HUT68780A - Surfactant derived from polyoxyalkylenes and substituted succinic anhydrides - 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

The present invention relates to surfactants, more particularly to surfactants based on substituted succinic acid derivatives, which are novel substances. The invention also relates to processes for the final use of surfactants. .

Today, there is a growing need to replace well-established surfactants with substances that are highly biodegradable. In practice, however, it is very difficult to develop materials that are realistic alternatives to high-performance surfactants, which have been introduced and sought for decades on the market.

No. 107,199. EP-A-4,179,125 relates to polyoxyalkylene glycol semi-esters of succinic acids substituted with C8-C12 alk (en) yl groups and their salts. These materials have been described as being particularly suitable for use in acidic pH media, as anionic surfactants that tolerate hard water.

The present invention is based on the surprising discovery that alkenyl succinic anhydrides, especially those containing C14-C22 alk (en) yl groups and / or functional substituents at any position in the molecule, can be formulated to have surprisingly they differ significantly from the surfactants described above. These novel surfactants have good efficacy as nonionic surfactants, especially in aqueous systems; their cloud point changes unexpectedly, indicating that they perform well at higher temperatures} and behave well under alkaline conditions. A further advantage of the surfactants of the invention is that they are readily biodegradable.

Thus, the present invention relates to formulas I and II.

- 3 compounds

YA ¹ -C? C- (HR) CC (HR ¹⁾ -ao-A (C _m H _2m O) _n -R ² (I) yA ¹ -C? C- (HR) CC (HR ^S) -CO-A (G _{II 1} H _2ia O) ₁₁ -C _p H _2p -A-CO- (HR ¹ C) -C ¹ H ₂ CO-A ¹ -! (II)

- in the formulas

One of R and R ¹ is C 6 -C 22 alkenyl or alkyl and the other is hydrogen,

The oxy group is a radical of the formula wherein R 1 is hydrogen or (C 1 -C 6) -alkyl, particularly preferably methyl or ethyl, n being from 2 to 100 (since n is an average value, it may be a fraction), m is 2 or 3, with the possibility that m may vary within the polyoxyalkylene chain,

R is hydrogen or (C 1 -C 6) -alkyl,

A is -O 2, -O 'or -NR 4 -, and in the latter R 1 is hydrogen or C 1-6 -alkyl is particularly preferably methyl or ethyl, and when A is -O,

Represents a cation Y, preferably an H ⁺ ion, an alkali metal cation (particularly sodium or potassium cation) 'or an ammonium cation (particularly NH 4 or an amine ammonium or alkanolamine ammonium cation), while A ^{1 is} oxy or -NR ^ - represents a group, then

Y is a C 1 -C 6 alkyl group (hereinafter referred to as R- ² port) or a group of the general formula: ···········································

- 4 ο is where R, m and n are as defined above, and p (II) wherein 2 or 3, with the proviso that when A is oxy or -O ^_ ion is, the R, R and R and or the sum of the carbon atoms in the R group is at least 13, preferably 13-50.

For the sake of simplicity, the compounds of formulas (I) and (II) containing the Y ⁺ H cation will hereinafter be referred to as free carboxylic acids. This definition encompasses both the ionized form of the free carboxylic acids, which typically occurs at relatively alkaline pH media, and the non-ionized form, which typically occurs at relatively acidic pH media.

Preferred compounds of formula (i) are those wherein A and A 4 are both oxy or both -NR 4 - (particularly preferably -ΝΉ) - and in which A is -NR 4 - (particularly preferably -NH) - group) and at the same time represents an oxy group. Accordingly, (I). Preferred groups of compounds of formula I are the following:

Compounds of formula (Ia)

Y. ~ 00 C - (HR) CC (HR ¹ ) -000- (C 1 H ² O) _n -R ² (Ia)

- in the formula p

m, n and R are as defined for formula (I);

Y is a cation as defined for formula (i); and R and r! one of which is hydrogen and the other is C14-C22 (more preferably C14-C20) alkenyl or alkyl.

Compounds of formula (ib) • · • ·····

-5Y-0-0G- (HR) CG (HR ¹ ) -G0-0- (C _m H _2ni 0) _n -R ² (Ib)

- in the formula p

m, n and R are as defined for formula (I)

Y is C 1 -C 6 alkyl or "(G _m ^H 2 _m 2 ^ n ^{R 2} " in formula I), and

One of R and R 1 is hydrogen and the other is C 6 -C 22 (preferably C 14 -C 22, more preferably C 14 -C 20) alkenyl or alkyl.

Compounds of Formula Ic YO-OG- (HR) CC (HR ¹ ) -CO-NH- (C _m H _2ni O) _n -R ² (Ic)

- in the formula p

Y, m, n and R are as defined in formula (I);

One of R and R ¹ is hydrogen and the other is C 6 -C 22 (preferably C 14 -C 22, more preferably C 14 -C 20) alkenyl or alkyl.

