AU679918B2 - Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides - Google Patents

Description

OPI DATE 24/01/94 AOJP DATE 14/04/94 APPI'% ID 43505/93 I hlilllilIlhl IIIIhiI PCT NUMBER PCT/GB93/01335 I II lllllIi I I111!I111li ii AU9343505 (51) International Patent Classification 5 :I international Publication Number: WO 94/00508 C08G 65/32, DOI C3/00 Al (3 nentoa ulctu ae aur 94(60,4 CI IB I1 /00,C08F 20/56(4)ItrtoallbIctlte 6Jnry94(609) (21) International Application Nurnber: PCT GlI930l335 (74) Agents: ROBERTS, Jonathan, Winstanley ct ICI Group Patents Services Dept, PO Box 6, Shire Park, (22) International Filing Date: 25 June 19931 (215.06.93) Welwyn Garden City, H~tfordshire AL7 I HI) (GB).

Priority data: (81) Designated States: AU, 13G, CA, CZ, Fl, HU, JP, KR, NO, 9213571.4 26 June 1992"(216.06.92) GB NZ, PL, RO, RU, SK, UA, US, European patent (AT, BE, CHi, DE, DK, ES, FR, GB, GR, IT, LU, MC, N L, PT, S E).

(71) Applicant (for all designated States except U'SJ: IMPERIAL CHEMICAL INDUSTRIES PLC IGIVGB]:, Imperial Chemical House, Milibank, London SWIP 3JP Published Irnh l iternational search report.

(72) Inventors-, and Inventors/Applicants (for LIS only) :CARPENTER, Neil, Michael [GBIGB]: 34 Green Road, Skelton, Saitburn, Cleveland TS12 2BQ McGREGOR, Gordon [GIll GB); 7 Springfield Avenue, Stockton on Tees, Cleveland7

Y

High Siddle, East Harstey, Northallerton, North Yorkshire DL6 2DZ (GB).

(54)TItle: SURFACTANTS DERIVED FROM POLYOXYALKYLENES AND SUBSTITUTED) SUCCINIC ANHY-

DRIDES

(57) Abstract Polyoxylalkylene esters and amides of alk(en)yl succinic anhydrides, of' the formulae YA '.OC(HR)CC(H RI)CO.A(CmHm0)n.R 2 and (11) YAI.OC(HR)CC(HRI)CO.A(CmH.1mO)n.CPH 2 pA.CO(HRI)CC(HR)CO.AtYwllere R, R1, A, Al, Y, R 2 mn, n and p are as defined, particularly where the alk(en)yl group is a C 14 to C 22 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 ci'fective in scouring wool and inverting polyacrylamide water in oil emulsions into water.

WO 94/00508 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 yeear there has been an increasing desire to replace well established surfactants with materials of increased biodegradability. 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 C 8 to C 12 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 C 14 to C;22 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 alkaline conditions.

Also the surfactants of this invention have good biodegradation properties.

The present invention accordingly provides a compound of the formulae or (II): Y.A1.OC.(HR)C.C(HR 1 ).CO.A.(CmH2mO)n.R 2

(I)

where one of R and R 1 is C 6 to C 22 alkenyl or alkyl and the other is hydrogen; A is 0 or NR 4 where R 4 is hydrogen or C 1 to C 6 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); WO 94(/00508 PCT/GB93/01335 2-

R

2 is hydrogen or Ci to C6 alkyl;

A

1 is 0 0- or -NR 4 where R 4 is hydrogen or C 1 to C 6 alkyl, particularly methyl or ethyl; such that when A I is 0-: Y is a cation, particularly and alkali metal cation especially a sodium or potassium cation, or an ammonium ion (especially NH4+, an amine ammonium or an alkanolamine ammonium ion); and when A 1 is 0 or -NR4-: Y is a Cl to C 6 alkyl group (R 3 or a group of the formula (CmH2mO)n.R 2 where m, n and R 2 are independently as defined above; provided that when A is 0 or A! is 0- the total number of carbon atoms in the groups R, R 1 and any groups R 2 and R 3 is at least 13, and is desirably 13 to or

Y.A

1

.OC.(HR)C.C(HR

l ).CO.A.(CmH2mO)n.CpH2p.A.CO.(HR 1 )C.C(HR)CO.Al.Y where: (II) n, m and each R, R 1 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 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 A and A 1 are desirably both 0 both NR4 particularly NH or A is NR 4 particularly NH and A 1 is 0 Accordingly, the following particular sub-groups of compounds of the formula form specific aspects of the invention (see also below about R and RI).

