CA2211412A1 - Dry cleaning system using densified carbon dioxide and a surfactant adjunct - Google Patents

Abstract

A system for dry cleaning soils from fabrics comprising densified carbon dioxide and a surfactant in the densified CO2. The surfactant has a polysiloxane, a branched polyalkylene oxide and a halocarbon group which is a functional CO2-philic moiety connected to a CO2-phobic functional moiety. The surfactant either exhibits an HLB of less than 15 or has a ratio of siloxyl to substituted siloxyl groups of greater than 0.5:1.

Description

W 096/27704 PCT/~,GI~Cell DRY ~T.~NTNG ~Y~l~ USTNG D~NSTFT~n ~R~ nT~T
~nn A sn~FACT~rr An TInNCT

F;~l~ o~ ~he Tnv~t; ~n The invention pertains to a dry cleaning system utilizing densified carbon dioxide and a surfactant adjunct. The invention also pertains to a method of dry cleaning ~abrics 10 utilising densified carbon dioxide and a surfactant.
adjunct.

Rz~c!k~rolln~ of l-he Tnv~l~ n Densified, particularly supercritical fluid, carbon dioxide 15 has been suggested as an alternative to halo-carbon solvents used in conventional dry cleaning. For example, a dry cleaning system in which chilled liquid carbon dioxide is used to extract soils from fabrics is described in U.S.
4,012,194 issued to Maffei on March 15, 1977.
Supercritical fluid carbon dioxide provides a nontoxic, inexpensive, recyclable and environmentally acceptable solvent to remove soils in the dry cleaning process. The solvent has been shown to be effective in removing nonpolar 25 stains such as motor oil, when combined with a viscous cleaning solvent, particularly mineral oil or petrolatum as described in US S/N 715,299, filed June 14, 1991, assigned to The Clorox Company and corresponding to EP 518,653.
Supercritical fluid carbon dioxide has been combined with 30 other components, such as a source of hydrogen peroxide and an organic bleach activator as described in US S/N 754,809, filed September 4, 1991 and owned by The Clorox Company, corresponding to EP 530,949.

35 The solvent power of densified carbon dioxide is low relative to ordinary liquid solvents and the carbon dioxide solvent alone is less effective on hydrophilic stains such as grape juice, coffee and tea and on compound hydrophobic stains such as lipstick and red candle wax, unless surfactants and solvent modifiers are added.

A cleaning system combining particular anionic or nonionic surface active agents with supercritical fluid CO2 is described in DE 39 04 514 Al published August 23, 1990.
These anionic and nonionic agents, such as alkylbenzene 10 sulfates and sulfonates, ethoxylated alkyl phenols and ethoxylated fatty alcohols, were particularly effective when combined with a relatively large amount of water (greater than or equal to 4~). The patented system appears to combine the detergency mechanism of conventional agents 15 with the solvent power of supercritical fluid carbon dioxide.

It has been observed that most commercially available surfactants have little solubility in supercritical fluid 20 carbon dioxide as described in Consani, K.A., J. Sup .
Fluids, 1990 (3), pages 51-65. Moreover, it has been observed that surfactants soluble in supercritical fluid carbon dioxide become insoluble upon the addition of water.
No evidence for the formation of water-containing reversed 25 micelles with the surfactants was found. Consani supra.

Thus, the dry cleaning systems known in the art have merely combined cleaning agents with various viscosities and polarities with supercritical fluid CO2 generally with high 30 amounts of water as a cosolvent. The actives clean soils as in conventional washing without any synergistic effect with the CO2 solvent.

The formation of water-containing reversed micelles is 35 believed to be critical for the solubility and removal of hydrophilic stains. Studies of the interaction of , . . _ . _ . . . _ . . .. . . _ . . . . .. . . _ _ _ _ _ _ W O 96/~7704 ~ ; ~CT~hY~
~ .

sur~actants in supercritical carbon dioxide with water, cosurfactants and cosolvents led to the conclusion that most commercially available sur~actants are not designed ~or the formation of reversed micelles in supercritical 5 carbon dioxide as described in McFann, G., Dissertation, University of Texas at Austin, pp. 216-306, 1993.
Therefore, the problem of developing an effective dry cleaning system utilizing supercritical ~luid carbon dioxide to clean a variety of consumer soils on fabrics has 10 remained unsolved until the present invention.
- :, Sl1mm~ry of ~he Inv~nt;on It is therefore an~?h~l~r~ of the present invention to provide a dry cleaning system utilizing an environmentally 15 safe, nonpolar solvent ~Irh ~53 densified carbon dioxide, which effectively removes a variety of soils on fabrics.
q,~
Another ~bjcc~ is the design of e~ective surfactants for use in supercritical fluid carbon dioxide.
Another ~b3~c~ of the invention is to provide a dry 20 cleaning system o~ solvent, sur~actant, enzyme and bleach for the total cleaning o~ fabrics using densified/supercritical fluid carbon dioxide that gives results equivalent to the cleaning demonstrated by .-- ~ ~
-~- conventional dry cleaning solvents.
In one aspect of the present invention, the dry cleaning system used for cleaning a variety o~ soiled fabrics comprises densified carbon dioxide and C~ou~ 0.001~ to C ~ 5~ of a surfactant in supercritical fluid carbon 30 dioxide. The surfactant has a supercritical ~luid C02-philic functional moiety connected to a supercritical fluid C02-phobic functional moiety. Preferred C0z-philic moieties o~ the surfactant include halocarbons such as fluorocarbons, chlorocarbons and mixed fluoro-35 chlorocarbo~s, polysiloxanes, and branched polyal]cyleneoxides. The C02-phobic groups for the surfactant contain hMEN~E~ SHEET

W O 96127704 ;~ ~ ', ~ T~s~

preferably polyalkylene oxides, carboxylates, C130 alkyl sulfonates, carbohydrates, glycerates, phosphates, sulfates and Cl30 hydrocarbons.

5 The dry cleaning system may also be designed to include a modifier, such as water, or an organic solvent up to only about 5~ by volume; enzymes up to about 10 wt.~ and a bleaching agent such as a peracid.

10 In a second aspect o~ the invention, a method for dry cleaning a variety of soiled fabrics is provided wherein a ~;
selected surfactant and optionally a modifier, an enzyme, bleaching agent or mixtures thereof are combined and the cloth is contacted with the mixture. Densified carbon~5 dioxide is introduce~ into a cl~aning ves~el which is then .C 4-~3x1~3K~J, ~ ~-4_ 10~'') pressurlzed ~rom about~700 psi~ to a~out~ ,000 psi~ and heated to a range of about 20~C to about 100~C. Fresh densified carbon dioxide is used to flush the cleaning vessel.
Rrief DescriDtion of the Drawing Figure l is a diagrammatic flow chart o~ the supercritical fluid carbon dioxide dry cleaning process according to the invention. ~-~~
Det~;le~ Descr;~t;o~ of Preferre~ ~mho~;m~nts The invention provides a dry cleaning system which replaces conventional solvents with densi~ied carbon dioxide in combination with selected cleaning surfactants.
30 Optionally, modifiers, enzymes, bleaching agents and mixtures thereof are combined with the solvent and surfactant to provide a total cleaning system.

For purposes of the invention, the following definitions 35 are used:

'4P~/\J~ED S~lEEr - W O 96 m 704 ' ~ 7 ' ' ' ~C~ o~a@8 '' 7 "Densified carbon dioxide" means carbon~dloO~d~$ ln a gas form which is placed under pressures excee~lng abo ~ (700 psi) at about 20~C.
"Supercritical fluid carbon dioxide" means carbon dioxide 5 which is at~or above the critical temperature of 31~C and a cr1tlcal ~LesJsure of~71 atmospheres) and which cannot be condensed into a liquid phase despite the addition of ~urther pressure.

10 The term "densified carbon dioxide-philic" in reference to surfactants ~Zn- wherein n and n~ are each independently l to 50, means that the functional group, Rn~ is soluble in ~ 3 ~S ~ -6-~-q~ ~J~
carbon aloxide a~ pressures a~500-10,000 pSl and ~emperatures of 0-100~C to greater than 10 weight percent.
15 Preferably n and n are each independently 1-35. Such ~unctional groups (Rn~) include halocarbons, polysiloxanes and branched polyalkylene oxides.

The term "densified carbon dioxide-phobic" in re~erence to 20 surfactants, RnZn, means that Zn-~ will have a solubility in carbon dioxl~el~. ~Fessures ofj(500-10,000 psi)and temperatures of 0-100~C of less than 10 weight percent.
The functional groups in Zn-~ include carboxylic acids, ~-~ phosphatyl esters, hydroxys, Cl30 alkyls or alkenyls, 25 polyalkylene oxides, branched polyalkylene oxides, carboxylates, Cl30 alkyl sulfonates, phosphates, glycerates, carbohydrates, nitrates, substituted or unsubstituted aryls and sulfates.

30 The hydrocarbon and halocarbon containing surfactants (i.e., ~Zn-, containing the C02-philic functional group, Rn~~ and the CO2-phobic group, Z~,-) will have an HLB of less than 15, preferably less than 13 and most preferably less than 12.

A~,lc~cD Sh'EET

W 096/27704 PCT/~r~G

The polymeric siloxane containing surfactants, RT~Zn,r also designated MD"D*"M, with M representing trimethylsiloxyl end groups, Dx as a dimethyl~iloxyl backbone (CO2-philic functional group) and D*y as one or more substituted 5 methylsiloxyl groups substituted with CO2~phobic R or R' groups as described in the Detailed Description Section will have a DXD*y ratio of greater than 0.5:1, preferably greater than 0.7:1 and most preferably greater than 1:1.

10 The term "nonpolar stains~ refers to those which are at least partially made by nonpolar organic compounds such as oily soils, sebum and the like.

The term '~polar stains" is interchangeable with the term 15 "hydrophilic stains" and refers to stains such as grape juice, coffee and tea.

The term "compound hydrophobic stains" refers to stains such as lipstick and red candle wax.
The term "particulate soils" means soils containing insoluble solid components such as silicates, carbon black, etc.

25 Densified carbon dioxide, preferably supercritical fluid carbon dioxide, is used in the inventive dry cleaning system. It is noted that other densified molecules having supercritical properties may also be employed alone or in mixture. These molecules include methane, ethane, propane, 30 ammonia, butane, n-pentane, n-hexane, cyclohexane, n-heptane, ethylene, propylene, methanol, ethanol, isopropanol, benzene, toluene, p-xylene, sulfur dioxide, chlorotrifluoromethane, trichlorofluoromethane, perfluoropropane, chlorodifluoromethane, sulfur 35 hexafluoride and nitrous oxide.

W O 96~7704 ' ''- . .''~CT~EP~6/~

During the dry cleaning process, the temperature range is between about 20~C and about 100~C, preferably 20~C to 60~C
and most preferably 30~C to about 60~C. T~e pressure . L ~-~3~o3K~;J ~c~ qx103~J
5 dUrlng ~ ~anlng lS labou~(700 ~pSl~ ~O a30Ut~10~000 pS~

5 pre~erablyi~800 ps~ o c~OU~_/,000 pSi) and most preferably S~XI~(80o psi) to abou ~6,00~ psi~

A "substituted methylsiloxyl group" is a methylsiloxyl group substituted with a CO2-phobic group R or R . R or R
10 are each represented in the following formula:
= :
~ ~CH2) a (C6H4) b (A) d-- [ (L)e(A')~]n~ ')gZ(G)h wherein a is 1-30, b is o-l, C6~4 is substituted or 15 unsubstituted with a C1_1Q alkyl or alkenyl and A, d, L, e, A-, F, n L , g, Z, G and h are defined below, and mixtures o~ R and R .

A "substituted aryl" is an aryl substituted with a Cl30 20 alkyl, alkenyl or hydroxyl, preferably a Cl20 alkyl or alkenyl.

A "substituted carbohydrate~ is a carbohydrate substituted with a Cl10 alkyl or alkenyl, preferably a Cls alkyl.
25 The terms ~'polyalkylene oxide", ~alkyl" and ~alkenyl~ each contain a carbon chain which may be either straight or branched unless otherwise stated.