Compounds of Formula (Id): R ² - ( ^C m ^{H 2} O ⁰ ) n N ^H -O-C- (HR) -CHR ¹ ) -G ^o -N ^H - ( ^C m ^{H 2 O} 10) n R ² (Id).

- in the formula p

m, n and R are as defined for formula (I); and 1

One of R and R ^x is hydrogen and the other is C 6 -C 22 (preferably C 14 -C 22, more preferably C 14 -C 20) alkenyl or alkyl.

Compounds of formula (II) are considered to be di- (substituted succinyl) derivatives of a polyoxyalkylene chain. In these compounds, the unique A, and Y and • ·· ···

Preferably, groups 6 have the same meaning. Thus, for example, compounds of formula II in which the two A groups are identical to an oxy group or a -NR ^ - group (preferably -NH-) are preferred, the two A ^ groups being both represented by -0 "to which Y is cation is attached. Similarly, the (II) R in the compounds of formula, or R-alk (en) yl groups consisting of ^one site are preferably identical groups.

When Y is a cation in the compounds of formulas (i) and (II), Y is preferably H ⁺ , an alkali metal cation or an ammonium cation (especially Nh 6, an amine ammonium cation such as tetramethylammonium cation or alkanol -ammonium-ammonium cation, such as ΗΟ-ΟΗ ₂ ΟΗ ₂ “ΝΗ ^ ion). C 1-6 alkyl at Y is preferably methyl, ethyl or straight or branched butyl.

In the compounds of the formulas I and II, R is preferably hydrogen, methyl, ethyl or straight or branched propyl or butyl. Compounds containing R at the hydrogen atom are relatively more hydrophilic, while those having R at the alkyl group are relatively less hydrophilic. The R group is selected according to the desired properties of the particular surfactant.

The compounds of the invention contain at least one polyoxyalkylene chain which is composed of ethylene glycol and / or propylene glycol residues. This polymer chain is a homopolymer chain composed exclusively of ethylene glycol residues or propylene glycol residues, or of ethylene glycol and propylene glycol residues.

A copolymer chain containing (7 in an array or in random distribution) aranes (7 in a block or random distribution) can be a 7 7 · β β ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦ ♦. In compounds containing more than one polyoxyalkylene chain, the individual chains may be the same or different.

The poly (- < ⁰ m ^H 2 _m ⁰⁾ n- in the compounds of formula (i) (including the compounds of formula (Ia), / Ib / ye / le /) and the compounds of formula (II) The oxyalkylene) chain length, i.e., the value of n, is usually selected according to the desired properties of the product to be formed. When the polyoxyalkyl petroleum chain is a polyoxyethylene chain, the chain may typically contain from 3 to 50, preferably from 3 to 35 (e.g. 10 to 35) ethylene glycol residues, while the polyoxypropylene - the number of propylene glycol residues forming the chain is typically 10 to 50, preferably 12 to 20. If the polyoxyalkylene chain contains either ethylene or propylene glycol residues in bulk or random distribution, the chain length within the ranges above is glycol and propylene glycol residues may vary with each other.

^M n ^H values representing the number of repeating units in the -alkylene) chain are average values. As with any surfactant containing a polyoxyalkylene chain, the longer the polymer chain and the greater the proportion of ethylene glycol residues in the chain, the more hydrophilic the product is. When m is constant in the polyoxyalkylene chain of the compounds of formula II, p is usually equal to m.

In the compounds of the invention, one of R and R 1 is preferably C 14 -C 22 alkenyl or alkyl,

8 are particularly preferably C 14 -C 20 alkenyl or alkyl, particularly preferably C 14 -C 18 alkenyl or alkyl. Compounds containing R or R 1 are alkenyl are more preferred than the corresponding R or R 1 -alkyl derivatives. Accordingly, a particularly preferred group of compounds of the present invention are those wherein R or alkenyl, particularly preferably C 14-20 alkenyl, is preferred.

A particularly surprising feature of the compounds of the present invention, especially those having an alkenyl or alkyl group having 14 or 22 carbon atoms in the R or R group, is that the compounds have a cloud point at the R or R 1 position. shows a tendency to increase with increasing chain length, especially when this chain is an alkenyl chain. In many cases, the carbon number of the chain is particularly noteworthy

Increase from 12 to 14 with increase in cloud point.

For carbon chains longer than carbon atoms, the cloud point may occasionally decrease slightly, but often still significantly exceed the cloud point for corresponding shorter compounds, such as 12 carbon atoms. Such a change in the cloud point indicates that the water solubility of the compounds increases with increasing carbon chain length, which is completely unexpected and contrary to what has been previously experienced with surfactants. However, at longer carbon chains, the wetting effect of the compounds is reduced, which is consistent with an increase in the hydrophobic nature of the R / R @ 4 group. As an example, it is given in Table A below

H ⁺ . "OOC- (HR) C-CKHR ¹ ) -CO-O- (C ₂ H ₄ O) _n -R ²

- 9 · 4 4 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · R and one are hydrogen and the other is a carbon hydrogen chain having the carbon number given in Table (A).

