 1.1-1.3 C0pl~icn Index.
Use of Dis~ersinq Aaents Ln Deterqent r~m~itions - Esters of the inNention are ~cp~o;~lly ~lc~ful as dispersiny agents of a type comF~; hl ~ in the laundry with conventional detersive ingredients such as thc6e t~pically fcund in liquid det~,L--, granular laundry d~ ~ ~ or laundry bars. A~ditionally, the esters are useful in laundry additive cr ~LLt~ .L compositions cc~phising the ~Ccpnl ;A1 ~ r ~ ~itions and conventional d~tl~.L
i~i~c, U.S. Patent 3,178,370, Okenfuss, issued ~pr. 13, 1965, describes laundry d~ L b rs and ~.~p~Pc for making them.
ph;li~ri~p Patent 13,778, ~k~, issued Sept. 23, 1980, describes S~ r~;O de~ laun~ry kars. ;~ for making laundry d~LtLye~L kars by varicus extrustion ~,O~5Pc are well known in the art.
Detersive Sulra~u,~ - The amcunt of detersive Sulr~
i~l-~P~ in the fully-formLlated detergent cn~rnfi;tions afforded by the ~cs~,L invention can vary f.~., akout 1% to about 99.9% by weight of the .~ ~ition depen~in~ upon the parti~ll~r surfactants used and the effects desired. Preferably, the detersive WO 94/22937 215 9 9 8 2 PCTrUS94/03740 .

surfactants comprise fl~,- a~out 5% to abcut 80% by weight of the a-~-*ition.
The detersive surfactant can be nonionic, anionic, ampholytic, zwitterionic, or cationic. Mixtures of these surfactants can also be used. Preferred detergent ~nrr~sitions of the ~Lts~lL invention ocmbine the cost-effectiveness of anionic surfactants with the increased compatibility of the anionic olig~m~ric esters of the invention with such ~--r~ . Pl`ereLL~ detergent crr~-~itions comprise anionic detersive surfa~u,Ls cr mixtures of anionic suLra~1Ju~L~ with okher Æ factants, Pcpe~;~lly nonionic S~rc~
Nonlimiting ~Y~mplFc of s~Lf~L~L useful herein include the oonventional C11-C18 alkyl ~ ~ ~ ~ sulfonates and prLmary and LCU~U alkyl sulfates, the C10-C18 alkyl alkoYy sulfates, the C10-C18 aIkyl polygly~c;~s and their ~U~L~ If~ng sulfated polygly~ci~Dc~ C12-C18 alpha-sulfu,~L~ fatty acid esters, C -C
aIkyl and alkyl phenol alko,Yylates (~C~e~;A1 1Y ethoYylate_ and m;~Y~ ethXY/~l~YU~Y), C12-C18 betaines and sulf~hPt~i~es ("sultAines"), C10-C18 am.~ne oxides, and the like. Other oonven-tional useful surfa ~culLs are listed in ~L~r~d text_.
ane parti~llAr cl~cc of adjunct nonionic surfa~cu,L~
Ocper;Ally useful herein comprise-c the polyhydroxy fatty acid amides of the formula:
O Rl (I) R2-C-N-Z
wk~ in A is H, Cl-C8 hydlu.duLrl, 2-hydroxyethyl, 2-hydroxy-propyl, or a mixture Ule~aof, preferably Cl-C4 alkyl, more prefer-ably C1 or C2 alkyl, mcs~ preferably C1 aIkyl (i.e., methyl); and R2 is a C5-C32 hydL~ rLyl moiety, preferably straight chain C7-Clg alkyl or aIkenyl, more preferably straight chain Cg-C17 alkyl or alkenyl, mo6t ~feL~bly strai~ht chain Cll-Clg alkyl or alkenyl, or D~hme U ~-~of; and Z is a polyhydroxyh~d~ .L~l moiety having a linear h~dlu.c~Lyl chain with at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyls (in the ~c~ of other reducing sugars) directly cu~ Led to the chain, or an alkoxylated ~ivative (preferably ethoxylated or propoxylated) thereof. Z
~,~f~ ably will be derived frcm a reducing sugar in a reductive amunation r~A~l nn; more preferably Z is a glycityl moiety.

