NZ253297A

NZ253297A - Polyoxyalkylene esters and amides of alk(en)yl succinic anhydrides; use as surface active agents in wool scouring and to invert polymer emulsions

Info

Publication number: NZ253297A
Application number: NZ253297A
Authority: NZ
Inventors: Neil Michael Carpenter; Gordon Mcgregor; Clive Edward Wilne
Original assignee: Ici Plc
Priority date: 1992-06-26
Filing date: 1993-06-25
Publication date: 1997-02-24
Also published as: ZA934479B; RU2118641C1; AU4350593A; SK159694A3; EP0647248A1; GB9313096D0; GB9213571D0; AU679918B2; WO1994000508A1; FI946075A0; TW256854B; JPH07508546A; RU94046395A; KR950702215A; CZ328094A3; CA2139003A1; FI946075A; HUT68780A

Description

<div class="application article clearfix" id="description"> New Zealand Paient Spedficaiion for Paient Number £53297 New Zealand No. International No. 253297 PCT/GB93/01335 ♦ Complete Specification Filed: Class: .9oic^33]poj...^.^c.3loo Publication Dote:.... 2 199?- P.O. Journal No: NEW ZEALAND PATENTS ACT 1953 COMPLETE SPECIFICATION Title of Invention: Surfactants derived from polyoxyalkylenes and substituted succinic anhydrides Name, address and nationality of applicant(s) as in international application form: IMPERIAL CHEMICAL INDUSTRIES PLC, a British company of Imperial Chemical House, Millbank, London SW1P 3JF, England (FOLLOWED BY PAGE 1A) 253297 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 C22 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 (I) or (II): where one of R and R1 is a straight chain Cq to C22 alkenyl or alkyl and the otfter is hydrogen; A is - 0 - or - NR^ where R* is hydrogen or Ci to C6 alkyl, particularly methyl or ethyl; n is 2 to 100 (and as it is an average it may be non-in Y.Ai.OC. (HR)C.C(HRl) .CO.A. (C^H2m°)n»R2 (I) m is 2 or 3 (and may vary along the polyoxyalkylene cha 253297 R2 is hydrogen or Ci to Cg alkyl; A1 is - 0 - 0" or -NR^- where R4 is hydrogen or Ci to Cg alkyl, particularly methyl or ethyl; such that when A1 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 ammonium or an alkanolamine ammonium ion); and when A1 is - 0 - or -NR^-t Y is a C]_ to Cg alkyl group (R3) or a group of the formula (CmH^mOn.R2 where m, n and are independently as defined above; provided that when A is - 0 - or A1 is - 0" the total number of carbon a* -Jms in the groups R, R1 and any groups R2 and R3 is at least 13 and is desirably 13 to 50; Y.Al.OC. (HR)C.C(HR1) .CO.A. (Cn^2mO)n-CpH2p.A.CO. (HR1)C.C(HR)C0.A1.Y n, m and each R, R1, A, A1 and Y are independently as defined above; and p is 2 or 3. In a further aspect the present invention provides 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 above. In a still further aspect the present invention provides 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 fori or where: (II) or (IT): - 2a - 253297 Y.A1.OC.(HR)C.C(HR1).CO.A.(C H, 0) .R2 (T) m n where one of R and R^ is; Cg to alkenyl or alkyl and the other is hydrogen; 4 4 A is - 0 - or -NR where R is hydrogen or C1 t<T alkyl; n is 2 to 100; m is 2 or 3 (and may vary along the polyoxyalkylene chain); 2 R is hydrogen or C« to C, alkyl; 1-4 4 A is - 0 - 0 or -NR where R is hydrogen or to Cg alkyl; such that when A^ is - o", Y is a cation; and 1 4 when A is - 0 - or -NR 3 Y is a C, to C, alkyl group (R ) or a group of the formula 2 '2 (C H„ 0) .R , wliere m, n and R are independently as defined above; n • n * _ provided that when A is - 0 - or A i6 - 0~ the total number of carbon 1 2 3 atoms in the groups Rt R and any groups R and R is at least 13* or Y.A^.OC.(HR)C.C(HR1).CO.A.(CmH2m°)n-CpB2p-A.CO.(HR1)C.C(HR)C0.A1Y where: n, m and each R, R1, A, A1 and Y are independently as defined above; and p is 2 or 3 J. arid subsequently diluting the water in oil emulsion into water to invert it. For convenience of definition, the free acid forms of compounds of the formula? (I), (!'), (II) and (IT) in are defined with Y as a IT 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) and (T)» A and A1 are desirably both - O -, both - NR* -, particularly - NH -, or A s - NR* -, particularly - NH and A1 is - 0 -. Accordingly, the following particular sub-groups of compounds of the formula (I) form specific aspect the invention (see also below about R and R1). - 3 - (la) Y.