WO2026027397A1

WO2026027397A1 - Polyalkoxylated phenol derivates

Info

Publication number: WO2026027397A1
Application number: PCT/EP2025/071371
Authority: WO
Inventors: Marie-Pierre Labeau; Patrick Moreau; Massimo GRILLO; Chirine BEN OSMAN; Mélanie HAUTE
Original assignee: Specialty Operations France SAS
Current assignee: Specialty Operations France SAS
Priority date: 2024-07-30
Filing date: 2025-07-24
Publication date: 2026-02-05
Anticipated expiration: 2027-01-30

Abstract

The present invention relates to polyalkoxylated phenol derivatives, their process of preparation and their use as surfactants and/or defoaming agents.

Description

Polyalkoxylated Phenol Derivates

This application claims priority to the application filed on 2024-07-30 in Europe with Nr 24315369.9, the whole content of this application being incorporated herein by reference for all purposes.

BACKGROUND OF THE INVENTION

The present invention relates to polyalkoxylated phenol derivatives, their process of preparation and their use as surfactants.

Polyalkoxylated terpenic derivatives which exhibit outstanding properties of defoaming aqueous media are disclosed in US 6,846,798.

The known polyalkoxylated terpenic compounds are derived from terpene which itself is derived from pine oil. Thus, the known compounds can be prepared from natural sources. However, the main end use of terpene is in the fragrance industry, which decreases its availability and increases its price.

Therefore, it is desirable to provide an alternative surfactant which has properties similar to or even better than the known polyalkoxylated terpenic compounds, in particular in emulsification power. Furthermore, it is desirable to provide such compounds which could at least partly be biosourced, in particular which can be obtained from a starting compound which is cheaper than terpene. Additionally, it is desirable to provide such compound which is biodegradable.

US 2006/247141 discloses the preparation of compounds that can be used as emulsifiers starting from eugenol. The main uses of eugenol being in fragrance and dental applications, its availability and cost are also critical.

BRIEF SUMMARY OF THE INVENTION

It has surprisingly been found that the above problems can be solved by copolymers that are obtainable by using a phenol, which is substituted with an alkoxy -group in ortho-, meta- or para-position to the OH-group of the phenol, as primer for copolymerization of propylene oxide and ethylene oxide and optionally other alkylene oxides.

Furthermore, the invention relates to a process for the production of the above copolymers, their use as surfactant and/or defoaming agents especially with a good emulsification power, and to aqueous compositions comprising said copolymers. DETAILED DESCRIPTION

The present invention relates to a copolymer obtainable by using a phenol, which is substituted with an alkoxy-group in ortho-, meta- or para-position to the OH-group of the phenol, as primer for copolymerization of propylene oxide (PO) and ethylene oxide (EO) and optionally other alkylene oxides (AO).

The phenol of the invention is substituted with an alkoxy -group in ortho-, meta- or para-position to the OH-group of the phenol, preferably the alkoxy group is in ortho-position. This wording means that the alkoxy-group is the only substituent of the phenol. In other words, according to the invention, the phenol is only substituted by the alkoxy-group.

Furthermore, it is preferred that the alkyl group of the alkoxy-group is selected from the group consisting of methyl, ethyl, propyl and butyl, more preferably the alkyl group is methyl.

In a preferred embodiment of the invention the phenol compound is orthomethoxyphenol i.e. phenol substituted only by a methoxy group in the ortho position, and also known as Guaiacol. Guaiacol is produced in a variety of plants and usually derived from guaiacum or wood creosote.

In another embodiment of the invention, in addition to PO and EO other alkylene oxides (AO) may be used to obtain the copolymer of the invention. The other alkylene oxides are higher alkylene oxides than propylene oxide. Preferably, the other alkylene oxides are selected from linear or branched alkylene oxides comprising 4 to 10 C-atoms, such as for example butylene oxide (BO), or mixtures thereof.

