CA2262710A1

CA2262710A1 - Process for making soil release polymer granules

Info

Publication number: CA2262710A1
Application number: CA002262710A
Authority: CA
Inventors: Benjamin Edgar Chapman; Michael Timothy Creedon
Original assignee: Individual
Current assignee: Procter and Gamble Co
Priority date: 1996-08-08
Filing date: 1997-08-01
Publication date: 1998-02-12
Also published as: CN1232490A; JP2000500810A; ZA977051B; US5770558A; BR9711125A; US5700386A; EP0920488A1; WO1998005747A1

Abstract

The subject invention involves processes for making granular compositions comprising soil release polymers, the polymers comprising at least about 10 %
of substantially linear esters having a backbone; the esters being uncapped or end-capped on one or both ends of the backbone; the esters comprising in their backbones oxyalkyleneoxy units and hydrophobic aryldicarbonyl units; the esters having a molecular weight of from about 500 to about 20,000; the polymers if in solid state having the tendency when exposed to moisture to spontaneously rearrange from an amorphous form which is readily soluble in water to a crystalline form which is relatively insoluble in water; the process comprising the following steps: a) taking the soil release polymers, in which are dispersed from 0 % to about 25 % alkylaryl or alkyl sulfonate crystallization-reducing stabilizers, in molten state at a temperature of at least about 180 ~C, and rapidly dissolving the molten polymers in water, forming an aqueous polymer solution having a polymer concentration of up to about 50 %, the average temperature of the solution being maintained below about 50 ~C; b) dispersing a nonionic surfactant in the molten polymers or in the water prior to step a), the surfactant being an alkylethoxy alcohol nonionic surfactant which is a condensation product of alkylalcohol and ethylene oxide, the alkyl portion being linear or branched, saturated or unsaturated, having from about 8 to about 22 carbon atoms, there being on average of from about 10 to about 100 moles ethoxy per mole surfactant, the nonionic surfactant being from about 2 % to about 20 % of the aqueous polymer solution, on a dry weight basis; and c) drying the aqueous polymer solution of b), thereby producing a granular composition having a water content of less than about 3 %. The subject invention also involves soil release polymer granules comprising such polymers and nonionic surfactant and, optionally, stabilizers.

Description

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PROCESS FOR MAKING SOIL RFI F'~SF POLYMER GRANULES

TECHNICAL FIELD
The subject invention involves p,ucesses for making granules of water-soluble soil release polymers useful as cor"~,oner,la of granular laundry products and water-soluble soil release polymer granules suitable for dry t ~nd~ ,9 with dete,yer,t granules.
BACKGROUND OF THE INVENTION
Various water-soluble soil release poly",era useful as con,~oner,La of laundry products are well-known. Such soil release poly",era may be co",ponenta of dt:lerge"L
laundry products or fabric softene,/anlisldlic products used for washing or rinsing fabrics.
A convenient way to i,l. or~,orale the soil release polymers in such products is as granules which are plill,ddly co",posed of the polymer. The polymer granules can be dry-blended with laundry detdryeril granules orland other granules at desired ratios. Stability of the polymers is generally enhanced by having them in sepaldle granules from some of the common laundry product co""~onenta.
The soil release polymers of interest in the subject invention process are made by a synthesis process which results in molten polymer at a high le,nperdture. In order to retain good activity of the polymer it is desi, t e to cool the polymer quickly in order to retain it in an ar"or~,hous state and not allow it to lldnaf~.llll into a crystalline state.
It is an object of the subject invention to provide a process for making soil release polymer granules from hot molten polymer that can be readily used for co"""ercial scale production of the granules.
It is a further object of the subject invention to provide such a process wherein most of the polymer is retained in its dlllGr~hous state.
~ It is also an object of the subject invention to provide soil release polymer granules of suitable size bulk density and stability for dry b 3nding with d~teryent granules in dry laundry products.
SUMMARY OF THE INVEN~ION
The subject invention involves prucesses for making granular cor"positions co, n~.rising soil release polymers the polymers co" ,priaing at least about 10% of substantially linear esters having a bacl~t,one; the esters being uncapped or end-capped on one or both ends of the backbone; the esters cG"~I.rising in their backbones oxyalkyleneoxy units and hy~l,uphob o aryk~ica,l.onyl units; the esters having a ".~ ?r weight of from about 500 to about 20 000; the polymers if in solid state having the tender,~ y when ~Yposed to moisture to spontaneously rea"a"ye in time from an a",or~hous form which is readily CA 02262710 1999-02-0~

soluble in water to a crystalline form which is relatively ill5-' ~L'e in water; the process cG",~,rising the following steps:
a) taking the soil release polymers, in which are dis,~er~ed from 0% to about 25%
alkylaryl or alkyl sulfonate stabilizers, in molten state at a te",pe,dlure of at least about 180~C, and rapidly di..folvillg the molten poly",e,~ in water, fomming an aqueous polymer solution having a polymer concer,t~dlion of up to about 50%, the average l~" ,pe, dlure of the solution being maintained below about 50~C;
b) dispel~i"g a non ~n ~ surfactant in the molten polymers or in the water prior to step a), the surfactant being an alkylethoxy alcohol non.-n ~ surfactant which is a condensalion product of alkylalcohol and ethylene oxide, the alkyl portion beinglinear or branched, saturated or unsaturated, having from about 8 to about 22 carbon atoms, there being on average of from about 10 to about 100 moles ethoxy per mole surfactant, the non- ~ nic surfactant being from about 2% to about 20% of the aq~leous polymer solution, on a dry weight basis; and c) drying the aqueous polymer solution of b), thereby producing a granular co",posi~ion having a water content of less than about 3%.
The subject invention also involves soil release polymer granules co" Ipl ising such polymers and nonionic surfactant and, optionally, stabilkers.
BR~EF DES~;.J. ~ OF THE DRAWINGS
Figure 1 is a scl)e" ,alic flow chart of a batch process of the subject invention.
Figure 2 is a schematic flow chart of a semi-continuous process of the subject invention.
DETAILED DESC.J. I IOI~ OF THE INVENTION
The subject invention involves processes for making particles containing soil release poly",er~, starting from the hot, molten polymer.
Many soil release polymers are made by p~ucesses which result in the polymer being present in a hot, molten state. P,efe"t:d soil release polymers of this type are ~ifolosed in U.S. Patent Nos. 4,877,896 issued to 1\1 '~'-nado, Trinh and Gosselink on October 31, 1989; 5,196,133 issued to Leslie and Clauss on March 23, 1993; 5,182,û43 issued to Morrall, Gosselink, Pan and Nayar on January 26, 1993; and 5,415,807 issued to Gosselink, Pan, Kellett and Hall on May 16, 1995, all of which are i"co,~or~lt~d herein by ,~r~nce.
All perc~e,.ldges herein are given on a weight basis, unless expressly otherwisei"d;cdted.
As used herein, "alkyl" means a hydrocarbyl chain, linear or branched, saturated or unsaturated. Unless o~l,er~;~,e indicated, alkyl are plt:f~ldbly linear, pre~,ably saturated or unsaturated with one or two double bonds, more prt:ferdbly saturated.

