Process for preparing fluorinated polymers

Abstract

The present invention relates to a novel method for producing fluorinated polymers, to novel fluorinated polymers produced according to the method, to formulations containing these polymers, and to the use of the polymers and formulations, in particular as surfactants or as surface-active additives in coating formulations, and to articles coated with such polymers or formulations.

Description

Technical Field

[0001] The present invention relates to a new method for preparing fluorinated polymers, new fluorinated polymers prepared according to this method, preparations containing these polymers, and the use of such polymers and preparations, in particular as surfactants or as surface-active additives in coating preparations, and articles coated with such polymers or preparations. Background Art

[0002] Fluorinated compounds are important components of industrial processing chemicals. Fluorine-containing compounds can be used in a variety of applications, such as for improving the wetting of surfaces or for antifouling coatings. Fluorinated surfactants are used, for example, as interfacial promoters, hydrophobizing agents, emulsifiers, foam stabilizers or viscosity reducers in inks, paints, coatings or adhesives.

[0003] However, due to their persistence and toxicity, the use of fluorinated compounds has raised concerns among users and the environment and has made them the focus of regulatory measures and restrictions. Thus, classical fluorine compounds typically consist of long-chain perfluorinated alkyl chains (C6-C8) and are considered to have potential bioaccumulative and toxic properties. The persistence and associated environmental risks of conventional C6-C8 compounds are problematic. Perfluorinated alkyl chains decompose in the environment through biological and other oxidative processes, in which case perfluoroalkyl carboxylic acids and perfluoroalkyl sulfonic acids are produced.

[0004] Therefore, there is a great need for new fluorine-containing compounds that are suitable as additives in coating preparations and exhibit favorable properties such as improved antifouling or oil repellency and / or improved wetting or leveling characteristics, while exhibiting favorable ecotoxicological properties as well as good biodegradability. In addition, there is a great need for a method for preparing such fluorine-containing compounds that can targetedly prepare fluorine-containing compounds with desired technical properties and compositions in a simple, low-cost and resource-saving manner with high yields.

[0005] Efforts to date have aimed at studying compounds with short chains and predefined cleavage positions, whereby as complete a decomposition (mineralization) of the fluorinated units as possible should be ensured. Short-chain fluorine structural units have more favorable ecotoxicological properties but generally exhibit poor properties in their fields of application.

[0006] On the one hand, as short-chain fluorine structural units as possible are helpful when it comes to discharging non-persistent compounds into the environment. On the other hand, the fluorine content is crucial for antifouling properties. The lower the fluorine content in the molecule, the poorer the antifouling effect. Therefore, it is desirable to synthesize functionalizable macromolecules with multiple repeating units from short-chain fluorine-containing molecules.

[0007] WO2019 / 063454A1 discloses, for example, epoxide (or oxirane) monomers having partially fluorinated side groups. Since these fluorinated side groups are relatively short-chain, they are incorporated into oligomers or polymers to improve their technical properties because this increases the fluorine content per molecule.

[0008] However, since fluorinated groups are sensitive to strong bases and amines, the classical methods of anionic polymerization used for preparing, for example, polyethylene oxides or perfluoroalkoxy polymers cannot generally be used here.

[0009] Thus, for example, classical anionic ring-opening polymerization is generally carried out under more severe conditions, especially due to the use of bases such as alkoxides and hydrides, and due to the often elevated temperature, which can lead to the degradation of base-labile monomers or side reactions such as chain transfer by proton extraction. In the case of the above-mentioned epoxide monomers having short-chain fluorinated side groups, this results in degradation reactions rather than polymerization, or in some cases only in oligomerization with side reactions.

