CA2139003A1 - Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides - Google Patents

Abstract

Polyoxylalkylene esters and amides of alk(en)yl succinic anhydrides, of the formulae (I) YA1.OC(HR)CC(HR1)CO.A(CmH2mO)n.R2 and (II) YA1.OC(HR)CC(HR1)CO.A(CmH2mO)n.CpH2pA.CO(HR1)CC(HR)CO.A1Y where R, R1, A, A1, Y, R2, m, n and p are as defined, particularly where the alk(en)yl group is a C14 to C22 group, are effective surfactants. They are especially notable because, very surprisingly, the cloud point tends to rise with increasing alk(en)yl group chain lenght. The surfactants are ef-fective in scouring wool and inverting polyacrylamide water in oil emulsions into water.

Description

W O 94/00508 213 9 0 ~ 3 PCT/GB93/01335 SURFACTANTS DERIVED FROM POLYOXYALKYLENES AND SUBSITUTED SUCCINIC ANHYDRIDES.

This invention relates to surfactants and in particular to novel surfactants based on derivatives of substituted succinic acids and to particular end uses for these surfactants.
In recent years there has been an increasing desire to replace well established surfactants with materials of increased biodegrad-ability. There is, however, great practical difficulty in devising alternatives to substances of excellent performance which have maintained an important position in the market for several decades.
EP 0107199 B relates to polyoxyalkylene glycol hemi-esters of Cg to C12 alk(en)yl substituted succinic acids and their salts. These materials are described as anionic surfactants with particular utility at acidic pHs and having hard water tolerance.
This invention is based on the discovery of compounds which can be derived from alkenyl succinic anhydrides having particularly C14 to Cz2 alk(en)yl groups and/or substituents of functional groups elsewhere around the molecule give materials which have significantly and surprisingly different properties. In particular they perform well as non-ionic surfactants, particularly in aqueous systems, having unexpected cloud point properties indicating good performance at elevated temperatures and have good behaviour in ~ l;ne conditions.
Also the surfactants of this invention have good biodegradation properties.
The present invention accordingly provides a compound of the formulae (I) or (II):

Y.Al.OC.(ER)C.C(HRl)-CO-A-(cmH2mO)n-R2 (I) where one of R and Rl is C6 to C22 alkenyl or alkyl and the other is hydrogen;
A is - O - or - NR4 -; where R4 is hydrogen or Cl to C6 alkyl, particularly methyl or ethyl;
n is 2 to 100 (and as it is an average it may be non-integral);
m is 2 or 3 (and may vary along the polyoxyalkylene chain);

W O 94/00508 ;. : PCT/GB93/01335 213900~

R2 is hydrogen or Cl to C6 alkyl;
Al is - 0 -, - 0~ or -NR4-where R4 is hydrogen or Cl to C6 alkyl, particularly methyl or ethyl;
such that when Al is - 0~:
Y is a cation, particularly H+, and alkali metal cation especially a sodium or potassium cation, or an ammonium ion (especially NH4+, an amine ~ or an alkanolamine l ammonium ion); and when Al is - 0 - or -NR4-:
Y is a Cl to C6 alkyl group (R3) or a group of the formula (CmH2mO)n.R2 where m, n and R2 are independently as defined above;
provided that when A is - 0 - or Al is - 0~ the total number of carbon atoms in the groups R, Rl and any groups R2 and R3 is at least 13, and is desirably 13 to 50;
or Y.Al.OC.(HR)C.C(HRl).CO.A.(CmH2mO)n.CpH2p.A.CO.(HRl)C.C(HR)CO.Al.Y
where: (II) n, m and each R, Rl, A, Al and Y are independently as defined above; and p is 2 or 3.
For convenience of definition, the free acid forms of compounds of the formulae (I) and (II) in are defined with Y as a H+ cation. Of course, this includes both the ionised form of the free acid that will typically predominate at relatively alkaline pHs and the non-ionised form, that will typically predominate at relatively acidic pHs.
In the general formula (I), A and Al are desirably both - 0 -, both - NR4 -, particularly - N~ -, or A is - NR4 -, particularly - NH -, and Al is - 0 -. Accordingly, the following particular sub-groups of c~ ,_~.ds of the formula (I) form specific aspects of the invention (see also below about R and Rl).

W O 94/00508 ~13 ~ O ~ 3 PCT/GB93/01335 (Ia) Y.-ooc.(HR)c-c(HRl) coo-(cmH2mo)n R2 where m, n and R2 are as defined above for formula (I); Y is a cation as defined above for formula (I); and one of R and Rl is a Cl4 to C22, especially a Cl4 to C20, alkenyl or alkyl group and the other is hydrogen.