S-~f~c~nt Adjl~nct 30 A surfactant which is effective for use in a densified carbon dioxide dry cleaning system requires the combination of densified carbon dioxide-philic functional groups with densified carbon dioxide-phobic functional groups (see definitions above). The resulting compound may form 35 re~ersed micelles with the CO2-philic functional groups extending into a continuous phase and the COz-phcbic A;~ c,~t ~ ET

. CA 02211412 1997-07-24 W O 96127704 . ~ ~C.T~o'~

~unctional groups directed toward the center of the micelle.
The surfactant is present in an amount o~ ~rom 0.001 to 10 wt.~, preferably 0.01 to 5 wt.~.
The CO2-philic moieties o~ the sur~actants are groups exhibiting low Hildebrand solubility parameters, as described in Grant, D. J. W. et al. "Solubility sehavior of Organic Compounds", Techniques of Chemistry Series, J.
10 Wiley & Sons, NY (lg90) pp. 46-55 which describes the Hildebrand solubility equation, herein incorporated by re~erence. These CO2-philic moieties also exhibit low polarizability and some electron donating capability allowing them to be solubilized easily in densi~ied ~luid 15 carbon dioxide.

As defined above the CO2-philic functional groups are soluble in densified carbon dioxide to greater than 10 ~3 ~s~6~ q wei ~t percent, pre~erably greater than 15 weight percent, ~u ~L ~Le~ssures o~(500-10,000 psi) and temperatures of 0-100~C.

Pre~erred densi~ied CO2-philic functional groups include halocarbons (such as fluoro-, chloro- and fluoro-chlorocarbons), polysiloxanes and branched polyalkylene 25 oxides.

The CO2-phobic portion o~ the surfactant molecule is obtained either by a hydrophilic or a hydrophobic functional group which is less than 10 weight percent 30 soluble in densified CO2, preferably less than 5 wt. ~, at ( 3-4 5 h~ G~-9~l~3 ~ ~ ~
a ~ressures of~500-10,000 psi)and temperatures of 0-100~C.
Examples of moieties contained in the CO2-phobic groups include polyalkylene oxides, carboxylates, branched acrylate esters, ~1-30 hydrocarbons, aryls which are 35 unsubstituted or substituted, sulfonates, glycerates, phosphates, sulfates and carbohydrates. Especially W O 96127704 PCT/~r,~i(J0311 preferred CO2-phobic groups include C220 straight chain or branched alkyls, polyal]~ylene oxides, glycerates, carboxylates, phosphates, sulfates and carbohydrates.

5 The CO2-philic and CO2-phobic groups may be directly connected or linked together via a linkage group. Such groups include ester, keto, ether, amide, amlne, thio, alkyl, alkenyl, fluoroalkyl or fluoroalkenyl.

10 Surfactants which are useful in the invention may be selected from four groups of compounds. The first group o~
compounds has the following formula:
[(CX3(CX2)a(CH2)b)c(A)d- [(L)e- (Al)~]n- (L~)g]oZ(G)h (I) wherein X is F, Cl, Br, I and mixtures thereof, preferably F and Cl;
a is 1 - 30, preferably 1-25, most preferably 5-20;
b is 0 - 5, preferably 0 - 3;
c is 1 - 5, preferably 1 - 3;
A and A' are each independently a linking moiety representing an ester, a keto, an ether, a thio, an amido, an amino, a Cl4 fluoroalkyl, a Cl4 fluoroalkenyl, a branched or straight chain polyalkylene oxide, a phosphato, a sulfonyl, a sulfate, an ammonium and mixtures thereof;
d is 0 or 1;
L and L' are each independently a Cl30 straight ch~;ned or branched alkyl or alkenyl or an aryl which is unsubstituted or substituted and mixtures thereof;
e is 0-3;
f is 0 or 1;
n is 0-10, preferably 0-5, most preferably 0-3;
g is 0-3;
o is 0-5, preferably 0-3;
Z is a hydrogen, a carboxylic acid, a hydroxy, a 35 phosphato, a phosphato ester, a sulfonyl, a sulfonate, a sulfate, a branched or straight-chained polyalkylene oxide, a nitryl, a glyceryl, an aryl unsubstituted or substituted with a Cl30 alkyl or alkenyl, (pre~erably C125 alkyl), a carbohydrate unsubstituted or substituted with. a Cl10 alkyl or alkenyl (preferably a Cls alkyl) or an ammonium;
5 G is an anion or cation such as H+, Na+, ~i+, K+, NH4+ Ca+2, Mg+2; Cl-, Br~, I-, mesylate, or tosylatei and h is 0-3, preferably 0-2.

- Preferred compounds within the scope of the formula I
10 include those having linking moieties A and A which are each independently an ester, an ether, a thio, a polyalkylene oxide, an amido, an ammonium and mixtures thereof;
L and L are each independently a C125 straight chain 15 or branched alkyl or unsubstituted aryl; and Z is a hydrogen, carboxylic acid, hydroxyl, a phosphato, a sulfonyl, a sulfate, an ~mmo~;um, a polyalkylene oxide, or a carbohydrate, preferably unsubstituted. G groups which are preferred include H+, Li+, Na+, NH+4, Cl-, ~r~ and 20 tosylate.

Most preferred compounds within the scope of formula I
include those compounds wherein A and A' are each independently an ester, ether, an amido, a polyoxyalkylene 25 oxide and mixtures thereof; L and L' are each independently a C120 straight chain or branched alkyl or an unsubstituted aryl; Z is a hydrogen, a phosphato, a sulfonyl, a carboxylic acid, a sulfate, a polyalkylene oxide and mixtures thereof; and G is H+, Na+ or NH4+.

Non-limiting examples of compounds within the scope of ~ormula I include the following:

W 096/27704 PCT~EP96/00811 Perhalogenated Surfactants CF3 (CF2) ,CH2CH2C (O) OX CF3 (CF2) ,CH2CH2S (CH2) mC (O) OG
CF3 ( CF2),LCH2C (O) OX CF3 ( CF2) ,CH2S ( CH2) mC ( O) OG
CF3 (CF2) ,C (O) OX CF3 (CF2) ,S (CH2) nC (O) OG

CF3 ( CF2) ,CH2CH2C (O ) O ( CH2)",CH3 CF, (CF2) ,CH2C (O) O (CH2) mCH3 CF3 (CF2) ,C (O) O (CH2) mCH3 CF3 (CF2) ,CH2CH2OP (O) (OH) 2 CF3 (CF2) ,CH2OP (O) (OH) z CF3 (CF2) ,OP (O) (OH) 2 [CF3 (CF2) ,CH2CH2O] 2P (O) (OH) [CF3 (CF2) ,CH2O] 2P (O) (OH) [CF3 (CF2) ,~] 2P (O) (OH) CFI ( CF2 ) ,CH2cH2s03G
CF3 ( CF2) ,CH2SO3G
CF3 ( CF2) ,SO3G

CF3 (CF2) ,CH2CH2C (O) (CH2) mCH3 CF3 ( CF2) ,CH2C (O ) ( CH2) ~CH3 CF3 (CF2),.C (O~ (CH2) mCH3 CF3 ( CF2) ,CH2CHzO ( CH2) ,CH3 a = 1- 3 0 CF3 (CF2) ,CH2O (CH2) mCH3 a ' = 1-20 CF3 ( CF2) ,O ( CH2)I"CH3 m = 1- 3 0 p = 1-50 CF3 (CF2) ,CH2CH2C (O) N [(CH2)mCH3]2 G = H', Na', K', NH.,', CF3 ( CF2) ,CH2C ( O) N [ ( CH2)"~CH3] 2 Mg~2 Ca~2 etc CF3 (CF2) ,C (O) N [(CH2)mCH3]2 W 096/27704 PCT/~r~G

Perhalogenated Surfactants (cont.) CF3 (CF2) ,CH2CH2C (O) OCH2CH2 [OCH2CH (CH3) ] pOH
CF3 (CF2) aCH2C (O) OCH2CH2 [OCH2CH (CH3) ] pOH
CF3 (CF2) ,~C (O) OCH2CH2 [OCH2CH ~CH3) ] pOH

CF3 (CF2) ,CH2CH2C (O) OCH2CH2 [OCH2CH2] pOH
CF3 (CF2) ,CH2C (O) OCHsCH2 [OCH2CH2] pOH
CF3 (CF2) aC (O) OCH2CH2 [OCH2CH2] pOH

CF3 (CF2) ,CH2CH2C (O) OCH2CH2OCH2CH (OH) CH2OH
CF, (CF2) ,CH2C (O) OCH2CH2OCH2CH (OH) CH2OH
CF3 (CF2) ,C (O) OCH2CH2OCH2CH (OH) CH2OH

CF3 (CF2) ,CH2CH20 (CH2) ,.C (O) O (CH2) ",CH3 CF3 (CF2) ,CH2O (CH2) ,.C (O) O (CH2) ,CH3 CF3 (CF2) ,O (CH2) ,.C (O) O (CH2) mCH3 CF3 (CF2) ,CH2CH2S (CH2) ,.C (O) O (CH2) ,CH3 CF3 ~CF2) ,CH2S (CH2) ,.C (O) O (CH2) ~CH3 CF3 (CF2) ,S (CH2) ,.C (O) O (CH2) mCH3 CF3 (CF2) ,CH2CH2O (CH2) ,. (OCH2CH2) pOH
CF3 (CF2) .CH2O (CH2) ,. (OCH2CH2) pOH
CF3 ( CF2 ) ,O ( CH2 ) ,. ( OCH2CH2 ) pOH

CF3 (CF2) ,CH2CH2O (CH2) ,. (OCH2CH (CH3) ) pOH a = 1-30 CF3 ( CF2 ) ,CH2O ( CH2 ) ,, ( OCH2CH ( CH3 ) ) pOH a ' = 1- 2 0 CF3 (CF2) ,O (CH2) ,. (OCH2CH (CH3) ) pOH m = 1-30 p = 1-50 CF3 (CF2) ,CH2CH2C (O) O (CH2) .. (OCH2CH2) pOH G = H~, Na+, Kt,CF3 (CF2) ,CH2C (O) O (CH2) ,. (OCH2CH2) pOH NH"', Mg~2, Ca~2, etc .
CF3 (CF2) .C (O) O (CH2) ,, (OCH2CH2) pOH

W 096/27704 PCTA~P96/00811 Perhalogenated Sur~actants (cont.) CF, (CF2) ,CH2CH2C (O) O (CH2) ,. (OCH2CH (CH3) )I,OH
CF3 (CF2) ~CH2C (O) O (CH2)," (OCH2CH (CH3) ) pOH
CF3 (CF2) ,C (O) O (CHl) ,. (OCH2CH (CH3) ) pOH

a = 1-30 a ' = 1-20 m = 1-30 p - 1-50 G - Ht, Na~, K~, NH"',Mg'2, Ca'2, etc.

Perhalogenated Surfactants (cont.) CF3 (CF2) ,CH2CH2OCH2CH2OCH2CH (OH) CH2OH
CF3 (CF2) ,CH2OCH2CH2OCH2CH (OH) CH2OH
CF3 (CF2) ,OCH2CH2OCH2CH (OH) CH2OH

[CF3 (CF2) ,CH2CH2C (O) OCH2] 2N (CH2) mCOOX
[CF3 ( CF2) ,CH2C ( O) OCH2] 2N ( CH2) ,COOX
[CF3 ( CF2) ,C (O) OCH2] 2N ( CH2)I,,COOX

[CF3 (CF2) ,CH2CH2C (O) OCH2] 2CH (CH2) mCOOX
[CF3 (CF2) ,CH2C (O) OCH2] 2CH (CH2) mCOOX
[CF3 ( CF2) ,C (O ) OCH2] 2CH ( CH2) mCOOX

[CF3 (CF2) ,CH2CH2S (CH2) ..C (O) N [ (CH2) mCH3] 2 [CF3 (CF2) ~CH2S (CH2) ,.C (O) N t (CH2)mCH3]2 [CF3 (CF2) ,S (CH2) ,,C (O) N [ (CH2) mCH3] 2 CF3 (CF2) ,CH2CH2O (CHl) ,,C (O) N [(CH2)mCH3]2 CF3 (CF2) ~CH20 (CH2) ,.C (O) N [ (CH2).~CH3] 2 CF3 (CF2) ~O (CH2) ,.C (O) N [(CH2)mCH3]2 CA 022ll4l2 l997-07-24 W 096/27704 PCT/~6l~J8 Perhalogenated Surfactants (cont.) CH2C (O) O (CF2) ~CF3 ~ CH (SO3G) C (O) (CF2) ,CF3 CH (SO,G) C (O) OCH2CH2 (CF2) ~CF3 CH2C (O) OCH2CH2 (CF2) ,CF3 CH2C (O) OCH2 (CF2) ,CF, CH (SO3G) C (O) OCH2 (CF2) ,CF3 CF3 (CF2) ,CH2CH2O (CH2) m ~3 SO3G

CF3 ( CF2 ) ,CH2O ( CH2 ) ~ 03G

CF3 ( CF2 ) ,O ( CH2 ) ~ ~ SOlG

CH20CH2CH2 (CF2) ,CF3 ~0 O~H

CH2OCH2 ( CFz ~ ,CF3 CH2O ( CF2 ) ,CF3 J_O J o OH OH OH OH

a = 1-30 a' = 1-20 m = 1-30 G = H+, Na+, K', Li ', Ca+2, Mg+2, NH4+, etc .

