EP2282988A1

EP2282988A1 - Fluorosurfactants

Info

Publication number: EP2282988A1
Application number: EP09761370A
Authority: EP
Inventors: Eckhard Claus; Fanny SCHOOREN; Martin Seidel; Wolfgang Herse; Peer Kirsch
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2008-06-12
Filing date: 2009-05-15
Publication date: 2011-02-16
Also published as: US20110088594A1; WO2009149807A1; JP2011522847A; DE102008027930A1

Abstract

The present invention relates to compounds of the formulae (I), (II) and (III), to the use of compounds containing at least one perfluoro-tert-butoxy group and at least one substituted or unsubstituted aromatic end group as surface-active agents, and to a process for preparing compounds of the formula (II).

Description

fluorosurfactants

The present invention relates to compounds of the formulas (I), (II) and (III), the use of compounds containing at least one perfluoro-tert-butoxy group and at least one substituted or unsubstituted aromatic end group as a surface-active agent and a process for Preparation of compounds of the formula (II).

Fluorosurfactants have a superior surface tension lowering ability, for example, in the hydrophobization of surfaces e.g. of textiles, paper, glass, building materials or adsorbents. In addition, it is possible to use them as an interface or emulsifier or viscosity reducer in paints, varnishes or adhesives.

Fluorosurfactants generally contain perfluoroalkyl substituents which are degraded in the environment by biological and / or other oxidation processes to perfluoroalkylcarboxylic acids (PFCA ^'s ) and sulfonic acids (PFAS ^'s ). In recent years, there has been accumulation of perfluoroalkylcarboxylic acids (PFCA ^'s ) and perfluoroalkylsulfonic acids

(PFAS ^' s) in nature cause for concern. PFCA ^'s and PFAS ^'s are highly persistent compounds whose long-chain variants (with perfluoroalkyl chains of 8 or more carbon atoms) have a bioaccumulative potential. They are sometimes suspected of causing harm to their health (GL Kennedy, Jr., JL

Butenhoff, GW Olsen, JC ^O'Connor, AM Seacat, RG Biegel, SR Murphy, DG Farrar, Critical Review in Toxicology, 2004, 34, 351-384)

In US 3,668,233 and US 3,385,904 perfluorinated tertiary alcohols and some derivatives of these alcohols are described. The company Omnova markets polymers whose side chains have terminal CF ₃ or C ₂ F ₅ groups. International Patent Application WO 03/010128 describes perfluoroalkyl-substituted amines, acids, amino acids and thioether acids which have a C 3-20 perfluoroalkyl group.

JP-A-2001/133984 discloses surface-active compounds containing perfluoroalkoxy chains, which are suitable for use in antireflection coatings. JP-A-09/111286 discloses the use of perfluoropolyether surfactants in emulsions.

In the earlier German patent application DE 102005000858 compounds which carry at least one terminal pentafluorosulfurane group or at least one terminal trifluoromethoxy group and have a polar end group are surface-active and are suitable as surfactants.

Furthermore, there is a need for alternative surface-active substances, preferably with a, the conventional fluorosurfactants, comparable property profile, as well as a large chemical versatility, which preferably degrade during the oxidative or reductive degradation not to long-chain persistent fluorocarboxylic or fluorosulphonic or preferably in significantly lower dosage effectively are as conventional fluorosurfactants.

It is therefore an object of the present invention to provide novel fluorinated compounds which preferably have one or more of the aforementioned advantageous properties.

This object is achieved by the compounds of the formula (I) according to the invention. Furthermore, it has been found that compounds containing at least one perfluoro-tert-butoxy group and at least one containing substituted or unsubstituted aromatic end group are suitable as surfactants.

A first subject of the present invention are therefore compounds of the formula I,

[Y _n -L x _m ] ₀ -Ar (I) where

Y = (CF ₃ ) _S CO,

L = linear or branched alkyl having at least 2 C atoms, wherein one or more non-adjacent carbon atoms may be replaced by O, S ₁ and / or N, and / or one or more double and / or

Triple bonds in the chain and / or the side chain can be included

X = O (O) C, NH (O) C, O, S, N, OSO ₂ Ar = an unsubstituted or mono- or polysubstituted aromatic ring or fused ring system having 6 to 18 C atoms, containing gfs. N, O and / or S, n = 1 -3, preferably 1 m = O or 1, preferably 1 and o = 1-3, preferably 1-2 where for o ≠ 1 different L and X may be present and

(Nonafluoro-tert-butoxy) ethyl tosylate and di (perfluoro-tert-butoxy-ethyl) phthalate are excluded.