(Ib) Y.o.oc.tHR)c.c(HRl)-co-o-(cmH2mo)n R2 where m, n and R2 are as defined above formula (I~; Y is a Cl to C6 alkyl group or a group of the formula (CmH2mO)n.R2 as defined above for formula (I); and R and Rl are as defined above for formula (I), but particularly where one of R and Rl is a Cl4 to C22, especially a Cl4 to C20, alkenyl or alkyl group and the other is hydrogen.

(Ic) Y.o.oc.(HR)c-c(HRl)-co-NH (cmH2mo)n R2 where Y, m, n and R2 are as defined above formula (I); and R and Rl are as defined above for formula (I), but particularly where one of R
and Rl is a Cl4 to C22, especially a Cl4 to Czo, alkenyl or alkyl group and the other is hydrogen.

(Id) R2.(CmH2mO)n.NH.OC.(HR)C.C(HRl).CO.NH.(CmH2mO)n.R2 where each m, n and R2 is independently as defined above for formula (I); and R and Rl are as defined above for formula (I), but particularly where one of R and Rl is a Cl4 to Cz2, especially a Cl4 to C20, alkenyl or alkyl group and the other is hydrogen. 0 The c- } ~s of the general formula (II) can be considered as di(substituted succinyl) functional derivatives of a polyosyalkylene moiety. Usually, the respective groups A and Al and Y will be the same. Desirably both groups A are - 0 - or - NR4 -, particularly - NH -, and both groups Al are - 0~ with Y being a cation. Simila~ly the alk(en)yl groups in the groups R and Rl will usually be the same.

W O 94/00508 213 .9 0 3 3~c PCT/GB93/01335 Where, in formulae (I) and (II) Y is a cation, it is desirably H+, an alkali metal cation or an ammonium cation, particularly NH4+, an amine ammonium cation, such as tetramethylammonium or an alkanolamine ammonium ion e.g. HO.CH2CH2.NH3+; where Y is a Cl to C6 alkyl group, it is particularly a methyl, ethyl or (straight or branched) butyl group.
The group RZ in formulae (I) and (II) is desirably either H or a methyl, ethyl, propyl or butyl (including branched propyl and butyl) group. Where R2 is H, the products tend to be relatively more hydrophilic and where it is an alkyl group, relatively less hydrophilic. The choice of the group R2 will be determined by the desired overall properties of the compound.
The compounds of the invention include at least one polyoxyalkylene chain made up of residues of ethylene glycol and/or propylene glycol. The chain may be a homopolymer chain of either ethylene glycol residues or of propylene glycol residues or a block or random copolymer chain cont~ining both ethylene glycol and propylene glycol residues. In compounds including more than one polyoxyalkylene chain, the chains can be the same or different.
Referring specifically to the polyoxyalkylene chain defined as the group (CmH2mO)n in formula (I) (including Ia, Ib and Ic) and (II).
The chain length of this group, i.e. the value of the parameter n, will generally be chosen to provide the desired properties in the intended product. Typically, where the polyoxyalkylene chain is a polyethylene glycol chain it will usually have 3 to 50, particularly 3 to 35 e.g. lO to 35, ethylene glycol residues and where it is a pol~o~yro~lene chain it will usually have lO to 50 and more preferably 12 to 20 propylene glycol residues. Where the chain is a block or random copolymer of ethylene and propylene glycol residues the chain length chosen will typically correspond to the above ranges but numerically according to the proportion of ethylene and propylene glycol residues in the chain. Of course, numerical values of the ~
repeat length of the polyoxyalkylene chain are average values. As is common to surfactants cont~;ning a polyoxyalkylene chain, the longer the chain and the higher the proportion of ethylene glycol residues, the more hydrophilic the product. In compounds of the formula (II), W O 94/00508 P ~ /GB93/01335 '- 213g~03' if along the polyoxyalkylene chain m is constant then p will usually be the same as m.
Among the compounds of the invention, those where the group R or Rl is a Cl4 to C22, particularly a Cl4 to C20 and very particularly a Cl4 to Clg, alkenyl or alkyl group are especially desirable.
Similarly, compounds where the group R or Rl is an alkenyl group are more desirable than those where the group is alkyl. C~ ,o~.ds where the group R or Rl is an alkenyl group, particularly a C14 to C20 alkenyl group form a specific aspect of the invention.
The compounds of this invention, and particularly those where the group R or Rl is a C14 to C22 alkenyl or alkyl group have properties that are entirely unespected in that the cloud point tends to rise with increasing length of the chain R or Rl, particularly where this chain is an alkenyl chain. The step from Cl2 to Cl4 chains is often particularly notable. At chain lengths longer than C14, the cloud point may tend to fall back somewhat, but often stays significantly above that for compounds with a chain length of say C12. This trend in cloud point indicates increasing water solubility of the compounds with increasing chain length which is completely unespected and runs counter to previous experience with surfactants. However, at longer chain lengths the compounds tend to be less effective wetters, which is consistent with the increasingly hydrophobic nature of the group R/Rl. By way of example in the series of compounds of the formula:
H+.-OOC.(HR)C.C(~Rl).CO.O.(C2~40)n.R2 where n and R2 as given below;
the cloud points (C) for compounds with R or Rl groups in the range 10 to 18 are as follows:

C atoms in group R/Rl 8 12 14 16 18 R2 _ CH3, n - 7 - 37 70-81 52-53 51-52 R2 _ H, n - 8 ~5 43 56.5 - -(The compounds in this table where R2 _ H and R/Rl chain length is~l2 or less are not compounds of this invention.) We have been unable to account for this behaviour and so far as we know it is unique in surfactants. It is of considerable practical importance in that in aqueous systems surfactants are usually most effective at or near their cloud points. Higher cloud points indicate W O 94/00508 213 ~ O a 3 P ~ /GB93/01335 materials that are likely to be effective at comparably higher temperatures and surfactants are often used at moderately superambient temperatures. The longer chain lengths are linked with increased oil solubility so the cloud point behaviour indicates that better oil solubility is likely to be linked to higher effective temperatures.
This is a very useful combination of properties. This effect is more noticeable for compounds where the group R or Rl is an alkenyl group, particularly as compounds where it is alkyl generally have lower cloud points than the correspo~ing alkenyl compounds.
The compounds of formula (I) where Al is -0~ and Y is H+ can be made by reacting an alkenyl or alkyl succinic anhydride with a compound of the formula:
H.A.(Cm~2mO)n.R2 (where A, m, n and R2 are as defined above).
The reaction between the anhydride and the polyalkylene glycol, poly-alkylene glycol mono alkyl ether or corresponding amine derivatives can be readily carried out, with or without catalysts, by bringing the glycol or amine derivative into contact with the alkenyl or alkyl succinic anhydride. Reaction occurs typically at temperatures below 200C and even below 100C. The reactants will usually be used in\at least approxi~tely stoichiometric proportions. Particularly where stoichiometric proportions are used, further purification does not usually appear to be necessary, but can be carried out if desired.
The product is typically a mixture of isomers correspon~;ng to the two senses of the anhydride ring opening reaction. We have noted that the alkenyl or alkyl chain seems to have a minor steric effect on the isomer ratio with the isomer ration being typically about 60:40, the major isomer arising from nucleophilic attack at the anhydride carbonyl group remote from the alkenyl or alkyl group.
Co .)~ds of the invention where Y is a different cation can be made by salt formation from the free acid (Y - ~+). Where Y is an alkali metal or ammonium cation formation of the salts is straightforward by reaction with the correspon~ing base e.g. alkali metal such as sodium or potassium, hydro~ide or car~onate, r ; A or amine, including alkanolamines such as ethanolamine.
C~ po~ds of the invention where Al is other than -0- i.e. Y is other than a cation, can be made by reaction from the free acid.
Typically, further reaction is by preparation of an ester, W 0 94/00508 213 9 ~ 0 3 P ~ /GB93/01335 _ particularly an ester with a Cl to C6 or polyalkylene glycol alkyl ether alcohol. Generally longer chain esters and the corresponding amides can be made from esters with short chain alcohols, especially methyl or ethyl esters, by trans-esterification or amidation with the corresponding alcohol (YOH) or P~ine (YNH2) (where Y is as defined above). The esterification of the free acid csn be csrried out in a conventionsl manner for example using an acid cstalyst which msy be sulphuric, toluene sulphonic or a phosphoric scid. Phosphoric acids csn be psrticulsrly useful ss, after neutralisstion, they may be a useful component of detergent compositions which include the surfsctsnts of this invention.
Compounds of the formulae Ia, Ib, Ic snd Id can, thus, be made as follows:

Ia reacting a polyoxyalkylene glycol or derivative of the formula:
HO.(CmHzmO)n.R2 with a Cl4to C22 alk(en)yl succinic anhydride to give a compound of the formula:
HOOC.(~R)C.C(HRl)-cO-O-(cmH2mO)n R2 and (where Y is other than H) reaction with an alkali material.

Ib esterifying a compound of the formula Ia, especislly where Y is H, with s low moleculsr weight alcohol, particularly methanol, ethanol or a butanol, followed, if necessary, by a trans-esterification with an alcohol YOH to give the desired product.

Ic reacting a amino polyoxyalkylene glycol or derivative of the formula: H2N.(CmH2mO)n.R2 with an slk(en)yl succinic anhydride to give a ci .a ~ of the formula:
EIOOC.(HR)C.C(HRl).CO.NH.(Cm~2mO)n R2 and (where Y is other than H) reaction with an alkali material.

