SK159694A3 - Surfactans derived from polyoxyalkylenes and anhydrides of substituted succinic acids and their using - Google Patents

Abstract

Polyoxylalkylene esters and amides of alk(en)yl succinic anhydrides, of the formulae (I) YA<1>.OC(HR)CC(HR<1>)CO.A(CmH2m0)n.R<2> and (II) YA<1>.OC(HR)CC(HR<1>)CO.A(CmH2m0)n.CpH2pA.CO(HR<1>)CC(HR)CO.A<1>Y where R, R<1>, A, A<1>, Y, R<2>, 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 effective in scouring wool and inverting polyacrylamide water in oil emulsions into water.

Description

Technology **

The invention relates to surfactants, and in particular to novel surfactants based on substituted succinic acid derivatives, and to the particular end use of these surfactants.

BACKGROUND OF THE INVENTION

In recent years, there has been an increasing effort to replace the established surfactants with substances with increased biodegradability. However, finding alternatives to excellently active substances that have retained an important position on the market for decades is associated with great practical difficulties.

EP 0107199 B relates to hemiesters of polyoxyalkylene glycols and succinic acids substituted with an alkyl or alkenyl group of 8 to 12 carbon atoms and their salts. These compounds are described as anionic surfactants particularly useful at acidic pHs that are hard water tolerant.

SUMMARY OF THE INVENTION

The invention is based on the discovery of substances which can be derived from alkenylsuccinic anhydrides containing, in particular, C14-C22 alk (en) yl groups and / or functional group substituents anywhere in the molecule, which are materials exhibiting substantially and surprisingly different properties. In particular, they act as non-ionic surfactants, especially in aqueous systems having an unexpected cloud point, indicating good action at elevated temperatures, and having good properties under alkaline conditions. The surfactants of the invention also exhibit good biodegradation properties.

Accordingly, the invention provides compounds of formulas I or II

Y (A) .OC (HR) CC (HR ¹ ) .CO.A (CHO) .R ² (I) n 2 x n n wherein one of R and R ¹ represents an alkenyl or alkyl group of 6 to 22 atoms carbon and the other is hydrogen,

A represents -O- or -NR ⁴ -, wherein

R ⁴ represents a hydrogen atom or a C 1 -C 6 alkyl group, in particular a methyl or ethyl group, n has a value of 2 to 100 (and, as an average value, the product may be nonuniform), m a value of 2 or 3 (and vary in the polyoxyalkylene chain)

R ² is H or alkyl of 1 to 6 carbon atoms,

A ¹ is -O-, -O "or -NR ⁴ -, wherein

R ⁴ represents a hydrogen atom or a C 1 -C 6 alkyl group, in particular a methyl or ethyl group, and when A ¹ represents -O ", Y represents a cation, in particular H *, an alkali metal cation, especially sodium or potassium cation, or ammonium an ion (especially NH4 *, an amine ion derived from an amine or an ammonium ion derived from an alkanolamine), and when A ¹ is -O- or -NR ⁴ -, Y represents an alkyl group R ³ of 1 to 6 carbon atoms or a group of the formula (CH 0) R ² , where m, n, and R ² to r 2 to r * i are independently as defined above, provided that when A represents an oxygen atom or A ¹ represents -O ", the total number of atoms carbon in the groups R, R ¹ and all of the groups R ² and R ^{3 of} at least 13 and preferably 13 to 50, or

YA ¹ .OC. (HR) CC (HR ¹ ) .CO.A. (CH 0) .CH .A.CO. (HR ¹ ) CC (HR) CO.A ¹ .Y m 2m np 2p (II) wherein n, each of R, R ¹ , A, A ¹ and Y are independently as defined above, and p is 2 or 3.

For the purposes of the definition, the free acid compounds of formulas I and II are defined by Y as the cation H ⁴ . Of course, this includes both the ionized form of the free acid, which typically predominates at a relatively alkaline pH, and its non-ionized form, which typically predominates at a relatively acidic pH.

In formula I, both A and A ^{1 are} preferably uncharged oxygen, both -NR ⁴ -, especially imino, or A is -NR ⁴ -, especially imino, and A ¹ is uncharged oxygen. Accordingly, the following specific subgroups of compounds of Formula I form specific embodiments of the invention (see also below with respect to R and R ¹ ):

Y.-OOC. (HR) CC (HR ¹ ) .C00. (CH 0). R ² m 2 mn (Ia) in which m, R ² are as defined above for formula I,

Y is a cation as defined above for formula I, and one of R and R ¹ is an alkenyl or alkyl group of 14 to 22 carbon atoms, in particular 14 to 20 carbon atoms, and the other is a hydrogen atom,

YOOC. (HR) CC (HR ¹ ) .CO.0. (CHO) .R ² (Ib) m 2 m n wherein m, on R ² are as defined above for formula I,