WO 94/22937 21~ 9 9 8 2 PCT/US94/03740 Suitable rP~cing sugars include glucose, fructose, maltose, l~rtofi~ rtnc~ ~ e, and xylose, as well as glyceraldehyde.
As raw matPrials, high dextrose corn syrup, high fructo6e corn s ~ , an~ high malto6e corn syrup can be utili 7~ as well as the individual s ~ listed above. These corn syrups may yield a mix of sugar ~.~ Ls for Z. It should be ~ ~tl~Locd that it is by no me2ns i~ h3~ to PYr~t~P other suitable raw materials. Z
preferably will be CDl Fr~~ frcm the group consisting of ~2-(CHOH) n~2~' -CX (CH20H) - (CK~H) n_l~20H, ~H2- (C~}OH) 2 (00R' ) -(C~H)~H2OH, wh~e n is an integer fran 1 to 5, inclusive, and R' i_ H or a cyclic ~n~ or poly- ~h~ride, an~ aLlcoxylat~
derivatives U~f. M~6t preferr~l are glycityls wherein n is 4, part;~'lArlY ~2-(C~)14~20~-In Fn~~ (I), R can be, for P~le, ~l..~Ulyl, N-ethyl, N ~L~ N-is.,yL~l~ N-hItyl, N-isohItyl, N-2-hydroxy ethyl, or N-2-hy~xy pr~yl. Fc~ hiql~st su~sing, * is preferably methyl or hydro~a~l. If lawer sudsing is desired, Rl is preferably C2-C8 aL~cyl, ~j;~l ly ~ rl, iso ~L~rl, n-butyl, iso-~tyl, per~yl, hexyl and 2 cthyl hexyl.
R2~ can be, for PY~rlO, r~;~ P~ s~ ide, ole~amide, lauramide, myristamide, capri~ , pa~mitamide, ~l l~,~mi~ etc.
D~L~ Puil~Prs - Optional d~L~_y~l~ compositions of the *~ invention cn~t~;n inorganic and/or organic detergent hl;l~rs to ~_c;ct in ~mineral ha~ ~as cantr~l. If used, these ~l;l~Pr~ comprise from about 5~ to akcut 80%, preferably frcm about 10% to about 50% by w~ight of the cn~rnC;tions.
Inorganic d~tL~ L hl;l~PrS include, but are not limited to, the alkali FY*al, ammoniu~ and alkanolammonium salts of polyphos-~lYaLæ~ (exemrl if i~ by the tripoly~ i~Ates, py~vL~L~ALea~ and gl_ssy polymeric meta ~ A~es), ~loa~ho~ c~ p ytic acid, ;rA~ ~r~ ir)g hi~ ~1; f'Arh~
ates), ~lFhAtes, an~ alum mosil;cAtes. However, l~" ~n~L~Le h~ rs are rcqyirc~ in some 1~rA1PC.
Examples of silicate hli l~Prs Are the alkali metal silicates, 3 5 par~ rly those having a SiO2:Na20 ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered ~o~;l~ silicates ~Pcrribed in U.S. Patent 4,664,839, ic~ed May 12, 1987 to H. P.
Rieck, avAilAhlp fr~m Tl~ under the trademark "SKS"; SKS-6 is W O 94/22937 215 9 9 ~ 2 PCT~US94/03740 an Pcp~c;~11y preferred layered silicate h~ Pr.
FY~P1~ of ~aLLO~Le h~ Prs are the alkaline earth and aIkali metal ~aLL~LeS as disclosed in German Patent ~plic~tion No. 2,321,001 ~7h~ichP~ on November 15, 1973.
Alumlnns;lir~te h~ prs are P~rpriAl ly useful in the ~L cClIL
invention. Preferred alumlnrs;lic~tes are zeolitP h~ Pr5 which have the fnr~llA
Na~t(A102)z (sio~)y] xH2o wherein z and y are i~J~ of at least 6, the molar ratio of z to y is in the range frcm 1.0 to akout 0.5, and x is an integer from about 15 to a~out 264.
Useful alumi~fi;lirAte ion exchange materials are commercially av~i lAhlP. m ese al ~ ilicAtes can be crystalline or ~r~,uus in stru3:~me and can be naturally-occurring alumin~c;l;rAt~c or s~ rAlly derived. A method for producLnq alumin~c;l;rAte ion e~ materials is ~;c~1~5~ in U.S. Patent 3,985,669, Krummel, et al, i~ o~n~ 12, 1976. Preferred synthP~;r crys~A~ e alum m ~ilirAte ion e~ ~e ma~rials useful herein are aVA;lAhlp under the designations Zeolite A, 7P~1ite P (B), and Jeolite X.
arganic hl;l~r5 include, but are not lLmited to pol~ ylate ccrlxlDIls such as ether polycarboxylates and ether hy~h~xcnpol~ ylates, copolymers of maleic anhydrid~ with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy ~ ~ 2, 4, 6-tr;~llrhnnic acid, ccu L~xymethyloxysuccinic ~acid, the various Alk~li metal, ammonium and su~stituted ammonium salts of polyArPtic acids such as ethylenediamine tetrA~rPtic acid and nitriluLL;Aret;~
acid, as well as polycarkoxylates such as mellitic acid, succinic acid, cxy~;~lrr-;ni~ acid, poly~lPic acid, ~ ~ 1,3,5-tricar-boxylic acid, ~ ymethyloxysuccinic acid, and 5~ hl~ salts U~_a~f.
Ci k ~te ~ ~rc, e.g., citric acid and c~lllhlP salts UleeLeof (par~i~llArly scdium salt), are preferred po~ rh ~ylate h~ P~5 that can also be used in g.ranular ~--;tions, ~p~c;Ally in combination with zeolite and/or layered silicate h~ rs.
Also suitable in the detergent cn~r~sitions of the yL~
invention are the 3,3-dic~rkoxy-4-oxa-1,6-hexanedioates and the related cnr~m~c ~;c~l~fiP~ in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid hlil~rs include the C5-c20 WO 9~/22937 215 9 9 8 2 PCT/US94/03740 alkyl and alkenyl succinic acids dnd salts thereof.
Fatty acids, e.g., C12-C18 monacarkoxylic acids, can also be il~uL~uLdLe~ into the f~nmro~itions alone, or in c~ambination with the aforecaid h~ rS, PCrFCiAl Iy citrate and/or the succinate S hlil~Prc, to provide additional hlil~Pr activity. Such uLce of fatty acids will g~nerally r~ lt in a tPf~lf~in~ of sudsing, which should be taken into aocount by the formulator.
In sit~l~t;~Y~c where ~oO~,uL~c-based hlil~Prs can be used, and f ~ iAlly in the formulation of barc llcA~ for hand-laundering ~ ~ aticnC, the variaus aIkali metal ~ L~s such as the well-known ~Q~;~ tripol~lo~hatPc, sodium pyL~ ~ate and ~c~;-~ u~ Le ~an be used. ~ ~Le hlil~prs such as ~U~ 1-hydroxy-1,1~ lUl~LP and other known ~hcO~v~Les (see, for example, U.S. ~L~lLs 3,159,581; 3,213,030; 3,422,021;
3,400,148 and 3,422,137) ~an also be us~d.
O~ticnal D~LtL~lL Inqredients - In addition to s~LLa_~u,Ls and hl;lflf~rc, the aompo6itions herein can qptionally include cne or mcre conNP~;~Y~l dt~ ~lL adjunct materials or other materials for A~C;C~;~g ~r ~ku~Lng cleaning perfu~ e, trea~meff~ of the suL~LL~L~ to be cleaned, or to modify the A~l l.el i~C of the d~i~L~lL compo6ition. Other cptional ingredients which can he ;n~ll~P~ in ~ yt~lL c~r~-~itions of the ~Le~*~lL invention, in their ccnvent;rnAl art-pc~hl;ch~ levels for use (generally f m m O
to about 20% of the d~LtL~ rrrrsjtion), include solvents, h~d~tLuy~ ~ol~-hi 1; ~;~g agents, soil release agents, chelating agents, clay soil remLvaltanti-r;~ cition agents, polymeric dispersing agentc, ~o~Ccing aids, antitarnish and/or anti-cor-m sion agents, dyes, fillers, optical hrightenerc, germicides, pH-sdjusting agents (monoethanolam m e, sc~ olL~Le, cr~;um hy~b~x~ide, etc.), perfumes, fabric softenlng cc~p~ .L~, static L~ul ~1PntC~ hlP~h;~g agents, bleach activators, bleach c~hili7~r5, suds 5~4yLeSSu~, su~s boo6ter8, and the like.
~ P~rsive F~Zvme-c - Optionally, the cnmrn~itionC emplcyed in the ~ ~ inNe~tion comprise detersive enzymes. Deter_ive enzymes are inr-l~p~ for a wide variety of f~hriC laundering p~cse~, including removal of protein-~ased, ~olL~ drate-b?cP~, or triglyceri~e L~sed stains, for example, and for the prevention of refugee dye Ll~ ~Ltr. m e enzymes to be il~L~UL~ ed include WO 94/22937 215 9 9 8 2 PCTrUS94/03740 prot~cPc~ amylases, l;p~c~c, cellulases, and peroxi~cPc, as well as mixtures U.e~eof. Other types of enzymes may also be i~rl~
They may be of any suitable origin, such as vegetable, animal, bacterial, fungal an~ yeast origin. However, their choi oe is go~erned hy several factars such as pH-activity and/or stability optima, ! ~r~ hi 1 ity, 5t~hi lity versus active detergent_, h~ rs and so on. In this L~eu~ A cterial or fungal enzyme_ are pr~ferred, such as bacterial amylases and prot~C~c~ and fungal Enzymes are nrr~lly i~ ~u.~ed at levels sufficient to provide up to about 5 mg hy weight, more typically about 0.01 mg to a_ w t 3 mg, of active enzyme per gram of the cr~rn~ition. Stated otherwise, the cnrrn~;tions herein will typically comprise from about 0.001% to about 5%, preferably 0.01%-1%, by weight of a ccmmercial enzyme ~L-l~rdlion. Enzymes are usually ~L~`U~ in such c~ cial ~L~o~Lions at levels sufficient to provide fr3m 0.005 to 0.1 Anson units (AU) of activity per gram of c -~-~ition.