WO 94/00508 PCT/GB93/01335 3 (la) Y.-OOC.(HR)C.C(HR).COO.(CmH2m0)n.R 2 where m, n and R 2 are as defined above for formula Y is a cation as defined above for formula and one of R and R 1 is a C14 to

C

22 especially a C 14 to C 20 alkenyl or alkyl group and the other is hydrogen.

(Ib) Y.0.OC.(HR)C.C(HRI).CO.0.(CmH2m0O)n.R 2 where m, n and R 2 are as defined above formula Y is a C 1 to C6 alkyl group or a group of the formula (CmH2m0)n.R 2 as defined above for formula and R and R 1 are as defined above for formula but particularly where one of R and R 1 is a C14 to C22, especially a C 14 to C 2 0, alkenyl or alkyl group and the other is hydrogen.

(Ic) Y.0.OC.(HR)C.C(HR 1 ).CO.NH.(CmH2mO)n.R 2 where Y, m, n and R 2 are as defined above formula and R and R 1 are as defined above for formula but particularly where one of R and R 1 is a C14 to C 22 especially a 014 to C 20 alkenyl or alkyl group and the other is hydrogen.

(Id) R 2 .(CmH2m0)n.NH.0C.(HR)C.C(HRl).CO.NH.(CmH2m0)n.R 2 where each m, n and R 2 is independently as defined above for formula and R and R 1 are as defined above for formula but particularly where one of R and R 1 is a C14 to C22, especially a

C

14 to C 20 alkenyl or alkyl group and the other is hydrogen.

The compounds of the general formula (II) can be considered as di(substituted succinyl) functional derivatives of a polyoxyalkylene moiety. Usually, the respective groups A and A 1 and Y will be the same. Desirably both groups A are 0 or NR4 particularly NH and both groups A 1 are 0- with Y being a cation. Similarly the alk(en)yl groups in the groups R and R 1 will usually be the same.

WO 94/00508 PCr/GB93/01335 4 Where, in formulae and (II) Y is a cation, it is desirably H+, an alkali metal cation or an ammonium cation, particularly NH 4 an amine ammonium cation, such as tetramethylammonium or an alkanolamine ammonium ion e.g. HO.CH 2

CH

2 .NH3 where Y is a C 1 to C 6 alkyl group, it is particularly a methyl, ethyl or (straight or branched) butyl group.

The group R 2 in formulae and (II) is desirably either H or a methyl, ethyl, propyl or butyl (including branched propyl and butyl) group. Where R 2 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 R 2 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 containing 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 (including la, 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. 10 to 35, ethylene glycol residues and where it is a polyoxypropylene chain it will usually have 10 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 i repeat length of the polyoxyalkylene chain are average values. As is common to surfactants containing 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),

I

WO 94/00508 PCT/GB93/01335 5 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

R

1 is a C 14 to 022, particularly a C 14 to C 20 and very particularly a

C

14 to C 18 alkenyl or alkyl group are especially desirable.

Similarly, compounds where the group R or R 1 is an alkenyl group are more desirable than those where the group is alkyl. Compounds where the group R or R 1 is an alkenyl group, particularly a C 14 to alkenyl group form a specific aspect of the invention.