-OOC.(HR)C.C(HR1).COO. (Cm^O)n-&2 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 R1 is a straight chain C14 to C22* especially a C14 to C20» alkenyl or alkyl group and the other Is hydrogen. (Ib) Y.O.OC. (HR)C.C(HRl) .CO.O. (Cn£2i&°>n*R2 where n, n and R2 are as defined above formula (I); Y is "2 Ci to C5 alkyl group or a group of the formula (CmH2mO)n.R2 as defined above for formula (I); and R and R1 are as defined above for formula (I), but particularly where one of R and R1 is a straight chain C14 to C22> especially a C14 to Cgo* alkenyl or alkyl group and the other is hydrogen. (Ic) Y.O.OC. (HR)C.C(HR1) .CO.NH.(Cn^2m0)n-R2 where Y, m, n and R2 are as defined above formula (I); and R and R* are as defined above for formula (I), but particularly where one of R and R1 is a straight chain Cj4 to C22» especially a C14 to C20» alkenyl or alkyl group and the other is hydrogen. (Id) R2. (0,^2010 )n.NH.OC.(HR)C.C(HRl).CO.NH.(C,na2mO)n-R2 where each m, n and R2 is independently as defined above for formula (I)i and R and R1 are as defined above for formula (I), but particularly where one of R and R1 is a straight chain C14 to C22» especially a C14 to C2o> alkenyl or alkyl group and the other is hydrogen. Preferred compounds for use in the method of the invention for inverting a water in oil emulsion are corresponding compounds of formula la', lb', Ic1 and Id1 wherein one of R and R1 is a straight or branched chain Cu to C^, especially C14 to C20, alkenyl or alkyl group and the other is hydrogen. The compounds of the general formula (II) and (IT) can be considered as di(substituted succinyl) functional derivatives of a polyoxyalkylene moiety. Usually, the respective groups A and A1 and Y will be the same. Desirably both groups A are - 0 - or - NR* particularly—' _ - NH -, and both groups A1 are - 0- with Y being a cation. --5imilarlf >- , 4' " the alk(en)yl groups in the groups R and R1 will usually t^e ..the same. o V < G M ^97 253297 253297 Where, in formulae (I), (T), (II) and (IT) Y is a cation, it is desirably BP, 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 Ci to Cg alkyl group, . it is particularly a methyl, ethyl or (straight or branched) butyl group. The group R2 in formulae (I), (T), (II) and (IT) 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 vhere 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 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 ps the group (Cn^2oP)n in formula (I) (including la, lb and Ic), (T) (including la', lb', Ic' and Id1), (II) and (IT). - The chain length of this group, i.e. the value of the parameter jar, • I J will generally be chosen to provide the desired properties in the. intended product.. Typically, where the polyoxyalkylene chain is a^CEi^ 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. Vhere 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 containing a polyoxyalkylene chain, the longer the chain *nd the higher the proportion of ethylene glycol residues, the more hydrophilic the product. In compounds of the formula (II) and (IT), 253297 5 if along the polyoxyalkylene chain m is constant then p will usually be the same as m. i Among the compounds of the invention, those where the group R or R1 is a straight chain Cu to C^ particularly a CM to and very particularly a C14 to C18, alkenyl or alkyl group are especially desirable. Similarly, compounds where die group R or R1 is a straight chain alkenyl group are more desirable than those where the group is a straight chain alkyl. Compounds where the group R or R1 is a straight chain alkenyl group, particularly a straight chain C14 to C20 alkenyl group form a specific aspect of the invention. 