A wide range of enzyme materials and means for their i~
oration into synt~ detergent granules is ~ ln5~ in U.S.
Patent 3,553,139, is5Nu~ January 5, 1971 to ~ Ly et al. Enzymes are funl~her ~icrlrs~ in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued Mbrch 26, 1985. Enzymes for use in de~ L-- can be 5t~hi l i 7~ by vari~C ~hni~c. Enzyme st2bilization techniquec are ~icC~ncP~
and exemplif;p~ in U.S. Patent 4,261,868, issued April 14, 1981 to Horn, et al, U.S. Patent 3,600,319, issued ALgust 17, 1971 to Gedge, et ~1, and Eoropedn Patent Application Publication No.
O 199 405~ ~rrli~ti~n No. 86200586.5, r-hliChP~ CC~h~r 29, 1986, V~nF~c. Enzyme ct~hi 1 i7~tion systemLS are also described, for example, in U.S. ~a~ 4,261,868, 3,600,319, and 3,519,570. All a~ove ~ 1 ~ nnes are i.~u,~uLated herein by reference.
~ crlc of Use - The disper_ mg agents of the invention, at crh~ LLaLions in an ~lP~C f~hriC laundering liquor of at least akout 1 ppm, ~ Lably from about 1 to about 50 ppm, and mo-ct ~,~f~,obly a~out 5 to about 30 ppm, provide effective, combined rl ~n; ~g and soil disper_ing trea~-LrLs for fabrics washed in an ~lP~lC~ preferably alkaline (pH range abaut 6.5 to abaut 11, re ~f~Lobly about 7 to about 10.5) envilu.~le~l~, in the ~e~x~ ~ of 215 9 9 8 2 PcT/US94/0374o typical detergent ingredients. Surprisingly (especially insofar as pH and anionic surfactant are concerned), all of the abave-identified detergent inqrF~;ents can be pL~ L in the wa_h water at their art ~;~OI~CA~ levels to perform their conventional tasks, e.g., for cleaning and softenLng f~t~rics or the like, without ill-effects on the soil dispersing ~L(~' Lies of the esters.
The -.tt,~rl of washing fabrics with the dispersing agents simply cc~pLises contacting said fabrics with an A~l~lC laundry liquor containing the conventional detersive ingredients descriked hereinabove, as well as the above-~i crl nCP~ effective levels of dispersing agent. Although this ~thn~ is not e~rPC;A11Y lLmited in terms of f~ L~ such as pH and surfactant types ~Le~lL, it ch~l~ be ~,a~iated that for best cleaning of fabric_, it is often ~crpciAl ly d_sirable to make use in the laundry ~LUC~55 of ~nion;~ SULr~ , such as conventional linear aLkyl~
sulfo~L~ and also to use high OE pH ranges as defined above.
Ihus, a ~.ereL.~d method for an oQ~imi~e~ combination of cleaning and soil ~i~pprcing provided by the invention constitutes using all of the following:
- the ~r~LLe~ levelc of dispersLng agent (5-30ppm);
-- Ani~i~ 8l~fa.~lL;
- pH of from about 7 to ~h~lt 10.5.
rl~An;~g benefits are surprisingly obtainable after a single use/laun~ry cycle comprising the following steps:
a) ~Yrnci~g said fabrics to soiling through normal wear or use;
b) .~.La~ing said p hrics with said ~ lC laundry liquor by soaking or by h2~ w~-~ing or in an autcmatic washing machine for periods ranging from about 5 minutes to akout 15 hcurs;
c) rinsing said fabrics with water; and d) line- or tumble-drying said fabrics.
In the above, step (b) i~r~ both hand ~hi~g and typical U.S., Jc~ e, or ~ UI washing machines operating under their conventional con~itions of time, temperature, fabric load, amounts of water and laundry product c~ ,Lrdtions. The detergent can be introduood to the system either by liquid or granular detergent or 215 9 9 8 2CTrUS94/03740 W o 94~22937 by synthetic deter~ent har. Also, in step (d), the "tumble-drying"
to which is referred involves use Of conventional hrands of r ~.. ~hl e laun~ry dryers (these are occasionally integral with the washinq machine) usinq the~ r conventional fahric loads, 5 t~,~ Llres and cperating times.
The followinq nonlimiting examples illustrate the use of a - typical ester Gn~rnC;tion of the invention as a dispersinq agent for thru-th~ w~ch application to a variety of f~hrics. The c~C;tons and E, C~y~cpc herein are ~c;pPcj~lly useful for hand-wash, but are also useful in any fabric laundering ~u~s which employs law f~hric:water ratios, such as the ~u~ LLaLed laun~ering ~o~ described in U.S. Patents 4,489,455 and 4,489,574, bcth issued to Spendel, Dec. 25, 1984.
FX~PLE VII
1~ A granular ~e~ cnm~n~ition is ~L~2Le~ ~l~rising the follawing ingr~ients and an ester cr~ ition ~ al~d following the ~L~CL3UreS set forth in Example IV.
~-~UI~ Weioht %
C13 linear alkyl L~,e sulfonate 22 ~ ~Le (as sodium tripol~lt~ Le) 30 Sodium Ldl~ul~Le 14 Sodium ~ A~P 3 Zeolite A (0.1-10 microns) 8.2 ~ loxy~en~ lfonate 3.2 Sodium ~t~LL~L~A 4.5 PlA~t (diethylenetrianL~K~ a~e~jc acid) 0.4 Sodium sulfate 5.5 Dispersing agent (Exam~le III) 0.4 ~innrS~ filler** and water Balance to 100%
* A~ particle size of 400 to 600 microns.
**Can ~e CPlP~A~ from convenient materials such as CaC03, talc, clay, silir~tes~ and the like.
In tPs ting the soil dispersLng perfor~ance of the dispersing tc, the following test ,~ ~1 is used:
~hite 100% cstton fa~ric, white poly w LLun fabric (50~/50 T-Shirt material), an~ an all synthetic material (81% acrylic, 15~
nylon, 4% ~ycra) are used in the testing. Using a Sears KENM~RE
wzsher, the fa~rics are dPcize~ with a c~.~.d~cial granular WO 94l22937 215 9 9 8 2 PCTrUS94/03740 deterqent (nA5H). The washing is conducted in o grains p~r gallon (gpq) water at a t~~ dL~re of 120 F (48.8 C) for 12 minutes, with hCR~lP~t rinsing in 0 gpq water at a ~l~k~aL~re of 120F
(48.8 &). This ~ci~ing step is done twi oe and is followed by two ad~itional wash cycles using only water. The ~ci 7Fd fabriGc are formed into s~ ~s (5 inches square).
Testing is done in a 5 pot Automatic Mini-Washer (AMW) to mLmic a 1~ operation usinq standar~ized conditions. Aft~r the AMW pots are filled with 7.6 liters (2 gallons) of water each, the ~t~,L cn~rrF;tion (above) and the dispersing agent are added to each pot. The clean test swatches are then added alone with an amcunt of UUT~ , dirty consumer ballast to bring the water/cloth ratio to the desired level of approximately 5:1 (lit 0 :kg). Ihe c~nswmer ballast is split into e~ual halves h~ ~ n the dispersing agent containing formula and a pot containing an identical control formula without dispersing agent.
The wash cycle is con~-rt~ in 8 grains per gallon (gpg) water at a temperature of 77F (25C) water. Ihe wash cycle consists of a 30 minute soak foll~ -~ by 10 minute agitation. After the wash cycle, there is a 2 minute spin cycle, fo~ r~ by two 2-minute rinse cycles using 8 gpg water at a temperature of 77F (25 &). For mLlti-cycle testing the test s~ es are dried and the above steps L~J-~IJp~ using the same test s~ es and new dirty ccrsumer hmt11 P~:.
Z5 At the end of the last rinse cycle, the test s~ es are dried in a dryer. Tr~ctiulus meter readings (L,a,b) are then dL*I3n:inod for each test swatch. Whiteness ~lfULI~U~ in terms of Hunter Whiteness Values (W) is then r~ 1~ 11 Ated acccrding to the folla~ing Pcr~;sn:
W = (7L2 - 40Lb)/700 m e higher the value for W, the ~etter the whiteness ~L~Lmance. All f~b~ics display significantly im~roved whiteness after laun~ering ~.~d with fabrics which have not been to the ~icp~rsing agents of this invention.
EX~MPLE vIII
A laundry ~ar sui~able for hand-washing soiled fabrics is ~t~aL~ by ~ kl~ extrusion ~ w ~sPs and comprises the follownng:

WO 94/22937 215 9 9 8 2 PCTrUS94/03740 .

~l~u~ Weiqht %
C12 linear alkyl benzene sulfonate 30 Phosphate (as ~n~il~ tripolyphosphate) 7 ~;t~ carbonate 25 ~c~;l~ pyL ~ ~ Le coconut .. ~lL~U~molamide 2 7~1ite A (0.1-10 mic~-on) 5 CoLL~ymethylnPl1~ cP 0.2 Polyacryl~te (m.w. 1400) 0.2 ~;crPrc;~g agent (Example V) 0.5 Bri~ , perfume 0.2 FL~ease 0.3 CaS04 M~S04 Water 4 Filler* Balance to 100%
*Can be cPloc~e~ from convenient materials such as CaC03, talc, clay, cilirA~Pc~ and th_ like.
In tE~ ng the _oil dispersing perfv"._~ ~ of the dispersing A~P~C~ the test method used in FY~m~lP VII is fol lr~ . All fabricc ~ y ci~nifirAntly imprcved whitenesc after laundering cYr~y~red with fabrics which have not been ~-Lf~l to the esters of the inNention.
I;~s~T.F~ IX
A li~ d~ compo6ition is ~,~ta~a~ c~,~rising the fnl l~rin~ ingredients and an ester ~ ;tion ~ a~d following the ~,oL~sllrcs set f~rth in Example rv.
C~rlxancnt ~ Weight %
C14 15 alkyl polyethoxylate (2.25) sulfonic acid 10 3 C12_13 linear aIkylL~ e sulfonic acid 8.5 C12_13 aIkyl polyethoxylate (6.5) 2.4 c~ium cumene sulfcnate 2.
~1 1.2 1,2 ~lukxuf3diol 5 cr~ium hydroxide 1.9 u,olamine 2.4 Citric acid 1.5 C12-14 fatty acid 1.9 W0 94/22937 21~ 9 9 8 2 PCT/US94/03740 Dispersing agent (Example III) 1.5 Brightener 0.1 Minors, filler* and waterBalance to 100%
*can ke selected from convenient materials such as CaC03, talc, clay, silicates, and the like.
In testing the soil dispersing perfoL,.~oe of the dispersing agents, the test ~ used in Fx~rle VII is followed. All fabrics display significantly improved whiteness after laundering c.u~ with fabrics which have not been ~YrnsP~ to the esters of the invention.
EX~E X
A cu~ Ll~Led liquid detergent c~rr~;tion is ~Le~d comprising the following ingredients and an ester composition ~q ~d following the ~L~ res set forth in Example III.
~wu~ Weiqht %
Cl4 15 aIkyl polyethoxylate (2.25) sulfonic acid 10.6 C12 13 linear aIkylL~ e sulfonic acid 12.5 C12-13 alkyl polyethoxylate (6.5) 2.4 Sodium cumene sulfonate 6 Ethanol 1.5 1,2 ~ ~1iol 4 Scdium hydrcxide 0.3 C12-14 fatty acid 2 n;c~P~i~g agent (FV~r1P II) 1.5 M~nLrs, fill OE * and water Balance to 100%
*Can be cPlPrt~ from c~nNenlent materials such as CaC03, talc, clay, Fil;~tpcl and the like.
In tPct;n~ the soil dispersLng perfo~ of the dispersing agents, the test ll.rYl l-cP~ Ln Example VII is follcw~ All fabrics display significantly Lmprove~ whiteness aftr~r laundering c~pared with f~hriCs which have not been ~Yr~A~ to the esters of the invention.
While the c~ ~Oitions and p~u~ccPc of the ~,es~,L invention are Pc~eci~lly useful in hand-wash fakric laundering operations, it is to ke u.~t~L~ that they are also useful in any cleaning system which inv31ves low water:fabric ratios. One such system is ~;crlqCP~ in U.S. Patent 4,489,455, Spendel, issued Dec. 25, 1984, WO 94/22937 ~15 g 9 8 2 PCT/US94/03740 .