The compounds of this invention, and particularly those where the group R or R 1 is a C 14 to C22 alkenyl or alkyl group have properties that are entirely unexpected in that the cloud point tends to rise with increasing length of the chain R or R l particularly where this chain is an alkenyl chain. The step from 012 to C 1 4 chains is often particularly notable. At chain lengths longer than C 14 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 unexpected 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/R

1 By way of example in the series of compounds of the formula: H+.-0OC.(HR)C.C(HR1).CO.0.(C2H40)n.R 2 where n and R 2 as given below; the cloud points (OC) for compounds with R or R 1 groups in the range to 18 are as follows: C atoms in group R/R 1 8 12 14 16 18

R

2

CH

3 n 7 37 70-81 52-53 51-52

R

2 H, n 8 <5 43 56.5 (The compounds in this table where R 2 H and R/R 1 chain length is 12 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 WO 94/00508 PCT/GB93/01335 6 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 compounus where the group R or R 1 is an alkenyl group, particularly as compounds where it is alkyl generally have lower cloud points than the corresponding alkenyl compounds.

The compounds of formula where A 1 is and Y is H can be made by reacting an alkenyl or alkyl succinic anhydride with a compound of the formula: H.A.(CmH2mO)n.R 2 (where A, m, n .nd R 2 are as defined above).

The reaction between the anhydride and the polyalkylene glycol, polyalkylene 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 200°C and even below 100 0 C. The reactants will usually be used in\at least approximately 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 corresponding to the two senses of the anhydride ring opening reaction. We have noted that the alkenyl or alkyl chain seems to have e. 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.

Compounds 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 corresponding base e.g. alkali metal such as sodium or potassium, hydroxide or carbonate, ammonia or amine, including alkanolamines such as etbanolamine.

Compounds of the invention where A 1 is other than 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, WO 94/00508 PCT/GB93/01335 7 particularly an ester with a C 1 to C 6 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 amine (YNH 2 (where Y is as defined above). The esterification of the free acid can be carried out in a conventional manner for example using an acid catalyst which may be sulphuric, toluene sulphonic or a phosphoric acid. Phosphoric acids can be particularly useful as, after neutralisation, they may be a useful component of detergent compositions which include the surfactants of this invention.

Compounds of the formulae la, Ib, Ic and Id can, thus, be made as follows: Ia reacting a polyoxyalkylene glycol or derivative of the formula: HO.(CmH2mO)n.R 2 with a C 14 to C 22 alk(en)yl succinic anhydride to give a compound of the formula:

HOOC.(HR)C.C(HR

1 ).CO.O.(CmH2mO)n.R 2 and (where Y is other than H) reaction with an alkali material.

Ib esterifying a compound of the formula la, especially where Y is H, with a low molecular weight alcohol, particularly methanol, ethanol or a butanol, followed, if necessary, by a transesterification with an alcohol YOH to give the desired product.

Ic reacting a amino polyoxyalkylene glycol or derivative of the formula: H2N.(CmH2mO)n.R 2 with an alk(en)yl succinic anhydride to give a compound of the formula:

HOOC.(HR)C.C(HR

1 ).CO.NH.(CmH2mO)n.R 2 and (where Y is other than H) reaction with an alkali material.

Id reacting a amino polyoxyalkylene glycol or derivative of the formula: HZN.(CmH2m0)n.R 2 with an alk(en)yl succinic anhydride to give a compound of the formula:

HOOC.(HR)C.C(HR.

I

.CO.NH.(CmH2mO)n.R 2 followed by esterification with a low molecular weight alcohol, WO 94/00508 PC/GB93/01335 8 particularly methanol or ethanol, followed by an amidation reaction with an amine YNH 2 to give the desired product.

Compounds of the formula (II) where Y is H+ 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 each A are independently as defined above.

Compounds where Y is another cation or a C 1 to C 6 alkyl group (R 3 or a group of the formula (CmH2mO)n.R 2 where m, n and R 2 are independently as defined above; can be made as described above for compounds of the formula 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 polyalkylene glycol chain length can be controlled by using a polyalkylene glycol or polyalkylene glycol alkyl ether of a narrow range 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 200Z excess at a temperature in the range 150 to 400 0 C and preferably 180 to 250 0

C

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 an described above the double bond normally lies in the 2-position in the alkenyl substituent.