10 The compounds of this invention, and particularly those where the group R or R1 is a straight chain C14 to C22 alkenyl or alkyl group have properties that are entirely unexpected in that the cloud point tends to rise with increasing length o£ the chain R or R1, particularly where tLj.s chain is an alkenyl chain. The step from C12 to C2.4 chains is often 15 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 Ci2» This tre^d in cloud point indicates increasing water solubility of the compounds with increasing chain length which is completely unexpected and runs 20 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/R1;*" By way~«f • example in the series of compounds of the formula: H+."00C. (HR)C.C(HR^) .CO.O. (C2B40)n.R2 where n and R2 as given below; 25 the cloud points (°C) for compounds with R or R* groups in t' 10 to 18 are as follows t (The compounds in this table where R2 - H and R/R1 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 35 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 C atoms in group R/R^ R2 - CH3, n - 7 30 R2 - H, n - Q <5 43 56.5 8 12 14 16 18 37 70-81 52-53 51-52 • 253297 - 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 . 5 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 R1 is an aJLkenyl group, particularly as compounds where it is alkyl generally have lower cloud points than the corresponding alkenyl compounds. i o The compounds of formula (I) or (T) where A1 is -O" and Y is IT can be made by reacting an alkenyl or alkyl succinic anhydride with a compound of the formulat H.A. (CfflH?tnO)r». R2 (where A, m, n and R2 are as defined above). The reaction between the anhydride and the polyalkylene glycol, poly-15 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 200°C and even below 100°C. The reactants will usually be used in\at 20 least approximately stoichiometric proportions. Particularly vhere 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 25 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. Compounds of the invention vhere Y is a differe: : cation can be 30 made uy salt formation from the free acid (Y «• H+). Vhere 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 ethanolamine. ' 25 Compounds of the invention where A^ 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, !/\M v337 C E 10 20 25 30 7 - 7 - particularly an ester with a Cj. to Cg or polyalkylene ftyWl all 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 (YNH2) (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 sthich 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, lb, Ic and Id can, thus, be made as follows: ia reacting a polyoxyalkylene glycol or derivative of the formula: HO.CQnHaaOX.R2 with a straight chain CM to Qq alk(en)yl succinic anhydride to give a compound of the formula: HOOC.(HR)C.C(HR1).CO.O.(CinH2m0)n-R2 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 trans- ^ esterification with an alcohol YOH to give the desired product. Ic reacting a amino polyoxyalkylene glycol or derivative of the formula: HjN^CJH^O^.R2 with a straight chain alk(en)yl succinic anhydride to give a compound of the formula* HOOC. (BK)C.C(HR1) .CO.NB. (C^H^O)n.R2 and (where Y is other than H) reaction with an alkali material. Id reacting a amino polyoxyalkylene glycol or derivative of the formula: H2N.(CmH2mO)n.R2 with a straight chain alk(en)yl succinic anhydride to give a compound of the formula: HOOC.(HR)C.C(HR1) .CO.NH. (0^21^0)n*K2 f - u followed by esterification with a low molecular weight al£oKol, k ' 1 6 JAN 1937 fC E - a - 253297 particularly methanol or ethanol, followed by an amielation reaction with an amine YNH2 to give the desired product. Corresponding compounds of formula la', lb', Ic1 and Id' wherein R or R1 is either a straight or branched chain C14 to Qa alkyl or alkenyl group may be similarly produced. Compounds of the formula (II) where Y is H+ can be made by reacting 2 moles of a straight chain alk(en)yl succinic anhydride with one mole of a compound of the formula: H«A. (CmH^TnO)n » CpH?p. A.H ■""* where m, n, p and each A are independently as defined above. Compounds where Y is another cation or a Ci to Cg alkyl group (R3) or a group of the formula (CmH9mO)n.R2 where m, n and R2 are independently as defined above; can be made as described above for compounds of the formula (I). Compounds of formula IT may be similarly produced. 