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W O 98/05747 PCT~US97/13558 As used herein "aryl" means an d,u",alic hydlucd,byl ring. P,~if~r,~d aryl are phenyl and naphthyl especially phenyl. "Alkylaryl" means aryl s~hstit~ted with one or more alkyl.
Taken in their ~ruadesL aspect the soil release poly",era of the subject ~ucesses encG",pass an o' g~ri.c:nc ester backt,one which is plerc-:~aLly end-capped on at least one end more pl_F~ .ably both ends, of the backl,ùl)e by end-capping units. The end-capping units are anionic hyJIuph 'es conne~tud to the ester bacl~bone by means of aroyi groups or by an ester or ether linkage. P~rdbly the anion source is a sulfùnated group.
~ oly~c~ of the subject invention p,ocesses enco",pass c'~n,eric (low ~ 'e u~~~
weight polymeric) substantially linear u"capped or end-capped esters. These esters coillpliael in their bachbones oxyalkyleneoxy preferably oxy-1 2-propylcneoxy and oxyethyleneoxy units and hyd~ph~ ~ aryldicarbonyl prc ferdbly ter~phtl,-'-yl units.
~cfc l,~d esters ad~itionally co"")rise units of sulfoisophll,alate and opLionally poly(oxyethylene)oxy units having a degree of polyr"eri~a~ion from about 2 to about 4.
Mixtures of such esters with reaction by-products and the like retain their utility as fabric soil release agents when such mixtures contain at least about 10% prehrc,bly at least about 25% more pl~f~.dbly at least about 50% by weight of the subject esters. The esters useful herein are of relatively low " s'e Jl_~ weight (i.e. generally below the range of fiber-forming polyesters) typically ranging from about 500 to about 20 000 preferdbly from about 650 to about 8000 also pr~Fe.dbly from about 650 to about 2500.
Pl~r,ed end-capping units include sulfoaroyl units espe~ 'Iy sulfobenzoyl units of the formula (MO3S)(C6H4)C(O)- wherein M is a salt-forming cation such as sodium or tetraalkyld"""on ~m p~f~rably sodium. P~ferably not more than about 0.15 mole fraction of the sulfobenzoyl end-capping units are in para-form. More preferred are the sulfubenzoyl end-capping units being essen- ~lly in ortho- or meta-form.
P~_f~.led end-capping units include those derived from sL;'unated poly-ethoxy/propoxy groups which are conn~cted to the backt,one by an ester linkage. P~t:Ftlled are those of the formula (MO3S)(CH2)m(R'O)n- wherein M is a salt-forming cation such as sodium or tetraalkyla",..,on'.urn; m is 0 or 1 p,eferably 0; R' is ethylene p,up/lene or a mixtures thereof p,~F~rably ethylene; and n is on average from 1 to about 20 p~e:f~:rdbly about 1-5. More pl~f~.led are capping units derived from using n~ono"~e~a selected from sodium 2-(2-hyd,uAy~;ho,~y)c lhanesulfonate sodium 2-(2-(hydroxyethoxy)ethoxy)eU,anesulfonate and 2-(2-(2-(hydroxyethoxy)ethoxy)ethoxy)ethane-sulfonate.
Preferred end-capping units include ethoxylated or propoxylated phenolsulfonate units of the formula MO3S(C6H4)(OR')p wherein M and R' are as defined above and p is from about 1 to about 20 preferd~ly from about 2 to about 10.

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W O 98/05747 PCT~US97/13558 Plt:r~ d end-capping units include modir,ed poly(oxyethylene)oxy monoalkyl etherunits of the formula R"O(CH2CH20)k- wherein R" is about C1-C4 pra~rdLly about C1-C2 saturated alkyl and k is from about 3 to about 100 prt:fe:rdbly from about 5 to about 50.
Pl ~r~, ed end-capped esters are essentially in the doubly end-capped form CCil "prising about 2 moles of the end-capping units per mole of the ester.
The ester ual.kbone" of the subject polymers by ~., 'ic n cG"~pnaes all the units other than the end-capping units all the bachbone units illcol,uo,d~d into the esters being i"l~ruonne- Ied by means of ester bonds.
The essential oxyalkyleneoxy units of the bachl,one of the subject poly",era aremixtures of s~ t~iual (a) -OCH2CH20--(oxyethyleneoxy) units with unsy"""t:t~i:al (b) --OCHtRa)CH(Rb)O- (oxy-1 2-alkyleneoxy) units wherein Ra and Rb are sel~vl-d so that in each of the units one of Ra or Rb is H and the other is a non-hydrogen R group (as 5~' q~d below) or Ra and Rb are different non-hydrogen R groups. For pr~f~r,ed (b) units one of Ra or Rb is H. The (b) units are believed to provide a sufticiently uua~lllllletli~dl cha~d. l~r required for stability of the desired a",oruhous physical form of the soil release poly"~era wl,e,~:as the (a) units are believed to provide sufFicient symmetry for soil release activity. A convenient measure of the l", .y" " "~l, ical cha, act~r required is given by the mole ratio of (a) units to (b) units. For the subject invention prucesses the ratio of (a) units to (b) units in the subject polymers pr~:t~rdl;ly varies from about 1:2 to about 4:1. At a ratio of greater than about 4:1 the polymers spor,ldneously change from alllcill,hous to crystalline form quickly and are not useful in co" " "ercidl scale prucesses where conce"t, ~ted aqueous solutions are pl~pdl~d and kept for more than a few minutes. At a ratio less than about 1:2 the poly",e,a have little tender,cy to change from a",o,uhous to crystalline form.
More pr~ft:r,ed ratios of (a) units to (b) units in the subject polymers is from about 1:1 to about3:1 morepfef~ dstillfromabout1.3:1 toabout2:1.
In the above pdlayld,uh R is p,~ F,_.dt,ly a nonhydrogen norichd,yed group has low ",e'e Illa weight (typically below about 500) is chemically unreactive (especially in that it is a noneattiq~t!e group) and is co"" rised of C and H or of C H and O. The pr~F~ d R
groups are sel~~d from lower n-alkyl groups such as methyl ethyl propyl and butyl especially methyl. Thus the pre~er,~d oxy-1 2-alkyleneoxy units are oxy-1 2-propyleneoxy oxy-1,2-butyleneoxy oxy-1 2-pe"lyleneoxy and oxy-1 2-hexyleneoxy units. Especially prcf~ d are oxy-1 2-propyleneoxy as (b) units.
The bachbones of the subject esters cGlll~riae~ per mole of ester from about 0.5 to about 66 moles of the oxyalkyleneoxy units pre:rt:rdbly from about 1 to about 22 moles more pl- f~.dbly from about 3 to about 16 moles.
Certain nohcha~yed~ hyd,.phobic aryl.l,cd,bcir,yl units are in the bachbone of the subject poly",era. Pl~f~.dLly these are exclusively terephtl, '~yl units. Other nonchd,yed CA 02262710 1999-02-0~