(The table

Cloud point, ° C when R / R R 8 12 14 16 contains carbon atoms 18 R ² = -CH ₃ , n = 7 - 37 70-81 52-53 51-52 R ² = Η, n = 8 / 5 43 56.5 -

It should be noted that those compounds of Table A wherein R is hydrogen and at the same time R 12 is less than or equal to 12 carbon atoms are not included in the present invention.

The cause of the above phenomenon has not been explored yet, and to our knowledge, this phenomenon is unique among surfactants. From a practical point of view, it is remarkable that surfactants in aqueous systems are usually most effective at temperatures close to or near their cloud point. A higher cloud point indicates that the material is effective at relatively higher temperatures, and that surfactants are often used at temperatures well below room temperature. Increased oil solubility is associated with longer carbon chains; so the change in cloud point described above also means that for higher efficiency temperatures

- 10 enhanced oil solubility · This is a very useful combination of properties. This effect is more pronounced for compounds containing R or R @ 4 alkenyl groups, since compounds with R or R @ 4 alkyl groups usually have a cloud point lower than their corresponding alkenyl compounds.

Compounds of formula (I) wherein A ^ -0 "means ion and YH ⁺ ions may be prepared to an alkenyl or alkyl succinic anhydride with a HA (C _m H 2 _m O) _n" ^R a general with a compound of formula (II)

- where A, m, n and R are as defined above. The reaction between the acid anhydride and the poly (alkylene glycol), poly (alkylene glycol) monoalkyl ether, or the corresponding amine derivative can be carried out simply by contacting the glycol or amine derivative, optionally in the presence of a catalyst. alkyl succinic anhydride. The reaction is typically carried out at temperatures below 200 ° C and sometimes below 100 ° C. The reagents are usually used in at least a stoichiometric ratio. If the reagents are used in stoichiometric ratios, further purification of the product is usually not required, but the product may be purified if desired.

The product is usually obtained in the form of a mixture of isomers which are capable of bi-directional opening of the anhydride ring. In our experience, the steric activity of the alkenyl or alkyl chain slightly affects the ratio of the isomers to one another. The ratio of the two isomers in the product to each other is typically about 60:40; the greater isomer is the result of a nucleophilic reaction on the anhydride-forming carbonyl group further away from the alkenyl or alkyl group.

Compounds containing a cation other than the hydrogen ion at Y can be prepared by salt formation from the corresponding free acids (Y = H ⁺ ). For example, compounds containing an alkali metal or ammonium cation at Y may be formed by reacting the free acid with a suitable base such as an alkali metal base (e.g., sodium or potassium hydroxide or carbonate), ammonia or amine (alkanolamines, including ethanolamine).

Compounds in which A has a meaning other than the ¹ -0 'ion (and therefore other than the Y cation) can be formed by further reacting the corresponding free carboxylic acids. Typical further reaction reactions include, for example, ester formation with C 1-6 alcohol or poly (alkylene glycol) -alkyl ether alcohol. Longer esters and the corresponding amidocate are usually formed from esters of lower alcohols, such as the corresponding methyl or ethyl ester, by transesterification or amidation with alcohols of the formula Y-OH or amines of the formula Y-NH8, in which Y is upper. The free acids may be esterified in a conventional manner in the presence of, for example, an acid catalyst (such as sulfuric acid, toluenesulfonic acid or phosphoric acid). Particularly preferred acid catalysts are phosphoric acids which, after neutralization, can be valuable components of detergent compositions of the present invention.

Accordingly, the compounds of formulas (Ia), (Ib), (Ic), and (Id) · ·.-12 may be prepared, for example, as follows:. For the preparation of compounds of formula (Ia), a polyoxyalkylene glycol or a polyoxyalkylene glycol derivative of the formula HO- (G _m H _{2 m} O) _n -R ^{2 is} prepared from a C 14 -C 22 alk. en) is reacted with succinic anhydride, and if desired, to form a product containing a cation other than hydrogen, Y

HOOC- (HEC-C (HR ¹ ) -CO-O- (CH ₂ H _{2 m} O) _n -R ² ) is reacted with a base.

For the preparation of compounds of formula (Ib), a compound of formula (Ia), preferably a derivative of which Y is H ⁺ , is esterified with a low molecular weight alcohol, preferably methanol, ethanol or butanol, and if necessary the resulting product is and esterified with alcohol.

(Ie) for the preparation of compounds of general formula (C _m H _2m O) amine poly (oxyalkylene) glycols or glycol derivative nR with an alk (en) yl-borostyáhkősav anhydride in an H ₂ N-, and optionally, to obtain a product containing a cation other than hydrogen ion, Y

HOOC- (HR) GC (HR ¹ ) -CO-NH- (C _m H _{2 m} O) _n -R ² is reacted with a base.