Id reacting s amino polyoxyalkylene glycol or derivative of the formula: H2N.(CmH2mO)n.R2 with an alk(en)yl succinic snhydride to give s compound of the formuls:
HOOC.(HR)C.C(HRl)-CO-NH-(cm~2mO)n R2 followed by esterificstion with a low molecular weight alcohol, W O 94/00508 ~ 1 3 9 ~ ~ 3 ~ P ~ /GB93/01335 particularly methanol or ethanol, followed by an amidation reaction with an amine YNH2 to give the desired product.

Compounds of the formula (II) where Y ls ~+ can be made by reacting 2 moles of an alk(en)yl succinic anhydride with one mole of a compound of the formula:
H.A.(CmH2mO)n.CpH2p.A.H
where m, n, p and esch A are independently as defined above.
Compounds where Y is another cation or a Cl to C6 alkyl group (R3) or a group of the formula (CmH2mO)n.R2 where m, n and R2 are independently as defined above; can be made as described above for compounds of the formula (I).
The compounds of the invention may be made by other methods. For example, the anhydride may be reacted with a lower alcohol and the resulting half ester esterified with a polyalkylene glycol or polyalkylene glycol alkyl ether or condensed with an alkylene oxide and if desired end capped with a further lower alcohol. The poly-alkylene glycol chain length can be controlled by using a polyalkylene glycol or polyalkylene glycol alkyl ether of a narrow rsnge of molecular weight, whereas the latter process gives a wide distribution of chain lengths.
Alkenyl succinic anhydrides may be produced by reacting maleic anhydride preferably with an excess of an olefin having 6 to 22, particularly 14 to 22, carbon atoms for example a 50 to 200~ excess at a temperature in the range 150 to 400C and preferably 180 to 250C
and removing excess olefin for example by distillation which is suitably carried out under vacuum. No catalyst is necessary, but is is preferred than an antioxidant be present. These anhydrides are well known commercial materials. In alkenyl succinic anhydrides prepared as described above the double bond normally lies in the

2-position in the alkenyl substituent.
To make products where the group R or Rl is an alkyl group then either the unsaturated products can be hydrogenated or, and preferably, the intermediate alkenyl succinic anhydride can be hydrogenated to give an alkyl succinic anhydride. Typically, the hydrogenation is carried out over a hydrogenation catalyst such as 2~ 390~3 .

Raney nickel or a PdtC catalyst. Temperatures of from 15 to 100C and pressures of O - 200 bar absolute may be used and, if desired a solvent may be present. For example, the hydrogenation reaction on an alkenyl succinic anhydride may be carried out at 20C using 5~ w/w of Pd/C catalyst over a period of for example 6 to 24 hours.
It is desirable that the R, Rl alkyl or alkenyl group of the compounds of the invention has a straight chain. Where the chain is not straight it is desirable that it has at most a total of two and preferably only one branch(es) on average. Preferably the whole molecule comprises at most three branches in total in all alkyl and alkenyl groups present.
The products are readily made with low odour and, since polyalkylene glycols and polyalkylene glycol alkyl ether or their amine derivatives are readily transportable can be made at locations distant from alkylene oxide plants if they are used as reactants.
Compounds according to the invention have emulsification properties and wetting and dispersion capabilities. These include use in oil in water emulsions for metal working fluids, based on semi-soluble oil and synthetics and for crude oil transportation and fuel systems, emollients for personal (skin) care; domestic detergent composition for esample laundry liquids; the dispersion or organic and inorganic powders in paints and coatings (e.g. filler and pigments) and agrorh 'c~l formulations (e.g. pesticides); wetters in so-called industrial and institutional cleaning products (e.g. traffic film removers, bottle washes).
Particular end uses for the surfactants of this invention include wool scouring and as inverting agents in the manufacture of acrylamide or similar products. These applications are described in more detail below.
As sheared from the sheep, the woollen fleece includes, in addition to the wool fibre, a variety of materials including wool wax.
Wool was is a comples mixture of fatty materials secreted onto the wool by the skin of the sheep. Wool was is L~ ved from the wool, prior to use of the wool in testiles, by washing the wool with an aqueous mis including surfactants typically at moderately elevated temperatures e.g. 40 to 80C, particularly 50 to 70C. This process is called wool scouring. Our testing indicates that the surfactants W O 94t00508 PCT/GB93/01335 of this invention are very effective wool scouring surfactants, in particular ret~ining their activity well after multiple scouring cycles, even when used in scouring wool with very fine fibres e.g.
merino wool, which is difficult to scour because the proportion of wool fat is relatively high and the fibres have a high surface area to be treated. Although the particular choice of a compound within the invention for this end use will depend on the specific operating conditions, we have found that compounds of the formula (Ia) above, particularly where m is 2, n is from 2 to 25, particularly 3 to lO, and where R2 is a Cl to C6 alkyl group, especially a methyl group are especially effective. The surfactant in this application is typically used at a concentration of from O.l to 5, particularly from 0.2 to 1.5, g.l-l.
The invention accordingly includes a method of treating wool to remove wool wax which method comprises washing the wool, cont~ining wool wax, with an aqueous miY including an effective amount of a compound of the formulae (I) or (II) above, in particular a compound of the formula (Ia) above, especially where m is 2, n is from 3 to lO
and where R2 is a Cl to C6 alkyl group, particularly a methyl group.
The invention also includes the use of such compounds of the invention as wool scouring surfactants.
The manufacture of polymers such as polyacryl~;de is usually ~
carried out by an emulsion polymerisation route in which the polymer is accumulated in an aqueous phase (in which it is soluble). It is well known that polyacrylamides can give aqueous solutions having high viscosities even at low concentrations; this is the basis of their use as ~hickpnprs and viscosity enhancers in aqueous systems. If the aqueous phase during polymerisation were the continuous phase, it would rapidly become very viscous, leading to difficulties in agitation and recovery of the product. To avoid this problem, the aqueous phase is normally the dispersed phase in an oil continuous phase i.e. as a water in oil emulsion, including an emulsifier to stabilise the water in oil emulsion. The viscosity of the oily phase does not increase during polymerisation, as does the aqueous phase, because the polymer remains in the aqueous phase. ~owever, the polymer is typically used in a aqueous environments, so at some point the emulsion must be inverted to give an aqueous continuous phase.