W O 98/05747 5 PCTrUS97/13558 hyd,uphct.- dicart~onyl units, such as isopr,lll~'Dyl, adipoyl, or the like, can also be present if desired, provided that the soil release prope, lies of the esters (especially polyester substantivity) are not sig"ificar,lly diminished. These other, noncha,yed, h~ ophcb dica,lon~l units can aid in providing sufficient irregularlity in the subject esters to avoid a too great tendenc~ to crystallize.
The bachbones of the subject esters cûn,prise, per mole of ester, from about 1 to about 40 moles of the hyd,uph~t c aryldicarbonyl units, pr~f~rdbly from about 2 to about 24 moles, more p,~:r~,al,ly from about 3 to about 14 moles.
Generally, if it is desired to modify the units of the esters, use of additionalhydrophilic units is preferable to use of additional nonchdlyed, h~JIùph~.b ~ units. For this, minor amounts, pre:tt:rdbly cGr"prisi"g less than about 5~/O of the ",~'e ~ weight of the ester, of additional units such as di- or tri- (oxyethylene)oxy units are i"co,l.o,dted into the esters.
It is also possible to introduce charged, hydrophilic units into the backL,on~;
pl~f~rdbly such units coi"prise less than about 20%, more p~e~ldbly less than about 14% of the bachl,one units. One exd",~'o is to i"co",ordte a charged moiety RC in place of one or more Ra or Rb moieties of the above oxy-1,2-alkyleneoxy units. Such Rc moiety p~r~ldbly has the structure MO3SL-, wherein M is a salt-forming cation such as sodium or tetraalkyld"""un ~n, and L is a side chain conne~;ling moiety s~0e~t-d from alkylene, oxyalkylene, alkyleneoxyalkylene, arylene, oxyarylene, a'kyleneûxyarylene, poly(oxyalkylene), oxyalkyleneoxyarylene, poly(oxy ":ylene)oxyarylene, ~ alkylenepoly(oxyalkylene), and mixtures thereof. As used in this pardy,dph, alkylene are about C2-C6, pl~f~,.db'~ ~ll,;lene or 1,2-propylene; arylene is pr~fe,dbly pher,~lene.
As another eAd",,9e, anionic hydrophilic units capable of forming two ester bonds may be included in the ba-,kl.one of the esters. Suitable anionic hydrophilic units of this specific type are well illustrated by sulfonated dicarbonyl units, such as su~fQsurxinyl, i.e., NaO3SCH(C(O))CH2C(O)-;
or more plefu.dLly, sulfoisophll,~ l, i.e.,--(O)C(C6H3)(S03M)C(O)--wherein M is a salt-forming cation, such as an alkali metal or tetraalhyla"~",ûn ~m ion.
The bachbones of the subject esters co",prise, per mole of ester, from 0 moles to about 20 moles of sLlr~,n~.t~d dicarbonyl units, pr~fe,dbly from about 0.5 moles to about 9 moles, more pref~,. dbly from about 1 moles to about 4 moles.
r~ef~.~ed soil release polymer esters useful in the subject processes comprise, per mole of the esters, (i) from about 1 to about 2 moles of sulfoaroyl end-capping units, pl~:ruldbly sulh.ben~oJI end-capping units of the formula (M03S)(C6H4)C(O)-, wherein M is a salt-forming cation such as an alkali metal or tetraalkyld"""on.um; or .

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from about 1 to about 2 moles of sulfond~ed poly-ethoxy/pr ,poxy end-capping units of the formula (MO3S)(CH2)m(CH2CH2O)(R O)n-- wherein M is a salt-forming cation such as sodium or tetraalkyla"""on.um m is 0 or 1 R is ethylene propylene or a mixture thereof and n is from 0 to about 4;
ii) from about 0.5 to about 66 moles of bachl,one units ~ele.~IPd from:
a) a mixture of oxyethyleneoxy and oxy-1 2-alkylel~eo-~y p~f~rdbly oxy-1 2-propyleneoxy units wherein the units are present in an oxyethyleneoxy to oxy-1 2-alkyleneoxy mole ratio ranging from about 4:1 to about 1:2; and b) a mixture of a) with poly(oxyethylene)oxy units wherein the poly(oxyethylene)oxy units have a degree of poly."e,i~dtion of from 2 to 4; provided that when the poly(oxyetl,ylane)oxy units have a degree of poly",e,i~dlion of 2 the mole ratio of poly(oxyethylene)oxy units to total group ii) units ranges from 0:1 to about 0.33:1; and when the poly(oxyethylene)oxy units have a degree of pol~",e,i~dtion of 3 the mole ratio of poly(oxyethylene)oxy units to total group ii) units ranges from 0:1 to about 0.22:1; and when the poly(oxyethylene)oxy units have a degree of poly",eri~tion of 4 the mole ratio of poly(oxyethylene)oxy units to total group ii) units ranges from 0:1 to about 0.14:1;
iii) from about 1 to about 40 moles of bacl~L.one hy.l~oph~ aryldicarbonyl pl~f~.ably leleph~ yl units; and iv) from 0 to about 30 moles of bacl~lone anionic dicarbonyl units pl~:f~ldbly 5-s~ isophthaloyl units of the formula -(O)C(C6H3)(SO3M)C(O)-- wherein M is a salt forming cation such as an alkali metal or tetraalkylam."on ~m ion.
A pl~f~ d type of polymer is illustrated by one co"",risi"g at least about 25%
p~Ee,ably from about 50% to about 100% by weight of ester having the empirical formula (CAP)x(EG/PG)y(T)z; wherein (CAP) ,t:p~ese-~t~ the sodium salt form of sulfuben~oyl end-capping unit from (i); (EG/PG) rt:pr~se~r,t~ oxyetl,~leneoicy and oxy-1 2-pr~pJleneoxy units from (ii); (T) ,~pr~sei,ts ~elt ph~ yl units from (iii); x is from about 1 to about 2 pr~f~.dLly about 2; y is from about 2.25 to about 9 pn~fe.dbly to about 7 more p,~ f~ .ably to about 5.5;
z is from about 1.25 to about 8 pr~f .dbly to about 6 more p,~f~rdl:ly to about 4.5; wherein x y and z I~Jleserll the average number of moles of the corlèspofi ,9 units per mole of the ester. In co"",ositions of this type the oxyethyleneoxy:oxy-1-2-propyleneoxy mole ratio plete,dbly ranges from about 1:2 to about 4:1 more prt:f~rdbly from about 1:1 to about 3:1 also p~fe.dLly from about 1.3:1 to about 2.5:1. These ester m~ )les (~ "er~) p,- rt~dbly have Ill~le lll-rweights ranging from about 600 to about 2 000 more p~fardbly from about 700 to about 1800 more preferdbly still from about 800 to about 1500.

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Another pr~ter,t:d polymer is illustrated by one col"prisi"g at least about 25%
pf~t~rdbly from about 50% to about 100% by weight of ester having the e~n, i, al formula (CAP)'d(EGlPG) e(T) f; wherein (CAP)' ,~pr~senls the sodium salt form of sulfunated poly-ethoxylpropoxy end-capping units from i); (EGIPG)' ,epresent~ oxyeLh;leneoxy oxy-12-propyleneoxy and poly(oxyethylene)oxy units from ii); (T) le:pl~serlla tc,r~:phtl,aloyl units from iii); d is from about 1 to about 2 p.t:fc:rdLly about 2; e is from about 0.5 to about 7 p(~f~:rdbly from about 1 to about 6; f is from about 1.5 to about 7,pr~f~rdbly from about 2 to about 6; wherein d e and f ,t:presenl the average number of moles of the cor,es~,ond ,9 units per mole of the ester. In cGIllpo:~iti~Jns of this type the oxyethyleneoxy:oxy-12-propyleneoxy mole ratio pr_ferdt,ly ranges from about 1:2 to about 4 1 more pl~f~ .dl,ly from about 1:1 to about 1:3. These ester ",-!e: ~ ~s (c'3e."er~) preferably have ~ e~ '~
weights ranging from about 500 to about 2 500 more p~f~rably from about 800 to about 1500.
As di~losed her~;.,at,-,ve the bachl,one of the esters herein are p,~ft:rdbly n,e~i9~d by i"cor~,oration of hydlophiks such as 5-sulf.i,sopr,tl,ald~e. This provides cGfi)positions such as those co"",ris;"g at least about 25% preferably from about 50 to about 100% by weight of ester having the em :. i, al formula (CAP) rtEG/PG) s(T) t(SlP)q; wherein (CAP)"
(EG/PG)" and (T)" are as defined for (CAP) and (CAP) (EG/PG) and tEG/PG) and (T) and (T) ,t:s~e~tiJaly in the preceding pardy,aphs and (SIP) represents the sodium salt form of 5-sulFoi;ophU,- ~yl units from iv); r is from 0 to about 2 pret~,dbly about 2; s is from about 0.5 to about 66 pr~F~ rdbly from about 2.25 to about 39 more preF~rdbly from about 3 to about 18; t is from about 1 to about 40 pr~f~rdbly from about 1.5 to about 34 more pr_'~.dLly from about 3 to about 15; q is from about 0.05 to about 26 preferably from about 0.5 to about 18 more pr~f~.dbly from about 1 to about 4; wherein r s t and q r~p~t:Senl the average number of moles of the corlespor, ,g units per mole of said ester. In these polymers the oxyethyleneoxy:oxy-1 2-p,u~,Jleneoxy mole ratio pref~,dbly ranges from about 1:2 to about 4:1 more p~f~ .dbly from about 1:1 to about 3:1. In a highly plef~ d polymer where (CAP)" rep~:ser,ts sulfunated poly-ethoxylpropoxy units r is about 2 s is about 5 t is about 5 q is about 1. In a highly p,e'~r,t:d polymer where (CAP) represents sulfobenzoyl units r is about 2 s is about 14 t is about 11 and q is about 2. F--e enl soil release cor"~.ositions of these types are those wherein the ester has a ",. e u'-~ weight ranging from about 500 to about 20 000 pr~f~rdbly from about 800 to about 5000 and the ratio of EG/PG in the ba- hLone is from about 1.3:1 to about 2.3:1 pl~t~:rdbly from about 1.5:1 to about 1.9:1.
Examples of p,~f~ d polymers of the subject invention p~cesses include the r~ y.
rol~.,c~J