For the preparation of compounds of formula (Id), an amino-polyoxyoxyalkylene glycol or glycol derivative of the formula H ₂ N- (G _m H _{2 m} O) _n -R ² with an alk (en) yl succinic anhydride reaction, so received

HOOC - (HR) CC (HR ¹ ) -CO-NH- (G 1 H ² O) _n »R ²

...........

• · · · " ··" · · · ··· ··" • · THE ·

The compound of formula 13 is esterified with a low molecular weight alcohol, preferably methanol or ethanol, and the resulting product is amidated with an amine compound of formula Y-ML.

Compounds of formula (II) wherein Y represents a hydrogen ion may be prepared by reacting 2 moles of alk (en) yl succinic anhydride with 1 mole of HA- (C _m H _{2 m} O) _n -CpH ₂ pAH. - m, n, p and the two substituents A are as defined above. The cation other than Y is hydrogen, C 1 -C 6 alkyl (i.e., R), or - (C _m H ₂ O) _n R where m, n and R are as defined above, having the analogous structure (i). may be prepared by the methods described above.

However, the compounds of the invention may be prepared by other methods. For example, the acid anhydride may be reacted with a lower alcohol, then the resulting ester ester esterified with the appropriate poly (alkylene glycol) or poly (alkylene glycol) alkyl ether, or condensed with an alkylene oxide, if desired. the end group of the resulting product is reacted with an additional lower alcohol. The length of the polyalkylene glycol chain can be controlled using a narrow molecular weight poly (alkylene glycol) or poly (alkylene glycol) alkyl ether reagent. The latter process provides a wide chain length product.

Alkenyl succinic anhydrides may be prepared by reacting maleic anhydride with olefins having from 6 to 22 carbon atoms, preferably from 14 to 22 carbon atoms. The olefin is preferably used in excess, for example 50-200% excess. The reaction is carried out at 150-400 ° C, preferably 180-250 ° C, and the excess olefin is removed, for example by distillation, preferably by distillation under reduced pressure. . No catalyst is required for the reaction, but it is preferable to carry out the reaction in the presence of an antioxidant. These anhydrides are well known commercially available materials. In alkenyl succinic anhydrides prepared by the method described above, the double bond is usually located at the 2-position of the alkenyl chain.

It is possible to prepare the products of the invention containing R or R 1 alkyl groups by hydrogenation of the corresponding unsaturated compounds, but it is more preferable to hydrogenate the alkenyl succinic anhydrides to provide the required alkyl succinic anhydride reagents. The hydrogenation is typically carried out in the presence of a hydrogen transfer catalyst such as palladium on a Raney nickel or carbon support. The hydrogenation reaction can be carried out at a temperature of 15-100 ° C and a pressure of 0-200 bar. If desired, the hydrogenation may be carried out in the presence of a solvent. For example, alkenyl succinic anhydrides may be hydrogenated at 20 ° C for 6-24 hours in the presence of 5% palladium on charcoal.

The alkyl or alkenyl groups in the compounds of the present invention which are R or R6 are preferably straight chain. If these groups are branched, the groups are preferably no more than two on average

More preferably, they contain only one - branching. Preferably, the alkyl and alkenyl chains in the whole molecule contain up to three chain linkages in total.

The products of the invention are readily formed in the form of a mild odor. Because poly (alkylene glycol), poly (alkylene glycol) alkyl ethers, and amine derivatives thereof are readily transported, these materials can be used as reagents for the preparation of the compounds of the present invention far from alkylene oxide production plants.

The compounds of the present invention have emulsifying, wetting and dispersing properties. Accordingly, the compounds may advantageously be used to form oil-in-water type emulsions, for example, in metalworking fluids containing partially soluble oils and synthetic materials, in crude oil delivery and in heating systems; they may be used as emollients in personal hygiene (for example, skin care); for use in household detergent compositions (e.g., washing liquids); it can be used to disperse organic and inorganic powders (e.g. fillers and pigments) in paints and coating compositions; it can be used for similar purposes in agrochemicals (for example, pest control products); furthermore, they can be used as wetting agents in so-called industrial and institutional cleaning products (e.g., traffic film removers and bottle washing liquids).

There are two specific areas of end use of the surfactants of the present invention for wool washing and inverting use in the manufacture of acrylamide and the like. These two areas of use are described in more detail in the following sections. * * · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Raw wool from sheep contains, in addition to wool yoghurt, several other substances, including wool grease. Wool grease is a complex mixture of different fats selected by sheep's skin for wool. The wool is removed from the wool before use in the textile industry by washing the wool with an aqueous mixture containing surfactants. The washing is typically carried out at slightly elevated temperatures, for example at 40-80 ° C, preferably at 50-700 ° C. This procedure is called wool washing. It has now been found that the surfactants of the present invention can be used very well for wool washing because they retain their activity even after several cycles of washing, even when used for washing very fine fiber wool (e.g. merino wool). It is known that wool of very fine fibers is difficult to wash because it contains relatively large amounts of wool fat and the specific surface area of the fibers to be treated is very large. Although the choice of the compounds most suitable for the above end use is determined by the particular operating conditions, it has generally been found that the compounds of formula (Ia) are particularly preferred for this purpose; especially those derivatives wherein m is 2, n is 2-25 (particularly preferably 3-10), and R is C 1-6 alkyl (particularly preferably methyl). In the above application, the surfactant is typically used in a concentration of 0.1 to 5 g / l, more preferably 0.2 to 1.5 g / l.