To make products where the group R or R 1 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 WO 94/00508 PCT/GB93/01335 9 Raney nickel or a Pd/C catalyst. Temperatures of from 15 to 10 OC and pressures of 0 200 bar absolute may be used and, if desired a solvent may be present. For example, the hydrogenation reaction on an alkanyl succinic anhydride may be carried out at 20 0 C using 5Z w/w of S Pd/C catalyst over a period of for example 6 to 24 hours.

It is desirable that the R, R 1 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 grov- 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 f"r crude oil transportation and fuel systems, emollients for personal (skin) care; domestic detergent composition for example laundry liquids; the dispersion or organic and inorganic powders in paints and coatings filler and pigments) and agrocaemical formulations pesticides); wetters in so-called industrial and institutional cleaning products 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 wax is a complex mixture of fatty materials secreted onto the wool by the skin of the sheep. Wool wax is removed from the wool, prior to use of the wool in textiles, by washing the wool with an aqueous mix including surfactants typically at moderately elevated temperatures e.g. 40 to 80 0 C, particularly 50 to 70 C. This process is called wool scouring. Our testing indicates that the surfactants

I

WO 94/00508 PCT/GB93/01335 10 of this invention are vert effective wool scouring surfactants, in particular retaining 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 (la) above, particularly where m is 2, n is from 2 to 25, particularly 3 to and where R 2 is a C 1 to C 6 alkyl group, especially a methyl group are especially effective. The surfactant in this application is typically used at a concentration of from 0.1 to 5, particularly from 0.2 to g.1- 1 The invention accordingly includes a method of treating wool to remove wool wax which method comprises washing *he wool, containing wool wax, with an aqueous mix including an effective amount of a compound of the formulae or (II) above, in particular a compound of the formula (Ia) above, especially where m is 2, n is from 3 to and where R 2 is a C 1 to C 6 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 polymilrs such as polyacrylamide is usually carried out by an emulsion polymerisation route in which th lymer is accumulated in an aqueous phase (in which it is soluble) 2t is well k1aown that polyacrylamides can give aqueous solutions having high viscosities even at low concentrations; this is the basis of their use as thickeners 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. However, the polymer is typically used in a aqueous environments, so at some point the emulsion must be inverted to give an aqueous continuous phase.

I

This is typically done on dilution of ;iwater in oil emulsion into water. Usually, a surface active agent that promote$ 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 invention for this end use will depend on the specific operating conditions, we have found that oompounds of the formula (1a) above, particularly where m is 2, n is from 8 to particularly 10 to 15, and where RZ is Hi or a C 1 to C 6 alkyl group, particularly a methyl, ethyl, propyl or butyl group, are especiall 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 5Z of the water in oil emulsion are typical.

The invention accordingly includes 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 or (11) above, in particular a compound of the formula (Ia) above, especially m is 2, n is from 8 to 25, particularly 10 to 0 15, and where R2 is H or a Cl to C 6 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.

Throughout the description and claims of the specification the word "comprise" and variations of the word, such as "comprising" and "comprises" is not intended to exclude other additives, components, integers or steps.

34 -~k WO 94/00508 PCT/GB93/01335 12 The following Examples illustrate the invention including the manufacture 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 (or minutes for slow wetters).

Foam height (FH) Ross Miles foam height was assessed by ASTM D 1173-53 at 60 0

C;

results are in mm.

Surface Tension (ST) was measured on a 0.1Z w/w solution by the drop method at 23°C; results are in mN.m- 1 (1 mN.m- 1 1 dyne.cm- 1 Synthesis Examples SE1 to SE24 Various compounds of the invention were made by reacting stoichiometric mixtures of an alkenyl succinic anhydride and poly-> ethylene glycol (PEG), an alkyl polyethylene glycol ether or amine derivative, as set out in Table 1 below, by heating the mixture to about 1000C. Samples taken every 30 minutes until the reaction was complete as determined by infra red spectroscopy and/or the acid val.e of the mixture.