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~C--O-- --CH2CHO--C ~C -O-- , CH2CHO--C ~--O-- --CH2CHO --C ~
S03Na R R R S03Na SO~Na '11 ' 'z wherein R = H or CH3 in about 2:1 ratio, respectively;
PolY,. erK

NaO35CH2CH20--C~CO----CH21 HO--C ~CO- --CH2 IHO--C~CO-- --CH2CH2S03Na S03Nà 2 wherein R = H or CH3 in about 2:1 ratio, r~spe~,ti./ely;
Polymer L

N~S(CH2CH20k3~ CH2CHO c~c o ~H2CHO c~ o--CH2CH20CH2CH2SO~N~
503N~ . 1 wherein R = H or Clt3 in about 1.7:1 ratio, respe..ti~/ely.
The p,ucess~s of the subject invention begin with the soil release polymers in molten state, pr~rdbly at a ~empe~dLLIre of at least about 180~C, more pl~hrdbly from about 185~C to about 280~C, more ple~erdbly still from about 190~C to about 260~C, also preh,dbly from about 200~C to about 250~C.
At lower telll~Jeldluresl the soil release polymers of the subject invention p,ucesses have a solid state a",or~hous form which is readily water-soluble and is useful as a soil-release polymer, and a solid state crystalline form which is not very water-soluble and is Ll,er~h~r~ inactive as a soil-release polymer. The amor,uhous form has the L~nden~;y to spontaneously change, in time, to the crystalling form, when the a,,,ûr~,hous form is eYposed to moisture, such as a humid dt",osphere.
Even at their high molten Le",pelaLures, the subject polymers are quite viscous and are difficult to transfer from the reaction vessel in which they are typically made. It has been found that the addition of certain crystallization-reducing stabilizers to the molten polymers help reduce their viscosity. Addition of such stabilizers to the polymers helps slow any . ~

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~,dnsi~ion of the polyll~era to the crystalline form and improves dissolution of the co" ~ ,dtion in aqueous media. Such stabilizers are ~ osed in U.S. Patent 5,415,807.
The crystallization-reducing stabilizers useful in the subject processes includesulfu"~ type stabilizers, such as linear or brdnched alkylbenzene sulfonates, paramn su'' na~5~s, and other thermally-stable alkyl sulfonate vdlidlions. Plefer~d stabilizers are alkylaryl or alkyl sulfonates, p, ~f~, dbly selected from:
1) alkylaryl sulfonates s~lected from:
a) (R3)Ar-SO3M;
b) (R1 )nAr-SO3M;
c) (R2)Ar(SO3M)-O-(R2)Ar(SO3M); and d) mixtures thereof, wherein Ar is aryl, prere,dbly phenyl; R3 is about Cs-C1g alkyl, pl~.dbly on average about Cg-C13; each R1 is about C1-C4 alkyl; each R2 is about C1-C1g alkyl, prt:terably on average about C10-C1g; n is from 0 to 3, p,~f~rably 1 or 2; and M is an alkali metal (e.g. sodium or pot~ssh~rn) or tetraalkyld"""onium ion"~r~f~,rdbly sodium;
2) alkyl sulfonates including paraffln sulfor,.,t~s and other ll,er", 'Iy-s'-'le alkyl sulfonate vd,idtions, such as olefin sulfonates and beta-alkoxysulfu,, '3$, withabout 4 to about 20 carbon atoms, preA_rdbly about 8 to about 18 carbon atoms;
provided the alkyl sulfùna~es are substantially free of subnt'~nts capable of entering into esleliri~dtionllldnseat~rificdtion ~actiûns under the conditions used for forming the soil release agents; and 3) mixtures thereof.
More pr~elled stabilizers are the alkylaryl sulforiates, especially the alkylben~ene sulfonates of 1) a) and b) above. Particularly pr~f~ntd stabilizers include, for exd",, ', sodium dodecyllJen~ene sulfonate, sodium cumene sulfonate, sodium toluene sulfonate, sodium xylene sulfonate, and mixtures thereof. When higher levels of stabilizers are used, mixtures are pl~f~,.led over pure conlponenta to insure full integration into the polymer and to reduce the possibility of crystallization of the stabilizers.
To substantially affect the v;;coaity of the molten polymer, the quantity of stabilizers added to the polymer is pr~ .dbly from about 2% to about 25%, more p,~raLly from about 3% to about 16%, more p,ef~rdbly still from about 4% to about 12%, still more p(efendLly from about 5% to about 8%.
The stabilizers may be added to the soil release polymers at a convenient stage during the making of the poly."e,a, or prt~feldbly to the molten polymer after its synthesis is con,,'e' d CA 02262710 1999-02-0~

W O 98/0S747 PCTnUS97113558 U.S. Patent 5182 043 in columns 7-10 illdicdLes that the soil release poly",er~
must be suba~dll 'Iy an,o,,uhous in cl1dla~ Ler at the time they are introduced into ~q~leo~s laundering solutions. This desired a"lor~ hous form of such polyn~era will sporltaneously rear,ange into a crystalline form which is inactive as a soil release polymer in ~queous laundering solutions. This patent states that rapid cooling of the hot molten polymer and PYC4Jsion from water will maintain such pOlyl"ela in the dlllol~Jhous form. Despite the adl"on :n of the 043 patent to avoid contact of the polymer with water the plefelled prd~Lical way to achieve such quick cooling of polymer for cGIlllllerl ial scale processes is to quench the molten polymer in water.
Quenching of the molten polymer in water p,~ f~rdbly results in a concerlLIdtdd solution of the water-soluble polymer in water. In order to rapidly quench the molten polymer a means of rapidly di_?erai,lg the molten polymer in the quencl, ,9 solubon is p~efe~dLly used. Rapid dissolution of the polymer in the quenching solution can be ach ~ved by e", )y."g a means for ~ ,9 up the viscous polymer as it flows into the quenchsolution or/and vigorous mixing means in the quench solution to rapidly di;.perse the viscous polymer. P~eferd~ly a high-shear apparatus is used to aid disperaion of the molten poly",e,a and their subsequent ~d;ssclution in the quench solution.
D,ss- ~ticn of the polymer in the quench solution may take place in a batch process a semi-continuous process or a continuous process. The maximum or final concent, dbon of the polymer in the quench solution is pl~ f~ .dbly up to about 50% more pn_f~r~bly from about 25% to about 40% more pl~f~.dbly still from about 30% to about 38% still more pleferdLJly from about 34% to about 37%. The solution also co""~naes any crystallization-reducing stabilizers previously added to the polymer. Also such stabilizers can alternatively be added directly to the quench solution either before or after addition of the polymer.
D;_pe,~ion and di~s~lution of the polymer occurs better in warmer water. The hotpolymer entering the quench solution causes te",perdL-Ire 9, IL~ in the quench solution which aids dissolubon. For d; s~'ution solution lelll~,e,dture at least locally where ~i~ sc ution is occurring, is pl~f~.dL,ly from about 10~C to about 70~C more pl~h.dLly from about 25~C to about 50~C more p,_~rdLly still from about 30~C to about 40~C.
In order to minimize lldll~f~JIllldtion of the polymer from a",o,l,hous to crystalline form the quench solution is pl~f~rdbly continuously cooled during addition of the molten polymer to prevent a continuous warming of the solution. The viscosity of the quench solution i"c~eases with time but lower le",perdl-lres slow the rate of vkcosit~ i"c,ease. The average ~elllpè,d~.lre of the quench solution is prereldbly maintained at less than about 50~C more pl~f~ .dbly from about 10~C to about 40~C more preféldbly still from about 15~C
to about 30~C. Pl f~r~!e further cooling of the quench solution after d;;s~ ~tion of the polymer is complete reduces the solution temperature further; p,~f~rdl;ly to less than about CA 02262710 1999-02-0~