which involve_ a washing machine apparatus which contacts fabrics with wash water containing detersive ingredients using a low water:
fabric ratio ~Ult~ than the conventional method of immersing r fabric-c in an ~ c bath. Typically, the ratio of water:fabric range_ from about O.5:l to abaut 6:l (liters of water:kg of - fabric).
EX~ ~:
Using the machine an~ operating conditions ~;~rlo~p~ in U.S.
Patent 4,489,455, cited above, 25 grams of a c ~ ;tion according to FY~rlP VII herein are used to launder fabrics. If desired, sudsing of the .~ ition can be mln;m; ~e~ by ~L~GLd~ing therein from 0.2% to 2% by weight of a fatty acid, secondary alcohol, or ;l;~ne ~ ~c controlling ingredient.
Dishwashinq ccmp~sition_ ~U~L AC~Frt of the ~LeS invention relates to dishwashing ~ -f~itions~ in part;~llAr automatic and m.~nual dishwa~hing compositions, ~Cp~c;~lly manual liquid ~ic~ --~ing cr~rncitions.
T.;~ ching ~ sitions acc~rding to the ~,e~
invention ~L~L~bly comprise frcm at least about 0.1%, more preferably from akout 0.5% to akout 30%, mcst preferably from about 1~ to about 15% of the partially oli~nm~rized ester and from about 1~ to about 99.9% of a detersive surfactant.
T-;~ dilt~lshlng ccmpositions according to the ~LtS~
invention may ccmprise any of the ingredients listed herein above.
In ad~ition the ~i ~ --~ing c~mpcsitions may comprise other ingrP~ tC such as bactericides, chelants, suds op~;fi~rs and ~ nm and ..~.,esium ions.
H~ o~ A hy~uLluye is typically added to the compocitions of the ~L~x~lL invention, and may be ~es~.L at levels of frcm about 0% to about 10%, preferably from about 1% to about 5%, by wr;qh~.
Useful h~ ~yes include ~n~ium, potAC-ci-~, and ammonium xylene ~~ e~, sodium, pot~Ccium, and ammonium toluene ~ i~ ~Le, ~o~ ~cil~ and ammonium cumene sulphonate, and r~c1Ires u~t~eur. Okher onn~ s useful as h~uLlu~es herein include polyrArhnyylates. Some polycarboxylat~c have calcium chelating ~ ukeLLies as well as hy~luLL~ic properties. An example of a ~ cially av~ hlp alkylpolyethoxy polycarboxylate which WO 9~/22937 21~ 9 9 8 2 PCT/US94/03740 can ke employed herein is POLYJTERGENT C, Olin Corporation, ~h~h; re, CT.
~ ~r .~ nd useful as a hy~L~LLuye is aLkyl amphodi-carboxylic acid of the generic formLla:
,.
(CH2)x Coo-RCNHCH2CH2N<
(CH2)x COoM