The invention further relates to a method for removing wool-17 fat from wool by washing the wool containing wool fat with an aqueous mixture of an effective amount of a compound of formula I or II. The compounds of formula (Ia) are preferably used for the washing. In a particularly preferred embodiment, the compounds of formula (Ia) in which m is 2, n is 3 to 10 and R is alkyl of 1-6 carbon atoms (preferably methyl) are used.

The invention also relates to the use of the compounds listed as wool salt surfactants.

Emulsion polymerization is widely used in the manufacture of polymers, such as polyacrylamide, in which the polymer accumulates in the aqueous phase which dissolves it. It is well known that polyacrylamides can form high viscosity aqueous solutions even at low concentrations; this property is based on the use of polyacrylamides as thickening and viscosity increasing agents in aqueous systems. If the aqueous phase were a continuous phase during polymerization, it would very soon become very viscous, which would make it difficult to mix and separate the product. To overcome this difficulty, oil is used as a continuous phase during the polymerization and the aqueous phase is dispersed therein. The polymerization is thus carried out in a water-in-oil type emulsion which also contains an emulsifier which stabilizes the water-in-oil type emulsion. Since the polymer remains in the aqueous phase, the viscosity of the oil phase does not increase as the polymerization proceeds, unlike the aqueous phase. However, the polymer is typically used in an aqueous environment, so at a certain point in the process the emulsion has to be inverted, i.e. an aqueous continuous phase is formed. Inverting is typically performed by diluting a water-in-oil type emulsion with water. Prior to aqueous dilution, a water-in-oil type emulsion is usually added with an inversion-promoting surfactant. In our studies, it has been found that the compounds of the present invention are useful as inverting agents in such emulsions. Although the compounds most suitable for the above end-use should be selected according to the particular operating conditions, it has generally been found that the compounds of formula (Ia) are particularly preferred for this purpose; especially those derivatives wherein m is 2, n is 8-25 (particularly preferably 10-15) and R is hydrogen or C 1-6 alkyl (particularly preferably methyl, ethyl, propyl or butyl). . The amount of surfactant required to invert the emulsions of the above type depends on the nature of the particular emulsion, in particular the proportion of the dispersed aqueous phase and the concentration of polymer in the aqueous phase; however, the inverting surfactant will generally be used in an amount of 1 to 5% of a water-in-oil type emulsion.

The invention further relates to a process for inverting a water-in-oil type emulsion containing a polyacrylamide in an aqueous phase, such that a water-in-oil type emulsion, preferably a compound of formula I or II, A compound of formula (Ia), particularly preferably a compound of formula (Ia), is preferred.

Wherein m is 2, n is 8-25, preferably 10-15, and R is hydrogen or C 1-6 alkyl, preferably methyl, ethyl, propyl or butyl, followed by water-in-oil dilute the emulsion with water.

The invention further relates to the use of the compounds of the invention for the inversion of water-in-oil emulsions containing polyacrylamide.

The invention is further illustrated by the following non-limiting Examples. The examples illustrate the preparation, properties, and end-use of the compounds of the invention and demonstrate the diverse and wide utility of the compounds of the invention. Unless otherwise stated in the examples, the percentages are by weight, and the fractions are parts by weight.

The following measurement methods were used in the examples:

The cloud point (ZP) is described in ASTM D 2024-65. standard; results are expressed in ° C.

Humidification (moisture) was measured on a bundle of yarns according to ASTM D 2281-68. standard (Draves Wetting); results are reported in seconds (s) or minutes (m) for slow-acting wetting agents.

The foam height (HM) is determined in accordance with ASTM D 1173-53. standard 60 ° C (Ross Miles foam height); results are expressed in mm units.

The surface tension (FF) was determined using a 0.1 wt% solution at 23 ° C; results are reported in mN.m "' ¹ · units (1 mN.m" ^ = • · · · 9 · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · * ·

- 20 = 1 dyn.cm "^).

Example SE1 - SE24 (Production Examples)

The compounds of formulas SE1-SE24 · listed in Table 1 · were prepared as follows:

The corresponding alk (en) yl succinic anhydrides were reacted with · a stoichiometric amount of poly (ethylene glycol) (PEG), poly (ethylene glycol) alkyl ether or an amine derivative. The reaction mixture was maintained at about 100 ° C and sampled every 30 minutes. The reaction was stopped when the reaction was complete by IR spectral analysis and / or acid number of the sample.