W O 98/05747 PCTrUS97113558 30~C, more p~f~irdbly to less than about 20~C, more plèrerdbly still to from about 0~C to about 15~C.
The quench solution of the subject invention prucesses also co""~riaes an alkylethoxy alcohol non ~n ~ surfactant which is a condensalion product of alkyl alcohol with ethylene oxide. The alkyl portion of such non:4nic surfactant is an alkyl chain which can be either linear or b,dncl,ed, saturated or unsaturated, cor~t..;., ~q from about 8 to about 22 carbon atoms, with an average of from about 12 to about 18 carbon atoms. Pl_f~,dLly the alkyl portion of such non ~nic surfactant contains an average of from about 12 to about 15 carbon atoms, also prerérdbly from about 16 to about 18 carbon atoms. rlererdbly the alkyl portion of such nor, -n ~ sulrd~;~llla are linear. Typically the non ~r, 4 sulfàl,6l~t~ useful herein are made from fatty alcohols derived from natural fat and oil sources, such as tallow, lard, coconut oil, soybean oil, palm stearin oil, palm kernel oil, etc. Mixtures of such alkyl chains are referred to herein by ,ef~r,i"g to such sources. All the fatty ",:: t es from such a source can be used, or only part (or a "cut"), of fatty moieties having the chain length and degree of saturation desired. Unsaturated i"~ es can be hydrDgen.'~ to make themmore or cor",~ le: !y saturated.
The term "tallow", as used herein, means alkyl ",o eLes derived lheréhorll~ where the alkyl mixture is typically derived from fatty acids having an approAi-"àle distribution of about 2-4% myristic, 25-35% palmitic, 20-25% stearic, 1-3% ps' " t~ 'e. 35-45% oleic, and 2-4% linoleic. Other sources with similar alkyl distributions, such as those derived from palm stearin oil and from various animal tallows and lard, are also included within the term "tallow". The bllow can also be ha.clened (i.e., hyd,ugendted) to convert all or part of the unsaturated alkyl n,~ s to saturated alkyl n,: t ~s.
The term "coconut" as used herein, means alkyl ",c:eties derived from coconut oil, where the alkyl miAture is typically derived from fatty acids having an approAilllale distribution of about 5-10% caprylic, 5-10% capric, 45-55% lauric, 15-20% myristic, 5-10%
palmitic, 1-3% stearic, 5-10% oleic, and 1-3% linoleic. Other sources with similar alkyl distributions, such as those derived from palm kernel oil and babasu oil, are included within the term "coconut".
For the subject non ~n ~ slllrdul~rlla~ the number of moles of ethoxy per mole of surfactant is, on average, from about 10 to about 100, prefelclbly from about 25 to about 80, more p,~ferdbly from about 35 to about 70, more preferdbly still from about 40 to about 60.
The non:~n ~ su,~uldnl~ useful in the subject invention p,ucesses p,efurdl,ly have a melting point above about 25~C, more p,~f~,ably from about 40~C to about 75~C, more pr~ferdbly still from about 50~C to about 60~C.
If the nonicn:~ surfactant does not begin to deco-"pose at the lelllpeldture of the molten polymer, it can be blended with the molten polymer prior to quench ,q in water. This CA 02262710 1999-02-0~

W O 98105747 PCTnUS97113558 has the advantage of helping to reduce the viscosity of the molten polymer. This can reduce or eliminate the need to add crystallization-reducing stabilizers to the molten polymer to achieve viscosity reduction. Altematively the non -nic surfactant can be di_pe,aed or/and di~.aolved in the quench water p,.if~rdbly prior to addition of the molten polymer to the quench water.
With the non ~ r ~ surfactant present the polymer quench solution exhibits a slower rate of ViSOOaity ill~lease upon aging (prior to polymer drying) than solutions without the nor :n: surfactant present. This is i",pG,Idnl because i"weasin9 solution viscosity is directly related to illrvleaaillg polymer crystallinity and inversely related to polymer soil release pe-fiJ""ance. Maintaining a low solution v;scosity is also illl~Jolldlll in the polymer drying process because it is generally desirous to spray small droplets of polymer solution in the drying apparatus. As the solution viscosity inc~eases it beco",es more difficult to control the ato",i~tion of the solution and obtain proper particle size and optimum drying pe,ru""ance.
The amount of the nonionic surfactant in the polymer quench solution expressed on a dry weight percent basis is from about 2% to about 2û% p,ef~.dbly from about 3% to about 12% more pr~ f~ably from about 4% to about 10% still more pfoF~ .dbly from about 5% to about 8%. On the same dry basis the amount of non ~n c surfactant plus crystallkation-reducing stabilizers in the quench solution is from about 6% to about 30%
pl~fu.dLly from about 8% to about 20% more p,~f rably from about 10% to about 17%
more pre'~.dLly still from about 11% to about 14%.
In order to minimize the conversion of the polymer from the a-"o,~hous form to acrystalline form the time which the polymer is retained in aqueous solution is kept to a minimum and the telllperdlure of the ~qLIeous solution is kept as low as practical. Even so for p-ucessi.,g of pl~f~ .led polylllera~ the polymers can be retained in such quench solution for several days prior to drying while retaining greater than about 75% pr~f~.dbly greater than about 90% more pl~h.dblJ greater than about 95% of the polymer in the a",o",hous form.
The quench solution is dried by a means which provides pa,li~ les of the soil release polymer which can be readily blended with dete~enl~ontaining granules to provide a granular laundry product. A highly pr~f~r,èd drying means is a spray dryer which is used in its normal manner to produce granules of the soil release polymers. The resulting granules are dried to a moisture content of less than about 3% prefel~bly less than about 2% more p,_f. .ably from 0% to about 1%.
The dried granules are pr~ferdbly passed through a large mesh screen (e.g. having about 833 micron openings or sGr"~wl ,a~ larger). Oversized product is retained on the large mesh screen collected and gently ground; then it is recycled onto the large mesh screen.