Y represents a (C 1 -C 6) alkyl group or a group of the formula (CHO) R ² as defined above for the formula (I) above, and

R ^{@ 1} and R ^{@ 1} are as defined above for formula I, but in particular one of R ^{@ 1} and R ^{@ 1} represents an alkenyl or alkyl group of 14 to 22 carbon atoms, in particular 14 to 20 carbon atoms, and the other is hydrogen,

YOOC. (HR) CC (HR ¹⁾ .CO.NH. (CHO), R ² m 2 τη rx (Ic) wherein

Y, m, and R ² are as defined above for Formula I, and

R ^{@ 1} and R ^{@ 1} are as defined above for formula I, but in particular one of R ^{@ 1} and R ^{@ 1} represents an alkenyl or alkyl group of 14 to 22 carbon atoms, in particular 14 to 20 carbon atoms, and the other is hydrogen,

(Id) wherein m, R ² are independently as defined above for Formula I, and

R ^{@ 1} and R ^{@ 1} are as defined above for formula I, but in particular one of R ^{@ 1} and R ^{@ 1} represents an alkenyl or alkyl group having 14 to 22 carbon atoms, in particular 14 to 20 carbon atoms, and the other one hydrogen.

The compounds of formula II can be considered functional derivatives of the polyoxyalkylene moiety with two substituted succinic acids. Typically, the groups A, ^A1 and Y are the same. Preferably, the groups A represent an uncharged oxygen atom or a group -ΝΗ ^Λ -, in particular an imino group, and both groups A ¹ are -O- with the proviso that Y is a cation. Similarly, the alk (en) yl groups in the groups R and R ^{1 are} usually the same.

When Y is a cation in formulas I and II, it is preferably H *, an alkali metal cation or an ammonium cation, especially NH *, an amine derived cation such as a tetramethylammonium cation or an alkanolamine derived ammonium ion, for example OH.CH. ₂ CH ₂ NH ₃ *; when Y represents an alkyl group having 1 to 6 carbon atoms, it is in particular a straight-chain or branched methyl, ethyl or butyl group.

The R ^{2 group} in formulas I and II is preferably either a hydrogen atom or a methyl, ethyl, propyl or butyl group (including branched propyl and butyl groups). When R ² is H, the products have a tendency to be relatively more hydrophilic and where an alkyl group, relatively less hydrophilic. The choice of R ² depends on the desired overall properties of the compound.

The compounds of the invention comprise at least one polyoxyalkylene chain consisting of ethylene glycol and / or propylene glycol residues. The chain may be a homopolymer chain either from ethylene glycol residues or propylene glycol residues, or it may be a block or random copolymer chain containing both ethylene glycol and propylene glycol residues. In compounds containing more than one polyoxyalkylene chain, the chains may be the same or different.

Specifically, with respect to the polyoxyalkylene chain defined as the group (CHO) in formula I (including Ia, Ib and Ic) and II, the chain length of this group, i. the value of the parameter n generally selects to achieve the desired properties of the product being manufactured. Typically, when the polyoxyalkylene chain is a polyethylene glycol chain, the chain typically contains 3 to 50, in particular 3 to 35, for example 10 to 35, ethylene glycol residues, and when it is a polyoxypropylene chain, it typically contains 10 to 50, and more preferably 12 to 30 propylene glycol residues. When the chain is a block or statistical copolymer of ethylene glycol and propylene glycol residues, the selected chain length typically corresponds to the above ranges, but numerically in accordance with the ratio of ethylene glycol and propylene glycol residues in the chain. Of course, the numbers of repeats in the polyoxyalkylene chain are average values. For surfactants containing a polyoxyalkylene chain, it is customary that the longer the chain and the higher the proportion of ethylene glycol residues, the more hydrophilic the product. If m is constant in the compounds of formula II in the polyoxyalkylene chain, then p is usually the same as m.

Among the compounds according to the invention, those in which R or R ^{@ 1 is an} alkylene or alkyl group having 14 to 22 carbon atoms, in particular 14 to 20 carbon atoms, and most preferably 14 to 18 carbon atoms, are particularly preferred. Similarly, compounds in which R or R ¹ is an alkenyl group are more preferred than those in which the group is an alkyl group. Compounds in which R ^{@ 1} or R ^{@ 1 is an} alkenyl group, especially a C14 to C20 alkenyl group, form a specific embodiment of the invention.