CA 022ll4l2 l997-07-24 W O 96/27704 PCT~EFS''-Ell Perhalogenated Surfactants (cont.) CF3~CF2),CH2CH2C(O)(CH2)mN(CH3)3G
~ CF3(CF2),CH2C(O)(CH2),N(CH3)3G
CF3(cF2)~c(o)(cH2)mN(CH3)3G

CClF2(CClF).CH2CH2C(O)OX
CClF2(CClF),CH2C(O)OX
CClF2(CClF),C(O)OX

CClF2(CClF),CH2CH2C(O)O(CH2)~CH3 CclF2(cclF)~cH2c(o)o(cHa)~cH3 CClF2(CClF),C(O)O(CH2)mCH3 CClF2(CClF),CH2CH20P(O)(OH) 2 CClF2(CClF),CH20P(O)(OH) 2 CClF2(CClF),OP(O)(OH) 2 [CClF2(CClF),CH2CH20]2P(O)(OH) [CClF2(CClF),CH20]2P(O)(OH) [CClF2(CClF),0]2P(O)(OH) CClF2(CClF),CH2CH2SO3G
CClF2(CClF),CH2SO3G
CClF2(CClF),SO3G

CClF2(cclF)~cH2cH2c(o)(cH2)mcH3 CclF2(cclF)~cH2c(o)(cH2)mcH3 CClF2(CClF),C(O)(CH2)mCH3 CClF2(CClF),CH2CH2S(CH2)~.C(O)O(CH2)mCH3 CClF2(CClF),CH2S(CH2),.C(O)O(CH2)mCH3 CClF2(CClF),S(CH2),.C(O)O(CH2)mCH3 PCT~E~9G

Perhalogenated Surfactants (cont.) CClF2(CClF),CH2CH2O(CH2),,(OCH2CH2)pOH
CClF2 (CClF) ,CH2O (CH2) ,. (OCH2CH2) pOH
CClF2 (CClF) ,O (CH2) ,. (OCH2CH2) pOH

CClF2 (CClF) ,CH2CH2O (CH2) ,, (OCH2CH (CH3) ) pOH
CClF2(CClF),CH2O(CH2),.(OCH2CH(CH3) ) pOH
CClF2(CClF),O(CH2),.(OCH2CH(CH3) ) pOH

CClF2(CClF),CH2CH2C(O)(CH2)mN(CH3)3G
CClF2 (CClF) ,CH2C (O) (CH2) mN (CH3) 3G
CClF2(CClF),C (O) (CH2)mN( CH3 ) 3G

CClF2 (CClF) ,CH2CH2O (CH2) mCH3 CClF2 (CClF) ,CH2O (CH2) mCH3 CClF2(CClF),O(CH2)mCH3 CClF2(CClF),CH2CH2C(O)N [ (CH2) mCH3] 2 CClF2 (CClF) ,CH2C (O) N [ (CH2) mCH3] 2 CClF2 (CClF) ,C (O) N t (CH2)mCH3]2 a = 1-30 a' = 1-20 m = 1-30 p = 1-50 G = H', Na', K~, NH~, Mg~2, Ca~2, Cl-,. Br~, -OTs, -OMs, etc.

W 096/27704 PCTAEP~'~a~ll Compounds of formula I are prepared by any conventional preparation method known in the art such as the one described in March, J., "Advanced Organic Chemistry", J.
Wiley ~ Sons, NY (1985).
Commercially available fluorinated compounds include compounds supplied as the Zonyl~ series by Dupont.

The second group of surfactants useful in the dry cleaning 10 system are those compounds having a polyalkylene moiety and having a formula (II).

R R
[H-[-CH-CH-O-]i-(A) d-[~L),-(A ) f]n~ (L )g]oZ(G) h (II) wherein R and R each represent a hydrogen, a Cl5 straight chained or branched alkyl or alkylene oxide and mixtures thereof;
i is 1 to 50, preferably 1 to 30, and A, A , d, L, L , e f, n, g, o, Z, G and h are as defined above.
Preferably R and R are each independently a hydrogen, a Cl3 alkyl, or alkylene oxide and mixtures thereof.

Most preferably R and R are each independently a hydrogen, C13 alkyl and mixtures thereof. Non-limiting examples of compounds within the scope of formula II are:

W 096/27704 PcT/~G

Polypropylene Glycol Surfactants HO (CH2CH (CH3) ~) l (CH2CH20) ~H
HO (CH (CH3) (CH20) 1 (CH2CH20) ,H
HO (CH2CH (CH3) ~) l (CH2CH20); (CH2CH (CH3) O) "H
HO (CH (CH3) CH20) 1 (CH2CH20) ~ (CH2CH (CH,) O) "H
HO (CH2CH (CH3) O) ~ (cH2cH2o); (CH2 (CH3) CH2~) lCH
HO (CH (CH3) CH20) ~ (CH2CH20) ~ (CH2 (CH3) CH20) "H

HO (CH2CH20) i (CH2CH (CH3) O); (CH2CH20) ,~H
HO (CH2CH20) 1 (CH (CH3) CH20) ~ (CH2CH20) "H

HO (CH (CH3) CH20) lC (O) (CH2) mCH3 HO (CHzCH (CH,) O) lC (O) (CH2) mCH3 HO ( CH ( CH3 ) CH20 ) i ( CH2 ) mCH3 HO ( CH2CH ( CH3 ) ~ ) 1 ( CH2 ) mCH3 HO (CH (CH3) CH2O) lC (O) O (CH2) mCH3 HO ( CH2CH ( CH3 ) O ) lC ( O ) O ( CH2 ) ~CH3 HO (CH (CH3) CH2O) lC (O) N ~ (CH2) mCH3] 2 HO ( CH2CH ( CH3 ) O ) ~ C ( O ) N [ ( CH2 ) mCH3 ] 2 HO (CH (CH3) CH2o) ~C (O) (CH2) mCOOG
HO ( CH2CH ( CH3 ) O ) lC ( O ) ( CH2 ) ,"COOG
HO ( CH ( CH3 ) CH20 ) 1 ( CH2 ) mCOOG
HO (CH2CH (CH3) ~) 1 (CH2) mCOOG
HO (CH (CH3) CH20) lC (O) O (CH2) mCOOG
HO (CH2CH (CH3) O) lC (O) O (CH2) mCOOG
HO (CH (CH3) CH2O) lC (O) N [ (CH2) mCOOG] 2 HO (CH2CH (CH3) O) iC (O) N [(CH2)mC~OG] 2 HO ( CH ( CH3 ) CH20 ) lC ( O ) ( CH2 ) ~nSO3G
HO (CH2CH (CH3) O) lC (O) (CH2) mSO3G
HO ( CH ( CH3 ) CH2o) 1 ( CH2) mSO3G
HO ( CH2CH ( CH3 ) ~) i ( CH2) ~SO3G

W O 96/27704 PCTAEPg''~_Ull Polypropylene Glycol Surfactants (cont.) HO (CH (CH3) CH20) ~C (O) CH2CHzOCH2CH (OH) CH20H
HO (CH2CH (CH3) O) ~C (O) CH2CH20CH2CH (OH) CH20H
HO (CH (CH3) CH20) ~.CH2CH20CH2CH (OH) CH20H
HO (CH2CH (CH3) O) lCH2CH20CHzCH (OH) CH20H

HO (CH (CH3) CH20) iC (O) (CH2) ,,N (CH3) 3G
HO ( CH2CH ( CH3 ) O ) ~C ( O ) ( CH2 ) ",N ( CH3 ) 3G
HO (CH (CH3) CH20) i (CH2) mN (CH3) 3G
HO ( CH2 CH ( CH3 ) ~ ) 1 ( CH2 ) mN ( CH3 ) 3G
HO (CH (CH3) CH20) lC (O) O (CH2) ",N (CH3) 3G
HO (CH2CH (CH3) O) ~C (O) O (CH2) ."N (CH3) 3G

HO ( CH ( CH3 ) CH20 ) lC ( O ) ( CH2 ) ~" ~ j~~

HO ( CH2CH ( CH3 ) O ) ~ C ( O ) ( CH2 ) m ~~~~~~~

COOG
HO (CH (CH3) CH20) lC (O) (CH2) ", ~

COOG
HO (CH2CH (CH3) O) ~C (O) (CH2) " _~~~

CH2C (O) O (CH (CH3) CH20) ~H
CH2 (SO3G) C (O) O (CH2CH (CH3) O) lH
CH2C (O) O (CH2CH (CH3) O) lH
CH2 (S03G) C (O) O (CH (CH3) CH20) lH
fH2C (O) N [ (CH (CH3) CH20) lH] 2 i = 1-50 CH2 (SO3G) C (O) N[(CH2CH(CH3) O) lH] 2 i = 1-50 fH2C (O) N [ (CH2CH (CH3) O) lH] k = 1-50 CH2 (SO3G) C (O) N[(CH (CH3) CH20) iH] 2 m = 1-30 G= H+, Na+, K+, NH,,+, Ca+2, Mg+2, Cl-, Br~, -OTs, -OMs, etc .

W 096127704 PCT/~r~Gl~~
.