CA 02262710 1999-02-0~

W O 98/05747 PCT~US97/13558 The granules are also pr~'~rably passed over a small mesh screen (e.g. having about 246 micron openings or sGr"e.vl,dt smaller) Fine palti. las passing through the small mesh screen are plerèrably recycled into polymer solution for fepr.cessi"g (e.g. in a previous stream or bnk or in a s~bsequent batch).
The granules produced by subject p~vcesses preta,ably have a bulk density of from about 300 g/l to about 850 9/1, more p~ft~ldbly from about 400 9/l to about 800 9/1, more prere~bly still from about 500 g/l to about 700 g/l.
The granules produced by the subject processes pre~é,cbly have a particle size distribution such that at least about 95% of the polymeric granules pass through a screen having about 833 micron oper, ,gs but are at least about 90% retained on an about 246 micron-opening screen more preferably at least about 98% pass through an about 833 micron-opening screen but at least about 95% are retained on an about 246 micron-opening screen. P,aft:rdbly no more than about 1% of the granules pass through an about 75 micron-opening screen.
The resulting granules cG"",rise from about 70% to about 94% soil release polymer pr~f~.dbly from about 82% to about 91% more pr~ferably from about 85% to about 89%;
from about 2% to about 20% non :n - surfactant pre~èrably from about 3% to about 10%
more pr~ferdbly from about 5% to about 8%; from 0% to about 25% crystallization-reducing stabilizers pl~fardbly from about 3% to about 14% more pr~fe.dl,lJ from about ~% to about 10%; and less than about 3% water prefa,dbly less than about2% more ple'. .dbly from 0% to about 1%. The granules pref~ rdbly co",prise non ~ n ~ surfactant plus such stabilizers of from about 6% to about 30% more pl_f~,dbly from about 8% to about 20% more plercrdbly still from about 10% to about 17% still more pr~rably from about 11% to about 14%.
Figure 1 depicts a batch process of the subject invention. A batch of molten soil release polymer A is made and retained in polymer reaction vessel 11. Stabilizers C are optionally added to the molten polymer in vessel 11 and uniformly blended into the polymer using mixer 23.
Molten polymer A is pumped from vessel 11 using pump 16 through a di_par~er 12 which cuts the molten polymer into smaller seg",ent~ and drops these molten polymer se~,ne"La into water D contained in quench tank 13. The molten polymer is rapidly d;ssolved in the water by vigorous agitalion with mixer 22. ~on :nic surfactant B can optionally be added to molten polymer A in vessel 11 if the surfactant is stable at the molten polymer ~e",perdl,ure or oLl,elu ae is added to the water D in quench tank 13 prior to pumping of the molten polymer into tank 13. During the addition of the molten polymer to quench tank 13 pump 17 continuously cycles the aqueous polymer solution through heat ex. I,anger 19 and open valve 20 back into quench tank 13 in order to retain the average CA 02262710 1999-02-0~

te",pe,dL.Ire of the aqueous polymer solution in tank 13 p,erérdbly below about 35~C. When pumping of the molten polymer from vessel 11 into quench bnk 13 has been con,r' ted, circulation and cooling of the solution is continued until its lelllpeldl-Jre is pr~f~rdbly below about 20~C. When the desired temperature for the aqueous polymer solution has been reached, valve 20 is closed and valve 21 is opened so that the aqueous polymer solution E
flows into storage tank 14.
Aqueous polymer solution E is pumped from storage tank 14 by pump 18 into spray dryer 15 where most of the water is removed from the polymer solution and polymer granules F are produced, the granules flowing out of spray dryer 15 to screer, ,9, grinding of oversize pa, li~,les if necessary, and storage. Fines can be ~ le~.
Figure 2 depicts a semi-continuous process of the subject invention. Molten polymer M is made and retained in polymer reaction vessel 31. Stabilizers P are optionally added to the molten polymer and uniformly blended therein using mixer 41.
Molten polymer M is pumped from vessel 31 using pump 36 into a section of pipe housing high-shear pipeline mixer 32 where it is rapidly di_per~ed into an aqueous polymer solution. Water Q is also fed into the pipeline mixer. N~n zn ~ surfactant N can optionally be diaper~ed in the molten polymer M in vessel 31, if the surfactant is stable at the le",pe,dture of the molten polymer, or .~I,en~;sc it is added to the stream of water Q, thus entering the high-shear pipeline mixer with the water. A portion of the aqueous polymer solution exiting high-shear pipeline mixer 32 is recycled to the mixer through heat eAcl)anger 38 which cools the solution. The remainder of the aqweous polymer solution R flows through heatexchanger 39 for cooling and into storage tank 34. ~ f~r,ed le""~e,dtures for these solution streams are as provided for the cor,esponding solution streams in the batch process above.
Aqueous polymer solution R is pumped from storage tank 34 to spray dryer 35 where most of the water is removed and polymer granules S are produced, the granules flowing out of spray dryer 35 to screening, grinding of oversize pa,ti-,les if necessary, and storage. Fines can be recycled.
The h'l~ .~ ;"g is a non-limiting exd",, 'o of the subject invention process.

T

CA 02262710 1999-02-0~

ExamPle Polymer L her~i. ,above is synthesized in a reaction vessel according to the formulation and general procedure ~i-,ulosed in Example V of U.S. Patent 5,415,807 (except for the modest difre~ence of EG/PG which requires alteration of the amounts of ethylene glycol and propylene glycol ",onG",ers). The ester c~",l.osition is made from sodium 2-(2-hydroxyethoxy)-ell,anesulfonate dimethyl te~ephll~alate dimethyl 5-sulfoisophtl,aldt~
sodium salt ethylene glycol and propylene glycol. To improve fluidity and solubility of the finished polymer an equal weight blend of 3 stabilizers. sodium dodecylbenzene sulfonate sodium toluene sulfonate and sodium cumene sulfonate are added to the polymer melt.
The amount of mixed sbbilizer is 6% by weight of the polymer This 6% mixed stabilizer ,epldces the 12% linear sodium dodecyl ber,~enesulfonate st~ er in Example V of U.S.
5,415,807. The lei"pe,dl.lre of the poly",ert~bilizer melt in the vessel at the conclusion of the synthesis is about 200~C.
A quench solution of water with alkylethoxy alcohol nonionic surfactant (C12-15l 50 ethoxy per mole) pre-d;ssolved in the water is prepd,ed at a ~e",pe,dlure of 35~C. The Polymer Ustabilizer melt is quickly emptied from the vessel in a molten state into the quench solution with aJi' 'kn forming a single phase solution in about 100 minutes. Thetemperature of the solution is maintained at 35~C. The resulting aqueous solution contains 37% by weight of the poly",e,/~labilizer and the non;on ~ surfactant is present at a level of 6% by weight of the polyl"er/~labilizer blend (appruki",alely 2.2% by weight of the total solution).
Following the ~ 'ution of the polymer in the aqueous quench solution the finished solubilized polymer solution is cooled to 10~C and is held at that lelllpe,dl.lre until drying.
The cool solution containing the non:-n - surfactant may be held for several days prior to drying. The cool solubilized polymer solution is dried in a spray dryer to remove water and form the finished granular soil release polymer cGr"position containing 1% moisture.
Oversized and l-"de,~i~ed pa~ les are removed by scféen ,9. The remaining granules have a bulk density of 650 9/l, 99% pass through a screen with 833 micron openings 98%
are retained on a screen with 246 micron openings and less than 1% pass through a screen with 75 micron openings. The granules are suitable for adi"iking into deter~ent formulations.
Samples of the finished soil release polymer are tested for soil release pe,h,r",ance as follows.
Polyester and polyc~ r/cullun blend fabrics of several types are pret,ealed in asldndar~ wash cycle with dcteryent wash solutions containing the soil release polymer (at a concenl,dlion of from 0.1% to 1.0% by weight of the detergent formulation). This allows the soil release polymer to "lay down" onto the fabric surface. The dried ~,el~ealed fabrics are CA 02262710 1999-02-0~