The compounds of the invention, and especially those in which R or R ^{1 is an} alkenyl or C 14 -C 22 alkyl group, exhibit properties that are completely unexpected in that the cloud point tends to increase with increasing chain length R or R ^1, in particular the following chain alkenyl chain. Often noticeable is the jump from a chain of 12 carbon atoms to a chain of 14 carbon atoms. At chain lengths greater than 14 carbon atoms, the cloud point tends to decrease somewhat, but often remains substantially above the cloud point of the compounds having a chain length of the 12 carbon atoms. This haze temperature trend indicates an increasing water solubility of compounds with increasing chain length, which is quite unexpected and is contrary to previous experience with surfactants. However, at longer chain lengths, the compounds tend to be less effective wetting agents, consistent with the increase in the hydrophobic nature of the R or R ^{1 group} . For example, in a series of compounds of formula H *. "00C. (HR) C. C (HR ¹ ). WHAT. 0. (C 1 O) _n. R ² , where the symbols on R ^{2 are} as defined below, the cloud points (in ° C) for compounds having R or R ¹ groups in the range of 10 to 18 carbon atoms are as follows:

number of carbon atoms

in the group R or R ¹ 8 12 and 14 16 18 R ² = CH, n = 7 - 37 70-81 52-53 51-52 ^R2 = H, n = 8 <5 43 56.5 - -

(The compounds in the table above, wherein R ² is H, and the chain length is 12 or less are not compounds of the present invention.)

This behavior cannot be explained and is apparently unique to surfactants. This is a matter of considerable practical importance in that surfactants in aqueous systems are usually most effective at their clouding temperatures or at temperatures close to that. Higher haze temperatures indicate that the substances are likely to be effective at relatively higher temperatures, and surfactants are often used at temperatures slightly higher than room temperature. Larger chain lengths are related to increased solubility in oil, so that a cloudiness temperature curve suggests that better solubility in oil is probably related to higher efficiency temperatures, which is a very useful combination of properties. This effect is more noticeable in compounds where R or R ^{1 is an} alkenyl group, especially since compounds in which the group is an alkyl group generally have lower cloud temperatures than the corresponding compounds containing an alkenyl group.

Compounds of formula I wherein A ¹ is -O- and Y is H * can be prepared by reacting an alkenyl or alkylsuccinic anhydride with a compound of the formula:

HA (CH 0) ^x m 2 m -1 ·.

-R ^: where A, m, R ^{2 are} as defined above.

This reaction between an anhydride and a polyalkylene glycol, a polyalkylene glycol monoalkyl ether or the corresponding derivative can readily be carried out, in the presence or absence of a catalyst, by contacting the glycol or amino derivative with an alkenyl or afkyl succinic anhydride. The reaction typically takes place at temperatures below 200 ° C and even below 100 ° C. The reactants are generally used in at least about stoichiometric ratios. Especially when stoichiometric ratios are used, further purification is usually not necessary, but can be carried out if desired.

The product is typically a mixture of isomers corresponding to two anhydride ring linearization reactions. The alkenyl or alkyl chain appears to have a slight steric effect on the ratio of isomers, the ratio of isomers being typically about 60:40, where the more abundant isomer arises from a nucleophilic attack on the carbonyl group of the anhydride remote from the alkenyl or alkyl group.

Compounds of the invention wherein Y is another cation can be made by forming a salt from the free acid (wherein Y is * H). When Y represents an alkali metal cation or an ammonium cation, the salt formation is simply carried out by reaction with a corresponding base, for example an alkali metal hydroxide or carbonate such as sodium or potassium, ammonia or an amine, including alkanolamines such as ethanolamine.

Compounds of the invention in which A ^x has a meaning other than -0 ", ie Y is not a cation, can be prepared by reaction from the free acid. Typically, the further reaction is the preparation of an ester, especially an ester with a C 1 -C 6 alcohol or an alkyl ether of an alcohol-containing polyalkylene glycol. In general, the longer chain esters and the corresponding amides can be prepared from short chain esters, especially methyl or ethyl esters, by transesterification or amidation with the corresponding alcohol (YOH) or amine (YNH _a ) (where Y is as previously defined). The esterification of the free acid can be carried out in a conventional manner, for example by using an acid catalyst, which can be sulfuric, toluenesulfonic or phosphoric acid. In particular, phosphoric acids may be suitable since, after neutralization, they may form a suitable component of detergent compositions containing the surfactants of the invention.

Thus, the compounds of formulas Ia, Ib, Ic and Id can be prepared as follows:

1a by reacting a polyoxyalkylene glycol or a derivative of the general formula HO (CHO) R ² with m 2 m n alk (en) yl-butyric anhydride containing from 14 to 22 carbon atoms in the alk (en) yl moiety to give a compound of the formula:

HOOC. (HR) CC (HR ¹ ) .CO.0. (CHO). R ² m 2m na (when Y is other than hydrogen) by reaction with an alkali metal.

Ib by esterifying a compound of formula Ia, especially when Y is a hydrogen atom, with a low molecular weight alcohol, in particular methanol, ethanol or butanol, and then, if necessary, transesterifying with YOH to obtain the desired product.