Ar is preferably one with halogen, alkyl, cycloalkyl, aryl, -OH, -OR ¹ , -

NR ¹ R ² , -C (O) OH, -COOR ¹ , -CONR ¹ R ² or -SO ₂ NR ¹ R ^{2 is} a mono- or polysubstituted aromatic ring or fused ring system, wherein R ¹ and R ² = independently of one another H, is linear or branched alkyl, cycloalkyl or alkylaryl.

Preferably, X = O (O) C. Preferably, L is linear alkyl.

The compounds according to the invention may contain one or more perfluorot.-butoxy groups, preferably one, two or three such groups. In particular, compounds with a perfluoro-tert-butoxy

Group are preferred.

The compounds according to the invention preferably contain no further fluorinated groups in addition to the perfluoro-tert-butoxy groups.

A preferred variant of the invention are compounds of the formula (II)

where z = 1-30, preferably z = 1-8, R = H, C ¹ -C 8 -alkyl, -OH, -OR ¹ , -NR ¹ R ² , -SO ₂ NR ¹ R ² ,

R ¹ and R ² = independently of one another H, C ¹ -C 8 -alkyl and p = 0-3, preferably 1.

Particularly preferred are compounds with z = 1-4, in particular z 1, p = 1 and R = H, -CH ₂ -CH ₂ -CH ₃ , -OH, -OEt, -NMe ₂ , -SO ₂ N (CH ₂ CHa) ₂ , SO ₂ N (CH ₂ CH ₂ CHs) ₂ .

In a further variant of the invention, compounds with the aromatic substituents in the para position are preferred. However, compounds with the aromatic substituents in ortho or may also be used Meta position, as well as a combination of substituents in ortho, meta and para position can be used.

Particularly preferred compounds of the present invention are the compounds of the formula (III)

in which

R = H ₁ CH ₂ -CH ₂ -CH _3, SO ₂ N (CH ₂ CH ₃₎ _2, SO ₂ N (CH ₂ CH ₂ CH ₃₎ _2, and z = 1-4, in particular, z = 1, ,

Advantages of the compounds according to the invention can be in particular:

a surface activity which is the same as or superior to conventional hydrocarbon surfactants in terms of efficiency and / or effectiveness, no degradation to long-chain persistent fluorocarbon or

Fluorosulfonic acids such as PFOA (perfluorooctanoic acid) or PFOS (perfluorooctanesulfonate),

- lower amounts used,

good processability in formulations and / or storage stability

The fluorosurfactants according to the invention are particularly suitable for use as hydrophobizing agents or oleophobicizing agents.

Applications include the use of the compounds of the invention as additives in non-aqueous

Surface coating preparations, such as radiation-curing and high-solid or low-solid coatings, adhesives, printing inks, paints, Paints, lacquers, photographic coatings, special coatings for semiconductor photolithography (resists, top antireflective coatings, bottom antireflective coatings) or in additive formulations for the addition of appropriate preparations. The compounds according to the invention for the application are usually incorporated in appropriately designed preparations.

Corresponding agents which comprise at least one compound according to the invention are likewise provided by the present invention. Such agents preferably contain one for the respective one

Use suitable carrier, and optionally other active ingredients and / or optionally adjuvants. Preferred agents are coatings, printing inks and adhesives. In addition, it is possible to use them as an interface or emulsifier or viscosity reducer in paints, varnishes or adhesives

A second object of the present invention is the use of compounds having at least one terminal perfluoro-tert-butoxy group and containing at least one substituted or unsubstituted aromatic end group as surfactants.

Preference is given to using compounds of the formulas (I) or (II). In particular, their preferred embodiments are preferred.

A third aspect of the present invention is a process for the preparation of compounds of the formula (II) which comprises the reaction of an alcohol of the formula (IV) where z = 1-30, preferably 1-8, with an aromatic carboxylic acid R-Ar-COOH or an aromatic

Carbonyl chloride R-Ar-COCl, preferably in the presence of a

Catalyst. In this case, z = 1 to 4, in particular z = 1, is particularly preferred.

The synthesis of the alcohol is known from the literature and in

US 3,385,904.

The compounds according to the invention can preferably be prepared by the following reactions.