W O 98/OS747 1 PCT~US97/135S8 then soiled with 5 drops of a sldndard greasy/oily/dirty stain ("dirty motor oil" from the crankcase of an internal combustion engine) and the stain allowed to age a minimum of 4 hours. The stained fabrics are then washed in a sldnddld wash cycle with dett:,ye"l wash solutions (without the soil release polymer) and dried.
The stains remaining on these test fabrics are co" ,~a(ed to those on control fabrics that were stained and washed the same but were p,~ d~ed with a wash without soil release polymer. A series of measu,~",er,la are made with a Hunter Mini-Scan Speul,uphoto,,,al~r unit Model MS/S 4500L; L a and b readings in the i"""edidle area of the stain are taken on the test and control fabrics. Three (3) sets of L a and b data are recorded for the fabric swatches in the "clean" (initial) "soiled" and "v,~._heu conditions. The data is ,~cordad as Lc ac and bc (clean reading); Ls aS and b5 (soiled reading); and Lw aw and bw (washed reading).
Analysis and co",pd,ison of the color data for these three (-~i ,gs for the test and control fabrics show enhanced soil removal pe,f~,""ance for fabrics treated with the soil release polymer.
While particular embodiments of the subject invention p,ucesses have been desc, ibed it would be obvious to those skilled in the art that various changes and ~lloll;r~ ;ons to the subject invention p,.cesses can be made without depa,~i.,g from the spirit and scope of the invention. It is i"l~nded to cover in the appended claims all such ",o.l:flcd~ions that are within the scope of this invention.

Claims

WHAT IS CLAIMED IS:

1. A process for making granular compositions comprising soil release polymers, the polymers comprising at least 10% of substantially linear esters having a backbone; the esters being uncapped or end-capped on one or both ends of the backbone, the end-capping units preferably being selected from sulfoaroyl units, sulfonated poly-ethoxy/propoxy groups which are connected to the backbone by an ester linkage, ethoxylated or propoxylated phenolsulfonate units, and modified poly(oxyethylene)oxy monoalkyl/ether units; the esters comprising in their backbones oxyalkyleneoxy units, preferably a mixture of oxyethyleneoxy units with oxy-1,2-propyleneoxy units in a ratio of from 1:2 to 4:1, and hydrophobic aryldicarbonyl units; the esters having a molecular weight of from 500 to 20,000; the polymers if in solid state having the tendency when exposed to moisture to spontaneously rearrange from an amorphous form which is readily soluble in water to a crystalline form which is relatively insoluble in water; the process comprising the following steps:
a) taking the soil release polymers, in which are dispersed from 0% to 25%, preferably from 3% to 16%, alkylaryl or alkyl sulfonate crystallization-reducingstabilizers, in molten state at a temperature of at least 180°C, and rapidly dissolving the molten polymers in water, forming an aqueous polymer solution having a polymer concentration of up to 50%, the average temperature of the solution being maintained below 50°C;
b) dispersing a nonionic surfactant in the molten polymers or preferably in the water prior to step a), the surfactant being an alkylethoxy alcohol nonionic surfactant which is a condensation product of alkylalcohol and ethylene oxide, the alkyl portion being linear or branched, saturated or unsaturated, having from 8 to 22 carbon atoms, there being an average of from 10 to 100 moles ethoxy per mole surfactant, the nonionic surfactant being from 2% to 20% of the aqueous polymer solution, on a dry weight basis; and c) drying the aqueous polymer solution of a) and b), thereby producing a granular composition having a water content of less than 3%.

2. The process of Claim 1 wherein:
a) the polymer solution formed comprises from 25% to 40%, preferably from 30% to 38%, said polymer; the dissolution of the molten polymer preferably being carried out at an average temperature of the solution from 15°C to 40°C;

b) the solution comprises on a dry weight basis: from 3% to 12%, preferably from 5% to 8%, said nonionic surfactant, the alkyl portion having from 12 to 18 carbon atoms, the surfactant having from 25 to 80, preferably from 40 to 60, moles ethylene oxide per mole surfactant; from 3% to 16%, preferably from 5% to 8%, said alkylaryl stabilizers; and from 8% to 20%, preferably from 10% to 14%, said nonionic surfactant plus said stabilizers;
c) spray drying is used to dry the solution resulting from a) and b), whereby the composition produced is granules having a water content of less than 2%, preferably less than 1%, and a bulk density of from 300 g/l to 850 g/l, preferably from 500 to 700 9/l.

3. The process of Claim 1 or 2 wherein the polymer comprises at least 25%
polymer esters having, per mole of the esters, i) from 1 to 2, preferably 2, moles of sulfobenzoyl end-capping units of the formula (MO3S)(C6H4)C(O)--, preferably in ortho or meta configuration, wherein M is a salt-forming cation, preferably sodium; or from 1 to 2, preferably 2, moles of sulfonated poly-ethoxy/propoxy end-capping units of the formula (MO3S)(CH2)m(CH2CH2O)(R1O)n--, wherein M is a salt-forming cation, preferably sodium; m is 0 or 1, preferably 0; R1 is ethylene or propylene or a mixture thereof, preferably ethylene; and n is from 0 to 4;
ii) from 0.5 to 66, preferably from 1 to 22, moles of backbone units selected from:
a) a mixture of oxyethyleneoxy and oxy-1,2-propyleneoxy units, wherein the units are present in an oxyethyleneoxy to oxy-1, 2-propyleneoxy mole ratio of from 4:1 to 1:2, preferably from 3:1 to 1:1; and b) a mixture of a) with poly(oxyethylene)oxy units wherein the poly(oxyethylene)oxy units have a degree of polymerization of from 2 to 4; provided that when the poly(oxyethylene)oxy units have a degree of polymerization of 2, the mole ratio of poly(oxyethylene)oxy units to total group ii) units ranges from 0:1 to 0.33:1; and when the poly(oxyethylene)oxy units have a degree of polymerization of 3, the mole ratio of poly(oxyethylene)oxy units to total group ii) units ranges from 0:1 to 0.22:1; and when the poly(oxyethylene)oxy units have a degree of polymerization of 4, the mole ratio of poly(oxyethylene)oxy units to total group ii) units ranges from 0:1 to 0.14:1;
iii) from 1 to 40, preferably from 2 to 24, moles of backbone terephthaloyl units; and iv) from 0 to 30, preferably 0.5 to 9, moles of backbone anionic 5-sulfoisophthaloyl units of the formula -(O)C(C6H3)(SO3M)C(O)-,wherein M is a salt forming cation, preferably sodium.

4. The process of Claim 3 wherein the polymers comprises at least 50% of esters having the empirical formula (CAP)X(EG/PG)y(T)z; wherein (CAP) represents the sodium salt form of the sulfobenzoyl end-capping units from (i); (EG/PG) represents oxyethyleneoxy and oxy-1,2-propyleneoxy units from (ii); (T) represents terephthaloyl units from (iii); x is from 1 to 2, preferably 2; y is from 2.25 to 9, preferably from 2.5 to 7; z is from 1.25 to 8, preferably from 1.5 to6; wherein x, y and z represent the average number of moles of the corresponding units per mole of the ester; wherein EG/PG is from 1:1 to 3:1 preferably from 1.3:1 to 2.5:1; and wherein the ester molecules have molecular weights of from 600 to 2,000, preferably from 800 to 1500.

5. The process of Claim 3 wherein the polymers comprise at least 50% of esters having the empirical formula (CAP)'d(EG/PG)'e(T)'f; wherein (CAP)' represent the sodium salt form of sulfonated poly-ethoxy/propoxy end-capping units from (i); (EG/PG)' represents oxyethyleneoxy, oxy-1,2-propyleneoxy units, and poly(oxyethylene)oxy units from (ii); (T)' represent terephthaloyl units from (iii); d is from 1 to 2, preferably 2; e is from 0.5 to 7, preferably from 1 to 6; f is from 1.5 to 7, preferably from 2 to 6; wherein d, eand f represent the average number of moles of the corresponding units per mole of the ester; wherein EG/PG is from 1:1 to 3:1; and wherein the ester molecules have molecular weights of from 500 to 2,500, preferably from 800 to 1500.