[0010] Therefore, there is a need for methods for polymerizing monomers having short-chain fluorinated side groups, especially epoxide monomers, optionally together with other structural units, which enable the synthesis of fluorinated polymers having a variety of technical properties, with good molecular weight control and high yields. These methods should also be able to incorporate additional non-fluorinated monomer units in a controlled manner in order to be able to optimize the property characteristics of the copolymers thus prepared and to match them to the planned applications. Summary of the Invention

[0011] Accordingly, one object of the present invention is to provide fluorinated polymers and methods for their preparation which, compared to the compounds and methods known from the prior art, have one or more of the above-mentioned advantages while not having the above-mentioned disadvantages or having them to a lesser extent.

[0012] It has surprisingly been found that this object can be achieved by the method for preparing fluorinated polymers according to the invention as described above and below and by the fluorinated polymers prepared according to this method.

[0013] In particular, it has surprisingly been found that polymers formed from short-chain fluorinated monomers are obtainable in high yields and with a well-controlled molecular weight by monomer-activated anionic ring-opening polymerization, also referred to below as "MAROP" (monomer activated anionic ring-opening polymerization, English: m onomer activated a nionic r ing o pening p olymerisation).

[0014] The MAROP process for the anionic ring-opening polymerization of propylene oxide or fluorinated epoxides is known from the literature. Thus, for example, C. Billouard, S. Carlotti, P. Debois, A. Deffieux, Macromolecules, 2004, 37, 4038 describe the rapid and controlled anionic polymerization of propylene oxide in the presence of an alkali metal alkoxide / trialkylaluminum system.

[0015] K. Sakakibara, K. Nakano, K. Nozaki, Macromolecules 2007, 40, 6136 and K. Sakakibara, K. Nakano, K. Nozaki, Chemical communications (Cambridge, England) 2006, 3334 describe the regiocontrolled or regioregular anionic ring-opening polymerization of epoxides carrying perfluoroalkyl groups in the presence of a combination of an alkoxide, ammonium or phosphonium compound and trialkylaluminum.

[0016] Compared to the conventional anionic ring-opening polymerization of epoxides, MAROP can be carried out under milder conditions. In this process, an organic salt such as tetrabutylammonium bromide is added as an initiator and a Lewis acid such as tributylaluminum as an activator or catalyst (hereinafter referred to as catalyst).

[0017] By coordination with the Lewis acid, the monomer is activated by the growing chain to perform a nucleophilic attack. At the same time, the nucleophilicity of the active chain end is reduced by the catalyst, making it possible to prevent the undesired transfer reaction to the monomer. This enables particularly sensitive monomers, such as epoxides carrying perfluoroalkyl groups, to be polymerized in mild reaction conditions with high molecular weight and high yield.

[0018] In contrast, according to the present invention, the use of this process for the preparation of polymers from epoxide monomers having short-chain, partially fluorinated side chains has not been described to date.

[0019] Therefore, the subject of the present invention is a process for the preparation of polymers, which process starts from one or more monomers preferably containing only ethylene oxide groups and one or more partially fluorinated organic groups and optionally from one or more further monomers, using an organic salt preferably ammonium halide or phosphonium halide or an alkali metal alkoxide or a macromonomer deprotonated by an organic salt as an initiator and a Lewis acid preferably trialkylaluminum or trialkylborane as a catalyst, by monomer-activated anionic ring-opening polymerization (MAROP) of the monomers.

[0020] Preferably, the further monomers contain, particularly preferably only contain ethylene oxide groups and one or more non-fluorinated organic groups.

[0021] In another preferred embodiment, one of the monomers, preferably an additional monomer, is a macromonomer.

[0022] Another subject of the present invention is a polymer prepared according to the method according to the invention as described above and below (also referred to hereinafter as "polymer according to the invention").

[0023] Another subject of the present invention is a preparation comprising a polymer according to the invention, optionally one or more binders, optionally one or more solvents and optionally one or more additives.

[0024] Another subject of the present invention is the use of a polymer according to the invention and a preparation for the production of functional coatings and / or for surface modification.

[0025] Another subject of the present invention is a method for producing functional coatings and / or for surface modification using a polymer according to the invention or a preparation according to the invention.