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 maieic anhydride preferably with an excess of an olefin having 6 to 22, particularly 14 to 22, carbon atoms for example a SO to 200Z excess at a temperature in the range 150 to 400°C and preferably 180 to 250°C -nd 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 th 2-position in the alkenyl substituent. To make products where the group R or R1 is an alkyl group 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 253297 Raney nickel or a Pd/C catalyst. Temperatures of from 15 to 100°C 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 alkenyl succinic anhydride may be carried out at 20°C using 5Z w/w of Pd/C catalyst over a period of for example 6 to 24 hours. It is desirable that the R, R1 alkyl or alkenyl group of the compounds used in the method of inverting an oil in water emulsion of the invention,also 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 elkenyl 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, baaed on semi-soluble oil and synthetics and for 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 (e.g. filler and pigments) and agrochemical 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 str.eep, the voellen 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°C, particularly 50 to 70°C. This process^" is called wool scouring. Our testing indicates that the surfactants WO 94/00508 PCT/G B93/01335 - 10 - 05 this invention are very 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 5 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 10, 10 and where R2 is a to Cq 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 1.5, g.1-1. The indention accordingly includes a method of treating wool to 1*5 remove woox 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) above, in particular a compound of the formula (la) above, especially where m is 2, n is from 3 to 10 and where R2 is a to alkyl group, particularly a methyl group. 20 The invention also includes the use of such compounds of the invention as wool scouring surfactants. The manufacture of polymers such as polyacrylamide 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 25 well known 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 30 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, 35 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. - 11 - 253297 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 invention for this end use will depend on the specific operating conditions, we have found that compounds of the formula (ia*) y.-ooc. (HR)C.C(HR1) .coo. (CoH2a0>n-R2 where _ m, n and R2 are as defined above for formula (F) ; Y is a cation as defined above for formula (I") t and one of R and R^ is a C14 "to C22. especially a C3.4 to C20. alkenyl or alkyl group and the other is hydrogen; particularly where m is 2, n is from 8 to 25, pSrticularly 10 to 15, and where R2 is H or a Cj. to Cg 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 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 formula (I') or (IT) in particular a compound of the formula (la1) above; especially m is 2, n is from 8 to 25, particularly 10 to 15, and vhere R2 is B or a Ci to Cg 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 formula T and II' of the invention as polyacrylamide water in oil emulsion inverting agents. ,VVO 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) 0 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 5 wetters]. Foam height (FH) Ross Miles foam height was assessed by ASTM D 1173-53 at 60°C; results are in mm. 20 Surface Tension (ST) was measured on a 0.1Z w/w solution by the drop method at 23°C; results are in rnN.m"^- (1 mN.nr^- « 1 dyne.cm"^). 