._ .

This is typically done on dilution of the water in oil emulsion into water. Usually, a surface active agent that promotes such inversion is added to the water in oil emulsion before dilution into water. Our testing indicates that the compounds of this invention are effective inverting agents for such emulsions. Although the particular choice of a compound within the lnvention for this end use will depend on the specific operating conditions, we have found that compounds of the formula (Ia) above, particularly where m is 2, n is from 8 to 25, particularly 10 to 15, and where R2 is H or a Cl to C6 alkyl group, particularly a methyl, ethyl, propyl or butyl group, are especially effective. The amount of surface active agent used to invert such emulsions will depend on the emulsion, in particular the proportion of disperse aqueous phase and the polymer concentration in the aqueous phase. Generally amounts in the range 1 to 5~ of the water in oil emulsion are typical.
The invention accordingly includes a method of inverting a water in oil emulsion con~in;ng polyacrylamide in the aqueous phase which comprises including in the water in oil emulsion a compound of the formulae tI) or (II) above, in particular a compound of the formula (Ia) above, especially m is 2, n is from 8 to 25, particularly 10 to 15, and where R2 is H or a Cl to C6 alkyl group, particularly a methyl, ethyl, propyl or butyl group, and subsequently diluting the water in oil emulsion into water. The invention also includes the use of compounds of the invention as polyacrylamide water in oil emulsion inverting agents.

W O 94/00508 ~ PCT/GB93/01335 2139~03 The following Exampies illustrate the invention including the manuracture and properties of the compounds of the invention and their end uses, particularly illustrating the versatility and utility of the compounds of the invention. All parts and percentages are by weight unless otherwise specified.

Test Methods Cloud Point (CP) was measured by ASTM D 2024 - 65; results are in C

Wetting (Wtg) Draves wetting was assessed using the skein test (ASTM D 2281 -68); results are in seconds (s) [or minutes (m) - for slow wetters].

Foam height (F~) Ross Miies foam height was assessed by ASTM D 1173-53 at 60C;
results are in mm.
Surface Tension (ST) was measured on a 0.1~ wlw solution by the drop method at 23C;
results are in mN.m~l (1 mN.m~l - 1 dyne.cm~l).

S m thesis E~amPles SEl to SE24 Various compounds of the invention were made by reacting stoichiometric mistures of an alkenyl succinic anhydride and poly-~
ethylene glycol (PEG), an alkyl polyethylene glycol ether or aminederivative, as set out in Table 1 below, by he~ting the misture to about 100C. Samples taken every 30 minutes until the reaction was complete as determined by infra red spectroscopy andlor the acid value of the misture.

W O 94/00508 21~ 9 0 ~ P ~ /GB93/01335 Corresponding sodium salts were made by addition of NaO~ solution to the acld product until the p~ had risen to 9. The sodium salt was then isolated by stripping or used as a solution in water.
Corresponding methyl esters were made by the addition of sulphuric acid and methanol. Methanol was distilled through the reaction at such a rate as to keep the volume constant for 2-12 hours. Sodium hydrogen carbonate was then added to neutralise the sulphuric acid and the product filtered. Other low alcohol esters were made by correspon~ing methods.
Comparative materials of s;m;lar structure were also prepared by the general method described but substituting the appropriate starting materials. These are identified by the prefis 'C' before a number.
Various properties of the compounds were measured and the results are given in Table 2 below. For further illustration a commercially available nonyl phenol ethosylate (with 9 moles of EO per mole phenol) is included in Table Z under the reference '~PE'.