[0026] Another subject of the present invention is a method for treating a substrate or an article, which comprises the steps of: applying a polymer according to the invention or a preparation according to the invention optionally in combination with one or more binders and / or one or more solvents and / or one or more additives, and optionally drying and / or removing the solvent. Another subject of the present invention is a substrate or an article that has been treated according to the above method.

[0027] Another subject of the present invention is the use of a polymer according to the invention and a preparation in waterproof and / or stain-proof and / or oil-proof preparations and coatings.

[0028] Another subject of the present invention is the use of a polymer according to the invention and a preparation in inks, paints, printing inks, protective paints, special coatings for electronic or optical applications, photosensitive paints (Photolack), fire extinguishers, lubricants (Gleit-und Schmiermitteln), de-icers, top anti-reflection coatings or bottom anti-reflection coatings, developer solutions and washing solutions, and photoresists for lithography methods, cosmetics, agrochemicals, floor polishes, hydrophobic coatings for fabrics or glass, photographic coatings or coatings for optical elements.

[0029] Another subject of the present invention is inks, paints, printing inks, protective paints, special coatings for electronic or optical applications, photosensitive paints, fire extinguishers, lubricants, de-icers, top anti-reflection coatings or bottom anti-reflection coatings, developer solutions and washing solutions, and photoresists for lithography methods, cosmetics, agrochemicals, floor polishes, hydrophobic coatings for fabrics or glass, photographic coatings or coatings for optical elements, which contain a polymer according to the invention or a preparation according to the invention. Description of the Drawings

[0030] Figures 1 - 4 Shows the dynamic surface tension as a function of the bubble lifetime of the copolymer of Examples 30 - 54. Detailed Description

[0031] A preferred subject of the present invention is a process for preparing a polymer which contains, preferably consists only of, one or more monomer units formed from one or more monomers of formula (I) and optionally one or more monomer units formed from one or more monomers selected from formulae (II) and (III),

[0032] (Rf-CHF-CF2-Y-CHR 1 ) m1 -L-X 1 (I)

[0033] (R 2 ) m2 -X 2 (II)

[0034] (R 3 ) m3 -X 3 (III)

[0035] wherein each group and index independently of one another and in the case of multiple occurrences identically or differently have the following meanings:

[0036] Rf is a perfluorinated alkyl group, preferably a perfluorinated C1 - C20 - alkyl group, which is straight - chain or branched and optionally contains one or more heteroatoms preferably selected from O, S and N atoms,

[0037] Y is O or S,

[0038] R 1 is H or an alkyl group, preferably a C1 - C6 - alkyl group,

[0039] L is a single bond or a divalent organic group, preferably an alkylene group, particularly preferably a C1 - C20 - alkylene group, which is straight - chain or branched and optionally contains one or more heteroatoms preferably selected from O, S and N atoms and optionally contains one or more functional groups,

[0040] R 2 is H or an alkyl group, preferably a C1 - C30 - alkyl group, which is straight - chain, branched, monocyclic or polycyclic and optionally contains one or more heteroatoms preferably selected from O, S and N atoms, and wherein one or more CH2 groups may also be replaced by CH═CH,

[0041] R 3is an alkyl group, preferably a C1-C30-alkyl group, which is straight-chain, branched-chain, monocyclic or polycyclic and optionally contains one or more heteroatoms preferably selected from O, S and N atoms, and in which one or more CH2 groups may also be replaced by CH═CH, and in which one or more H atoms are replaced by the group X 4 is replaced by

[0042] X 1 , X 2 and X 3 are each independently of one another an epoxyethyl group or a glycidyl group,

[0043] X 4 is a functional group, preferably an ethylenically unsaturated group, a silyl group, an epoxyethyl group, a glycidyl group or a tertiary amino group,

[0044] m1 is 1, 2 or 3, preferably 1 or 2,

[0045] m2 and m3 are each independently of one another 1 or 2, preferably 1,

[0046] The process is carried out by monomer-activated anionic ring-opening polymerization of monomers of the formula (I), (II) and / or (III) using an organic salt, preferably an ammonium halide or a phosphonium halide or an alkali metal alcoholate or a macromonomer deprotonated with an organic salt as initiator and a Lewis acid, preferably a trialkylaluminium or a trialkylborane, as catalyst.