Furthermore, it is preferred that the copolymer of the invention is a copolymer of formula Z - (XO)n-(EO)p-(XO)q-H wherein

Z is the phenoxyl radical substituted with an alkoxy-group in ortho-, meta- or para-position to the phenolic oxygen-group, preferably in the ortho-position;

XO is PO eventually in mixture with BO, but preferably PO, n being a mean value which ranges from 2 to 15, preferably 5 to 10, more preferably 7 to 10; p being a mean value which ranges from 6 to 8, preferably 5 to 10, preferably 6 to 8, more preferably about 6. q being a mean value which ranges from 0 to 4, preferably from 0 to 4, more preferably from 0 to 3.

The mean values of n, p and q are preferably chosen so that a 1% by weight solution in distilled water of the said compound exhibits a cloud point of less than 40°C.

In a first preferred embodiment, q is 0 and in that case, the reaction product is preferably either Z - (XO)n-bloc-(EO)p-H or Z - (XO)n-stat-(EO)p-H, wherein Z is the radical deriving from Guaiacol.

In a second embodiment, q is not 0 and in that case, the reaction product is preferably either Z - (XO)n-bloc-(EO)p-bloc-(XO)q-H or Z - (XO)n-bloc- [(EO)p-stat-(XO)q]-H or Z -[(XO)n-stat-(EO)p]-bloc-(XO)q-H, wherein Z is preferably the radical deriving Guaiacol and wherein “stat” stands for a random copolymer.

The embodiment according to which the reaction product is Z - (XO)n-bloc- (EO)p-H gives good results in practice, especially when XO is PO and more particularly when Z is the radical deriving from Guaiacol.

Therefore, in a preferred embodiment of the invention, the copolymer comprises one polyoxypropylene block [PO] and one polyoxyethylene block [EO], i.e., the copolymer is preferably a di-block copolymer and more preferably, a copolymer of the formula above where q is equal to 0. In that case, it is a copolymer having the formula (II) wherein n and p are as defined above.

In formula (II) above, the ratio n/p is generally comprised between 0.6 and 1.6. This ratio does preferably not exceed 1.6 since above this value the cloud point is below 25°C which could impact the solubility of the surfactant. In case foaming is an issue (for instance for spray applications), this ratio is preferably superior to 1.0 and at most equal to 1.6. A defoamer agent could also be added for spray applications.

The copolymer of the invention can be prepared by successively carrying out polyalkoxylation reactions with the substituted phenol as defined above as primer and polypropylene oxide and polyethylene oxide. In another embodiment of the invention, further poly alkylene oxides as defined above are additionally used in the preparation process of the invention.

According to the invention, it is preferred that in a first step the substituted phenol as defined above reacts with the polypropylene oxide and in a second step with the polyethylene oxide to obtain the copolymer of the invention.

The polyalkoxylation reactions are carried out according to well-known methods at a temperature greater than 100°C, preferably between 120 and 250°C, very particularly between 150 and 200°C, in the presence of a catalyst (strong bases, aliphatic amines, Lewis acids). The operation is advantageously carried out in the presence of an inert gas (nitrogen) or of a rare gas (argon or carbon monoxide), preferably at a pressure of the order of 1 to 4 bar. This type of reaction is given in greater detail in International Application WO 96/91245.

The propylene oxide and the ethylene oxide, and optionally the other alkylene oxides, are introduced successively. The amounts of propylene and ethylene oxide, and optionally of the other alkylene oxides, employed correspond to the numbers of molar equivalents n, p and q as desired. The conditions for carrying out such a procedure are well known to a person skilled in the art.

Another subject-matter of the present invention is the use of at least one compound as defined above as surfactant and/or defoaming agent, agents especially with a good emulsification power, in aqueous media capable of forming foams. Such aqueous media are for instance aqueous media for degreasing metal parts (e.g., metal sheets, metal coils etc.), aqueous media for degreasing drilling platforms, aqueous media employed for cleaning oil drilling wells and aqueous detergent media use in household detergency or in industrial and institutional detergency. In a specific embodiment, the compound as described above is used as surfactant for hard surface cleaning, e.g. metal cleaning, or as metal working fluid (MWF).