The properties of compound SEl are as follows:

Surface Tension (0.lZ w/w solution) (Drop Method at 23C) mN.m~l 28.4 Pour Point (C) -15 Viscosity (cps/25C) 165 Foam Heights (mm) 0 min 5 min (Ross Miles at 60C) 7.5 3 Density (g.cm~3 at 23C) 1.006 Wetting (Draves - seconds) 10.5 secs Cloud Point C 40 - 53 W O 94/00508 --- P ~ /GB93/01335 _ 14 -TABLE l Ex Formulal R/RlA I Al m n R2 y I No (1) 1 (2) (1) 5I SEl I 14u 1 -0- -0- 2 3.7 1 H
SE2 I 12u 1 -0- -0- 2 13.6 H
SE3 II 18u 1 -NH- -0- 2 34 - H
SE4 II 12u 1 -0- -0- 2 18.2 - H
SE5 I 12u 1 -0- 1 -0- 2 7 1 H
SE6 1 I 14u 1 -0- 1 -0- 2 7 1 H
SE7 I 16u 1 -0- -0- 2 7 1 H
SE8 I 18u 1 -0- -0- 2 7 1 H
Cl I 8u 1 -0- -0- 2 8 H H
C2 I 12u -0- -0- 2 8 H H
C3 I 12u -0- -0- 2 12 H H
SE9 1 I 14u -0- -0- 2 8 H H
SElO I 12u 1 -0- -0- 2 4 1 H
~5¦ SEll I 12u -0- -0- 2 12 H 4 SEl2 I 14u -0- -0- 2 45 1 H
SE13 I 14u -0- -0- 2 10 4 H
SE14 I 14u -0- -0- 2 12 H
SE15 I 14u -0- -0- 2 12 H 4 SE16 I 16u -0- -0- 2 45 1 H
SE17 I 18u -0- -0- 2 17 1 H
SE18 I 18u -0- -0- 2 45 1 H
SEl9 I 14u -0- -0- 2 12 H H
SE20 II 12u -0- -0- 2 34 - H
SE21 II 14u -0- -0- 2 34 - H
SE22 II 14u -NH- -0- 2 34 - H
SE23 II 18u -0- -0- 2 34 - H
SE24 I 14s 1 -0- -0- 2 8 H H
I SE25 I 14s 1 -0- -0_ 2 12 H H
I SE26 ¦ I 18s 1 -0- -0_ 2 12 H H

1 the number of carbon atoms in the substituent chain is given, for R/Rl 'u' indicates that the substituent is an alkenyl group 's' indicates that the substituent is an alkyl group;
for R2 H - hydrogen and a number the length of an alkyl group.
for Y H indicates Y H~ and a number the alkyl chain len~th.

2 integral values for n may be rounded values;
for compounds of the formula (II) the value for 'n' in this table is n+p in formula (II) as given above (with p - m).

W O 94/00508 213 9 0 ~ 3 PCT/GB93/01335 ST CP FH Wtg Ex I (mN.m~l)(C) (mm) (s) No Omin 1 5min SEl 28.4 40-53 7.5 3 10.5 SE2 30.3 98 87 SE3 34.0 SE4 31.9 10 55 SE5 30.2 37 21 SE6 30.7 70-81 46 SE8 - Sl-52 >300 Cl 34 <5 C2 33.8 43 C2 34.6 54 66 SE9 35.7 56.5 SE10 28.3 21 6.5 SEll 31.2 78 72 58 SElZ
SE13 28.8 60-65 14 SE16 >96 SE18 >96 SEl9 38.7 66 SE20 31.6 63 SE21 35.1 SE22 34.1 SE23 34.0 NPE 29.9 W O 94/00508 P ~ /GB93/01335 Applications Exam~les AEl to AE4 Exam~le AEl - Semi Aaueous Cleaners Semi aqueous cleaning involves the cleaning of, e.g. metal, components with a solvent followed by a water rinse stage. Frequently solvents derived from terpenes are used in this application. Surface active agents can be added to expedite the removal of the solvent from the components being cleaned during the water rinse stage. Such surface active agents, or rinse aids as they are known, must fulfil two criteria. Firstly they must effect good solvent removal and b\e soluble in the cleaning solvent. Secondly they must not stabilise mistures of the solvent and water thus preventing effective separation of the misture with adverse implications on waste disposal. Materials A and B below have the desired surface active properties to be effective rinse aids in semi aqueous cleaning formulations. They are also soluble in terpene solvents. Surprisingly tests have demonstrated that they exhibit rapid and more effective solvent and water separation as compared to other surfactants commonly used in this application.
The following experimental data demonstrate the effect.
Mixtures of 0.6~ surfactant, 9.4~ terpene solvent and 90~ water were prepared by shaking 5 times in a measuring cylinder. The mixtures were allowed to stand at room temperature for twenty hours, during which time a periodic assessment of the level of phase separation was made. The following table records the results obtained.