[0047] In the monomers of the formula (I), (II) and (III), Rf preferably denotes a perfluorinated C1-C12-alkyl group, which is straight-chain or branched-chain and optionally contains one or more O, S or N atoms, preferably one or more O atoms.

[0048] Preferably, Rf is selected from the following groups:

[0049] CF3-(CF2) 0-3 -,

[0050] CF3-(CF2) 0-3 -O-

[0051] CF3-(CF2) 0-3 -O-(CF2) 1-3 -

[0052] CF3-(CF2) 0-3 -O-(CF2) 1-3 -O-

[0053] CF 3- (CF2) 0-3 -O-(CF2) 1-3 -O-CF2-

[0054] CF3-(CF2) 0-3 -O-(CF2-O) 1-8 -, and

[0055] CF3-(CF2) 0-3 -O-(CF2-O) 1-8 -CF2-.

[0056] Particularly preferably, Rf is selected from the following groups:

[0057] CF3-(CF2) 1-2 -,

[0058] CF3-(CF2) 1-2 -O-,

[0059] CF3-O-(CF2) 1-3 -, CF3-(CF2) 1-2 -O-CF2-,

[0060] CF3-O-(CF2) 1-2 -O-,

[0061] CF3-O-(CF2) 1-2 -O-CF2-,

[0062] CF3-O-(CF2-O) 1-8 -, and

[0063] CF3-O-(CF2-O) 1-8 -CF2-.

[0064] Highly particularly preferably, Rf is selected from the following groups:

[0065] CF3-(CF2) 1-2 -,

[0066] CF3-(CF2) 1-2 -O-,

[0067] CF3-O-(CF2) 1-3 -, CF3-(CF2) 1-2 -O-CF2-,

[0068] CF3-O-(CF2) 1-2 -O-, and

[0069] CF3-O-(CF2) 1-2 -O-CF2-,

[0070] especially selected from CF3-(CF2) 1-2-and -CF3-(CF2) 1-2 -O-.

[0071] R 1 preferably represents H or a C1-C6-alkyl group, particularly preferably H or a C1-C3-alkyl group.

[0072] L preferably represents a single bond or a saturated C1-C20-alkylene group, particularly preferably a C1-C4-alkylene group, which is straight-chain or branched and optionally contains one or more heteroatoms selected from O, S, and N atoms, especially heteroatoms selected from O and S atoms, and optionally contains one or more functional groups.

[0073] Particularly preferably, L represents methylene, ethylene, or propylene, very particularly preferably methylene.

[0074] R 2 preferably represents a C2-C20-alkyl group, which is straight-chain or branched and optionally contains one or more heteroatoms selected from O, S, and N atoms, especially O atoms.

[0075] Particularly preferably, R 2 represents a C6-C18-alkyl group.

[0076] R 3 preferably represents a C1-C20-alkyl group, particularly preferably a C1-C12-alkyl group, which is straight-chain or branched and optionally contains one or more heteroatoms selected from O, S, and N atoms, especially O atoms, wherein one or more CH2 groups may also be replaced by CH=CH, and wherein one or more H atoms, especially exactly one H atom, is replaced by the group X 4 is replaced.

[0077] Particularly preferably, R 3 represents the group -(CH2-O) p -(CH2) o -X 4 , where o is an integer from 1 to 12, preferably 1, 2, or 3, p is 0 or 1, and X 4 has one of the meanings given above and below.

[0078] X 4 preferably represents -SiR 0 3, -NR 00 3, -CH=CH2, an epoxy group, an allyloxy group, an acrylate group, or a methacrylate group, where R 0 in each occurrence represents the same or different C1-C6-alkyl, C1-C6-alkoxy, C3-C12-trialkylsilyloxy, or C6-C12-aryloxy, where at least one group R 0is not an alkyl group, and R 00 represents, each time it appears, identically or differently, an alkyl group, preferably a C2-C12-alkyl group.