The aqueous media, for which it is preferable to limit the volume of foam which can be formed during their use, are in particular aqueous media for degreasing metal sheets in alkaline medium, aqueous media for degreasing drilling platforms, aqueous media employed for cleaning oil drilling wells drilled by means of oil-based fluids, and aqueous detergent media used in household detergency (washing machines, dishwashers, washing of hard surfaces) or in industrial and institutional detergency.

During the use of aqueous media for degreasing metal sheets in alkaline medium, the formation of foam can result from the presence in the degreasing composition of foaming detergent surface-active agents, as well as the presence of soaps resulting from fatty acids or from esters present in the contaminating medium to be removed.

These same difficulties can appear during the degreasing of oil platforms. It should be noted that, in the field of oil exploitation, the foaming can also be caused by the presence of foaming compounds in the crude oil. The phenomenon of foaming is very often dangerous in this specific application. Thus, in addition to the obvious problems of safety present on platforms which have become slippery, the creation of foam in the well itself, during the operation of cleaning the latter before the latter is brought into production, has the consequence of decreasing the relative density in the well (by inclusion of air) and can, for example, result in the uncontrolled eruption of the oil if it is a gusher.

During the use of aqueous detergent media in household detergency or in industrial and institutional detergency, the appearance of foam can be due to the presence, in the detergent composition, of foaming detergent surface-active agents, as well as to the presence of certain residues, such as food proteins of the albumin type, milk, and the like.

The surfactant/defoaming agent according to the invention can be employed in an aqueous medium, , either via degreasing or detergent compositions, by introduction of the said agent into the said compositions at the time of the manufacture of the latter or by introduction of the said agent into the said compositions at the time of use of the latter, or alternatively by direct addition of the said agent to the aqueous medium.

In aqueous media for degreasing metal sheets in alkaline medium, the said surfactant/defoaming agents can be generally present in a proportion of the order of 0.01 to 5 g/1, preferably of the order 0. 1 to 5 g/1, of the said medium.

In the field of oil exploitation, more particularly the degreasing of platforms, the aqueous media comprise of the order of 0.005 to 0.05 g/1, preferably of the order of 0.015 to 0.025 g/1, of the said medium (after dilution) of surfactant/defoaming agents. For what relates more particularly to the cleaning of the well, the amount of surfactant/ defoaming agent is employed with a concentration of between 0.5 and 10% by weight in the aqueous solution, preferably 1 to 5%.

In the field of washing-machine household detergency, amounts of surfactant/ defoaming agents of the order of 2 to 10%, preferably of the order of 3 to 5%, by weight with respect to the dry content of the detergent medium, for a conventional detergent formulation containing of the order of 5 to 15% of anionic and/or nonionic surface-active agents, are recommended. In dishwasher household detergency, these amounts can be of the order of 0.5 to 10%, preferably in the order of 1 to 3%.

In the aqueous media used in industrial and institutional detergency, the said surfactant/ defoaming agents can be generally present in a proportion of the order of 0.005 to 0.05 g/1, preferably of the order of 0.015 to 0.025 g/1, of the said medium (after dilution).

The degreasing or detergent aqueous media comprising the said surfactant/ defoaming agent of the invention is preferably used at a temperature above its cloud point (CP). Generally, the use temperature is of at least 50°C.

Another subject matter of the present invention is an aqueous formulation for degreasing metal surfaces in alkaline medium or oil drilling wells or detergents comprising at least one compound as defined above.

Should the disclosure of any patents, patent applications, and publications which are incorporated herein by reference conflict with the description of the present application to the extent that it may render a term unclear, the present description shall take precedence.

The following examples are given by way of illustration.