The corresponding sodium salts were prepared by adding sodium hydroxide solution to a pH of 9. The sodium salts were isolated by stripping or used as an aqueous solution.

Sulfuric acid and methanol were added to the acidic product to produce the corresponding methyl esters. Methanol was redistilled for 2 to 12 hours at a rate such that the volume of the mixture was constant. The sulfuric acid was then neutralized with sodium bicarbonate and the product was filtered off. Similarly, other lower alkyl esters were prepared.

Compounds of similar structure to those of the present invention were also prepared using the appropriate starting materials and reagents using the methods described above. These reference substances are designated as C1, C2 and C3 in Tables 1 and 2, respectively.

- 21 • · · «· * ·· ·« · ♦ · »· (

The physical properties (cloud point, wetting, foam height, surface tension) of the compounds listed in Table 1 were determined using the methods described above. The results are reported in Table 2. For purposes of comparison, Table 2 also shows the corresponding data for a commercially available nonylphenol ethoxylate (NPE code) containing 9 moles of ethylene oxide per mole of phenol compound.

The physical properties of the compound SE1 code are as follows:

surface tension (FF); 0.1% solution by dropping at 23 ° C: freezing point:

Viscosity at 25 ° C:

foam height (HM) at 60 ° C (Ross Miles

28.4 mN.m ”· ¹ · -15 ^P C

165 cPs foam height):

min: 7.5 mm min: 3 mm density at 23 ° C:

Draves Wetting:

10.5 sec cloud point:

"Notes to Table_L · ^

* The number of carbon atoms in the substituent carbon chain is given. The term ⁿ u "for R / R ^ means that the group is an alkenyl group, while" s ^M "means that the group is an alkyl group.

2

Does the number in Group R represent the carbon number of the alkyl moiety at the R position? H means that R is hydrogen. A'.z in Y represents H *; noticed by group Y * · ·

- 22 figures represent the carbon number of the alkyl group at the Y position.

The integers given to n can also be rounded figures. For compounds of Formula II, the value of n in Table 1 corresponds to the sum of n + p, where p is equal to m.

Table 1

The compound R / R ¹ Λ ¹ m n 3EX R ² · X Y X coded formula X THE SB1 · (I) 14u -0- -0- 2 3.7 1 H SE2 (I) 12u -0- -0- 2 13.6 H 1 SE3 (II) 18U NH -She- 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- -She- 2 8 H H C3 (I) 12u -0- -0- 2 12 H H SE9 (I) 14u -0- -0- 2 .8 H H SE1O (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

··· · · • ····· »» ···

The compound R / R ¹ In ^{Figure 1} m n XX K ² X Y X coded formula X THE SE17 (I) 18U -She- -0- 2 17 1 H SE18 (I) 18U -0- -0- 2 45 1 H SE19 (I) 14u -0- -0- 2 12 H H SE20 (II) 12u -0- -0- 2 34 - H SE21 (II) 14u -0- -0- 2 34 - H SE22 (II) 14u -EH- -0- 2 34 - H SE23 (II) 18U -0- -She- 2 34 - H SE24 (I) 14s -0- -0- 2 8 H H SE25 (I) 14s -0- -0- 2 12 H H SE26 (I) 18s -0- -0- 2 12 H H

Table 2

Code symbol for the compound FF ZP ° C HM, mm Wet 0 minutes 5 minutes SE1 28.4 40-53 7.5 3 10.5 SE2 30.3 98 87 SE3 3 to 4.0 SE4 31.9 10 55 SE5 30.2 37 21 SE 6 30.7 70-81 46 SE7 52-53 70 SE8 51-52 > 300 01 34 <5 02 33.8 43 C3 34.6 54 66

··· • · · · · · · · · · · · · · · · · · · · · · · · · · · ·

Code symbol for the compound FF _Λ HM, mm σρ θΗ Rowena. mN.m ¹ 0 minutes 5 minutes s SE9 35.7 56.5 SE1O 28.3 21 6.5 SE11 31.2 78 72 58 SE13 28.8 60-65 14 SE14 SE15 SE16 96 SE17 86-87 SE18 96 SE19 38.7 66 SE20 31.6 63 SE21 35.1 - SE22 34.1 SE23 34.0 SE24 43-50 SE25 62 SE26 74-80 NPE 29.9 Example AE1-AE4 · (application technology examples) AE1. example Use for semi-aqueous cleaning

The term "semi-aqueous cleaning" * refers to a process in which an object, such as a metal object, is first cleaned with a solvent and then rinsed with water. Terpene is often used as a solvent for this purpose.

type solvents. Surfactants are often used in aqueous rinsing to help remove solvent from the article to be cleaned during the rinsing operation. Such surfactants (also known as rinse aids) must meet two requirements. The first requirement is that the surfactants effectively remove the solvent and dissolve in the cleaning solvent. The second requirement is not to stabilize the solvent-water mixture, as this would make sewage treatment more difficult. The two materials described below have suitable surfactant properties for use as a rinse aid in semi-aqueous cleaning operations. These materials are also soluble in terpene-type solvents. Surveys conducted have surprisingly shown that these materials allow faster and more perfect water / solvent separation than other surfactants commonly used in semi-aqueous cleaning operations.