WO 94/00508 PCT/GB93/01335 13 Corresponding sodium salts were made by addition of NaOH solution to the acid product until the pH 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 corresponding methods.

Comparative materials of similar structure were also prepared by the general method described but substituting the appropriate starting materials. These are identified by the prefix before a number.

Various properties of the compounds were measured and the results are given in Table 2 below. For further illustration a commercially 1 5 available nonyl phenol ethoxylate (with 9 moles of EO per mole phenol) is included in Table 2 under the reference 'NPE'.

The properties of compound SE1 are as follows: Surface Tension (0.1Z w/w solution) (Drop Method at 23 0 C) mN.m- 1 Pour Point (OC) Viscosity (cps/25 0

C)

Foam Heights (mm) (Ross Miles at 60°C) Density (g.cm- 3 at 23 0

C)

Wetting (Draves seconds) Cloud Point °C 28.4 165 0 min 5 min 7.5 3 1.006 10.5 sees 40 53 WO 94/00508 PCT/GB93/01335 14 TABLE 1 I Ex IFormulaI R/R1 A I Alj m n R 2 y INo 1(1)1 I 1(1)l(1) SEI I I 14u I 2 3.7 i1 H SE2 I I 12u I 2 13.6 H 1 SE3 II I18u 2 34 H SE4 II 12u 2 18.2 SES I 12u 2 7 1 H SE6 I 14u 2 7 1 H SE7 I 16u 2 7 1 H SE8 I 18u 2 7 1 H C1 I 8u 2 8 H H C2 I 12u 2 8 H H C3 I 12u 2 12 H H SE9 I 14u 2 8 H H SEI0 I !2u 0-1-0- 2 4 1 H SEllI I 12u 2 12 H 4 SE12 I 14u 2 45 1 H SE13 I 14u 2 10 4 H SE14 I 14u 2 12 H i I 14u 2 12 H 4 SE16 I j16u 2 45 1 H SE17 I 18u 2 17 1 H SEIB I 18u 2 45 1 H SEI9 I 14u 2 12 H H Il 12u 2 34 H SE21 II 14u 2 34 H SE22 II 114u 2 34 H SE23 I 18u 2 34 H SE24 I 14s 2 8 H H I 14s 2 12 H H SE26 I 18s 2 12 H H the number of carbon atoms in the substituent chain is given, for R(R 1 indicates that the substituent is an alkenyl group for R 2 for Y indicates that the substituent is an alkyl group; H hydrogen and a number the length of an alkyl group.

H indicates Y H and a number the alkyl chain length.

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

WO 94/00508 I'CTr/GB93/01335 15 TABLE 2 I *I r T r ST j CP FH Wtg Ex i (mN.m-l) I 0 C) I (nm) (S) No I I O OminlSmin Si I I I i SE j 28.4 40-53 I 7.5 I 3 10.5 I ISE2 F 0.3 198 j87 ISE3 34.0 ISE4 31.9 10 30.2 37 21 I SE6 30.7 I 70-81 I 46 ISE7 52-53 I i SE j I 51-52 I F >300 IC I 34 1 1C2 33.8 43 IC2 34.6 I 54 I I 66 ISE9 35.7 56.5 I I SE10 I 28.3 21 6.5 I SEll j 31.2 78 I 72 j 58 I SE12

I

I SE13 j 28.8 I 60-65 I I 14 I SE14

I

I SE15

I

ISE16I 96 ISE17I 86-87

I

ISEIBI >96 ISE19 38.7 66 31.6 63 I SE21 35.1 SEZ2 34.1 I SE23 I 34.0 1SE241 43-50

I

1SE251 62 1SE261 74-80 I NPE 29.9

I

i I 1 WO 94/00508 PCT/GB93/01335 16 Applications Examples AEI to AE4 Example AE1 Semi Aoueous 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 be soluble in the cleaning solvent. Secondly they must not stabilise mixtures of the solvent and water thus preventing effective separation of the mixture 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 0.6Z surfactant, 9.4% terpene solvent and 90Z 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.