EXAMPLE 1: SYNTHESIS OF THE COPOLYMERS

Preparation of guaiacol - n PO - m EO (dibloc copolymer)

Guaiacol (2 -Methoxyphenol) (124 g, 1 mole) and sodium hydroxide 100% (0,8 g, 0,02 moles) were introduced into an alkoxylation reactor.

The reaction mixture was dehydrated at about 110°C under full vacuum to arrive at a water content of less than 500 ppm. Then, the reactor was pressurized with an inert gas (nitrogen) up to 0,5 barg, the mixture was heated between at about 150°C and propylene oxide (from 290 to 580 g, from 5 to 10 moles) was introduced, controlling the increase of the total pressure of the reactor from 1 barg to 5 barg.

At the end of the addition of propylene oxide, ethylene oxide (from 264 to 352 g, from 6 to 8 moles) were introduced, controlling the increasing of the total pressure of the reactor from 1 barg to 5 barg.

After completion of the reaction, the reaction mixture was cooled at about 60°C and then neutralized by addition of acetic acid or iso-nonanoic acid until a pH of 7 was obtained.

Preparation of guaiacol n PO - m EO - p PO (triblock copolymer)

The reaction mixture was dehydrated at about 110°C under full vacuum to arrive at a water content of less than 500 ppm. Then, the reactor was pressurized with an inert gas (nitrogen) up to 0,5 barg, the mixture was heated at about 150°C and propylene oxide (290 g, 5 moles) was introduced, controlling the increasing of the total pressure of the reactor from 1 barg to 5 barg.

At the end of the addition of propylene oxide, ethylene oxide (264 g, 6 moles) was introduced, controlling the total pressure of the reactor between 1 and 5 barg.

At the end of the addition of ethylene oxide, a further quantity of propylene oxide was introduced (174 g, 3 moles), controlling the increasing of the total pressure of the reactor from 1 barg to 5 barg.

After the completion of the reaction, the reaction mixture was cooled at about 60°C and then neutralized by addition of acetic acid or isononanoic acid until a pH of 7 was obtained.

Preparation of guaiacol - n PO - m EO (random copolymer)

Guaiacol (2 -Methoxyphenol) (124 g, 1 mole) and sodium hydroxide 100% (0,8 g, 0,02 moles) were introduced into a alkoxylation reactor.

The reaction mixture was dehydrated at about 110°C under full vacuum to arrive at a water content of less than 500 ppm. Then, the reactor was pressurized with an inert gas (nitrogen) up to 0,5 barg, the mixture is heated at about 150°C and propylene oxide (464 g, 8 moles) and ethylene oxide (264 g, 6 moles) were introduced, controlling the increasing of the total pressure of the reactor from 1 barg to 5 barg.

The introduction of propylene oxide and ethylene oxide was done in "random" mode, by reacting propylene oxide and ethylene oxide simultaneously. The molar ratio between propylene oxide and ethylene oxide (1.33) was kept constant during the course of the reaction.

EXAMPLE 2

Biodegradability of the compounds prepared in example 1 was tested. All samples were tested according to OECD 301F. All samples passed the test for biodegradability.

EXAMPLE 3

The cloud points of the compounds obtained in example 1 were measured at a concentration of 1% by weight in deionized water and in an internal builder (composed of 0.225% by weight of potassium hydroxide, 0.15% by weight of potassium phosphate tribasic, 0.075% by weight of potassium pyrophosphate, 0.15% by weight of potassium carbonate and 0.075% by weight of sodium gluconate in water). By heating slowly the solutions, they became turbid and the temperature of the bath at that moment (which is by definition the cloud point) was recorded. Two tests were carried out and the average value is listed in Table 1 below.

Table 1: Cloud point measurement of Guaiacol-based surfactants in water and alkaline formulation

(*) n/p

** Surfactant with 5PO-6EO-3PO

Increasing the molar ratio PO/EO leads to a decrease of the cloud points of the surfactants. The cloud points in internal builder at the same dosage lw% are lower than those measured in water due to the high salts concentration in builder.