wherein R is a C8 to C18 aIkyl grcup, x is from 1 to 2, M is preferably cho6en frcm alkali metal, aIkaline earth metal, ammanium, monc-, di-, and tri-ethanolammonium, most preferably from ~, pot~ ~, ammonium, and mixtures thereof with magnesium ions. The ~L~fel~dd alkyl chain length (R) is a C10 to C14 alkyl grcup and the ~i rArh~Yylic acid functionally is ~i A~P~j r acid and/or diprc~;nnic acid.
A suitable example of an alkyl ~mrhn~ir~ ylic acid is the ançl~_ic ~f~culL Miranol R 2CM Ccnc. ma~lfAr~lred by Miranol, Inc., Dayton, NJ.
Orga~i~ solvent The ~r~-;tions of the invention will most ~L~ ably cantain an organic solvent system ~Les~,L at levels of from akout 1% to about 30% by weight, ~Lef~L~bly f m m about 1~ to about 20~ by wri~ht, mcre preferably fr~-- a~cut 2% to abcut 15% by w-;~h~ of the composition. The organic solvent syste'm may be a mono, or mixed solvent system. Preferably, at least the major ccD~xlY3nt of the solvent system is of low volatility. Suitable organic solvents for use herein has the general formula:
R~
( ~ )n wherein R is an alkyl, alkenyl, or aIkyl aryl grcup having frcm a~aut 1 to abaut 8 carbon atoms, R' is eith OE H or ~ , and n is an ~ J~r fram 1 to 4. P~eferably, R is an alkyl group containing 1 to 4 r~rh~n atoms, and n is 1 or 2. F~rpc;~lly preferred R groups are n-~utyl or iso- bu~yl. Preferred solvents of this type are ~5 1-n-butox~u~i~ 2-ol (nFl); an~ 1(2-n-butoxy-1-methylethoxy)-2-ol (n=2), and mixtures thereof.
Other solvents llCPfUl herein Lnclude the water soluble CARBLl~L or ~.rnS~r~E solvents. These solvents are c~ ds of W O 94/22937 215 9 9 8 2 PCT~US94/03740 the 2-(2-alkoxyethoxy)ethanol class wherein the alkoxy group is derived from ethyl, propyl or butyl.
Other sui~hle solvents are benzyl aloQhol, and diols such as 2-ethyl-1,3-hexanediol an~ 2,2,4-trimethl-1,3-pentanediol. The lcw S mol P~ll ~r weight, water-soluble, liquid polyethylene glycols are - also suitable solvents for .-c~ herein.
The aIkane mLno and diols, Pcpe~iAlly the Cl-C6 alkane mono and diols are suitable for use herein. C1-C4 monohydric Al nnhnl (eg: ethanol, ~Lu~xu~l, is~y-~yar~l, butanol and mixtures U.~u~f) are preferrad, with ethanol part;~llArly preferred. The Cl-C4 dihydric Alnnhnl~ including propylene glycol, are also preferred.
Thickeninq aqents - The ~ q~itions acuurding to the ~Y~
invention may additionally comprise thickening agents, such as polyquaterium cP~ 6p cationic polymer, for PY~mrle QuatrisoftR
15 av~ i l Ahl P fiuthe Americhol C~L~ulaLion.
Calcium - G~ fi;tionc acoording to the ~Le5~ invention may cptionally comprise from akout O.01% to akout 3%, more preferably from about 0.15% to about 0.9% of rAlc;~ ions. The calcium ions can, for PY~rlP, be added as a chloride, hydroxide, oxide, formate or ArP~te, or nitrate salt. If the anionic surfactants are in the acid form, the calcium can be added as a rAlr;~ oxide or rAlci-~
hydroxide slurry in water to neutralise the acid.
~he calcium ions may be ~Les~.L in the cr~rnsitions as salts.
The amount of c~lril~ ions ~L~c~-.L in c ~ tions of the invention may be d~ ~.L upon the amount of total anionic surfactant e~*~.L herein. The molar ratio of c~lr-i-~ ions to total anionic sLL~ is preferably from akout l:O.l to about 1:25 more ~f~lably from about 1:2 to about 1:10, for a~ ~itions of the invEntion.
~lritmn ~bilisi~q aqent - In order to provide gocd product c~Ahility, and in parti~ll~r to prevent the precipitation of ril~ salts malic, ~lPir or a oe tic acid, or their salts, or cPrtain lime soap dispersant cf~y~-~ds may be added to the ~,~u~ition of the ~ PIL invention camprising r~lcil~ . Where c~ ~ is ~.t~ alic, maleic or acetic acid, or their salts can be added at levels of from about 0.05% to akout 10% of the ~ ;tion and a molar ratio with calcium of from akcut lO:l to about 1:10.