25 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 100°C. Samples taken every 30 minutes until the reaction was complete as determined by infra red spectroscopy and/or the acid value 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 5 acid and methanol. Methanol wa« 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. ^ to 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 '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 *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: 20 Surface Tension (0.1Z w/w solution) (Drop Method at 23°C) mN.m"^ 28.A Pour Point (°C) -15 Viscosity (cps/25°C) 165 Foam Heights (mm) 0 min 5 min 25 (Rosg Miles at 60°C) 7.5 3 Density (g.cm-3 at 23°C) 1.006 Vetting (Draves - seconds) 10.5 sees Cloud Point °C 40 - 53 O 94/00508 PCT/GB93/01335 - 14 -TABLE 1 i Ex . I j Formula R/R1 t A A1 - T m — n R2 l Y | | No (1) (2) (1) (1) | | SE1 i I 14u -0- -0- 2 3.7 1 H | ! SE2 | I 12u -0- -0- 2 12.6 H 1 j 1 SE3 1 H 18u -NH- -0- 2 34 - H I | SE4 1 II 12u -0- -0- 2 18.2 - H | | SE5 | I 12u -0- -0- 2 7 1 H i j SE6 | I 14u -0- -0- 2 7 1 H i | SE7 | I 16u -0- -0- 2 7 1 H | | SE8 | I 18u -0- -0- 2 7 1 H I 1 ci 8u -0- -0- 2 8 H H I | C2 | I 12u -0- -o- 2 8 H H j | C3 | I 12u -0- -0- 2 12 H H I ! SE9 | I 14u -0- -0- 2 8 H H I | SE10 i I 12u -0- -0- 2 4 1 H | I SE11 | I 12u -0- -0- 2 12 H 4 | | SE12 | I 14u -0- -0- 2 45 1 H | | SE13 | I 14u -0- -0- 2 10 4 H | SE14 1 I 14u -0- -0- 2 12 H 1 j I SE15 | I 14u -0- -0- 2 12 H ^ 1 | SE16 j I 16u -0- -0- 2 45 1 H | | SE17 | I 18u -0- -0- 2 17 1 H I | SE1B | I 18u -0- -0- 2 45 1 H I | SE19 14u -0- -0- 2 12 H H | | SE20 1 II 12u -0- -0- 2 34 - H I | SE21 1 II 14u -0- -0- 2 34 - H I | SE22 I II 14u -NH- -0- 2 34 - H | | SE23 18u -0- -0- 2 34 - H 1 I SE24 | I 14s -0- -0- 2 8 H H | | SE25 1 I 14s -0- -0- 2 12 H H 1 | SE26 1 | I I 18s 1 -0- ' -0- 2 12 l. H i H | i ' 1 the number of carbon atoms in the substituent chain is given, for R/R1 '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 length. 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 «■ n»). AVO 94/00508 PCT/GB93/01335 - 15 - TABLE 2 5 15 20 t Ex No 1 ST | (mN.m"1) j CP (°c> FH (mm) 1 Omin | • ■ 5 min Wtg (s) SE1 28.4 | 40-53 i 1 7.5 | 3 10.5 SE2 30.3 j 98 | 87 SE3 34.0 j 1 SEA 31.9 | 10 1 55 SE5 30.2 | 37 1 21 SE6 30.7 j 70-81 1 46 SE7 | 52-53 1 70 SE8 | 51-52 1 >300 CI 34 | <5 1 C2 33.8 | 43 1 C2 34.6 j 54 1 66 SE9 35.7 | 56.5 1 SE10 28-3 j 21 1 6.5 SEll 31.2 j 78 72 | 58 SE12 1 SE13 28.8 | 60-65 1 14 SE14 1 SE15 1 SE16 >96 1 SE17 86-87 1 SE18 >96 1 SE19 38.7 | 66 1 SE20 31.6 | 63 1 SE21 35.1 | 1 SE22 34.1 j 1 SE23 34.0 | 1 SE24 43-50 I SE25 62 1 SE26 74-80 1 NPE t T 29.9 | l • 1 , _ I 30 O 94/00508 PCT/GB93/01335 - 16 - Applications Examples AE1 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 b^ 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, 9.4Z 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 - 17 - PCT/GB93/01335 Surfactant Appearance after Comments 20 Hours None c CIO alcohol 3 EO 1o Alkyl phenol 4.5 EO SE10 15 SE1 Both layers clear 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 10Z and a water layer of 90Z of 20 the total volume. Example AE2 - Wool Scouring Ten 20g samples of wool were washed successfully in the same bath 25 of a 0.12 w/w solution of surfactant in water (1 litre) at 60°C. The residual grease in the last sample to be washed was then measured by extraction with an organic solvent, typically dichloromethane or chloroform. The results are set out in the following table: 30 Product "SYNPERONIC" NP9 (**) "SYNPERONIC" 87K (*) SE1 35 ** Commercially available C]_3_]_5 alcohol alkoxylate * Commercially available nonyl phenol ethoxylate Z Residual Grease 1.71 2.16 1.24 JVO 94/00508 PCT/GB93/01335 - 18 - Example AE3 - Wool Scouring JO Further tests of wool scouring were carried out using fine merino wool (ca. 20 (im diameter fibres) at a surfactant dose of 0.5 g.l-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°C in the scour detergent bowls and at 50°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: 15 20 Code Product Name C3 Lissapol TN450 C4 Lissapol BD20 C5 Lissapol BD30 C6 Softanol 90 Source ICI Australia ICI Australia ICI Australia Nippon Shokubai Table 3 Description nonyl phenol ethoxylate biodegradable wool scourer biodegradable wool scourer secondary alcohol ethoxylate 25 30 1 \ | Run | Surfactant 1 ' i Nn t- i i 1 1 i i SE1 C3 1 C4 C5 C6 | i i 1 i 1 1.13 0.81 1 | 1.08 1.02 0.77 | 1 2 | 0.96 0.95 | 1.38 0.87 0.73 | 1 3 1 0.96 1.22 | 1.15 0.89 0.86 | 1 4 1 0.93 1.02 | 1.10 1.01 0.94 | 1 ^ 1 0.98 1.19 | 1.74 0.90 ' 1.04 | 1 6 1 0.93 1.07 | 1.36 1.12 0.97 | 1 7 1 0.98 1.02 | 1.18 1.02 1.19 | 1 8 1 i i 1.04 1.20 | 1.76 i 1.17 1.46 | l 35 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. </div>