WO 94/00508 B93/01335 17 Surfactant Appearance after Hours Both layers clear Comments None alcohol 3 EO Alkyl phenol

EO

Oil and water layers cloudy Oil and water layers slightly cloudy Oil and water layers very slightly cloudy Slight haze in both layers Separation complete after 0.5 hours Separation incomplete after 20 hours Separation complete after 10 hours Separation complete after 12 hours Separation complete after 8 hours Complete separation means oil layer of the total volume.

10Z and a water layer of 90Z of Example AE2 Wool Scouring 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 60°C. The residual grease in the last sample to be washed was then meL:ured by extraction with an organic solvent, typically dichloromethane or chloroform. The results are set out in the following table: Product "SYNPERONIC" NP9 "SYNPERONIC" 87K SE1 Z Residual Grease 1.71 2.16 1.24 Commercially available C13-1 5 alcohol alkoxylate Commercially available nonyl phenol ethoxylate WO 94/00508 PCT/GB93/01335 18 Example AE3 Wool Scouring Further tests of wool scouring were carried out using fine merino wool (ca. 20 pm diameter fibres) at a surfactant dose of 0.5 g.1-1 in an aqueous scouring solution containing 4Z by weight of KC1 (to simulate salt accumulation during repeated use of the scouring solution). The scouring was operated at 65 0 C in the scour detergent brls and at 50 0 C in the rinse bowls. The scouring solutions were\ reused a number of times and the weight percentage of residual wool wax on the wool after each treatment was noted and is given in Table 3 below. The product of SE1 was compared with four other scouring surfactants: Code Product Name Source Description Lissapol Lissapol Lissapol Softanol TN450 BD20 BD30 90 ICI Australia ICI Australia ICI Australia Nippon Shokubai nonyl phenol ethoxylate biodegradable wool scourer biodegradable wool scourer secondary alcohol ethoxylate Table 3 Run Surfactant No I SSE1 C3 C4 C5 C6 I I I I I I* I 1 1.13 0.81 1.08 1.02 0.77 2 0.96 0.95 1.38 0.87 0.73 3 i 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 I I The results given in invention performs well shows good retention of even in treating a wool Table 3 show that the compound of this as a wool scouring agent and in particular performance as compared with current agents, that is known to be difficult to scour.

l WO 94/00508 PCT/GB93/01335 19 Example AE4 Polvacrylamide Emulsion Inversion The following mixture was polymerised by heating to about using as the primary emulsifier a commercially available polymeric surfactant sold under the trade name "HYPERMER" 2296.

Acrylamide Acrylic acid Demin Water Hydrocarbon Solvent (Isopar L) Sodium hydroxide Ethylene diamine tetra acetic acid (EDTA) Azobisisobutyronitrile (AIBN) Primary emulsifier 135.0g 58.0g 179.0g 168.Og up to pH 6 5.2g 0.4g 8-12g 3% of each of the surfactants jelow was added as an inverting agent to a sample of the polymer emulsion and the mixture allowed to rest for 2-3 days. A sample of emulsion was then taken and a 1Z blend 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: "SYNPERONIC" NP9 SE11 SE19 C3 Viscosity (mPa.s) After 2 mins After 15 mins 12000 26000 11500 26000 24000 24500 coagulated These results show that SE11 is equivalent to the conventional inverting agent "SYNPERONIC" NP9 and SE19 is superior and that compound C3 does not act effectively as an inverting agent.