6. The process of Claim 3 wherein the polymers comprise at least 50% of esters having the empirical formula (CAP)"r(EG/PG)"s(T)"t(SlP)q; wherein (CAP)"
represent end-capping units from (i), preferably said sulfonated polyethoxy/propoxy end-capping units; (EG/PG)" represents oxyethyleneoxy, oxy-1,2-propyleneoxy and poly(oxyethylene)oxy units from (ii); (T)" represent terephthaloyl units from (iii); (SIP) represents 5-sulfoisophthaloyl units from (iv); r is from 1 to 2 preferably 2; s is from 0.5 to 66 preferably from 3 to 18; t is from 1 to 40 preferably from 3 to 15; q is from 0.05 to 26 preferably from 1 to 4; wherein r, s, t and q represent the average number of moles of the corresponding units per mole of the ester; wherein EG/PG is from 1:1 to 1:3 preferably from 1.3:1 to 2.3:1; and wherein the ester molecules have molecular weights of from 500 to 20 000 preferably from 800 to 5000.

7. The process of any of Claims 1-6 wherein a high-shear apparatus is preferably used to aid dispersion of the molten polymers and their subsequent dissolution; and wherein the solution resulting from a) and b) comprises on a dry weight basis from 8% to 15% said nonionic surfactant plus said stabilizers; the nonionic surfactant having an alkyl with an average of from 12 to 16 carbon atoms from 35 to 70 moles of ethoxy per mole of surfactant and a melting point of from 40°C to 70°C; the stabilizers being selected from alkylbenzene sulfonates having one alkyl with an average of from 9 to 13 carbon atoms alkylbenzene sulfonates having one or two alkyl with an average of from 1 to 4 carbon atoms and mixtures thereof.

8. Soil release polymer granules comprising.
(a) from 70% to 94% preferably from 82% to 91% polymers comprising at least 25% polymer esters having per mole of esters i) from 1 to 2 moles of sulfobenzoyl end-capping units of the formula (MO3S)(C6H4)C(O)- preferably in ortho or meta configuration wherein M is a salt-forming cation preferably sodium; or from 1 to 2 preferably 2 moles of sulfonated poly-ethoxy/propoxy end-capping units of the formula (MO3S)(CH2)m(CH2CH2O)(R'O)n--, wherein M is a salt-forming cation preferably sodium; m is 0 or 1 preferably 0; R' is ethylene or propylene or a mixture thereof preferably ethylene; and n is from 0 to 4;
ii) from 0.5 to 66 preferably from 1 to 22 moles of backbone units selected from:
a) a mixture of oxyethyleneoxy and oxy-1 2-propyleneoxy units wherein the units are present in an oxyethyleneoxy to oxy-1, 2-propyleneoxy mole ratio of from 4:1 to 1:2 preferably 3:1 to 1:1; and b) a mixture of a) with poly(oxyethylene)oxy units wherein the poly(oxyethylene)oxy units have a degree of polymerization of from 2 to 4; provided that when the poly(oxyethylene)oxy units have a degree of polymerization of 2, the mole ratio of poly(oxyethylene)oxy units to total group ii) units ranges from 0:1 to 0.33:1; and when the poly(oxyethylene)oxy units have a degree of polymerization of 3, the mole ratio of poly(oxyethylene)oxy units to total group ii) units ranges from 0:1 to 0.22:1; and when the poly(oxyethylene)oxy units have a degree of polymerization of 4, the mole ratio of poly(oxyethylene)oxy units to total group ii) units ranges from 0:1 to 0.14:1;
iii) from 1 to 40, preferably from 2 to 24, moles of backbone terephthaloyl units; and iv) from 0 to 30, preferably from 0.5 to 9, moles of backbone anionic 5-sulfoisophthaloyl units of the formula -(O)C(C6H3)(SO3M)C(O)-, wherein M is a salt forming cation, preferably sodium;
(b) from 3% to 12%, preferably from 5% to 8%, alkylethoxy alcohol nonionic surfactant, the alkyl portion being linear or branched, saturated or unsaturated, having an average of from 12 to 18, preferably from 12 to 16, carbon atoms, there being from 25 to 100, preferably from 35 to 70, moles ethoxy per mole surfactant, the surfactant preferably having a melting point of 40°C to 70°C;
(c) from 3% to 14%, preferably from 5% to 10%, alkylaryl or alkyl sulfonate crystallization-reducing stabilizers; the stabilizers preferably being selected from alkylbenzene sulfonates having one alkyl with an average of from 9 to 13 carbon atoms, alkylbenzene sulfonates having one or two alkyl with an average of from 1 to 4 carbon atoms, and mixtures thereof; and (d) no more than 2%, preferably no more than 1%, water;
the granules having a bulk density of from 300 g/l to 850 g/l, preferably from 500 g/l to 700 g/l; and the granules being of a size such that at least 95%, preferably at least 98%, by weight pass through a 833 micron-opening screen, at least 90%, preferably at least 95%, are retained on a 246 micron-opening screen, and preferably no more than 1% pass through a 75 micron-opening screen.

9. The granules of Claim 8 wherein the polymers comprises at least 50% of esters selected from those having the empirical formulas:
(a) (CAP)X(EG/PG)y(T)z; wherein (CAP) represents the sodium salt form of the sulfobenzoyl end-capping units from (i); (EG/PG) represents oxyethyleneoxy and oxy-1,2-propyleneoxy units from (ii); (T) represents terephthaloyl units from (iii); x is from 1 to 2; y is from 2.25 to 9; z is from 1.25 to 8; wherein x, y and z represent the average number of moles of the corresponding units per mole of the ester; wherein EG/PG
is from 1:1 to 3:1; and wherein the ester molecules have molecular weights of from 600 to 2,000; and (b) (CAP)'d(EG/PG)'e(T)'f; wherein (CAP)' represents the sodium salt form of sulfonated poly-ethoxy/propoxy end-capping units from (i); (EG/PG)' represents oxyethyleneoxy, oxy-1,2-propyleneoxy units, and poly(oxyethylene)oxy units from (ii); (T)' represents terephthaloyl units from (iii); d is from 1 to 2; e is from 0.5 to 7; f is from 1.5 to 7; wherein d,e and f represent the average number of moles of the corresponding units per mole of the ester; wherein EG/PG is from 1:1 to 3:1; and wherein the ester molecules have molecular weights of from 500 to 2,500.

10. The granules of Claim 8 w herein the ester has the empirical formula (CAP)'r(EG/PG)"S(T)"t(SlP)q, wherein (CAP)" represents end-capping units from (i), preferably sulfonated poly-ethoxylpropoxy end-capping units;
(EG/PG)" represents oxyethyleneoxy, oxy-1,2-propyleneoxy and poly(oxyethylene)oxy units from (ii); (T)" represents telephthaloyl units from (iii); (SIP) represents 5-sulfoisophthaloyl units from (iv); r is from 1 to 2, preferably 2; s is from 0.5 to 66, preferably from 3 to 18; t is from 1 to 40, preferably from 3 to 15; q is from 0.05 to 26, preferably from 1 to 4; wherein r, s, t and q represent the average number of moles of the corresponding units per mole of the ester; wherein EG/PG is from 1:1 to 1:3, preferably from 1.3:1 to 2.3:1; and wherein the ester molecules have molecular weights of from 500 to 20,000, preferably from 800 to 5000. EG/PG is from 1.3:1 to 2.3:1, and the ester molecules have molecular weights of from 800 to 5000.