Claims

<div class="application article clearfix printTableText" id="claims">



_WO 94/00508 PCT/GB93/01335 

- 19 - 

Example AE4 - Polyacrvlam-irie Emulsion Inversion 

The following mixture was polymerised by heating to about 40°C using as the primary emulsifier a commercially available polymeric surfactant sold under the trade name "HYPERMER" 2296. 

Acrylami.de 135. Og 

Acrylic acid 58.Qg 

Demin Water 179.Og 

Hydrocarbon Solvent (Isopar L) 168.Og 

Sodium hydroxide ' up to pH 6 

Ethylene diamine tetra acetic acid 5.2g (EDTA) (51) 

Azobisisobutyronitrile (A1BN) 0.4g 

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 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: 

Viscosity (mPa.s) 

After 2 mins Aftr- 15 mins 

"SYNPERONIC" NP9 12000 26000 

SEll 11500 26000 

SE19 24000 24500 

C3 coagulated 

These results show that SEll 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. 

253297 

WHAT WE CLAIM IS: 

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 straight chain C6 to C22 alkenyl or alkyl and the other is hydrogen; 

A is - O - or -NR4-, where R4 is hydrogen or C1 to C0 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; 

A1 is - O -, - 0~ or -NR4-, where R4 is hydrogen or C1 to C6 alkyl; 

such that when A1 is - O", Y is a cation; and 

14 3 

when A is - O - or -NR -: Y is a C1 to C6 alkyl group (R ) or a group of the formula above; 

t when 1 

groups R, R1 and any groups R2 and R3 is at least 13. 

or 

Y.A1.OC.(HR)C.C(HR1).COA(CmH2mO)n.CpH2p.A.CO.(HR1)C.C(HR)CO.A1Y (II) where: n, n p is 2 or 3. 

2 2 

formula (CmH2mO)n.R , where m, n and R are independently as defined provided that when A is - O - or A1 is - O" the total number of carbon atoms in the where: n, m and each R, R1, A, A1 and Y are independently as defined above; and
2 A compound as claimed in claim 1 in which one of R and R1 is straight chain C14 to C22 alkenyl or alkyl and the other is hydrogen.
3 A compound as claimed in either claim 1 or claim 2 wherein one of R and R1 is straight chain alkenyl and the other is hydrogen. 