Claims (10)

1. 8. A compound as claimed in any one of claims 1 to 7 wherein mis 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.
2. 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 (111) or (IV) as defined below: Y.A 1 .OC.(HR)C.C(HR').CO.A.(CmH 2 mO)n.R 2 where S 15 one of R and R 1 is Ce to C22 alkenyl or alkyl and the other is hydrogen; *4 A is or -NR 4 where R 4 is hydrogen or C1 to C6 alkyl; n is 2 to 100; m is 2 or 3 (and may vary along the polyoxyalkylene chain); R is hydrogen or C1 to C6 alkyl; 20 A 1 is -O or -NR 4 where R 4 is hydrogen or C, to C6 alkyl, such that when A 1 is -O0, Y is a cation; and 4 when A' is or -N 4 Y is a C, to C6 alkyl group (R 3 or a group of the formula (CmH2mO)n.R 2 wherein m, n and R 2 are independently as defined above; C.\WINWORDUULIESPECIES\43505-93 DOC 23 provided that when A is or A 1 is the total number of carbon atoms in the groups R, R' and any groups R 2 and R 3 is at least 13. or Y.A'.OC.(HR)C.C(HR 1 ).CO.A.(CmH 2 mO)n.CpH 2 p.A.CO.(HR 1 )C.C(HR)CO.A 1 Y (IV) where: n, m and each R, R 1 A, A 1 and Y are independently as defined above; and p is 2 or 3.
3. 10. A method as claimed in claim 9 wherein the compound is a compound of the formula (la) where m is 2, n is from 3 to 10 and where R 2 is a C 1 to C6 alkyl group.
4. 11. A method of inverting a water in oil emulsion containing polyacrylamide in S 15 the aqueous phase which comprises including in the water in oil emulsion a compound of the formulae (III) or (IV) as defined in claim 8 and subsequently diluting the water in oil emulsion into water to invert it:
5. 12. A method as claimed in claim 11 wherein the compound is a compound of 20 the formula (la) where m is 2, n is from 8 to 25, and R 2 is H or a C 1 to C6 alkyl group.
6. 13. A compound of the formulae or (II): a. Y.A'.OC.(HR)C.C(HR').CO.A.(OnH 2 mO)nR. 2 (I) where one of R and R' is straight chain C 6 to C22 alkenyl or alkyl and the other is hydrogen; A is or -NR 4 where R 4 is hydrogen or C, to C6 alkyl; C \WINWORDUUUSPECIES43505-93 DOC i. n is 2 to 100; m is 2 or 3 (and may vary along the polyoxyalkylene chain); R 2 is hydrogen or C, to C6 alkyl; A' is O or -NR 4 where R 4 is hydrogen or C, to Co alkyl; such that when A' is Y is a cation; and when A' is or -NR 4 Y is a C, to C6 alkyl group (R 3 or a group of the formula (CmH2mO)n.R 2 where m, n and R 2 are independently as defined above; provided that when A is or A' is the total number of carbon atoms in the groups R, R 1 and any groups R 2 and R 3 is at least 13. or Y.A'.OC.(HR').CO.A.CmH 2 mO)n.OpH 2 p.A.CO.(HR')C.C(HR)CO.AY (II) where; S.n, m and each R, R 1 A, A' and Y are independently as defined above; and p is 2 or 3.
7. 14. A compound as claimed in anyone of claims 1 to 8 wherein one of R and R' is straight chain C6 to C22 alkenyl or alkyl and the other is hydrogen.
8. 15. A compound according to claim I or claim 13 substantially as hereinbefore described with reference to any one of the examples. DATED: 25 March 1997 PHILLIPS ORMONDE FITZPATRICK Attorneys for: IMPERIAL CHEMICAL INDUSTRIES .C O tipIECt 1IcIM WO kA I t INTERNATIONAL SEARCH REPORT lntieadoWa Application No PCT/GB 93/01335 I. CLASSIFICATION OF SUBJECT MArrE (if several classfication sytabots apply, Indica%# all)' According to Inrnational Paient Classification (IPC) or to both National Classificatin and ArC Int.Cl. 5 C08G65/32; 001C3/OO; C111311/OO; C08F20/56 H. FIELDS SEARCI[ED Minimum Documentation Stitched, Classification System JClassifi Cation Symbols Int.Cl. 5 CO8G Documentation Stirched other thin Minimum Documentation to the Extent that such Documents are