1. Esterification using NN ^{'dicyclohexylcarbodiimide} (DCC) and A- (dimethylamino) pyridine (DMAP)

R = H, CH ₂ CH ₂ CH ₃ , SO ₂ N (CH ₂ CH ₃ ) ₂ , SO ₂ N (CH ₂ CH ₂ CH ₃ ) ₂

2. Esterification using N- (3-dimethylaminopropyl) -N ^'- ethylcarbodiimide hydrochloride (EDCI) and 4- (dimethylamino) pyridine (DMAP)

R = H ₁ CH ₂ CH ₂ CH ₃ , SO ₂ N (CH ₂ CH _j ) ₂ , SO ₂ N (CH ₂ CH ₂ CH ₃ ) ₂ 3.: Esterification via the acid chloride

The preparation of further compounds of the formula (II) according to the invention can be carried out analogously to the reactions shown above.

The preparation of further compounds of the formula (I) according to the invention can be carried out by other methods known to the person skilled in the art, as is shown below by way of example with reference to some compounds with z = 1.

Mitsunobu

In addition to the preferred compounds mentioned in the description, their use, compositions and methods, further preferred combinations of the subject matters of the invention are disclosed in the claims.

The disclosures in the cited references are hereby also expressly incorporated into the disclosure of the present application.

The following examples further illustrate the present invention without limiting the scope of protection. In particular, those in the Examples described characteristics, properties and advantages of the compounds underlying the examples in question also applicable to other substances and compounds not mentioned in detail, but covered by the scope, unless otherwise stated elsewhere. Incidentally, the invention is embodied in the entire claimed area and is not limited to the examples mentioned here.

Examples

Example 1: Esterification by means of DCC and DMAP

R = SO _j N (CH ₂ CH ₂ CH ₃ ) _J

In a round-bottomed flask, 4.91 g (0.0175 mmol) of 2- (perfluoro-tert-butoxy) -ethan-1-ol, 5.00 g (0.0175 mmol) of 4-dipropylsulfamoylbenzoic acid and

0.22 g (0.0018 mmol) of 4- (dimethylamino) -pyridine (DMAP) in 50 μl

Submitted tetrahydrofuran and cooled to 0 ⁰ C. At this temperature, a solution of 4,02g (0,0193mmol) N, N ^{'dicyclohexylcarbodiimide} (DCC) is slowly added dropwise into 2OmL of tetrahydrofuran. The reaction mixture is warmed to room temperature and stirred for 24 hours.

The precipitated solid is filtered off and the filtrate is concentrated in vacuo.

The crude product is dissolved in a little ethanol and in six times the amount

Water is added, whereby a white solid precipitates. This is filtered off and dried in a drying oven.

Substance: C ₁₉ H ₂₂ F ₉ NO ₅ SM = 547.433 g / mol

¹ H-NMR (400 MHz, DMSO) 8,12 (d); 7.99 (d); 4.60 (t); 4.48-4.43 (m); 3.08 (t); 1, 52-1, 42 (m); 0.80 (t) ppm.

¹³ C-NMR (100 MHz, DMSO)

163.98; 143.52; 132.16; 129.69; 126.82; 123.75; 120.85; 117.93; 115.02;

68.00; 62.83; 49.00; 20.98; 10.42 ppm.

¹⁹ F NMR (375 MHz, DMSO)

-69,976 ppm.

MS (70 eV) m / z:

547 (M ⁺ , 5%); 518 (100%).

Example 2: Esterification by means of EDCI and DMAP

R = CH ₂ CH ₂ CH ₃

In a round-bottom flask, 8.80 g (0.0314 mmol) of 2- (perfluoro-tert-butoxy) -ethan-1-ol, 5.16 g (0.0314 mmol) of 4-n-propylbenzoic acid and 0.39 g (0.0031 mmol) 4- (dimethylamino) pyridine (DMAP) in 6OmL N ₁ N-dimethylformamide and cooled to 0 ⁰ C. At this temperature, a solution of 6,69g (0,0346mmol) N- (3-dimethylaminopropyl) -N ^'is - ethylcarbodiimide hydrochloride (EDCI) is slowly added dropwise in 15 mL N, N-dimethylformamide (5% deionized water). The reaction mixture is warmed to room temperature and stirred for 24 hours. The solvent is removed in vacuo.

The crude product is dissolved in a little ethanol and added to six times the amount of 1N sodium hydroxide, whereby a pale yellow oil settles. The water phase is decanted and the oil is washed again with water. The oil is dried in vacuo. Substance: Ci ₆ Hi ₅ F ₉ O ₃ M = 426.274 g / mol ¹ H-NMR (400 MHz, DMSO)

7,87 (d); 7,37 (d); 4.52 (t); 4.45-4.40 (m); 2.63 (t); 1, 68-1, 56 (m); 0.89 (t) ppm.

¹³ C-NMR (100 MHz, DMSO)

164.91; 147.84; 128.54; 128.23; 126.37; 123.77; 120.85; 117.93; 115.03;

68.09; 62.13; 36.60; 23:11; 12.94 ppm.