_ - 17 _ Surfactant Appearance after Comments 20 Hours .

None Both layers clear Separation complete after 0.5 hours C10 alcohol 3 EO Oil and water layers Separation incomplete cloudy after 20 hours 10Alkyl phenolOil and water layersSeparation complete 4.5 EO slightly cloudy after 10 hours SE10 Oil and water layers Separation complete very slightly cloudy after 12 hours SEl Slight haze in both Separation complete layers after 8 hours Complete separation means oil layer of 10Z and a water layer of 90Z of the total volume.

EsamPle AE2 - Wool Scourin~

Ten 20g samples of wool were washed successfully in the same bath of a 0.1Z w/w solution of surfactant in water (1 litre) at 60C. The residual grease in the last sample to be washed was then measured by estraction with an organic solvent, typically dichloromethane or chloroform. The results are set out in the following table:

Product Z Residual Grease ~SYNPERONIC~ NP9 (**) l.tl ~SYNPERONIC~ 87R (*) 2.16 SEl 1.24 ** Commercially available Cl3_1s alcohol alkosylate * Commercially available nonyl phenol ethosylate W O 94/00508 21 ~ 9 0 0 3 PCT/GB93/01335 - 18 _ Exam~le AE3 - Wool ScourinR

Further tests of wool scouring were carried out using fine merino wool (ca. 20 ~m diameter fibres) at a surfactant dose of O.S g.l-l in an aqueous scouring solution containing 4Z by weight of ~Cl (to simulate salt accumulation during repeated use of the scouring solution). The scouring was operated at 65C in the scour detergent bowls and at 50C in the rinse bowls. The scouring solutions were\
reused a number of times and the weight percentage of residual wool wa~ on the wool after each treatment was noted and is given in Table 3 below. The product of SEl was compared with four other scouring surfactants:

Code Product Name Source Description C3 Lissapol TN450 ICI Australia nonyl phenol ethoxylate C4 Lissapol BD20 ICI Australia biodegradable wool scourer C5 Lissapol BD30 ICI Australia biodegradable wool scourer C6 Softanol 90 Nippon Sho~b~i secon~ry alcohol etho~ylate Table 3 Run Surfactant No SEl C3 C4 C5 C6 1 1.13 0.81 1.08 1.02 0.77 2 0.96 0.95 1.38 0.87 0.73

3 0.96 1.22 1.15 0.89 0.86

4 0.93 1.02 1.10 1.01 0.94 0.98 1.19 1.74 0.90 1.04 6 0.93 1.07 1.36 1.12 0.97 7 0.98 1.02 1.18 1.02 1.19 8 1.04 1.20 1.76 1.17 1.46 The results given in Table 3 show that the compound of this invention performs well as a wool scouring agent and in particular shows good retention of performance as compared with current agents, even in treating a wool that is known to be difficult to scour.

W O 94'~0508 213 9 0 0 3 P ~ /GB93/01335 _ .

Example AE4 - Polyacrylamide Emulsion Inversion The following mixture was polymerised by heating to about 40C
using as the primary emulsifier a commercially available polymeric

5 surfactant sold under the trade name "HYPERMER" Z296.

Acrylamide 135.0g Acrylic acid 58.0g Demin Water 179.0g 10 ~ydrocarbon Solvent (Isopar L) 168.0g Sodium hydroxide up to pH 6 Ethylene diamine tetra acetic acid 5.2g (EDTA) (5~) Azobisisobutyronitrile (AIBN) 0.4g 15 Primary emulsifier 8-12g 3Z of each of the surfactants below was added as an inverting agent to a sample of the polymer emulsion and the mi~ture allowed to rest for 2-3 days. A sample of emulsion was then taken and a 1~ blend 20 in water produced. After 2 minutes of stirring the viscosity was measured. Stirring was then continued and after 15 minutes the viscosity was measured again. The measured viscosities were:

Viscosity (mPa.s) After 2 minsAfter 15 mins n SYNPERONIC n NP9 12000 26000 SEll 11500 26000 SEl9 24000 24500 C3 coagulated These results show that SEll is equivalent to the conventional inverting agent ~SYNPEaONIC~ NP9 and SEl9 is superior and that compound C3 does not act effectively as an inverting agent.