EXAMPLE 4

Gardobond® test panels from Chemetall (MBZ = galvanized steel, Al 6014, MBS = steel, Hot dip galvanized= HDG) were tested according to the following protocol.

Substrates panels (automotive and general industry grade) with dimensions of 1x190x105mm, were immersed in a solvent (Isopropanol/heptane: 50:50) for 20 minutes under magnetic stirring at 500 rpm in order to remove traces of oil on the surface. After solvent draining, they were oiled by deposing of anticorrosion oils drops as Ferrocote® 6130 and Anticorit® PL 3802-39S to get a coating weight of 2g/m2. Then the oiled panels were suspended at RT (Room Temperature) then used for cleaning tests or siccativated at 130°C for 20 min (VDA 230-213) in an oven and tested.. A degreasing medium (pH 11.5) was prepared by diluting an aqueous detergent containing of 45% by weight of active material and composed of 0.225% by weight of potassium hydroxide, 0.15% by weight of potassium phosphate tribasic, 0.075% by weight of potassium pyrophosphate, 0.15% by weight of potassium carbonate and 0.075% by weight of sodium gluconate in water followed by adding 1.5-3g/L active of tested surfactants. Fresh and aged oils are cleaned in Dip and Spray within 1-2 min. The degreasing temperature was 55 °C and the alkaline bath was maintained under magnetic stirring at 6L and under recirculation at 50L. At 6L scale, after dipping, the panels were rinsed with tap water then DI water at RT for 30 seconds each. At 50L scale, dipped panels were rinsed in spray with tap water 30 seconds followed by DI water rinse for 30seconds. Cleaning results as Water Break Film (WBF), Flash Rust (FR) and Reflectance Fluorescence Unit (RFU) of 3 surfactants with different PO/EO ratios are summarized in tables 2, 3 and 4 below.

The Water Break Film (WBF) test depends on water/metal and water/oil affinities. This test uses running water, allowing it to form a film across the surface. Breaks in the water film indicate the presence of hydrophobic/oil residues. It is a visual control. Once cleaned, the panel is rinsed 30s with Tap Water and 30s with DI water. Then, the water film is observed for 30 s. The assessment of WBF is carried out regarding the continuity of the water film on panel: for example, if half panel presents a continuous water film, the WBF is 50%. The higher the WBF, the better (with 100'% WBF, the water film is continuous).

The Flash Rust (FR) test is a corrosion test used just for steel. The cleaned panel is exposed to corrosion, the more the corrosion, the better the performance. The cleaned panel is dipped in 3% nitric acid in water for 1 min without stirring. Then, the panel is immediately immersed in a DI water beaker and left to dry for 24h. The flash rust rating is based on the % of corroded area. If half panel is corroded, the flash rust rating is 50%.

The CleanoSpector is a tool to measure the thickness of a contaminated surface based on the fluorescence of organic surfaces. A fluorescent molecule, called a fluorophore, has the property of absorbing light energy and releasing it as fluorescent light leading to a higher Relative Fluorescence Unit (RFU). When RFU < 100, the cleaning is good. The lower the RFU, the better the cleaning.

Table 2: Cleaning performance of 3 surfactants in Dip process on different substrates at 1.5g/L at 50L scale

*The dash means that the test has not been done

Table 3: Cleaning performance of 3 surfactants in Spray process at 1.5g/L at 50L scale

The tested surfactants are able to clean fresh and aged oils on Multimetal in 1-2 min in Spray and Dip processes.

Table 4: Compared cleaning performance of Guaiacol#6 dibloc, tribloc and random on 6L-dip cleaning at 3g/L at 55°C

The Guaiacol#6 with different structures of PO/EO (diblo, tribloc and random) is able to clean the MBS panels in dip process at 6L scale in 6 minutes leading to WBF > 60%. The cleaning performance of the dibloc copolymer is however better than the one of the triblock and random copolymers.