The tests were carried out as follows: 0.6% surfactant, 9.4% terpene-type solvent and 90% water were filled into a graduated cylinder and the components were mixed by shaking five times. The mixture was allowed to stand at room temperature for 20 hours, during which time the extent of phase separation was examined periodically. The observed results are reported in Table 3 *.

The term "perfect separation" as used in Table 3 means the state where 10% of the total volume is in the oil phase and 90% in the aqueous phase.

• · «« 4 ··· ···

Table 3

After overactivity Note

There is no condensate of carbon alcohol with 3 moles of ethylene oxide

Alkylphenol with 4.5 moles of ethylene oxide. formed condensate

SE10 code compound t

Compound SE1

Both phases are transparent

The oily and aqueous phases are both cloudy

The oily and aqueous phases are slightly cloudy

The oily and aqueous phases are slightly turbid

Slight opalescence in both phases

Perfect separation After 0.5 hours, there is no perfect separation

Perfect separation after 10 hours

Perfect separation after 12 hours

Perfect separation after 8 hours

ΑΕ2 »example

Use for wool washing

Ten wool samples of 20 g each were washed successively in the same bath. The wool salt bath used was 1 liter of water containing 0.1% by weight of surfactant and washing was carried out at 60 ° C. The residual fat content of the last washed cotton sample was then determined by organic solvent extraction. The extraction solvent used was dichloromethane or chloroform.

The results are shown in Table 4.

The Synperonic NP9 surfactant shown in Table 4 is commercially available

C13-C15 alcohol alkoxylate, while Synperonic 87K • ··. ··. ........

···. ··: ···: ..

..... · ... ·· surfactant is a commercially available nonyl phenol ethoxylate.

4 «Table

Surfactant Fat Remaining,% Synperonic NP9 1.71 Synperonic · 87K 2.16 Compound SE1 1.24 Example A3 · consumption gyapjumosáshoz

Further woolening tests were performed on fine merino wool (fiber diameter about 20 µm). 0.5 g surfactant water per liter of wool salt solution was added and 4 wt.% Potassium chloride was added to simulate salt accumulation upon re-use of the salt solution. Washing was carried out in a detergent pan at 65 ° C and in a rinse pan at 50 ° C. The wool saline solutions were reused for several cycles and the percentage of fat remaining on the wool was determined after each wash cycle. The results are reported in Table 5. In this series of experiments, SE1 (a compound of the present invention) was compared with the following four known surfactants for wool washing:

Code Material: Lissapol TN450 (Nonyl Phenol Ethoxylate Manufactured by: ICI Australia) Code Material: Lissapol BD20 (Biodegradable Wool Saline; manufactured by ICI Australia). Material: Lissapol BD30 (Biodegradable Wool Salt; Manufactured by: 101 Auatralia) Code Sign Material: Softanol 90 (Secondary alcohol ethoxylate;

manufactured by Nippon Shokubai)

5 «Table

Fat Fat Remaining Wool,% Cycle SE1 03 04 05 _Y C6 Code Codes After Wash with Surfactant

First 1.13 0.81 1.08 1.02 0.77 Second 0.96 0.95 1.38 0.87 0.73 Third 0.96 1.22 1.15 0.89 0.86 4th 0.93 1.02 1.10 1.01 0.94 5th 0.98 1.19 1.74 0.90 1.04 6 0.93 1.07 1.36 1.12 0.97 7th 0.98 1.02 1.18 1.02 1.19 8th 1.04 1.20 1.76 1.17 1.46

From the data listed in Table 5, it can be seen that the compound of the present invention has a very good advantage as a surfactant for wool blending, and has the particular advantage of maintaining a good washing effect over a long period of time even when washing wool. hard to wash.

AE4> Example

Use for inverting poly (acrylamide) emulsion

The polymerization was carried out in the following composition at a temperature of about 40 ° C:

- 29 ···

·· ♦ ···

Acrylamide

acrylic acid

Deionized water

Hydrocarbon solvent (Isopar L)

Sodium hydroxide

Ethylenediaminetetraacetic acid (EDTA, 5%)

Azobis (isobutyronitrile) (AIBN)

Primary emulsifier

135.0 g

58.0 g

179.0 g

168.0 g to pH 6

5.2 g

0.4 g

8-12 yrs

Hypermer 2296 (a commercially available polymeric surfactant) was used as the primary emulsifier.

To the polymer emulsion samples were added 3-3% of the surfactant listed in Table 6 as inverting agent and the mixtures were allowed to stand for 2-3 days. The emulsions were then sampled and mixed with 1% aqueous mixtures. After stirring for 2 minutes, the viscosity of the aqueous mixtures was measured. Stirring was then continued and viscosity was again measured after 15 minutes. The results are reported in Table 6.