Included In the Fields Searchedl IDI. DOCUMENTS CONSIDERED TO BE RELEVANT' Claegory f Citation of Document, It with Indication, where appropriate, of the relevant passage%' 2 Relevant to Claim No.LI X WG,A,8 700 856 (THE LUBRIZOL CORPORATION) 1,2,7-8 i2 February 1987 see claim 1 see page 7, paragraph 2 see page 8, paragraph 1 see page 8, paragraph 2 see page 9, line 6 line 8 X GBA,2 131 820 (CHEVRON RESEARCH CO.) 1-3,7,8 27 June 1984 see examples 1,2 X EP,A,O 384 605 (TEXACO DEVELOPMENT CORP.) 1,2,6,7, 29 August 1990 8 see claim 1 see page 6, line 15 line S pedal categories of Cited documents.-1 'To later document puablished after the International filing date the enerl stte f th ~notor priority date and not in conflict with the application but WA document defining tegnrlsaeothatwicIsotCited to understand the principle or theory uniesiying the considered to be of prmular relevanceIneto OEr earlier document but publIshe on or after the International Xr document of particular relevance; the claimed Invention filing date cannot be considered novel or cannot be consWdre to IV' document which may throw doubts co priority clIm=(s) or Involve an inventive step which Is cited to establish the publication date of another e document Vf particular relevance; the claimed Invention cdttion or other special reaso (as specied) cauot be cnasiderd to Involve an inventive step whem the '00 docment referting to an oral disclosume use, exhibition or docoment Is combined with one or more other such docu- other mumn meats such combination being obvious to a person skiiled 'P document published prior to the International filing date but In 111%,!W4 later than the priority date Claimed W& document member of the same patent famUy MV CERTIFICATION Date of the Actual Completion of the International Search Date of Miling of this International Search Report 24 SEPTEMBER 1993 1 2. 10. 93 International Searching Authority Signature of Authorized Officer EUROPEAN PATENT OFFICE O'SULLIVAN T.P. PCr/S120lcs t h (awE~my MAes I.International ApplIcation No PCT/GB 93/0133b 13. DOCUMENTS CONSIDERED TO BIE RELEVANT (CONTINUED FROM THE SECOND Categor,# Citation of Document, with Indication, whers appropriate, of the relevant panssa ldsvant to Claim No. A EP,A,O 107 199 (CHINOIN ETC) 1,2,8-12 2 May 1984 cited In the applicatioai see claims 1-3 I-i Fr PCT/15A210 Iexir 1"d) POSMa7 1915) -WOMMMMMUMM" 4 q ANNEX TO THE INTERNATIONAL SEARCH REPORT G ON INTERNATIONAL PATENT APPLICATION NO. GB 9301335 75532 This annex list the patent family membere relating to the patent documents cited in the above-waietioried International serc report. The mnembers an as contained in the European Patent Office EDP file on The European Patent Office is in no way liable for theme particulars which ame merely given for the purpose of information. 24/09/93 Patent document Publication IPatent famnily I Publication cited in search report I date Imember(s) dae WO-A-8700856 12-02-87 US-A- AU-B- AU-A- EP-A, B JP-T- US-A- 4661275 595226 6144186 0231287 63500725 4749500
9. 28-04-87
10. 29-03-90 05-03-87 12-08-87 17-03-88 07-06-88 GB-A-2131820 27-06-84 BE-A- 898441 30-03-84 DE-A- 3345058 14-06-84 OE-A- 3348402 19-03-92 FR-A- 2537454 15-06-84 JP-A- 59115733 04-07-84 NL-A- 8304253 02-07-84 SE-B- 459789 07-08-89 SE-A- 8306812 14-06-84 US-A- 4695401 22-09-87 US-A- 4915786 10-04-90 EP-A-0384605 29-08-90 US-A- 4968321 06-11-90 AU-B- 621710 19-03-92 AU-A- 4913890 09-08-90 CA-A- 2009287 06-08-90 EP-A-0107199 02-05-84 EP-A,B 0032289 22-07-81 0I ea For more details about this annex -see Official Journal of the European Patent Office, No. 12182