Ic by reacting an aminopolyoxyalkylene glycol or a derivative thereof of the general formula H N. (CHO) .R ² with an acid anhydride of 2 m 2 min of alk (en) yl succinic acid to give a compound of the general formula

HOOC. (HR) CC (HR ¹ ) .CO.NH. (CHO) .R ² and (when Y is other than hydrogen) by reaction with an alkali metal.

Id reacting a amino polyoxyalkylene glycol or its derivative by deri11 formula H N (CH 0), R ² anhydride τη 2 m ts alk (en) yl succinic acid to obtain a compound of formula

HOOC. (HR) C. C (HR ¹ ) .CO.NH. (CHO) .R ² m 2m for subsequent esterification with a low molecular weight alcohol, in particular methanol or ethanol, followed by amidation with amine YNH ₂ to give the desired product.

Compounds of formula II wherein Y is H ⁺ may be prepared by reacting two moles of alk (en) yl succinic anhydride with one mole of a compound of formula

H.A. (C H 0 .CH .A.H τη 2m n 2 jp and each of the symbols A independently of the above wherein Y represents a different cation or alkyls wherein m, n, p is as defined above

Compounds in which the group has 1 to 6 carbon atoms (R ³ ) or a group of the general formula (CHO) R ² , where m, on R ² independently have the meaning defined above, can be prepared as is described above for compounds of Formula I.

The compounds of the invention may also be prepared by other methods. For example, the anhydride can be reacted with a lower alcohol and the resulting half ester esterified with a polyalkylene glycol or an alkyl ether of a polyalkylene glycol or condensed with an alkylene oxide and, if desired, terminated with another lower alcohol. The length of the polyalkylene glycol chain can be controlled by using a polyalkylene glycol or an alkyl ether of a polyalkylene glycol within a narrow molecular weight range, while in the latter manner chains are obtained over a wide range of lengths.

The alkenylsuccinic anhydrides can be prepared by reacting maleic anhydride preferably with an excess of 6 to 22, in particular 14 to 22, carbon atoms, for example an excess of 50 to 200% at a temperature ranging from 150 to 400 ° C and preferably from 180 to 250 ° C followed by removal of the excess olefin, for example by distillation, which is conveniently carried out under vacuum. A catalyst is not required, but the presence of an antioxidant is preferred. These anhydrides are well known commercially available substances. In the alkenylsuccinic anhydrides prepared as described above, the double bond is normally located at the 2-position of the alkenyl substituent.

For the manufacture of products in which R or R ^{1 is an} alkyl group, either an unsaturated product can be hydrogenated or, preferably, an intermediate alkenylsuccinic anhydride can be hydrogenated to obtain an alkylsuccinic anhydride. Typically, the hydrogenation is carried out using a hydrogenation catalyst such as Raney nickel or palladium on carbon. Temperatures of 15 to 100 ° C and pressures of 0 to 20 MPa can be used, and a solvent may be present if desired. The hydrogenation reaction of alkenylsuccinic anhydride can be carried out, for example, at 20 ° C using 5% (w / w) palladium on carbon catalyst for, for example, 6 to 24 hours.

It is desirable that the alkyl or alkenyl group R 1 or R ^{1 of the} compound of the invention have a straight chain. If the chain is not straight, it is desirable to have at most two and preferably only one side chain. Preferably, the entire molecule comprises a total of at most three side chains in all alkyl and alkenyl groups present.

The products are easy to manufacture and odorless, and since polyalkylene glycols and alkyl ethers of polyalkylene glycols or their amino derivatives are readily transportable, they can be produced at locations remote from alkylene oxide production plants when used as reactants.

The compounds of the invention exhibit emulsifying properties and act as wetting and dispersing agents. They can be used in oil-in-water emulsions for metalworking liquids based on partially soluble oils and synthetic materials and for oil transport and fuel systems, and personal care (skin) softeners, as well as household detergents such as liquids for washing laundry, in dispersing or organic and inorganic powders for coatings and coatings (for example, fillers and pigments) and agrochemical preparations (for example, pesticides), industrial and orderly cleaning products (for example, road stripping products, bottle washing products).

Particular end uses of the surfactants of the invention include wool washing and use as inverting agents in the manufacture of acrylamide and the like. These uses are described in more detail below.

After shearing the sheep, the wool fleece contains, in addition to the wool fiber, a variety of materials including sheep wool wax. Sheep wool wax is a complex blend of fatty materials excreted on wool from sheep skin. Sheep wool wax is removed from wool prior to use in the textile industry by washing the wool with an aqueous composition containing surfactants typically at slightly elevated temperatures, for example 40 to 80 ° C, especially 50 to 70 ° C. This process is called wool washing. Testing suggests that the surfactants of the invention are very effective wool scouring surfactants, particularly since they maintain their effectiveness well after repeated scouring cycles, even when used for scouring very fine fiber wines such as merino wool , which are difficult to wash as the fat content of the sheep's wool is relatively high and the fibers have a large surface area to be treated. While the particular choice of the compound of the invention for this end use depends on the specific conditions of the operation, it has been found that the compounds of the above general formula (Ia), in particular those in which the value of 2, n has a value of 2 to 25, and R ² represents an alkyl group having 1 to 6 carbon atoms, in particular a methyl group. The surfactant in this use is typically used at a concentration of from 0.1 to 5 gI ^-1 , in particular from 0.2 to 1.5 gI ^-1 .