Claims (14)

Claims

1 A compound of the formulae (I) or (II):

Y.A1.OC.(HR)C.C(HR1).CO.A(CmH2mO)n.R2 (I) where one of R and R1 is C6 to C22 alkenyl or alkyl and the other is hydrogen;
A is - O - or or -NR4-, where R4 is hydrogen or C1 to C6 alkyl;
n is 2 to 100;
m is 2 or 3 (and may vary along the polyoxyalkylene chain);
R2 is hydrogen or C1 to C6 alkyl;
A1 is - O -, - O- or -NR4-, where R4 is hydrogen or C1 to C6 alkyl;
such that when A1 is - O-, Y is a cation; and when A1 is - O - or -NR4-:
Y is a C1 to C6 alkyl group (R3) or a group of the formula (CmH2mO)n.R2, where m, n and R2 are independently as defined above;
provided that when A is - O - or A1 is - O- the total number of carbon atoms in the groups R, R1 and any groups R2 and R3 is at least 13.
or Y.A1.OC.(HR)C.C(HR1).CO.A.(CmH2mO)n.CpH2p.A.CO.(HR1)C.C(HR)CO.A1Y

where: (II) n, m and each R, R1, A, A1 and Y are independently as defined above; and p is 2 or 3.

2 A compound as claimed in claim 1 in which one of R and R1 is C14 to C22 alkenyl or alkyl and the other is hydrogen.

3 A compound as claimed in claim 1 of the formula (Ia):

(Ia) Y.-OOC.(HR)C.C(HR1).COO.(CmH2mO)n.R2 where m, n and R2 are as defined in claim 1; Y is a cation and one of R and R1 is a C14 to C22 alkenyl or alkyl group and the other is hydrogen.

4 A compound as claimed in claim 1 of the formula (Ib):

(Ib) Y.OOC.(HR)C.C(HR1)-COO-(CmH2mO)n.R2 where R, R1, m, n and R2 are as defined in claim 1; and Y is a C1 to C6 alkyl group or a group of the formula (CmH2mO)n.R2 where m, n and R2 are independently as defined in claim 1.

A compound as claimed in claim 1 of the formula (Ic):

(Ic) Y.-OOC.(HR)C.C(HR1).CO.NH.(CmH2mO)n.R2 where R, R1, m, n and R2 are as defined in claim 1 and Y is a cation.

6 A compound as claimed in claim 1 of the formula (Id):

(Id) R2.(CmH2mO)n.NH.OC.(HR)C.C(HR1).CO.NH.(CmH2mO)n.R2 where R and R1 and each m, n and R2 is independently as defined in claim 1.

7 A compound as claimed in any one of claims 4 to 6 in which one of R and R1 is a C14 to C22 alkenyl group and the other is hydrogen.

8 A compound as claimed in any one of claims 1 to 7 wherein m is 2;
p, if present, is 2;
n is from 3 to 50 and Y is a cation it is H+, an alkali metal cation, or an ammonium cation, or a methyl, ethyl or butyl group.

9 A method of treating wool to remove wool wax which method comprises washing the wool, containing wool wax, with an aqueous mix including an effective amount of a compound of the formulae (I) or (II) as defined in any one of claims 1 to 8.

A method as claimed in claim 9 wherein the compound is a compound of the formula (Ia) where m is 2, n is from 3 to 10 and where R2 is a C1 to C6 alkyl group.

11 A method of inverting a water in oil emulsion containing polyacrylamide in the aqueous phase which comprises including in the water in oil emulsion a compound of the formulae (I) or (II) as defined in any one of claims 1 to 8 and subsequently diluting the water in oil emulsion into water to invert it.

12 A method as claimed in claim 11 wherein the compound is a compound of the formula (Ia) where m is 2, n is from 8 to 25, and R2 is H
or a C1 to C6 alkyl group.

- 23a -

13 A compound of the formulae (I) or (II):
Y.A.1.OC.(HR)C.C(HR1).CO.A.(CmH2mO)n.R2 (1) where one of R and R1 is straight chain C6 to C22 alkenyl or alkyl and the other is hydrogen;
A is - O - or or -NR4-, where R4 is hydrogen or C1 to C6 alkyl;
n is 2 to 100;
m is 2 or 3 (and may vary along the polyoxyalkylene chain);
R2 is hydrogen or C1 to C6 alkyl;
A1 is - O -, - O- or -NR4-, where R4 is hydrogen or C1 to C6 alkyl;
such that when A1 is -o-, Y is a cation; and when A1 is - o - or -NR4-:
Y is a C1 to C6 alkyl group (R3) or a group of the formula (CmH2mO)n.R2, where m, n and R2 are independently as defined above;
provided that when A is - O - or A1 is -O- the total number of carbon atoms in the groups R, R1 and any groups R2 and R3 is at least 13, or Y.A.1.0C.(HR)C.C(HR1).CO.A.(CmH2mO)n.OpH2p.A.CO.(HR1)C.C(HR)CO
.A1Y
where:
n, m and each R, R1, A, A1 and Y are independently as defined above;
and p is 2 or 3.

14 A compound as claimed in any one of claims 1 to 8 wherein one of R and R1 is straight chain C6 to C22 alkenyl or alkyl and the other is hydrogen.