^ t u r
4 A compound as claimed in claim 1 of the formula (la): / 

11 

f' ^ 

JAN $97 

-21 - 

253297 

Y."OOC.(HR)C.C(HR1).COO.(CmH2mO)n.R2 (la) 

2 1 

where m, n and R are as defined in claim 1; Y is a cation and one of R and R is a straight chain C14 to C22 alkenyl or alkyl group and the other is hydrogen. 

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

Y.OOC.(HR)C.C(HR1).COO.(CmH2mO)n.R2 (lb) " 

1 2 

where R, R , m, n and R are as defined in claim 1; and Y is a C1 to C6 alkyl group or a 

2 2 

group of the formula (CmH2mO)n.R where m, n and R are independently as defined in claim 1. 

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

Y.'OOC.(HR)C.C(HR1).CO.NH.(CmH2mO)n.R2 (Ic) 1 2 

where R, R , m, n and R are as defined in claim 1 and Y is a cation. 

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

R2.(CmH2mO)n.NH.OC.(HR)C.C(HR1).CO.NH.(CmH2mO)n.R2 (Id) 

1 2 

where R and R and each m, n and R is independently as defined in claim 1. 

8 A compound as claimed in any one of claims 5 to 7 in which one of R and R1 is a straight chain C14 to alkenyl group and the other is hydrogen. 

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

10 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 9. 

11 A method as claimed in claim lOwherein the compound is a compound of the formula 

2 

(la) where m is 2, n is from 3 to 10 and where R is a C1 to C6 alkyl group. 

/V 

" \ - ' 

{ 

\1t 

X; 

; r1* 

V337 

C E 

253^7 

12 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 (T) or (IT): 

Y.A1.OC.(HR)C.C(HR1).CO.A.(CmH2mO)n.R2 (T) 

where I 

1 »• 

one of R and R is C6 to C22 alkenyl or alkyl and the other is hydrogen; 

A is - O - or -NR*-, 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 

A A 

when A is - O - or -NR -, Y is a C1 to C6 alkyl group (R ) 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 - 0~ the total number of carbon atoms in the 

1 2 3 

groups R, R and any groups R and R 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 (IT) where n, m and each R, Rl, A,"Al and Y are independently as defined above; and p is 2 or 3, 

and subsequently diluting the water in oil emulsion into water to invert it. 

13 A method as claimed in claim 12 wherein one of R and R1 is a straight chain alkenyl group and the other is hydrogen. 

14 A method as claimed in either claim 12 or claim 13 in which one of R and R1 is C14 to C22 alkenyl or alkyl and the other is hydrogen. 

15 A method as claimed in any one of claims 12 to 14 wherein the compound is a compound of the formula (la'): . 

(la') Y."OOC.(HR)C.C(HR1).COO.(CmH2mO)n.R2 

v ■ 

y 

L: <\r 

... V 

253297 

2 1 

where m, n and R are as defined in claim 12 ;Y is a cation and one of R and R isaC14 

to C22 alkenyl or alkyl group and the other is hydrogen. 

16 A method as claimed in claim 15;wherein in the compound of the formula (la1) m is 2, n is from 8 to 25, and R2 is H or a C1 to C6 alkyl group. 

17 A method as claimed in any one of claims 12 to 16 wherein in the compound of the formula (T) m is 2; p, if present, is 2; n is from 3 to 50 and Y is a cation which is H+, an alkali metal catioh, or an ammonium cation, or a methyl, ethyl or butyl group. 

18 A compound of the formulae (I) or (II) as defined in claim 1 substantially as herein described with reference to any example thereof. 

19 A method as defined in claim 10 of treating wool to remove wool wax substantially as herein described with reference to any example thereof. 

20 A method as defined in claim 12 of inverting a water in oil emulsion containing polyacrylamide in the aqueous phase substantially as herein described with reference to any example thereof. 

■ICI £HFM'Q4<- PTWrS fV; By the authorised agents A. J "irk & Son 



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