Accordingly, the invention includes a method of treating wool to remove wax from sheep's wool, comprising washing wool containing sheep's wax with an aqueous composition comprising an effective amount of a compound of formula I or II above, particularly a compound of formula Ia above, in particular m is 2, n is from 3 to 10 and R ² is alkyl of 1 to 6 carbon atoms, especially methyl. The invention also encompasses the use of such compounds of the invention as wool surfactants.

The preparation of polymers such as polyacrylamides is usually carried out by an emulsion polymerization process in which the polymer accumulates in the aqueous phase (in which it is insoluble). It is known that polyacrylamides can form aqueous solutions of high viscosity even at low concentrations, which are the basis of their use as thickeners and viscosity enhancers in aqueous systems. If the aqueous phase is a continuous phase during polymerization, it quickly becomes very viscous, leading to problems associated with moving the mixture and isolating the product. In order to avoid this problem, the aqueous phase is a normally dispersed phase in an oil-continuous phase, i.e. a water-in-oil emulsion that contains an emulsifier to stabilize the water-in-oil emulsion: The viscosity of the oil phase does not increase during polymerization phase, since the polymer remains in the aqueous phase. However, the polymer is typically used in an aqueous environment, so at some point the emulsion must be inverted to make the aqueous phase a continuous phase, which is typically done by diluting the water-in-oil emulsion with water. Typically, a surfactant that promotes such inversion is added to the water-in-oil emulsion prior to dilution in water. Tests show that the compounds of the invention are effective inverting agents for such emulsions. While the particular choice of the compound of the invention for this end use depends on the specific conditions of the operation, it has been found that the compounds of the above formula la are particularly effective, especially those in which m has a value of 2, n has a value of 8 to 25, and R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in particular a methyl, ethyl, propyl or butyl group. The amount of surfactant used to invert such emulsions depends on the emulsion, in particular the proportion of the dispersed aqueous phase and the polymer concentration in the aqueous phase. In general, typical amounts are in the range of 1 to 5% of a water-in-oil emulsion.

Accordingly, the invention includes a method of inverting a water-in-oil emulsion comprising a polyacrylamide in an aqueous phase, characterized in that a compound of the above formula I or II, in particular a compound of the above formula Ia, is added to the water-in-oil emulsion. wherein m has a value of 2, n has a value of 8 to 25, in particular 10 to 15, and R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, in particular a methyl, ethyl, propyl or butyl group, water-in-oil type diluted with water. The invention also encompasses the use of the compounds of the invention as polyacrylamide-containing water-in-oil emulsion inverting agents.

The following Examples illustrate the invention, including the manufacture and properties of the compounds of the invention and their end uses, in particular illustrating the universality and use of the compounds of the invention. Unless otherwise indicated, all proportions and percentages are by weight.

DETAILED DESCRIPTION OF THE INVENTION Sf

Test methods:

The cloud point (TZ) is measured according to ASTM D 2024-65, the results are given in

C.

Wettability (S)

Draves wettability is determined using a yarn test (according to ASTM D 2281-68), the results are given in seconds (or minutes - with slow wetters).

Foam height (VP)

The Ross Miles foam height is determined according to ASTM D

1173-53 at 60 ° C, results are given in millimeters.

The surface tension (PN) is measured using a 0.1% (w / w) solution by a drop method at 23 ° C, the results are given in mN.m ^-1 .

Synthesis Examples SE1 to SE24

The various compounds of the invention are prepared by reacting stoichiometric mixtures of alkenylsuccinic anhydride and polyethylene glycol, polyethylene glycol alkyl ether or an amino derivative as shown in Table 1 below by heating the mixture to a temperature of about 100 ° C. Samples are taken every 30 minutes until the reaction is complete as determined by infrared spectroscopy and / or by acid number of the mixture.

The corresponding sodium salts are prepared by adding a sodium hydroxide solution to the acid product until the pH is raised to 9. The sodium salt is then isolated by evaporation or used as a solution in water.

The corresponding methyl esters are prepared by adding sulfuric acid and methanol. During the reaction, methanol is distilled off in such a way as to maintain a constant volume for 2 to 12 hours. Sodium bicarbonate was then added to neutralize the sulfuric acid and the product was filtered off. Other esters with lower alcohols are prepared accordingly.

In a general manner as described above, with the exception that the respective starting materials are substituted, comparative materials of similar structure are also prepared. These materials are preceded by a letter C.