Polypropylene Glycol Surfactants (cont.) CH2(OCH(CH3)CH2)~OH
~~~ .
~ OH O~
oQ OH

CH2(OCH2CH(CH3))~OH
,Lo ~ OH O~

i = 1-50 j = 1-50 k = 1-50 m = 1-30 G= H', Na', K+,NH~, Ca~2, Mg'2, Cl-, Br~, -OTs, -OMs, etc.

W 096127704 PCTAE~95'~C~ll Compounds of formula II may be prepared as is known in the art and as described in March et al., Supra.

5 Examples of commercially available compoùnds of formula II
may be obtained as the Pluronic series from BASF, Inc.

A third group of surfactants useful in the invention contain a fluorinated oxide moiety and the compounds have a 10 formula:

[(CX3(XO)r (T) 8) C (A) d- [ (L)e-(A ) f ~ ] n (L )g]oZ(G) h ( III) wherein XO is a halogenated alkylene oxide having Cl6 15 straight or branched halocarbons, preferably Cl3, r is 1-50, preferably 1-25, most preferably 5-20, T is a straight chained or branched haloalkyl or haloaryl, s is o to 5, preferably 0-3, X, A, A', c, d, L, L , e, f, n, g, o, Z, G and h are as defined above.

Non-limiting examples of halogenated oxide containing compounds include:

W 096/27704 PCT/~l3 Perhaloether Surfactants CF3 ( CF2CF20) r (CH2CH20) tH
CF3 (CF2CF20) r (CH2CH (CH3) O) tH
CF3 ( CF2CF (CF3 ) ~) r ( CH2CH2~) tH
CF3 (CF2CF (CF3) O) r (CH2CH (CH3) O) tH

CF3 (CF2CF20) rP (O) (OH) 2 CF3 (CF2CF20) rCF2P (O) (OH) 2 CF3 (CF2CF20) rCF (CF3) P (O) (OH) 2 [CF3 (cF2cF2o) r] 2P (O) (OH) [CF3 (cF2cF2o) rcF2] 2P (O) (OH) [CF3 (CF2CF20) rCF (CF3) ] 2P (O) (OH) CF3 (CF2CF (CF3) O) rP (O) (OH) 2 CF3 (CF2CF (CF3) O) rCF2P (O) (OH) 2 CF3 (CF2CF (CF3) O) rCF (CF3) P (O) (OH) 2 [CF3 (CF2CF (CF~) O) r] 2P (O) (OH) [CF3 (CF2CF (CF3) O) rCF2] 2P (O) (OH) [CF3 (CF2CF (CF3) ~) rCF (CF3) ] 2P (O) (OH) CF3 (CF2CF20) rC (O) OG
CF3 (CF2CF20) rCF2C (O) OG
CF3 (CF2CF20) rCF (CF3) C (O) OG
CF3 (CF2CF (CF3) O) rC (O) OG
CF3 (CF2CF (CF3) O) rCF2C (O) OG
CF3 (CF2CF (CF3) O) rCF (CF3) C (O) OG

CF3 (CF2CF20) rC (O) O (CH2) mCH3 CF3 (CF2CF20) rCF2C (O) O (CH2) mCH3 CF3 (CF2CF20) rCF (CF3) C (O) O (CH2)mCH3 CF3 (CF2CF (CF3) O) rC (O) O (CH2) mCH3 CF3 ( CF2CF ( CF3 ) ~ ) rcF2c ( O ) O ( CH2 ) mCH3 CF3 (CF2CF (CF3) O) rcF (CF3) C (O) O (CH2) mCH3 W 096/27704 pcT/~r Perhaloether Surfactants (cont.) CF3 (CF2CF20) nC (O) OCH2CHlOCH2CH (OH) CH20H
CF3 (CF2CF20) ~CF2C (O) OCH2CH20CH2CH (OH) CH20H
CF3 (CF2CF (CF3) O) nC (O) OCH2CH20CH2CH (OH) CH20H

CF3 ( CF2CF20 ) rC ( O ) N [ ( CH2 ) ",CH3] 2 CF3 (CF2CF20) rCF2C (O) N [ (CHl) ~CH3] 2 CF3 (CF2CF20) rCF (CF3) C (O) N t (CH2) mCH3] 2 CF3 (CF2CF (CF3) O) rC (O) N [ (CH2) ,,CH3] 2 CF3 (CF2CF (CF3) O) rCF2C (O) N [ ~CH2) ,CH3] 2 CF3 (CF2CF (CF3) O) rCF (CF3) C (O) N [ (CH2) ~CH3] 2 CF3 ( CF2CF20 ) r~ ( CH2 ) ~CH3 CF3 (CF2CF20) rCF2~ (CH2) mCH3 CF3 ( CF2CF20 ) rCF ( CF3 ) O ( CH~ ) mCH3 CF3 (CF2CF (CF3) ~) r~ (CH2) ~CH3 CF3 (CF2CF (CF3) O) rCF20 (CH2) mCH3 CF3 (CF2CF (CF3) O) rcF (CF3) O (CH2) ,I,CH3 CF3 (CF2CF20) rC (O) O (CH2) "SO3G
CF3 (CF2CF20) rCF2C (O) O (CH2) ~S~3G
CF3 (CF2CF20) rCF (CF3) C (O) O (CH2) mSO3G
CF3 (CF2CF (CF3) O) rC (O) O (CH2) mSO3G
CF3 (CF2CF (CF3) O) rCF2C (O) O (CH2) ,~,SO3G
CF3 ( CF2CF ( CF3 ) O) rCF ( CF3 ) C (O) O ( CH2 ) mSO3G

CF3 (CF2CF20) rC (O) O (CH2) mCO3G
CF3 (CF2CF20) rCF2C (O) O (C~I2) mCO3G
CF3 ( CF2CF20 ) rCF ( CF3 ) C ( O ) O ( CH2 ) mCO3G
CF3 (CF2CF (CF3) O) rC (O) O (CH2) mCO3G
CF3 (CF2CF (CF3) O) rcF2c (O) O (CH2) ~C03G
CF3 (CF2CF (CF3) O) rcF (CF3) C (O) O (CH2) ~CO3G

W 096/27704 PCT/~G/00811 Perhaloether Surfactants (cont.) CF~ (CF2CF2O) rC (O) (CH2) mCH3 CF3 ( CF2CF2O ) rCF2C ( O ) ( CH2 ) ,CH3 CF3 ( CF2CF2O ) rCF ( CF3 ) C ( O ) ( CH2 ) mCH3 CF3 ( CF2CF ( CF3 ) O ) rC ( O ) ( CH2 ) mCH3 CF3 (CF2CF (CF3) ~) rCF2C (O) (CH2) ",CH3 CF3 ( CF2CF ( CF3 ) O ) rCF ( CF3 ) C ( O ) ( CH2 ) ,CH3 CF3 (CF2CF2O) rC (O) (CH2) mN (CH3) 3G
CF3 (CF2CF20) rCF2C (O) (CH2) ,"N (CH3) 3G
CF3 ( CF2CF2O ) rCF ( CF3 ) C ( O ) ( CH2 ) mN ( CH3 ) 3G
CF3 (CF2CF (CF3) O) rC (O) (CH2) mN (CH3) 3G
CF3 ( CF2 CF ( CF, ) O ) rCF2 C ( O ) ( CH2 ) ~N ( CH3 ) 3G
CF3 (CF2CF (CF3) O) rCF (CF3) C (O) (CH2) mN (CH3) 3G

r = 1-30 t = 1-40 m = 1-30 G = H~, Na', K', Li', NH~+, Ca~2, Mg~2, Cl-, Br~, -3Ts, -OMs, etc.

W 096/27704 PCT/~G

Perhaloether Surfactants (cont.) CF3(CF2CF20)rC(O)O(cH2) m ~ SO3G

CF3 (CF2CF20) rCF2C (O) O (CH2) ~> SO3G

CF3 (CF2CF20) rCF (CF3) C (O) O (CH2) m~ SO3G

CF3 (CF2CF (CF3) O) rC (O) O (CH2) ,, ~ SO3G

CF3(CF2 CF ( CF3 ) O ) rCF2 C ( O ) O ( CH2 ) m ~ SO3G

CF3 (CF2CF (CF3) O) rCF (CF3) C (O) O (CH2), ~ SO3G

CF3 ( CF2CF20 ) r ( CH2 ) m ~> SO3G

CF3 (CF2CF20) rCF2~ (CH2)m ~ SO3G

CF3 ( CF2CF20 ) rCF ( CF3 ) O ( CH2 ) m _~) SO3G

CF3 ( CF2CF20) rCF ( CF3 ) O ( CH2) m ~ SO3G

CF3 ( CF2CF ( CF3 ) ~ ) rCF20 ( CH2 ) m ~ SO3G

CF3 ( CF2CF ( CF3 ) ~ ) rCF ( CF3 ) O ( CH2 ) m_~> SO3G

PCT/~l3G

Perhaloeter Sur~actants (cont.) CH20C ( O ) ( CF2CF2~ ) rCF3 CH (SO3G) OC (O) (CF2CF2O) rCF3 CH20C (O) (CF2CF20) rCF3 CH (SO3G) OC (O) CF2 (CF2CF2O) rCF3 CH2OC (O) CF (CF3) (CF2CF2O) rCF3 r = 1-30 CH (SO3G) OC (O) CF (CF3) (CF2CF2O) rCF3 CH2OC ( O ) ( CF2CF ( CF3 ) O ) rCF3 m = 1- 3 0 CH (SO3G) OC (O) (CF2CF2 (CF3) O) rCF3 CH2OC (O) CF2 (CF2CF (CF3) O) rCF3 CH (SO3G) OC (O) CF2 (CF2CF (CF3) O) rCF3 CH2OC (O) CF (CF3) CF2CF (CF3) O) rCF3 CH (SO3G) OC (O) CF (CF3) (CF2CF (CF3) O) rCF3 G = H~, Na', Li ,NH~', Ca~2, Mg'2, Cl-, Br~, -OTs, -OMs, etc.

W O 96/27704 PCT~EPg6/00811 Perhaloether Surfactants (cont.) CclF2(cclFcclFO)r(cH2cH2o~tH
CClF2(CClFCClFO)r(CH2CH(CH3)0)tH
CClF2(CClFCF(CClF2)~r(CH2CH2)0)tH
CClF2tCClFCF(CClF2)0rtCH2CH(CH3)0)tH

CClF2(CClFCClFO)rP(O)(OH~ 2 CClF2(CClFCClFO)rCF2P(O)(OH) 2 CClF2(CClFCClFO)rCF(CF3)P(O)(OH)2 [CClF2(CClFCClFO) r] 2P (O) (OH) [CClF2(CClFCClFO)rCF2]2P(O) (OH) [cclF2(cclFcclFO)rcF(cF3)]2P(o)(OH) CClF2(CClFCF(CClF2)0)rP(O)(OH) 2 CclF2(cclFcF(cclF2)o)rcF2p(o) (OH) 2 CClF2(CClFCF(CClF2)0)rCF(CF3)P(O)(OH)2 [CClF2(CClFCF(CClF~)O)r]2P(O)(OH) [CClF2(CClFCF(CClF2)0)rCH2]2P(O)(OH) [cclF2(cclFcF(cclF2)o)rcH2]2P(o)(OH) CClF2(CClFCClFO)rC(O)OG
CClF2(CClFCClFO)r(CH2)C(O)OG
CClF2(CClFCClFO)r(CH(CF3)C(O)OG
CClF2(CClFCF(CClF2)0)rC(O)OG
CClF2(CClFCF(CClF2)0)rCF2C(O)OG
CClF2(CClFCF(CClF2)0)rCF(CF3)C(O)OG

r = 1-30 t = 1-40 G = H', Na~, Li~, K', NH~', Mg'2, Ca'2 C1-, Br~, -OTs, -OMs, etc.

Examples of commercially available compounds within the scope of formula III include those compounds supplied under the Krytox~ series by DuPont having a formula:

Il CF3(CFCF2O)XCFCO-NH4+

wherein x is 1-50.
Other compounds within the scope of formula III are made as known in the art and described in March et al., Supra.

The fourth group of surfactants useful in the invention include siloxanes containing surfactants of formula IV

MDxD*yM (IV) wherein M is a trimethylsiloxyl end group, Dx is a 20 dimethylsiloxyl backbone which is CO2-philic and D~y is one or more methylsiloxyl groups which are substituted with a CO2-phobic R or R' group, wherein R and R each independently have the following formula:

(CH2) ~ (C6H4) ~ (A) d- [ (L) e~~ (A ) f~] n~ (L )gZ(G) h wherein a is 1-30, preferably 1-25, most preferably 1-20, b is 0 or 1, C6H4 is unsubstituted or substituted with a C110 alkyl or alkenyl, and A, A', d, L, e, f, n, L , g, Z, G and h are as defined above and mixtures of R and R' thereof.

- ~ ~= =

W 096/27704 PCTAEP~G~ Lll The DX:D*y ratio of the siloxane cont~; n; ng surfactants should be greater than 0.5:1, preferably greater than 0.7:1 and most preferably greater than 1:1.

5 The siloxane compounds should have a molecular weight ranging from 100 to 100,000, preferably 200 to 50,000, most preferably 500 to 35,000.

Silicones may be prepared by any conventional method such 10 as the method described in Hardman, B. "Silicones" the ~.ncycl ope~;a of Poly~er Science ~n~ ~ng; ~eer; ng, V. 15, 2nd Ed., J. Wiley and Sons, NY, NY (1989).

Examples of commercially available siloxane containing 15 compounds which may be used in the invention are those supplied under the ABIL series by Goldschmidt.

Suitable siloxane compounds within the scope of ~ormula IV
are compounds of formula V:

~ . ~ -- --.

(CH3)3-Si-O Si-O- Si-O Si-O- Si-(CH3)3 (V) the ratio of x:y-and y' is greater than 0.5:1, preferably greater than 0.7:1 and most preferably greater 30 than 1:1, and R and R are as defined above.

Preferred CO2-phobic groups represented by R and R include those moieties of the following formula:

(CH2)a(C6H4)~(A) d- [ (L)e-(A~)~~]~(L~)gZ(G) h W 096/27704 PCTnEP96100811 - wherein a is 1-20, b is 0, C6H4 is unsubstituted, A, A', d, L, e, f, n, g, Z, G and h are as defined above, and mixtures of R and R'.

Non-limiting examples of polydimethylsiloxane surfactants substituted with CO2-phobic R or R groups are:

Polydimethylsiloxane Surfactants C~ H3 ,CH3 ~CH3 (CH3) 3--Si-o Si--O--~;i--O Si--O_Si- ~CH3) 3 (V) X y Y

x = 1-300; y = 1-100; y' = 1-100 R or R = (CH2),CH, ( CH2 ) ,CH3 = CH ( CH2 ) ,CH3 ( CH2 ) ,O ( CH2 ) ,CH3 ( CH2 ) ,S ( CH2 ) ,CH3 = (cH2)~N[(cH2)~cH3] 2 W O 96/27704 PCT~EF~'~ 811 Polydimethylsiloxane Surfactants (cont.) R or R = (CH2),C(O)O(CH~),CH3 = (CH2),C(O)(CH2),CH3 (CH,),C(O)N[(CH2),CH3] 2 ~ (CH2),(CH3) R or R = (CH2), (CH2), = (CH2)~CH=CH(CH2)m a = 1-30 m = 1-30 W 096/27704 PCTnEP96/00811 Polydimethylsiloxane Surfactants (cont.) (CH3) 3--Si-O Si--O--Si--O Si--O _Si- (CH3) 3 (V) CH3 R R' " _ ~ y~ y ~

x = 1-300; y = 1-100; y' = 1-100 R or R = (CH2) ~ (CH2CH2O) pH
(CH2) ~ (CH2CH2O) yCH3 ( CH~ ), ( CH2CH2O ) y ( CH2 ) mCH3 (CH2) ~ (CH2CH (CH3) O) pH
( CH2 ) ~ ( CH2CH ( CH3 ) O ) pCH3 ( CH2 ), ( CH2CH ( CH3 ) O ) p ( CH2 ) mCH3 ( CH2 ) . COOG
( CH2 ) .SO3G
(CH2) ,OP (O) (OG) 2 [ (CH2) ,0] P (O) (O (CH2)l"CH3) (OG) ( CH2 ) "0 ( CH2 ) mCOOG
( CH2 ) ,S ( CH2 ) mCOOG
= (CH2)~N[(CH2)mC~~G] 2 ( CH2 ) ,0 ( CH2 ) mSO3G
( CHZ ) .S ( CH2 ) mSO3G
(CH2)~,N[ (CH2)mS03G] 2 = (CH2)~O(CH2)mOP(O)(oG)2 a = 1-30; m = 0-30 = (CH2) ~S (CH2) m~P (O) (OG) 2 P = 0-50i P ~ 50 G = H+, Na+, K+, NH~+, ( CH2 ) "0 ( CH2 ) mN ( CH3 ) 3G Mg+2 Ca+2 Cl- Br~
( CH2 ) ,O ( CH2 ) mN ( CH3 ) 3G -OTS, -OMs, etc .

W O 96/27704 PCT~EP9''~

Polydimethylsiloxane Surfactants (cont.) R or R = (CH,),(CH2CH20)pH
= (cH2)~(ocH2cH2o)p(ocH2cH(CH3))p-OH
= (cH2)~(ocH2cH2o)p(OcH(CH3)cH2)p~OH
= (CH~)~(OCH2CH2O)p(CH2)~COOG
(CH2), (OCH2CH20) p (CH2) mS~3G

R = (CH2)~ ~ COOG

= (CH~)~ ~ SO3G

= (CH2)~O(CH2)~ ~ COOG

= (CH2)~S(CH2)~ ~ COOG

(CH2)~0(CH2)m ~--503G

~ /'=\
- (CHz)~S(cH2)m ~ 03G

CH20 (CH2) nCH3 ~0~
HO ~ OH 0~
OH

W O 96/27704 : - : ''p~T~5P~5/00;2~1 F~n zyrn e B
Enzymes may additionally be added to the dry cleaning system of the invention to improve stain removal~ Such enzymes include proteases (e.g., Alcalase, Savinase and 5 Esperase from Novo Industries A/S); amylases (e.g., Termamyl from No~o Industries A/S); lipases (e.g~, Lipolase ~rom Novo Industries A/S); and oxidases. The enzyme should be added to the cleaning drum in an amount from 0.001~ to 10~, preferably O.01% to 5% The type o~