Foam test The foam test was carried out at 55°C (work temperature) using the hand shaking method. 100 ml of the alkaline bath described above (pH = 10.5) containing 0.1% by weight of surfactant were introduced in 250 ml cylinder and with 0.2% by weight of oil (Ferrocote® 6130 or Anticorrit® PL 3802-39S). The cylinder was kept 24h at 55°C then shaked 10 times. The foam height was recorded at different times. The foam height results are listed in Tables 5 to 6 below.

Table 5: Foam height at 55°C for bath containing Ferrocote® N6130 Table 6: Foam height at 55°C for bath containing Anticorit® PL 3802-39S

Emulsification test

5 mL of oil (Ferrocote or Anticorrit) was added in 95 mL of cleaner (3g/L of the tested surfactant in the above described internal builder) at pH = 11.5. The mixture was stirred 55°C for 5 min under 500 rpm and then the mixture was transferred into a cylinder kept for lOmin at 55°C in a thermo regulated bath. The supernatant was skimmed till 95 mL. The 95 mL were transferred to a beaker and 5 mL of oil was added at 55°C for 5 min, at 500rpm. The mixture was then transferred to the cylinder kept at 55°C for 24h. The cream and oil volume after addition of Ferrocote N6130 and Anticorrit were measured and listed in Tables 7 and 8 below.

Table 7: Emulsification results when Ferrocote N 6130 was added

Table 8: Emulsification results when Anticorrit was added

The lower the volume of oil + cream, the better the emulsification power.

Claims

C L A I M S

1. A copolymer obtainable by using a phenol, which is substituted with an alkoxy-group in ortho-, meta- or para-position to the OH-group of the phenol, as primer for copolymerization of propylene oxide and ethylene oxide and optionally other alkylene oxides.

2. The copolymer of claim 1, wherein the phenol is substituted with the alkoxy-group in ortho-position of the OH-group of the phenol.

3. The copolymer of claim 1 or 2, wherein the alkoxy-group is selected from the group consisting of methoxy, ethoxy, propoxy and butoxy.

4. The copolymer of any one of claims 1 to 3, wherein the other alkylene oxides are selected from linear or branched alkylene oxides comprising 4 to 10 C-atoms or mixtures thereof, preferably the other alkylene oxide is butylene oxide.

5. The copolymer of any one of claims 1 to 4, is a copolymer having the formula Z - (XO)n-(EO)p-(XO)q-H, wherein

Z is the phenoxyl radical substituted with an alkoxy-group in ortho-, meta- or para-position to the phenolic oxygen-group, preferably in the orthoposition;

6. The copolymer of claim 5, which is a copolymer having the formula (II) wherein preferably the ratio n/p is comprised between 0.6 and 1.6.

7. A process for the preparation of a copolymer of any one of claims 1 to 6, comprising the steps of successively carrying out polyalkoxylation reactions with a phenol, which is substituted with an alkoxy -group in ortho-, meta- or para-position to the OH-group of the phenol, as primer and polypropylene oxide and polyethylene oxide to obtain the copolymer.

8. Use of a copolymer as defined in any one of claims 1 to 6 as surfactant and/or defoaming agent, especially with a good emulsification power, preferably in aqueous media.

9. The use according to claim 8, wherein the aqueous media are aqueous media for degreasing metal parts, aqueous media for degreasing drilling platforms, aqueous media employed for cleaning oil drilling wells and aqueous detergent media use in household detergency or in industrial and institutional detergency.

10. The use according to claim 8 or 9, for hard surface cleaning.

11. An aqueous formulation for degreasing metal surfaces in alkaline medium or oil drilling wells or detergents comprising at least one compound as defined in any one of claims 1 to 6.

12. A method for manufacturing a copolymer according to any one of claims 1 to 6, wherein the phenol is a renewable material and leads to a copolymer which is biodegradable, which enables a reduction of water pollution.

13. The method of claim 12 wherein the phenol is Guaiacol.