Various properties of these compounds were measured and the results are shown below in Table 2. For further illustration, Table 2 includes commercially available ethoxylated nonylphenol containing 9 moles of ethylene oxide per mole of phenol under the designation NPE.

The properties of SE1 are as follows:

Surface tension (0.1% (w / w) solution, drop method at 23 ° C) in mN.m ^-1 28.4

The pour point in ° C -15

Viscosity in Pa.s at 25 ° C 0.165 min 5 min

Ross Miles foam height at 60 ° C in mm 7.5 3

Density in g.cm ^-3 at 23 ° C 1.006

Draves wettability in seconds 10.5

Turbidity temperature in ° C

Table 1

Example no. general formula R / R ¹ (2) A A ¹ m n (2) R ² (H Y (1) SE1 I 14u -0- -0- 2 3.7 1 H SE2 I 12u -0- -0- 2 13.6 H 1 SE3 II 18U NH -0- 2 34 - H SE4 II 12u -0- -0- 2 18.2 - H SE5 I 12u -0- -0- 2 7 1 H SE6 I 14U -0- -0- 2 7 1 H SE7 I 16U -0- -0- 2 7 1 H SE8 I 18U -0- -0- 2 7 1 H Cl I 8u -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 I 14u -0- -0- 2 8 H H SE10 I 12u -0- -0- 2 4 1 H 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 I 14u -0- -0- 2 12 H 1 SE15 I 14u -0- -0- 2 12 H 4 SE16 I 16U -0- -0- 2 45 1 H SE17 I 18 ^ -0- -0- 2 17 1 H SE18 I 18U -0- -0- 2 45 1 H SE19 I 14u -0- -0- 2 12 H H SE2O II 12u -0- -0- 2 34 - H

Continuation of Table 1

SE21 II 14u -0- -0- 2 34 - H SE22 II 14u NH -about- 2 34 - H SE23 II 18U NH -0- 2 34 - H SE24 I 14s -0- -0- 2 8 H H SE25 I 14s -0- -0- 2 12 H H SE26 I I8s -0- -0- 2 12 H H

Legend to Table 1:

(1) the number of carbon atoms in the substituent chain for R / R ^{* 1 is given} : u indicates that the substituent is an alkenyl group s indicates that the substituent is an alkyl group, for R ² : H is a hydrogen atom and the number indicates the length of the alkyl group; for Y

H means that lo denotes

Y represents a cation H *, and the alkyl chain number (2) the cumulative values of n can be rounded, in the compound of formula II, n in this table denotes the sum of & + p in formula II as above (with p = m).

Table 2

Example no. Surface tension (mN.m ” ¹ ) temperature surgery (° C) Foam height (mm) wettability (with) 0 min 5 min SE1 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 SE7 - 52-53 70 SE8 - 51-52 over 300 CI 34 under 5 C2 33.8 43 C2 34.6 54 66 SE9 35.7 56.5 SE1O 28.3 21 6.5 SE11 31.2 78 72 58 SE12 SE13 28.8 60-65 14 SE14 SE15 '& SE16 over 96 SE17 86-87 SE18 over 96

Continuation of Table 2

SE19 38.7 66 SE2O 31.6 63 SE21 35.1 SE22 34.1 SE23 34.0 SE24 43- SE25 62 SE26 74- NPE 29.9

Legend to Table 2:

NPE refers to commercially available ethoxylated nonylphenol containing 9 moles of ethylene oxide per mole of phenol

Example of use AE1 to AE4

Example AE1

Detergents applied when using water

Purification using water involves cleaning, for example, metal parts with solvent and subsequent washing with water. Often terpene-based solvents are used. Surfactants may be added to accelerate solvent removal from the cleaned components during the water wash. Such surfactants or washing aids, as indicated, must meet two requirements. First, they must remove solvents well and be soluble in the solvent used for cleaning. Secondly, they must not stabilize solvent / water mixtures and thus prevent effective separation of the mixture with adverse consequences for waste disposal. The materials A and B below exhibit desirable surface-active properties, so that they are effective washing aids in detergents applied using water. They are also soluble in terpene-based solvents. Surprisingly, the tests show that these compounds exhibit rapid and more efficient solvent separation from water compared to other surfactants commonly used for this purpose.

This effect is demonstrated by the following experimental data. Mixtures of 0.6% surfactant, 9.4% terpene solvent and 90% water are prepared by shaking five times in a graduated cylinder; The mixtures were allowed to stand for 20 hours at room temperature, during which periodic phase separation was evaluated. The results obtained are shown in the following table.

Surface active agent Appearance after 20 hours remark no both layers clear department full after 0.5 hour decyl oil and water incomplete department ethoxylated 3 mol layer cloudy after 20 hours ethylene oxide alkylphenol oil and water full department ethoxylated 4.5 mol layer weakly after 10 hours ethylene oxide cloudy SE10 oil and water full department layer very after 12 hours lightly cloudy SE1 faint haze full department

in both layers after 8 hours

Table legend:

Complete separation means that the oil layer is 10% and the aqueous layer is 90% of the total volume.