6 »Table

Surfactant Viscosity, mPa.s. 2 minutes after 15 minutes eÍtéltével Synperonic NP9 12 000 26 000 SE11 11 500 26 000 SE19 24 000 24 500 Material code 03 coagulated

Table 6 shows that SE11 is equivalent to SE19 pe * ·· · **. : ···; ··· ·· ♦ ... ...

- 30 digs more effective than Synperonic NP9, traditionally used as an ingot ingot. At the same time, C3 code material is essentially unsuitable as an inverting agent.

Claims (12)

Claims Compounds of formula (I) and (II) YA ¹ -C? C- (HR) CG (HR ¹⁾ -CO-A (C _m H _2ni O) _n -R ² (I) Y ¹ -OC- (HR) C-C ¹ H ¹ ) -CO-A- (C _m H _{2 n} O) _n -C _p H _2p -A-CO- (HR ¹ ) CC (HR) -CO-A 4 - Y (II) - in the formulas One of R e is C 6 -C 22 alkenyl or alkyl and the other is hydrogen, The oxy group or the group -NR 1 - - in the latter case R 1 is hydrogen or C 1 -C 6 alkyl, n is from 2 to 100, and n can be a fraction, m is 2 or 3, with the poly ( within the oxyalkylene chain), the value of m may vary, R is hydrogen or (C1-C6) -alkyl, A * ¹ * is -O, -O or -NR ^ -, and in the latter case R 'is hydrogen or (C1-C6) -alkyl when A means then Y represents a cation, whereas when A represents an oxy group or a -NR ^ - group it represents Y is C 1 -C 6 alkyl (i.e., csoportτ) or (C _m ^H _{2 m} O) _n -R wherein R, m and n are as defined above and p is 2 or 3, provided that when The oxy group or -0 "ions, the sum of the carbon atoms in the R, R and R and / or R · 'groups is at least 13 · ··· * ·“. ; · * ·; * ··. ··· ··. ... ..... ... · - 32 - Compounds of formula (I) and (II) according to claim 1, wherein one of R and R is hydrogen and the other is C 14 -C 22 alkenyl or alkyl. · Compounds of formula (Ia) as defined in claim 1, which are a narrow group Y'OOG- (HR) GC (HR ¹ ) -GOO- (G _m H _2m O) _n -R ² (Ia) wherein m, n and R are as defined in claim 1, Y is cation and one of R and R ¹ is hydrogen and the other is C 14 -C 22 alkenyl or alkyl. 4 Compounds of general formula (Ib) according to claim 1, which are a narrow group Y-OOC- (HR) CC ^{(HR; L)} -COO- (C _m H _2ni O) _n H ² (Ib) 1 z 2 Z z wherein R, R, m, n and R are as defined in claim 1 2, and Y is C 1 -C 6 alkyl, or ( ^G _m ^H 2 m 0 ^ n ^R , wherein m, n and R are as defined in claim 1). · Compounds of general formula (Ie) as defined in claim 1, which are a narrow group of compounds Y 'OOG- (HR) CG (HR ¹⁾ -CO-NH- (C _m H _2m O) _n ~ ^R2 (Ic) 1 2 wherein R, R, m, n and R are as defined in claim 1 and Y is cation. 6. A compound of the formula (I) as defined in claim 1, which is a narrow group of compounds of formula (Id). prodrugs R ² - (CmH2m0) n -NH-0C- (HR) CC (HR ¹⁾ C 0-RH (CMH _2w 0) _n ^-R2 (W Έ 2 wherein R, R, m, n and R are as defined in claim 1. 7 · A 4-6. Compounds according to any one of claims 1 to 5, wherein one of R and R ¹ is hydrogen and the other is Represents a C 14 -C 22 alkenyl group. Compounds according to any one of claims 1-7, wherein m is 2, p is 2, if present in the molecule, n is 3-50, and n can be a fraction, and Y represents a cation H ⁺ , an alkali metal cation or an ammonium cation or represents a methyl, ethyl or butyl group. 9. A method of treating wool to remove wool grease, wherein the wool containing wool grease comprises an effective amount of a wool grease according to any one of claims 1-8. The mixture is washed with an aqueous mixture of a compound of formula (I) or (II) according to any one of claims 1 to 3. The process according to claim 9, wherein 1, wherein the compound of formula (I) is a compound of formula (Ia) wherein m is 2, n is 3-10 and R is C 1-6 alkyl. 11. A process for inverting a water-in-oil type emulsion containing a polyacrylamide in the aqueous phase, wherein the water-in-oil type emulsion is prepared according to any one of claims 1-8. A compound of formula (I) or (II) according to any one of claims 1 to 6 is added and the water-in-oil-in-oil emulsion is inverted by diluting with water. 12. The process of claim 11, wherein the compound is of formula (Ia) wherein m is 2, n is 8-25, and R is hydrogen or (1-6C) alkyl.