10 soil dictates the choice of enzyme used in the system. The enzymes should be delivered in a conventional manner, such =~
as by preparing an enzyme solution, typically o~ 1~ by volume (i.e., 3 mls enzyme in bu~fered water or solvent).

15 Mo~;~;ers In a pre~erred embodiment, a modi~ier such as water, or a useful organic solvent may be added with the stained cloth in the cleaning drum in a small volume. Pre~erred amounts of modifier should be 0.0~ to about 10~ by volume, more 20 preferably 0.0% to about 5% by volume, most preferably 0.0%
to about 3~. Preferred solvents include water, ethanol, acetone, hexane, methanol, glycols, acetonitrile, Cl10 alcohols and Cs1s hydrocarbons. Especially preferred g~
solvents include water, ethanol and methanol.
Per~c;d Precursors Organic peracids which are stable in storage and which solubilize in densified carbon dioxide are effective at bleaching stains in the dry cleaning system. The selected 30 organic pera~id should be solub~e in carbon dioxide to ~ 3.~5 ~ 6~ qxlO3~ ~J
greater than O.~)Ul w~ s a~ pressures ofl(SOO-10,000 psi) and temperatures of 0-100~C. The peracid compound should be present in an amount of about 0.01~ to about 5~, preferably 0.1% to arbout 3%.

~IE~DE~ S~7 W 096/27704 PCT~E~

The organic peroxyacids usable in the present invention can contain either one or two peroxy groups and can be either aliphatic or aromatic. When the organic peroxyacid i8 aliphatic, the unsubstituted acid has the general formula:

O
HO~O~C~(CH2)n~y where Y can be, for example, H, CH3, CH2Cl, COOH, or COOOH;
10 and n is an integer from 1 to 20.

When the organic peroxy acid is aromatic, the unsubstituted acid has the general formula:

UO

wherein Y is hydrogen, alkyl, alkylhalogen, halogen, or COOH or COOOH.

W 096/27704 PCTi~G~'~C~ll Typical monoperoxyacids useful herein include alkyl peroxyacids and aryl peroxyacids such as:
(i) peroxybenzoic acid and ring-substituted peroxybenzoic acid, e.g. peroxy-a-naphthoic acid;
(ii) aliphatic, substituted aliphatic and arylalkyl monoperoxy acids, e.g. peroxylauric acid, peroxystearic acid, and N,N-phthaloylaminoperoxycaproic acid tPAP)i and (iii) amidoperoxy acids, e.g. monononylamide of either peroxysuccinic acid (NAPSA) or of peroxyadipic acid 10 (NAPAA).

Typical diperoxy acids useful herein include alkyl diperoxy acids and aryldiperoxy acids, such as:
(iii) 1,12-diperoxydodecanedioic acid;
(iv) 1,9-diperoxyazelaic acid;
(v) diperoxybrassylic acid; diperoxysebacic acid and diperoxyisophthalic acid;
(vi) 2-decyldiperoxybutane-1,4-dioic acid;
(vii) 4,4'-sulfonylbisperoxybenzoic acid; and (viii) N,N~-terephthaloyl-di(6-aminoperoxycaproic acid) (TPCAP).

Particularly preferred peroxy acids include PAP, TP~AP, haloperbenzoic acid and peracetic acid.
D~y Cl ~n; n~ Proce s A process of dry cleaning using densified carbon dioxide as the cleaning fluid is schematically represented in Figure 1. A cleaning vessel 5, preferably a rotatable drum, 30 receives soiled fabrics as well as the selected surfactant, modifier, enzyme, peracid and mixtures thereof. The cleaning vessel may also be referred to as an autoclave, particularly as described in the examples below.

35 Densified carbon dioxide, such as supercritical fluid carbon dioxide, is introduced into the cleaning vessel from .. . , . , . ~

. CA 02211412 1997-07-24 W 096127704 ~ . ~. P~Tn~P9~/008il ~ "

a storage vessel l. Since much of the CO2 cleaning fluid is recycled within the system, any losses during the dry cleaning process are made up t~rough a CO2 liquid supply vessel ~. The CO fluid is pu~ped into the cleaning vessel ~4-~4 an~ 6~9 ~1O3~J
5 by a pump ~ at ~es~L~s ranging between ~00 and l0,000 ~-52 ~ ~1'4x1~3K~J ~
ps~, pre~era~ly~ to 5000 ps~. The CO2 fluid is heated to its supercritical range of about 20~C to about 60~C by a heat exchanger 4.

lQ During operation, the densified CO2 is transferred ~rom the t_,. 5upply vessel 2 to the cleaning vessel 5 through line 7 ~or a dry cleaning cycle of between about lS to about 30 minutes. Before or during the cleaning cycle, surfactants, modi~iers, enzymes, peracid and mixtures thereof as 15 discussed above are introduced into the cleaning vessel, pre~erably through a line and pump system connected to the cleaning vessel.

At the end of the dry cleaning cycle, dirty CO2, soil and 20 spent cleaning agents are trans~erred through an expansion valve 6, a heat exchanger 8 by way of a line 9 into a ~lash drum lO. In the ~lash drum pressures are reduced to 5- 5~ ~103 i~ ), pS,) (~ ;~C103./~lJ~J
Detween a~out~800~and about)~l,0~0 ~ psi) and to a ~- . temperature of about 20~C to about 60~C. Gaseous CO2 is 25 separated ~rom the soil and spent agents and transferred via line ll through a filter 12 and condenser 13 to be recycled back to the supply vessel 2. The spent agents and residue CO2 are trans~erred via line 14 to an atmospheric tank 15, where the rPm~; n; ng C02 iS vented to the 30 atmosphere.

Other processes known in the art may be used in the claimed dry cleaning system such as those described in Dewees et al., US Patent No. 5,267,455, owned by The Clorox Company, 35 herein incorporated by reference.
AMENDED SHEET

W O 96/27704 ~ : P~lf~GiO~1 ~b&fsl~d 3, S ~ d l~ ~I b ~
The following examples¦will more fully illustrate the embodiments of the invention. All parts, percentages and proportions referred to herein and in appended claims are by weight unless otherwise indicated. The de~inition and 5 examples are intended to illustrate and not limit the scope of the invention. ~aY~pl~S ~r~be~ , 4 o~ 9 ~ ¦ Z
~Q ~Cv~ C~ m ~v'C
~x~le 1 Hydrocarbon and fluorocarbon containing surfactants useful lo in the invention must exhibit a hydrophilic/lipophilic balance of less than 15. This example describes the .
calculation of HLB values for various surfactants to determine their effecti~eness in supercritical carbon dioxide. This calculation for various hydrocarbon and 15 fluorocarbon surfactants is reported in the literaturel and is represented by the following equation:

HLB = 7 + ~(hydrophilic group numbers) -~(lipophilic group numbers) The hydrophilic and lipophilic group numbers have been assigned to a number of common surfactant functionalities including hydrophilic groups such as carboxylates, sulfates and ethoxylates and lipophilic groups such as -CH2, CF2 and ~v 25 PPG's.l These group numbers for the functional groups in surfactants were utilized to calculate the HLB number for the following hydrocarbon or fluorocarbon surfactant:

AM~NDED SHEET

CA 022ll4l2 l997-07-24 W 096l27704 PCT~Er~C

Sll~f~ct~nt Tr~ m~ E~
l CF3 (CF2) ~CH2H2O (CH2CH2O) rN Zonyl FSN2 2.1

2 CF3 (CF2 ) ~CH2CH2O (CH2CH20) l2HZonyl FSo3 3.4

3 CF3 (CF) "CH2CH2C tO) O (CH2) loCH3 ------ 4 . 6

4 CF3 (CF2) l2CH2CH2C (O) O (CH2) sCH3 7 .1 CF3 (CF2) ~CH2CHzC ~O) ONa ------ 17 . 3 6 CF3 (CF2) l2CH2C~2C (O) ONa ------ 13 . 8 7 CF3 (CF2)~CH2CH2SO3Na Zonyl TBS~ 9 . 2 8 CF3 (CF2) l2CH2CH2SO3Na 5 . 7 9 HO (C~2CH2O) 3 (CH (CH3) C~20) 30 (CH2CH20) 3H Pluronic 3.o 10 HO (CH2CH2O) 2 (CH (CH3) CH2O) 16 (C~2CH20) 2H Pluronic 4.5 L3l6 11 HO (CH2CH2O) 8 (CH (CH3) CH2O) 30 (CH2CH2O) ~H Pluronic 7 . 0 12 (CH2CH2O) 7 (CH (CH3) CH2O) 2~ (CH2CH20) 7HPluronic 12 . O
~43~
13 HO (CH (CH3) CH2O) ll (CH2CH2O) g (CH2CH (CH3) O) l2H Pluronic 8.0 17~29 14 Polyethylene glycol surfactant (PEG) Akyporox NP 19. 2 15 PEG 100- Laurate 19.1 16 Linear alkyl benzene sulfonate 20 . 0 17 Sodium lauryl sulfate 40.0 18 Sodium Cocoyl Sarcosinate 27 . O

Attwood, D.; Florence, A. T. "Surfactant Systems: Their chemistry, pharmacy and biology.", Chapman and Hall, NY, 1983, pp. 472-474.
2-4 Supplied by Dupont.

5-9 Supplied by BASF.
o Supplied by Chem-Y GmbH of Germany.

The conventional surfactants (Nos. 14-18) exhibit an HLB
value of greater than 15 and are not effective as dry cleaning components in the invention.

W O 96/27704 ' ~ ' ; ~CT ~ 6j~0~11 ~ple 2 Supercritical fluid carbon dioxide only as a cleaning medium was used to dry clean several hydrophobic stains on cotton and wool fabrics.

The stained fabrics were prepared ~y taking a two inch by three inch cloth and applying the stain directly to the cloths. The cloths were allowed to dry.

The stained fabrics were then placed in a 300 ml autoclave having a gas compressor and an extraction system. The ~_ stained cloth was hung ~rom the bottom of the autoclave's overhead stirrer using a copper wire to promote good agitation during washing and extraction. After placing the cloth i~ ~he autoclave and sealing it, liquid CO2 at a tank 5 ~ ~ ~103~'r~ ~--pressul~ ufl(850 psi)was allowed into the system and was heated to reach a temperature of about 40~C to 45~C. When the desired temperature was ~eached i3n ~e autoclave, the pressure inside the autoclave ~d~ lllCreaSea~(4, 000 pSi) by pumping in more CO2 with a gas compressor. The stirrer was then turned on for 15 minutes to mimic a wash cycle. At the completion of the wash cycle, 20 cubic feet of fresh CO2 were passed through the system to mimic a rinse cycle.
The pressure of the autoclave was then released to atmospheric pressure and the cleaned cloths were removed from the autoclave. To measure the extent of cleaning, the cloths were placed in a Reflectometer- supplied by Colorguard. The R scale, which measures darkness ~rom black to white, was used to determine stain removal.
Cleaning results were reported as the percent stain removal according to the ~ollowing calculation:

~ stain removal = st~in remove~ = cle~ne~ cloth re~ing -st~ine~ cloth re~;ng x 100~
~ stain applied unstained cloth reading - stained cloth reading ~HS a~

W096/27704 PCT~6/00811 The cleaning results fox the cotton and wool cloths dry cleaned with supercritical ~luid carbon dioxide alone are in Table 1 below.

T~hle 1 Dry Cl~n; n~ Resul~s on Several Hydrophobic Stains Using Supercritical Carbon Dioxide Only A~ Cle~n;n~ Medium Stain Cloth % Stain Remo~al Ragu spaghetti Cotton 95 sauce Sebum Wool 99 Olive Oil with Wool 97 Blue Dye Lipstick Wool *

The results confirm what was known in the art: that hydrophobic stains are substantially removed with supercritical ~luid carbon dioxide alone. However, the lipstick stain, which is a compound hydrophobic stain with pigment particulates, was removed only to the extent of its waxy components. The colored portion of the stain fully rem~;ned.

~ e 3 The hydrophilic stain, grape juice, was dry cleaned using supercritical fluid carbon dioxide, a polydimethylsiloxane surfactant, water as a modifier and mixtures thereof according to the invention.