W O 94/22937 215 9 9 8 2 PcTlus94lo374o Maqnesium - Frcm about 0.01% to about 3%, most preferably from about 0.15% to about 2%, by weight, of magnesium ions are preferably added to the liquid detergent c~rn~itions of the invention for improved product stability, as well as improved sudsing.
If the anionic surfactants are in the acid form, then the ~ium can be added by neutralisation of the acid with a l~yl~ium oxide or magnesium hydroxide slurry in water. Calcium can be LL~aLel c;~il~rly. This technique mi~ c the addition of chloride ions, which reduces coLLu~ive ~Luy~LLies. The neutralized surfactant salts and the h~dluL~u~e are then added to the final mixing tank and any optional ingredients are added before adjusting the pH.
~H of the Compo6itions - The c~rr~;tion according to the ~Les~lL invention formulated for use in manual ~; ch~ g ~ ir~tions are ~Q~f~lobly formulated to have a pH at 20 & of fram akout 3 to about 12, ~f~cbly from akaut 6 to abaut 9, mo6t ~fe~dbly from akaut 7 to abaut 8.5.
In ~ aspect of the ~.e~ invention the ~;c~ g compo6ition may be formulated for use as in pre-L~ IL
~l;r~t;o~c whereby the cr~Y~ition is ~rrliP~ in essentially the ~x~ Le~ fonm onto the dishes. Preferably the ~n~rnC;tion is ~11~. ' to remain on the dishes for a period of time. Compocitions for use in such ~r~lir~tions preferably have a pH of f~ ~. about 3 to akout 14, mLre preferably from about 3 to about 5 or greater than about 8.
FxamPles XII
The follcwnng liquid ~ itions of the ~LC~ invention are ~ o~ by muxIng the listed ingrP~;ents in the given amounts.
% bV weiqht of the total cn~csition C12/13 alkylethcn~ hAte 17 9 10 10 - - 10 C8 alkyl~llph~te - - - - 7 2 *n;cr~rcing agent (ex. III) 7 9 3 12 2 1.5 20 ave. C12/14 alkyl amine oxide 2 2 5 2 0.5 0.5 2 ave. C16 aIkyl amine oxide - 10 - - - 1 2 C12/14 aIkyl dImethyl betaine - 1.5 2 - - - 2 W O 94l22937 215 9 9 8 2 pcT~uss4/o374o .

% by weiqht of the total comPOSitiOn C12 a ~yl ~ U-yl ~mi~ 9 6 10 12 0.5 0.55 Clo alkyl ethoxylate (av. 8) lo 5 - 5 - - 4 S C8 alkyl e ~ late (av. 6) - - - - lo oic acid ~ - 10 _ _ _ 5 C12/14 alkyl ethcxy r~rh~Yylate _ - 5 Mg++ ion 0.5 - 0.3 0.6 - - 0.3 Ca++ ion - 0.3 0.2 0.1 - - 0.2 Maleic acid - 0.2 0.3 Citric acid - - - - - 6 MiranoLR -- 2 Butyl Carbitol - - - - - 3 eonx~mopyl~ b~1 -- -- -- -- -- 8 Sodium hydroxide - - - - 0.7 0.6 Polyt~~ -- -- 2 T .; ~CP -- -- O . 02 A~1A~ -- -- O . 01 - 0.05 NeodolR23-3 - - - - 4 Minors up to 100%

~Dispersing agent having a 4 ~ n index of 2.3 and an EG/PG =
1.5.

The di ~ ing agent ~-CP~ Ln the above ~Y~m~l ~c may ke rPrlAr~ by any of the dispersing agents dPcrr;ho~ herein.

~H~r IS ~T~TMFn IS:

Claims (16)

WHAT IS CLAIMED IS:

1. A method for cleaning fabrics, said method comprising contacting said fabrics in an aqueous liquor comprising conventional detergent ingredients and at least 1 ppm of a dispersing agent which comprises a mixture of:
A) from 0% to 95% of fully oligomerized esters of the formula:
(CAP)2(EG/PG)v(T)y(SI)z wherein i) (CAP) represents sulfonated end-capping units selected from the group consisting of:
(a) MO3S(CH2)m(CH2CH2O)(RO)n-, wherein M is a salt-forming cation, R is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is from 0 to 4;
(b) sulfobenzoyl units of the formula (MO3S)(C6H4)C(O)-, wherein M is a salt-forming cation; and (c) mixtures of (a) and (b);
ii) (EG/PG) represents oxyethyleneoxy units, oxy-1,2-propyleneoxy units, or mixtures thereof;
iii) (T) represents terephthaloyl units; and, optionally, iv) (SI) represents 5-sulfoisophthaloyl units of the formula -(O)C(C6H3)(SO3M)C(O)-, wherein M is a salt-forming cation; v is from 0.25 to 50, y is from 1.25 to 30, and z is determined by the formula y/(z+1) = 1.25 to 5;
wherein, v, y and z represent the average number of moles of the corresponding units per mole of said ester; and B) from 5% to 100% of partially oligomerized esters of A) with a number average molecular weight of no more than 70% of the molecular weight of the fully oligomerized esters, A);
such that the number average molecular weight of the dispersing agent is from 400 to 3,000.