¹⁹ F NMR (375 MHz, DMSO)

-70.21 ppm.

MS (70 eV) m / z:

426 (M ⁺ , 22%); 164 (100%).

Example 3: Esterification via the acid chloride

R = H

In a round bottom flask 8,80g (0,0314mmol) 2- (perfluoro-tert-butoxy) - submitted ethan-1-ol and 4,79mL (0,0346mmol) of triethylamine in 9OmL of toluene and cooled to 0 ⁰ C. At this temperature, a solution of 4.01 mL

(0.0346 mmol) of benzoyl chloride in 2OmL toluene was added dropwise slowly. The

Reaction mixture is stirred at reflux for 24 hours.

The crude product is dissolved in tert-butyl methyl ether, treated with 1 N sodium hydroxide solution and the phases separated. The organic phase is washed with water and saturated sodium chloride solution and dried over sodium sulfate.

The solvent is removed in vacuo.

Substance: Ci ₃ H ₉ F ₉ O ₃ M = 384.194 g / mol ¹ H-NMR (400 MHz, DMSO)

7.96 (d); 7.72-7.62 (m); 7.56 (t); 4.55 (t); 4.46-4.42 (m) ppm.

¹³ C-NMR (100 MHz, DMSO)

164.93; 161, 83; 133.04; 128.75; 128.53; 128.33; 123.78; 120.88; 117.96; 115.03; 68.09; 62.31 ppm.

¹⁹ F NMR (375 MHz, DMSO)

-70.11 ppm.

MS (70 eV) m / z:

384 (M ⁺ , 4%); 105 (100%).

Claims

claims

1. Compounds of the formula (I)

[Yn-L ^] _0-Ar (I)

in which

Y = (CFa) ₃ CO, L = linear or branched alkyl having at least 2 C atoms, wherein one or more non-adjacent C atoms may be replaced by O, S, and / or N and / or double and / or

May contain triple bonds in the chain and / or the side chain, X = O (O) C, NH (O) C, O, S, N, OSO ₂ ,

Ar = an unsubstituted or mono- or polysubstituted aromatic ring or fused ring system with 6 to 18 C

Atoms containing gfs. N, O and / or S, n = 1 - 3, m = O or 1 and o = 1 - 3, where for each of O ≠ 1 different L and X may be present and (nonafluoro-tert-butoxy) ethyl tosylate and di (perfluoro-tert-butoxy-ethyl) phthalate are excluded.

2. Compounds according to claim 1, characterized in that Ar = a with halogen, alkyl, cycloalkyl, aryl, -OH, -OR ¹ , -NR ¹ R ² , -C (O) OH ₁ -COOR ¹ , -CONR ¹ R ² or -SO ₂ NR ¹ R ^{2 is} a mono- or polysubstituted aromatic ring or fused ring system, wherein R ¹ and R ² = independently of one another are H, linear or branched alkyl, cycloalkyl or alkylaryl.

3. Compounds according to one or more of claims 1 to 2, characterized in that X = O (O) C is.

4. Compounds according to one or more of claims 1 to 3, characterized in that L = linear alkyl.

5. Compounds of the formula (II)

be used, where z = 1 -30,

R = H, C ¹ -C 8 -alkyl, -OH, -OR ¹ , -NR ¹ R ² or -SO ₂ NR ¹ R ² ,

R ¹ and R ² = independently of one another are H, C ¹ -C 8 -alkyl and p = 0-3.

6. Compounds of the formula (III)

in which

R = H, CH ₂ -CH ₂ -CH ₃ , SO ₂ N (CH ₂ CHs) ₂ , SO ₂ N (CH ₂ CH ₂ CHa) ₂ and z = 1.

7. Use of compounds containing at least one

Perfluoro-tert-butoxy group and at least one substituted or unsubstituted aromatic end group as a surfactant.

8. Use according to claim 7, characterized in that

Compounds of formulas (I), (II) or (III) can be used.

9. A process for the preparation of compounds of the formula (II) which comprises the reaction of an alcohol of the formula (IV)

wherein z = 1-30, with an aromatic carboxylic acid R-Ar-COOH or an aromatic carboxylic acid chloride R-Ar-COCl, preferably in the presence of a catalyst.

10. The method according to claim 9, characterized in that the reaction in the presence of a) N, N ^{'dicyclohexylcarbodiimide} or N- (3-dimethylaminopropyl) ^-N' -ethylcarbodiimidhydrochlorid and b) A- (dimethylamino) -pyridine is performed.