Two inch by three inch polyester cloths were cut and stained with concentrated grape juice which was diluted 1:10 with water. The grape juice stain was then dried and was approximately 2 wt.~ and 7 wt.~ grape juice stain after drying. The cloths were then placed in the autoclave as ~ CA 02211412 1997-07-24 W O 961Z7704 . , ~ P~T~ n6/~08~1 described in E~ample 2, except these experiments were run ~ 4l ~o3Kr~J
at a press~re o~l(6,000 ps~.

Two di~erent polydimethylsiloxane sur~actants were used alone or in combination with O.S ml of water and supercritical fluid car~on dioxide. The control was supercritical fluid carbon dioxide alone.

The water was added directly to the bottom of the autoclave and noti on the stain itself and the surfactant was applied directly to the stain on the cloth. A~ter the wash and rinse cycles, cleaning results were evaluated and the results are reported in Table 2 below.

T~hle 2 Dry Cleaning Results on Grape Juice Stains ~sing Supercritical Carbon Dioxide and Polydimethylsiloxane Surfac tant ' stain~ Cloth-r-~, Surfacta~t ~._Modlfler: %-.stal~.
~ Remo~al 2~ grape Polyester None None 18 ~ ulce 2~ grape Polyester O.2 g ABIL None O
juice 88184l (darker) 7~ grape Polyester None 0.5 ml 21 ~ulce water 7~ grape Polyester O.2 g ABIL O.5 ml 49 juice 88184 water 7~ grape Polyester O.2 g ABIL O.5 ml 51 f juice 88512 water A~,N~ S~'t~

W 0~6/27704 PCTnEP96/008 A polydimethylsiloxane having a molecular weight of 13,200 and 5~ of its siloxyl group substituted with a 86/14 ethylene oxide/propylene oxide chain supplied by Goldschmidt of Virginia.

2 A polydimethylsiloxane having a molecular weight of 7,100 and 14~ of its siloxyl yroup substituted with a 75/25 ethylene oxide/propylene oxide chain also supplied by Goldschmidt.

It was observed that the combination of water as a modifier with the selected polydimethylsiloxane surfactants improved dry cleaning results in supercritical fluid carbon dioxide.
In fact, none of the three components alone removed substantially any of the grape juice stain.

~mple 4 As a comparison with the prior art, a conventional alkane surfactant was used alone or in combination with a modifier and supercritical CO2 to dry clean the hydrophilic stain, grape juice, on polyester, as described in Example 3 above.

The surfactant, linear alkylbenzene sulfonate is a solid and has an HLB value of 20. The LAS was added to the bottom of the autoclave with varying amounts of water. The following cleaning results were observed and are reported in Table 3 below.

W 096127704 PCTAEF7G~'~CUll T~h~e 3 Dry Cl~; n~ ResultQ on Grape Juice Stain~ Using Supercritical Carbon Dioxide and T-; ~e~ Al]cylbenzene Sulfonate Surfactant (hAS) Stain Cloth Surfactant Modifier ~ Stain : Remo~al .
2~ grape Polyester None None 18 juice 7~ grape Polyester 0.25 g LAS 0.5 ml 0 juice water(darker) 7~ grape Polyester 0.25 g LAS 6.0 ml 75 juice water 2~ grape Polyester 0.12 g LAS 6.0 ml 84 juice water 2~ grape Polyester 0.12 g LAS 0.5 ml Stain juice water moved on cloth It was observed that LAS was only effective in a larger amount of water (6 ml). When the modifier was reduced from

6 ml to 0.5 ml, the stain only wicked up the cloth and was not removed.

It i8 noted that DE 3904514 describes dry cleaning using supercritical fluid carbon dioxide in combination with a conventional surfactant. The publication exemplifies cleaning results with LAS. The experimental conditions in the examples state that the stained cloth has only minimal contact with supercritical fluid carbon dioxide, namely a 10 minute rinse only. It appears that the cleaning obtained with LAS and the large amount of water is similar to spot W 096/27704 PCTI~r~G~'~ ell or wet cleaning, since the cloth rP~;n~ wet at the end of the process. There appears to be little to m;n;m~l influence of the supercritical fluid carbon dioxide on spot removal under these conditions.

~dditionally, in a dry cleaning process, the use of LAS
with supercritical fluid carbon dioxide would not be possible with water-sensitive fabrics such as silks and wools since such large amounts of water are necessary.

~ le 5 A hydrophilic stain, namely grape juice, was dry cleaned using polydimethylsiloxane surfactants with water and supercritical fluid carbon dioxide according to the invention.

Polyester cloths were stained with 7~ grape juice stain as described in Example 3 above. Two different polydimethylsiloxane surfactants were used with varying amounts of water and supercritical fluid carbon dioxide.
In comparison, LAS, the conventional surfactant, used with the same amounts of water was used to remove the grape juice stains. The cleaning results for the two types of surfactants are reported in Table 4 below.

W 096/27704 PCTAEF9''~-~11 T~hle 4 Dry Cle~n;~ Re~ult~ on Grape Juice Stai3ls Using Supercritical Carbon Dioxide and Surfactants with Increased Water Levels Stain Cloth Surfactant Modifier % Stain . ~ Removal

7~ grape Polyester 0.25 g.6.0 ml 75 juice LAS water 7~ grape Polyester0.25 g. 0.5 ml o juice LAS water(darker) 7~ grape Polyester 0.2 g ABIL 6.0 ml 41 juice 88184l water 7~ grape Polyester 0.2 g ABIL 0.5 ml 49 juice 88184 water 7~ grape Polyester 0.2 g ABIL 6.0 ml 43 juice 88184 water 7~ grape Polyester 0.2 g ABIL 0.5 ml 51 juice 88512 water A polydimethylsiloxane having a molecular weight of 13,200 and 5~ of its siloxyl group substituted with a 86/14 ethylene oxide/propylene oxide chain supplied by Goldschmidt.

2 A polydimethylsiloxane having a molecular weight of 7,100 and 14~ of its siloxyl group substituted with a 75/25 ethylene oxide/propylene oxide chain also supplied by Goldschmidt.

W o 96J27704 ~ ~Cl~EP~/O;a8~I

It was observed that the modi~ied polydimethylsiloxane surfactants according to the invention are more effective in the presence of less water (0.5 ml vs. 6.0 ml) as cleaning was reduced from 50~ to 40~ when the water levels were increased. The opposite effect was observed with LAS, as stain removal increased ~rom 0~ to 75~ as the water levels were increased to 6.0 ml. Thus, the claimed siloxane surfactants provide better cleaning results with less water which is bene~icial for water sensitive fabrics.

le 6 _ Polydimethylsiloxanes having varying molecular weights and alkyl substituted moieties were tested as surfactants with supercritical fluid carbon dioxide in the inventive dry cleaning process. Various types of stained cloths were tested under the dry cleaning conditions described in Example 2 above.

A compound hydrophobic stain, red candle wax, was placed on both cotton fabrics as follows. A candle was lit and approximately 40 drops of melted wax were placed on each cloth so that a circular pattern was achieved. The cloths . = ~
-~ were then allowed to dry and the crusty excess wax layer was scraped off the top and bottom of each stain so that only a flat waxy colored stain was left.

Red candle wax was placed on the wool cloth by predissolving the red candle in hexane and then pipetting an amount of the hexane solution onto the fabric. The ~abric was dried and the resulting fabric contained about 10 wt.% stain.

As stated abov~, the pressure of therautoclave during the . ~ 4~ /03~ ~~
washlny cycle was~(6000 ps~ at a temperature of 40~C with a AMENDEI~ s~'r-'~

15 minute cycle. Twenty cubic feet of supercritical fluid carbon dioxide was used for the rinse cycle.

Five types of modified polydimethylsiloxanes ha~ing formula v:
~ .~ ., _ .
~H3 fH3 CH3 (CH3)3-Si-o Si-o _ Si-O _ Si-O - Si - (CH3)3 (V) ~ J ~
X y y.

wherein x:y and y' ratio is 2 0.5:1 and R and R' are each independently a straight or branched Cl30 alkyl chain were prepared. The compound formula is represented as MDX
D*~M(Cz) wherein M represents the trimethylsiloxyl end groups, Dx represents the dimethylsiloxane backbone (CO2-philic), D*y represents the substituted methylsiloxyl group (CO2-phobic) and (Cz) represents the carbon length of the alkyl chain of R.

Molecular weights of the siloxanes ranged from 1,100 to 31,000. The polydimethylsiloxanes straight chain alkyl group ranged from C8 to Cl8 carbons. The red wax stained cloths were cleaned and the cleaning results were observed and are reported in Table 5 below. No modifier was used.

W096/27704 PCT~P96/00811 T~hle 5 Red Candle Wax Stains Dry Cleaned with Modified PolydimethylsiloY~es A~d Supercritical C~ho~ Dioxide Stain Cloth Surfactant. % Stain (0.2 g) ~- v~l ... . . . ~ , . . . . . .. ~
Red candleCotton None 13 wax Red candleCottonMD10oD*2M(cl8) 20 wax Red candleCottonMD40oD*8M(c8) 38 wax Red candleCottonMD153D*lsM(cl2) 60 wax Red candleCottonMD27oD*13M(Cl2) 64 wax Red candleCottonMD124D*11M(Cl2) 59 wax Red candle Wool None 33 wax Red candle WoolMD153D*1.5M(Cl2) 54 wax A copolymer of polydimethylsiloxane and a stearyl substituted silicon monomer having a molecular weight of

8,200 and prepared as described in Hardman, B., "Silicones"
The Encyclopedia of Polymer Science and Engineering, v. 15, 2nd ed., J. Wiley and Sons, NY, NY (1989).

2 A copolymer of polydimethylsiloxane and an octyl substituted hydrocarbon silicon monomer having a molecular weight of 31,000 and prepared as described in I~ardman Sl~pr~.

3 A copolymer of polydimethylsiloxane and a lauric substituted hydrocarbon silicon monomer having a molecular weight of 1,500 and prepared as described in Hardman, Sl~pr~ .

4 A copolymer of polydimethylsiloxane and a lauric substituted hydrocarbon silicon monomer having a molecular weight of 2,450 and prepared as described in Hardman, .~t~pr~ .

5 A copolymer of polydimethylsiloxane and a lauric substituted hydrocarbon silicon monomer having a molecular weight of 1,170 and prepared as described in Hardman, sl~r~.

It was observed that the modified polydimethylsiloxanes in combination with supercritical fluid carbon dioxide significantly improved removal of a compound hydrophobic stain from both cotton and wool fabrics over the use of CO2 alone. It was also observed that the lower molecular weight silicone surfactant5 (e-g-, MDl2.4D1.1*M(C12);
MD153D*1sM(Cl2); and MD270 D*11M(C12)) are more effective at stain removal than the silicone surfactants having higher molecular weights (e.g., MDlooD*2M(Cl8) and MD400D*8M(C8)) regardless of chain length of the alkyl moiety. Especially beneficial were lower molecular weight silicones with chain lengths of C1014.

- W 0 96/27704 ~ C~yE~6~0,~81 le 7 ., A glycerated siloxane surfactant having a formula MD~*yM
wherein D*y is substituted by -(CH2)30C~2CX(OH) CH20H was used to dry clean a grape juice stain on a polyester cloth under the dry cleaning conditions described in Example 2 above.
About 0.2 gram o~ the sur~actant was combined with 0.5 ml.
water. The glycerated siloxane is a polydimethylsiloxane with a glycerol side chain having a molecular weight o~ 870 and prepared as described in Hardman, Su~r~.