Example AE2

Washing wool

Ten wool samples of 20 g each are washed successively in the same bath, which constitutes 1 liter of a 0,1% (w / w) surfactant solution in water at 60 ° C. The residual fat in the last washed sample is then determined by extraction with an organic solvent, typically dichloromethane or chloroform. The results are shown in the following table:

Product of residual fat

SYNPERONIC " NP9 (* **) 1.71 SYNPERONIC 87K (*) 2.16 SE1 1.24

br

Table legend:

** commercially available alkoxylated alcohol of 13 to 15 carbon atoms * commercially available ethoxylated nonylphenol

Example AE3

Washing wool

Further wool washing is performed using merino fine wool (fiber diameter approximately 20 m) at a surfactant dose of 0.5 gl ^-1 in an aqueous wash solution containing 4% by weight. potassium chloride (to mimic the accumulation of salt during repeated use of the wash solution). The washing is carried out at a temperature of 65 ° C in a detergent bath and at 50 ° C in a washing bath. Washing solutions are used several times in succession and, after each operation, the weight percent residual wax from sheep wool per wool is determined. The results are shown in Table 3 below. SE1 was compared with four other wool scouring surfactants:

Labeling Product name Source Description

C3

Lissapol TN45O

ICI

Australia ethoxylated nonylphenol

C4

Lissapol BD20

ICI

Australia biodegenerable wool washing agent

C5

Lissapol BD30

ICI

Australia biodegenerable wool washing agent

C6 Softanol 90 Nippon

Shokubai secondary ethoxylated alcohol

Table 3 Run no. Surface active agent SE1 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 5 0.98 1.19 1.74 0.90 1.04 6 0.93 1.07 1.36 1.12 1.97 7 0.98 1.02 1.18 1.02 1.19 8 1.04 1.20 1.76 1.17 1.46

The results shown in Table 3 indicate that the compound of the invention acts well as a wool scrubbing agent and, in particular, in comparison to conventional agents, maintains performance well, even when scouring wool which is known to be difficult to wash.

Example AE4

Inversion of polyacrylamide emulsion

Using a commercially available polymeric surfactant sold under the trade name HYPERMER 2296 as the primary emulsifier, the following mixture is polymerized by heating to about 40 ° C:

acrylamide 135.0 g acrylic acid 58.0 g demineralized water 179.0 g hydrocarbon solvent (Isopar L) 168.0 g sodium hydroxide to pH 6% ethylenediaminetetraacetic acid (EDTA) 5.2 g azobisisobutyronitrile (AIBN) 0.4 g primary emulsifier 8-12 g

3% of each of the surfactants listed below is added to the polymer emulsion sample as an inverting agent and allowed to stand for 2-3 days. A 1% mixture with water is then formed from the emulsion sample. After stirring for 2 minutes, the viscosity is measured. Stirring is then continued and after a further 15 minutes the viscosity is measured again. The following viscosity values were measured:

agent

Viscosity (mPa.s) after 2 minutes after 15 minutes

SYNPERONIC NP9 12 000 26 000 SE11 11 500 26 000 SE19 24 000 24 500

C3 coagulated

These results show that SE11 is equivalent to the conventional SYNPERONIC NP9 inverting agent and SE19 is superior to this agent, and that C3 does not perform as effectively as the inverting agent.

Claims (13)