2. The method according to Claim 1, wherein the (CAP) units are i)(a) and v is determined by the formula v = y+z to y+z-1.

3. The method according to Claim 1, wherein the (CAP) units are i)(b) and v is determined by the formula v = y+z+1.

4. The method according to Claim 1, wherein the (CAP) units are i)(c) and v is determined by the formula v = y+z1.

5. The method according to Claim 1 wherein said ester composition has a number average molecular weight of from 500 to 1,100 and wherein said detergent ingredients comprise from 5% to 80% by weight of detersive surfactant.

6. The method according to Claim 5 wherein said detergent ingredients further comprises from 5% to 80% by weight detergent builder and from 0% to 20% of conventional detersive adjuncts.

7. The method according to Claim 6, wherein said fabrics are subjected to one ormore cycles each comprising the following steps:
(A) exposing said fabrics to soiling through wear or use;
(B) contacting said fabrics with said laundry liquor for periods ranging from 5 minutes to 15 hours;
(C) rinsing said fabrics with water; and (D) line- or tumble-drying said fabrics.

8. A method of hand-washing fabrics according to Claim 7 comprising contacting and agitating by hand fabrics in an aqueous laundry liquor comprising at least 300 ppm of said laundry detergent and at least 1 ppm of said dispersing agent.

9. A method for dispersing soils in an aqueous laundry liquor comprising contacting fabrics in an aqueous laundry liquor comprising at least 1 ppm of said dispersing agent which is further characterized in that it consists essentially of the oligomeric product of reacting compounds comprising:
(A) monovalent cation salts of said sulfonated end-capping monomers;
(B) dimethyl terephthalate;
(C) dimethyl sulfoisophthalate; and (D) ethylene glycol, propylene glycol or a mixture thereof; and said aqueous laundry liquor is further characterized in that it has a pH from 7 to 11.

10. A method according to Claim 9 wherein said oligomeric product comprises:
(A) 1 mole of monovalent cation salts of said sulfonated end-capping monomers;
(B) 5 moles of dimethyl terephthalate;
(C) 1 mole dimethyl sulfoisophthalate; and (D) 12 moles of ethylene glycol, propylene glycol or a mixture thereof

11. A detergent composition in granule form comprising:
i) from 1% to 99.9% by weight of a detersive surfactant; and ii) at least 0.1% by weight of a dispersing agent comprising:
a) from 0% to 95% by weight of fully oligomerized esters of the formula:

and b) from 5% to 100% by weight of partially oligomerized esters of ii)a) with a Completion Index of 6.

12. A detergent composition in bar form comprising:
i) from 1% to 99.9% by weight of a detersive surfactant;
ii) at least 0.1% by weight of a dispersing agent comprising:
a) from 0% to 95% by weight of fully oligomerized esters of the formula:

and b) from 5% to 100% by weight of partially oligomerized esters of ii)a) with a Completion Index of approximately 6.

13. A detergent composition in liquid form comprising:
i) from 1% to 99.9% by weight of a detersive surfactant;
ii) at least 0.1% by weight of a dispersing agent comprising:

a) from 0% to 95% by weight of fully oligomerized esters of the formula:

and b) from 5% to 100% by weight of partially oligomerized esters of ii)a) with a Completion Index of approximately 3.

14. A method for modifying isethionate comprising reacting an excess of polyol reactant with isethionate.

15. A method according to Claim 14 wherein said polyol reactant and said isethionate are present in a molar ratio of at least 2:1.

16. A liquid dishwashing detergent composition comprising from 1% to 99.9% of a detersive surfactant and at least 0.1% of an ester compositions comprising:
A) from 0% to 95% of fully oligomerized esters of the formula:
(CAP)2(EG/PG)v(T)y(SI)z wherein i) (CAP) represents sulfonated end-capping units selected from the group consisting of:
(a) MO3S(CH2)m(CH2CH2O)(RO)n-, wherein M is a salt-forming cation, R
is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is from 0 to 4;
(b) sulfobenzoyl units of the formula (MO3S)(C6H4)C0)-, wherein M is a salt-forming cation; and (c) mixtures of (a) and (b);
ii) (EG/PG) represents oxyethyleneoxy units, oxy-1,2-propyleneoxy units, or mixtures thereof;
iii) (T) represents terephthaloyl units; and, optionally, iv) (SI) represents 5-sulfoisophthaloyl units of the formula -(0)C(C6H3)(SO3M)C(0)-, wherein M is a salt-forming cation; v is from 0.25 to 50, y is from 1.25 to 30, and z is determined by the formula y/(z+1)=1.25 to 5;
wherein, v, y and z represent the average number of moles of the corresponding units per mole of said ester; and B) from 5% to 100% of partially oligomerized esters of A) with a number average molecular weight of no more than 70% of the molecular weight of the fully oligomerized esters, a);
such that the number average molecular weight of the dispersing agent is from 400 to 3,000.