.
It was observed that the glycerated siloxane removed 33~ of the grape juice stain.

~am~le 8 Various fluorinated sur~actants, either alone or with water, were used with supercritical fluid carbon dioxide to clean several types of stained fabric under the dry cleaning conditions described in Example 2.
I O ~ ~J_~
Specifically, the pressure in the autoclave was~(4000 psi) and the temperature was 40~C to 45~C.
_'~ .
Cotton stained with red candle wax and polyester stained with grape juice were cleaned with the ~luorinated surfactants and the following cleaning results were observed as reported in Table 6 below.
.

c,~'~C~

W 096/27704 PCTAEP9G,'~C~ll T~hle 6 Stains Dry Cleaned with Fluorinated Surfactants and Supercritical Fluid Carbon Dioxide Sta'ln~ - Clot~.-~ ~.Sùrfactant. Modifier ~ Stain Red candle Cotton None None 13 wax Red candle Cotton 0.6 g None 70 wax Krytox~
2~ grape PolyesterNone None 18 juice 2~ grape Polyester~0.25 g 0.5 ml 11 juice FSA2 water 2~ grape Polyester0.2 g FSO- 1.0 ml 43 juice 10 o3 water 2~ grape Polyester0.2 g FSN4 1.0 ml 48 juice water 2~ grape Polyester ~0.2 g FSA 1.0 ml 9 juice water l A fluorinated polyether ammonium carboxylate supplied as Krytox~ surfactant by DuPont, Inc. of Delaware.

2 A fluorinated nonionic having a lithium carboxylate salt supplied under the Zonyl surfactant series by DuPont, Inc.
of Delaware.

3 A fluorinated nonionic surfactant supplied under the Zonyl surfactant series by DuPont, Inc. of Delaware.

W O 96~27704 ; . PCl~E~61Q~811 .

4 A fluorinated nonionic surfactant supplied under the Zonyl sur~actant series by DuPont, Inc., of Delaware.

It was observed that all of the fluorinated surfactants equalled or improved dry cleaning of the tested stains over the use of supercritical fluid carbon dioxide alone. It was further observed that the ~luorinated nonionic surfactants (FSO-lO0 and FSN) were more effective than the fluorinated nonionic having a lithium carboxylate salt (FSA).

~x~le 9 Various bleaching peracids were combined with supercritical fluid carbon dioxide to dry clean stained fabrics.

The bleaching peracids tested include m-chloroperbenzoic acid (m-CPBA), p-nitroperbenzoic acid (p-NPBA) and 6-phthalimidoperoxy hexanoic acid (PAP) in an amount of about 0.2 to 0.5 grams each. Cotton stained with red candle wax was cleaned as described in Example 5. The wash cycle o~
~ 4x103~
the dry cleaning Sys~1.1 was run at~(6000 psi)and 45~C as described in Example 2. The coffee stains were applied to F .:-~~ polyester and wool cloths.

At the end of the cleaning cycle, the stained cloths were evaluated and the results are reported below in Table 7.

~ ~t'''-~' .

W O 96127704 - .~CT~EP96/O~

T~hle 7 Stains Dry Clea~ed with B1~h; ng Peracids and Supercritical Fluid Carbon Dioxide Stain Cloth Surfact. Modi~ier % Stain ~ ; ; Remo~al Red Cotton None None 13 candle wax Red Cotton 0.5 g m- None 94 candle CPBA
wax Red Cotton 0.11 g None 72 candle p-NPBA2 wax Red Cotton 0.26 g None 50 candle PAP3 wax Coffee Polyester 0.5 g m- None45 CPBA
Coffee Wool None None O

1 m-chloroperbenzoic acid having a solubility of )0.15 g at f3~ 3~ 9oo psi), at 45~C, in 59.8 g CO2 and supplied by Aldrich Chemical Co.

2 p-nitroperbenzoic acid having a solubility of )0.05 g at ~3-1x)O ~ ~1900 ps~, at 45~C, in 59.8 g CO2 and supplied by Aldrich Chemical Co.

_t,t~ t--l~t~_, i W O 96/Z7701 ~ ~ ~CT~EF~6/O~B~l 3.~xl~l<~6-phthalimidoperoxy hexanoic acid having a solubility of 0.05g a~2,000 ps~, at 45~C, in 59.8 g CO2 supplied by Ausimont.

The results show that the three peroxides tested signi~icantly improved stain removal on the two types of stains cleaned over supercritical fluid carbon dioxide alone ~t,~C,iTQ~ 1 e 10 -, Protease enzyme was used in supercritical carbon dioxide to _ . , clean spinach stains from cotton cloth. Three (3) mls of protease enzyme (Savinase supplied by Novo, Inc.) was added to buffered water to ~orm a 1~ solution and then added to each cloth. The cloths were then washed and rinsed as described in Example 2 above. The cleaning results observed and calclllated are as shown in Table 8 below:

T~hle 8 Stain~ Drycleaned with Savina~e in Supercritical Carbon Dioxide ,--" Stain Cloth Enzyme Modifier % Stain Solution Removal Spinach cotton none none 6.9 Spinach cotton Savinase none 26.5 These results show enhanced cleaning of the spinach stain over supercritical carbon dioxide alone when the enzyme is added to the system.

~,t~ ,C~ t~ ~ r W 096/27704 PCT~6100811 ~Y~ e 1 1 Lipolase enzyme (1% enzyme solution of 3 mls in buffered wear) was used in supercritical carbon dioxide to clean red c~ndle wax stains from rayon cloth. The procedure used was identical to that of Example 10. The results are summarized in Table 9 below.

T~hle 9 Stains Dry Cleaned with Lipolase in Supercritical Carbon Dioxide Stain Cloth Enzyme Modifier % Stain Solution Removal Red Candle rayon none none 51 Wax Red Candle rayon Lipolase none 60 Wax Red Candle cotton none. none 13 Wax Red Candle cotton Lipolase none 64 Wax The results in Table 9 show enhanced cleaning of the red candle wax stain when lipolase is used in conjunction with supercritical carbon dioxide, on both rayon and cotton cloths.

~m~le ~2 Amylase enzyme (1~ enzyme solution of 3 mls enzyme in buffered water) was used to dryclean starch/azure blue W ~ 96127704 ~ - pc~E~6/eG

stains on wool cloth in supercritical carbon dioxide. The blue dye is added to make the starch stain visible so that ~ its removal may be detected by the reflecto~eter. The drycleaning procedure used was identical to that of example lO, and the results are presented in Table 10 below.

T~hle 1O
Dry Cl~n;ng o:~ Starch/Azure Blue Dye Stai~ on Wool Using Amylase i~ Supercritical Car~on Dioxide Staln Cloth E~zyme Modi~ier % Stai~
Solution Removal Starch/Az wool none none cloth gets ure Blue darker Starch/Az wool Termamyl none 25.6 ure Blue The results in Table 10 show that the Termamyl enzyme is effective at cleaning the starch stain from wool cloth in , . supercritical carbon dioxide.

~ le 13 Dry cleaning of grape juice stain was conducted on cloths other than polyester fabric. The experiments on rayon and silk cloth were conducted using the same procedure as in Example 3, using cloths with 23w~t~%, grape ju~e~s6txali~ns~p~
with water as a modifier at pressures of~(6000 psi) an~;(40 0 psi)as noted in Table 11.

W O 96/27704 PCTJ~l~

T~hle 1l Dry C~ n;ng of Grape Juice Stain~3 on Rayon and Silk Using Supercritical Carbon Dioxide and Polydimethylsiloxane Surfactant Stain Cloth Pressure Surfactant Modifier % Stain Remo~al Grape rayon 6000 psi none 0.5 ml2.4 Juice water Grape rayon 6000 psi 0.2g Abil 0.5 ml 75. 5 Juice 88184 water Grape silk 6000 psi none0.5 ml 2.0 Juice water Grape silk 6000 psi 0.2g Abil 0.5 ml 30.4 Juice 88184 water Grape silk 4000 psi noneo. 5 ml 3.9 Juice water Grape silk 4000 psi 0.2g Abil 0.5 ml 27.5 Juice 88184 water These results show significantly enhanced cleaning of the grape juice stain on rayon and silk when the polydimethylsiloxane surfactant Abil 88184 is added to the supercritical carbon dioxide dry cleaning system.

~m~le 14 Dry cleaning of red candle wax stains was conducted on several different types of fabric, using an alkyl modified polydimethylsiloxane surfactant, MD153D15M ~C12), having a molecular weight of 1475 g/mole. The surfactant was synthesized as described in Hardman, Sl~pr~. The dry W O 96/27704 PCT~EF~C~C811 cleaning procedure used was the same as that used in example 5, and the cleaning results are presented in the ~ollowing table.

Ts~hle 1~ , Dry Cle~n;~ of Red C:~ndle Wax Stains on Various Fabrics Using an Alkyl-Modified Polydimethyl~iloxane Surfactant in Supercritical Carbon Dioxide Stain Cloth Surfactant % Stain Remo~al Red Candle cotton none 13 . O
Wax Red Candle cotton o . 2 - O . 3g 52 . 9 Wax MDls 3D l.sM
(Cl2) Red Candle wool none 36 . O
Wax Red Candle wool O . 2 - O . 3g 51. 6 Wax MDls 3D 1 sM
(Cl2) Red Candle silk none 61. 3 Wax Red Candle silk O . 2-0 . 3g 77 . 3 Wax MDl5 3D l sM
(Cl2) Red Candle rayon none 51. 2 Wax Red Candle rayon O . 2-0 . 3g 50 .1 Wax MDl5 3D 1 sM
(Cl2) CA 022ll4l2 l997-07-24 W 096/~7704 PCT/~Jr~ ~

The dry cleaning results ~how significantly enhanced cleaning of the red candle wax stain on all fabrics except for rayon, which shows no cleaning enhancement from addition of the su~factant. The cleaning results for the silk cloth are especially high, giving a cloth which looks very clean to the eye.

.~A~pl e 15 Dry cleaning of grape juice on polyester cloth and of red candle wax on cotton cloth was investigated at different pressures to determine the effect of the pressure of supercritical carbon dioxide on the cleaning effectiveness of the system. The dry cleaning procedures used were the same as those used in examples 3 and 6 except for the variations in pressure, and the results are presented in the following table.
T~h1e 13 Dry Cle~n~n~ of Grape Juice and Red Candle Wax Stains at Different Pressure~
Stain Cloth Pressure Surfactant Modifier % Stain Removal Red Candle cotton 6000 psi MDls3DlsM none 52.9 Wax tC12) Red Candle cotton 3000 psi MDis3D l5M none 51.0 Wax (Cl2) Red Candle cotton 2000 psi MDls3DlsM none 39.3 Wax (Cl2) Grape ~uice polyester 6000 psi Abil 88184 0.5 ml 61.0 water Grape Juice polyester 4000 psi Abil 88184 0.5 ml 55.4 water Grape Juice polyester 3000 psi Ahil 88184 0.5 ml 33.8 water ,~ - W O 96/27704 PCTJE~96/QC811 The results presented in the table~show that the cleaning ~ 20-7q~l~ n3~(~j o~ red candle wax stal~s ~ inlshes between~3000 and 2000 psi~ while the cleaning of grape juice stains diminishes ~between~(4000 and 3000 psi).
G q.~d 20-~x10~
le 16 Further dry cleaning experiments were conducted on polyester stained with grape juice using other ethylene oxide/propylene oxide modi~ied polydimethylsiloxane surfactants. The cleaning efficacy of these surfactants was compared to that o~ the Abil 88184 surfactant, whose cleaning results are presented in example 3. The dry cleaning procedure used was that same as that in example 2.
Water (0.5 ml) was applied to the stained cloth before each experiment was conducted. The results are presented in the ~ollowing table.

...
..... ~

c~ iC~

W 096127704 PCT/t~

T~hle 14 Dry Cl~n;n~ of Grape Juice on Polyester in Supercritical Carbon Dioxide and Polydimethylsiloxane Surfactant~

Stain Cloth Surfactant Pressure % Stain Removal Grape polyester Abil 6000 psi 60.6 Juice 88184l Grape polyester Abil 4000 psi 55.4 Juice 88184l Grape polyester Abil 88782 4000 psi 38.6 Juice Grape polyester Abil 88483 4000 psi 41.5 Juice Grape polyester MDl27D1M 6000 psi 41.4 Juice EOlo Grape polyester MD20D2M 6000 psi 43.7 Juice Eolo5 lA polydimethylsiloxane having a molecular weight of 13,200 and 5~ of its siloxyl groups substituted with a 86:14 ethylene oxide/propylene oxide chain. Supplied by Goldschmidt.