PATENT CLAIMS A substituted succinic acid derivative of the formula I or II YA ¹ .OC. (HR) CC (HR ¹ ) .CO.A. (CH 0) .R ² (I) τ 2 τη τ * v in which one of R and R ¹ represents an alkenyl or alkyl group having 6 up to 22 carbon atoms and the other is hydrogen, A represents -O- or -NR ⁴ -, wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n having a value of 2 to 100 m having a value of 2 or 3, and may differ in the polyoxyalkylene chain), R ² is H or alkyl of 1 to 6 carbon atoms, A ¹ is -O-, -O "or -NR ⁴ -, wherein R ⁴ represents a hydrogen atom or an alkyl group of 1 to 6; carbon atoms, provided that if A ¹ is -0-, Y is a cation, and when A ¹ is -O- or -NR ⁴ -, Y represents an alkyl group R ³ having 1 to 6 carbon atoms or R = (CH 0) .R ² in which the symbols m, n, and R n ² m 2 m each independently as defined above, provided that when a is -0- and a ¹ is O ^-, the total number of carbon atoms in R R ¹ and all R ² and R ³ groups of at least 13, or YA ¹ .0C. (HR) CC (HR ¹ ) .CO.A. (CH 0) .CH .A.CO. (HR ¹ ) CC (HR) CO.A ¹ .Y ^{in 7} '' ^x m 2m 'n 2p' ⁷ ' ⁷ (II) wherein n, each of R, R ¹ , A, A ¹ and Y are independently as defined above, and p is 2 or 3. The substituted succinic acid derivative according to claim 1, wherein one of R ¹ and R ¹ represents an alkenyl or alkyl group of 14 to 22 carbon atoms and the other represents a hydrogen atom. 3. A compound according to claim 1 of the formula la 6r Y.-OOC. (HR) CC (HR ¹ ) .C00. (CH 0) .R ² (Ia) ' ⁷ ' ⁷ 'm 2 m n wherein m, R ² are as defined in claim 1, Y is a cation, and one of R and ^R1 represents an alkenyl or alkyl group having 14 to 22 carbon atoms, and the other is hydrogen, 4. A compound according to claim 1 of the formula Ib ». Y. OOC. (HR) C C (HR ¹⁾ .C00. (CH 2) R ² (Ib) m 2 m n wherein R, R ¹ , m, and R ² are as defined in claim 1, and Y is alkyl of 1 to 6 carbon atoms or R = (CH 0), R ^2, wherein the symbols m, n and R ² each independently as defined in claim l. 5. A compound according to claim 1 of the formula Ic *. ₍ Y) OOC. (HR) CC (HR ¹ ) .CO.NH. (CHO) .R ² (Ic) m 2 mn in which R, R ¹ , m, and R ² are as defined in claim 1; Y is a cation. A compound according to claim 1 of the formula Id R ² . (CHO). NH. τη 2xn η CC (HR) CC (HR ¹ ) CO 2 NH (CHO) .R ² xn 2 mn (Id) in which R and R ¹ and each of symbols m, n and R @ ² are independently meaning defined in  Claim i. 7. Derivative substituted of amber by Claims 4 to 6, wherein one of R and R ¹ is an alkenyl group of 14 to 22 carbon atoms, and the other is a hydrogen atom. m P n Y waves, The substituted succinic acid derivative according to claims 1 to 7, having a value of 2, if present, having a value of 2, a value of 3 to 50, and representing a cation which is H *, an alkali metal cation, or an ammonium cation, or methyl, ethyl or butyl. 9. A method for treating wool to remove wax from sheep, wherein the wool containing the wax from sheep wool is washed with an aqueous composition comprising an effective amount of a substituted succinic acid derivative of formula I or II as defined in claims 1-8. A process according to claim 9, wherein the substituted succinic acid derivative is a compound of formula Ia wherein m has a value of 2, n has a value of 3 to 10, and R ² represents an alkyl group having 1 to 6 carbon atoms. * 11. A process for inverting a water-in-oil emulsion comprising a polyacrylamide in an aqueous phase, which comprises adding to the water-in-oil emulsion a substituted succinic acid derivative of the formula I or II as defined in claims 1 to 8 and subsequently the water-in-oil emulsion is diluted with water for its inversion. 12. A method according to claim 11, characterized in that the derivative of a substituted succinic acid derivative is of formula Ia, wherein m is 2, • n is 8-25, _and R ² is H or alkyl of 1 to 6 carbon atoms. 13. A substituted succinic acid derivative of the formula I or II Y. A ³ . OC. (HR) C. C (HR ¹ ). WHAT . A. (CHO) R ² (I) m 2 n n wherein one of R ¹ and R ¹ represents a straight chain alkenyl or alkyl group having 6 to 22 carbon atoms and the other represents a hydrogen atom, A is -O- or -NR ⁴ -, wherein R ⁴ means carbon a hydrogen atom or an alkyl group having from 1 to 6 alkyl, n my value 2 to 100 m my value 2 or 3, and may be in polyoxyalkylene strings vary) R ² is H or alkyl of 1 to 6 carbon atoms, A ¹ is -O-, -O- or -NR ⁴ -, wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, wherein when A ¹ represents -O ", Y represents a cation, and when A ¹ represents -O- or -NR ⁴ -, Y represents an alkyl group R ³ having 1 to 6 carbon atoms; R ⁶ wherein m, n, and R ^{2 is} m ² m n independently as defined above, provided that when A is -O- or A ¹ is -O ^- the total number of carbon atoms in the groups R, R ¹ and all the groups R ² and R ^{3 is} at least 13, or YA ¹ .OC. (HR) CC (HR ¹ ) .CO.A. (CH 0) .CH .A.CO. (HR ¹ ) CC (HR) CO.A ¹ .Y ' ⁷ ' ⁷ 'm 2m ⁷ p tx> 2p '' (II) wherein n, m and each R, R ^x, a, a ¹ and Y are independently as defined above, and p is 2 or 3rd The substituted succinic acid derivative according to claims 1-8, wherein one of R ¹ and R ¹ represents a straight chain alkenyl or alkyl group of 6 to 22 carbon atoms and the other represents a hydrogen atom.