2A polydimethylsiloxane having a molecular weight of 674 and having one siloxyl group substituted with a 100 ethylene oxide chain. Supplied by Goldschmidt.

3A polydimethylsiloxane having a molecular weight of 901 and having one siloxyl group substituted with a 8.5:4.5 ethylene oxide/propylene oxide chain. Supplied by Goldschmidt.

~ I W O 961Z7704 : .................................................. PC~ '/0~8~1 ._ ., ~ . .......................................... .......

~A polydimethylsiloxane having a molecular weight o~ 1660 ~ and 6.4~ of its siloxyl groups substituted with a 100~
ethylene oxide chain. Synthesized according to Hardman, Supr~.

~A polydimethylsiloxane having a molecular weight of 2760 and 8.3~ of its siloxyl groups substituted with a 100~
ethylene oxide chain. Synthesized according to Hardman, Su~ra.

The dry cleaning results in the table show that all of the .
~ ~ surfactants tested are ef~ective at removing ~he grape juice stain from the polyester cloth, although the Abil G 3~ 88184 is slightly better, even when the pressure is reduced to ~000 psi). A dry cleaning run with no surfactant cleans only 21~ o~ the grape juice stain.

~xam~le 17 The following tables show dry cleaning results on grape juice stains made on polyester cloth where the stained cloths were prepared by dipping the entire cloth in the staining solution. The cloths are prepared with 2 wt.
... .
~~ stain, and otherwise, the drycleaning procedure is identical to that of Example 3, including the use of 0.5 ml water on each cloth prior to cleaning.

AM~5~E~ St~r W 096127704 PCT~r~lU~811 T~hle 15 Dry Cle~n~ n~ of Dipped Grape Juice Stain~ Using Modi~ied Polydimethylsiloxane ~urfactants in Supercritical Carbon Dioxide Stain Cloth Surfactant Pressure % Stain Removal Grape polyester Abil 6000 psi 50.2 Juice 881841 Grape polyester MD20D~2M 6000 pSi 48.0 Juice EOlo2 Grape polyester MD20D~2M 3000 psi 30.9 Juice EOlo2 Grape polyester MD20D2M 4000 psi 46.1 Juice EOlo2 Grape polyester MDlz7DlM 4000 psi 51.5 Juice Eolo3 A polydimethylsiloxane having a molecular weight of 13,200 and 5~ of its siloxyl groups substituted with a 86:14 ethylene oxide/propylene oxide chain. Supplied by Goldschmidt.

2A polydimethylsiloxane having a molecular weight of 2760 and 8.3~ of its siloxyl groups substituted with a 100~
ethylene oxide chain. Synthesized according to Hardman Sl~pr~.

3A polydimethylsiloxane having a molecular weight of 1660 and 6.4~ of its siloxyl groups substituted with a 100~
ethylene oxide chain. Synthesized according to Hardman ~l~pr~.

W O 961~7~04 . . ' PC7~rr~o~i8II

The dry cleaning results presented in this table show that the synthesized surfactants (entries 2 and 3) are just as e~fective at cleaning as Abil ~8184 In addition, the new s~ ~actants are just as e~ectlv ~ (4000 psi) as they are at~C6000 psi), although their cleaning ability ~l m; n; shes ~ ~ Zo ~~xlo~
som~wllaL dL~UL~U pS~!.

~ le 18 These experiments comprised the cleaning of both red candle wax and grape juice stains simultaneously in the high ~ pressure autoclave. One o~ each stained cloth was used with its respective surfactant and modi~ier (i.e. water added to the grape juice stained cloth). The grape juice stained cloth was prepared by the dipping method.pDry cleaning was conducted as described in example 2 dllCi ~, at~(6000 psi~ and 43-45~C, and the results are presented in the following table.

T~hle 16 ~ixed Cloth Dry Cleaning in Supercritical Carbon Dioxide ClothtStain Surfactant % Stain --;
Removal Red Wax/Cotton 0.5g Krytox~ 0.2g 77.2 Grape MDl2,DlM EOlo 45 9 Juice/Polyester Red Wax/Cotton 0.5g Krytox~ 71.0 Grape 0.2g Abil 88184 29.8 Juice/Polyester Red Wax/Cotton 0.2g MDls3Dl5M Cl2 50-4 Grape 0.2g MDl2~,DlM EOlo 52-8 Juice/Polyester hMEN~ED Sh~ET

W 096127704 P ~ AEF~6/~BlI

The results in the table show that the surfactants provide compatible amounts of cleaning of both stains, except for the combination of Krytox(R) with Abil 88184, (entry 2), where the effectiveness of the Abil 88184 at cleaning the grape juice is ~im;n;shed. The cleaning ability of the Krytox on red candle wax is actually enhanced somewhat in combination with polydimethylsiloxane surfactants.

Claims (15)

1. A dry cleaning system for removing stains from fabrics comprising:

a. an effective amount of densified carbon dioxide;
b. 0.001% to 10% by weight of a surfactant which is soluble in the densified carbon dioxide and which is represented by a formula RnZn wherein Rn - is a densified CO2-philic functional group, R is a halocarbon, a polysiloxane, or a branched polyalkylene oxide and n is 1-50, and Zn-is a densified CO2-phobic functional group, and n' is 1-50 and at pressures of 3.45 to 68.9 x 10 3 KPa (500-10,000 psi) and temperatures of 0-100°C, the Rn - group is soluble in the densified carbon dioxide to greater than 10 Wt.
percent and the Zn - group is soluble in the densified carbon dioxide to less than 10 wt.
percent, and wherein R of the surfactant is the halocarbon or the branched polyalkylene oxide the surfactant has an HLB value of less than 15 and wherein R is the polysiloxane, the surfactant has a ratio of dimethyl siloxyl to substituted methyl siloxy groups of greater than 0.5:1;
c. 0 to 10% by volume of a modifier;
d. 0 to 3% by weight of an organic peracid; and e. 0 to 10% by weight of an enzyme solution, to substantially dry clean stains from fabrics.

2. A system according to claim 1 wherein the Z of Zn - is a densified CO2 phobic group having a functional moiety selected from the group consisting of a carboxylic acid, a hydroxyl, a phosphato, a phosphato ester, a sulfonyl, a C1-30 alkyl sulfonate, a sulfate, an aryl which is unsubstituted or substituted with a C1-30 alkyl or alkenyl, a branched or straight chained polyalkylene oxide, a nitro, a glyceryl, a C1-30 straight chained or branched alkyl or alkenyl and a carbohydrate unsubstituted or substituted with a C1-10 alkyl or alkenyl.

3. A system according to claim 1, or 2 wherein the HLB value of the surfactant is less than 13.

4. A system according to any preceding claim, wherein n and n' are each 1-35.

5. A system according to any preceding claim, wherein the modifier is selected from the group consisting of water, ethanol, methanol, hexane, acetone, glycol, acetonitrile, a C1-10 alcohol, a C5-15 hydrocarbon and mixtures thereof.

6. A system according to claim 5, wherein the modifier is present in an amount of 0.0% to about 4% by volume.

7. A system according to any preceding claim wherein the organic peracid is selected from the group consisting of PAP, TPCAP, a haloperbenzoic acid and peracetic acid.

8. A system according to any preceding claim, wherein the enzyme is selected from the group consisting of a protease, an amylase, a lipase, an oxidase and mixtures thereof.

9. A system according to any preceding claim wherein the surfactant is a compound selected from the group consisting of i) compounds of formula I

[(CX3(CX2)a(CH2)b)c(A)d-[((L)e-(A')f]n-(L')g]oZ(G)h (I) wherein X is F, C1, Br, I and mixtures thereof;
a is 1 - 30;
b is 0 - 5;
c is 1 - 5;
A and A' are each independently a linking moiety representing an ester, a keto, an ether, a thio, an amido, an amino, a C1-4 fluoroalkyl, a C1-4 fluoroalkenyl, a branched or straight chain polyalkelene oxide, a phosphate, a sulfonyl, a sulfate, an ammonium and mixtures thereof;
d is 0 or 1;
L and L' are each independently a C1-30 straight chained or branched alkyl or alkenyl or an aryl which is unsubstituted or substituted and mixtures thereof;
e is 0-3;
f is 0 or 1;
n is 0-10;
g is 0-3;
o is 0-5;
Z is a hydrogen, a carboxylic acid, a hydroxy, a phosphato, a phosphato ester, a sulfonyl, a sulfonate, a sulfate, a branched or straight-chained polyalkylene oxide, a nitryl, a glyceryl, an aryl unsubstituted or substituted with a C1-30 alkyl or alkenyl, a carbohydrate unsubstituted or substituted with a C1-10 alkyl or alkenyl or an ammonium;
G is an anion or cation such as H+, Na+, Li+, K+, NH4+
Ca+2, Mg+2, Cl-, Br-, I-, mesylate, or tosylate; and h is 0-3;

ii) compounds of formula II

[H-[]i-(A)d-[(L)e-(A')f]n-(L')g]oZ(G)h (II) wherein R and R' each represent a hydrogen, a C1-5 straight chained or branched alkyl or alkylene oxide and mixtures thereof;
i is 1 to 50;
A, A', d, L, L', e f, n, g, o, Z, G and h are as defined above, iii) compounds of formula III

[(Cx3(XO)r(T)s)c(A)d-[(L)e-(A')f-]n( L') g]OZ(G)h (III) wherein XO is a halogenated alkylene oxide having a C1-6 straight or branched halocarbon;
r is 1-30;
T is a straight chained or branched haloalkyl or haloaryl;
s is 0-5;
X, A, A', c, d, L, L', e, f, n, g, o, Z, G and h are as defined above, iv) compounds of formula IV

MDXD*yM (IV) wherein M is a trimethylsiloxyl end group, Dx is a dimethylsiloxyl backbone which is C02-philic and D*y is one or more methylsiloxyl groups which are substituted with a CO2-phobic R or R' group and mixtures of R and R', wherein R and R' are each independently defined in the formula (CH2)a(C6H4)b(A)d-[(L)e-(A')f-]n(L)gZ(G)h wherein a is 1-30, b is 0 or 1, C6H4 is unsubstituted or substituted with a C1-10 alkyl or alkenyl, and A, A', d, L, e, f, n, L', g, Z, G and h are as defined above, and mixtures of compounds of formulas I-IV.

10. A system according to claim 9 wherein the compounds of formulas I - IV are those wherein A and A' are each independently an ester, an ether, a thio, a polyalkylene oxide, an amido, an ammonium and mixtures thereof; Z is a hydrogen, a carboxylic acid, a hydroxyl, a phosphato, a sulfonyl, a sulfate, an ammonium, a polyalkylene oxide and an unsubstituted carbohydrate; and G is H+, Li+, Na+, NH4+, C1-, Br' and tosylate.

11. A system according to claim 10, wherein the compounds of formulas I - IV are those wherein A
and A' are each an ester, an ether, an amido, a polyoxyalkylene oxide and mixtures thereof; L and L' are each independently a C1-20 alkyl or an unsubstituted aryl, Z is a hydrogen, a phosphato, a sulfonyl, a carboxylic acid, a sulfate and a polyalkylene oxide; and G is H+, Na+ or NH4+.

12. A system according to claim 9, wherein the compounds of formula IV have a DX:D*y ratio of greater than 1:1.

13. A system according to claim 12, wherein the compounds of formula IV have a molecular weight in a range of from 100 to 100,000.

14. A system according to claim 13, wherein the molecular weight of the compounds of formula IV is from 200 to 50,000.

15. A system according to claim 1, wherein R of the Rn-group is the polysiloxane.