[0079] Preferably, R 0 is an alkoxy group OR 000 , where R 000 is equal to a C1-C4-alkyl group, in particular a C1-alkyl group or a C2-alkyl group.

[0080] Very particularly preferably, X 4 is an allyloxy group, an acrylate group, a methacrylate group, a trimethoxysilyl or a triethoxysilyl group.

[0081] m1 preferably represents 1 or 2.

[0082] m2 and m3 preferably each represent 1.

[0083] Particularly preferred are the monomers of the formulae (I), (II) and (III), where

[0084] Rf is selected from CF3-(CF2) 1-2 -, CF3-(CF2) 1-2 -O-, CF3-O-(CF2) 1-3 -, CF3-O-(CF2) 1-3 -O-, CF3-(CF2) 1-2 -O-CF2-, CF3-O-(CF2) 1-2 -O-CF2-, CF3-O-(CF2-O) 1-8 - and CF3-O-(CF2-O) 1-8 -CF2-,

[0085] R 1 represents H or CH3,

[0086] L represents a C1-C4-alkylene group, which is straight-chain or branched and optionally contains one or more O atoms,

[0087] R 2 represents a C2-C20-alkyl group, which is straight-chain or branched and optionally contains one or more O atoms,

[0088] R 3 represents a C2-C12-alkyl group, which is straight-chain or branched and optionally substituted by one or more groups X 4 and optionally contains one or more O atoms,

[0089] X 1 、X 2 and X3 represents an oxiranyl group or a glycidyl group,

[0090] X 4 represents an allyloxy group, an acrylate group, a methacrylate group, trimethoxysilyl or triethoxysilyl, and

[0091] m1, m2 and m3 each independently of one another represent 1 or 2.

[0092] Particularly preferred monomers of formula (I) are selected from the following sub-formulas:

[0093]

[0094]

[0095] wherein Rf, each time it occurs, is the same or different and has the meaning given above and below.

[0096] Particularly preferred are monomers selected from formulas (Ia), (Ib) and (Ic), wherein Rf is CF3-CF2-CF2-O-, CF3-CF2-O- or CF3-O-.

[0097] Very particularly preferred are monomers of formula (Ia), especially those wherein Rf is CF3-CF2-CF2-O- or CF3-O-.

[0098] Particularly preferred monomers of formula (II) are selected from the following sub-formulas:

[0099]

[0100] wherein i is an integer from 1 to 20, preferably from 5 to 17, and k is an integer from 1 to 6, preferably 1, 2 or 3.

[0101] Very particularly preferred monomers of formula (II) are selected from the following sub-formulas:

[0102]

[0103]

[0104] Particularly preferred monomers of formula (III) are selected from the following sub-formulas:

[0105]

[0106] wherein X 4 has one of the meanings given above and below and o is an integer from 1 to 12.

[0107] Particularly preferred are monomers of formulas (IIIa) and (IIIb), wherein X 4represents a trimethoxysilyl group, a triethoxysilyl group, an allyloxy group, an acrylate group or a methacrylate group, with an allyloxy group, an acrylate group or a methacrylate group being particularly preferred.

[0108] Very particularly preferred monomers of formula (III) are selected from the following sub-formulas:

[0109]

[0110]

[0111] wherein, o represents an integer from 1 to 12, preferably 1, 2 or 3, Me represents a methyl group and Et represents an ethyl group.

[0112] In another preferred embodiment, the polymer according to the invention additionally contains one or more monomer units formed from one or more monomers containing an anionic polymerizable group different from ethylene oxide, and the monomers are preferably selected from dimethylcyclosiloxanes, particularly preferably hexamethylcyclotrisiloxane (D3) and octamethylcyclotetrasiloxane (D4).

[0113] The monomers of formula (I), (II) and (III) and their sub-formulas can be prepared by simple standard methods known to those skilled in the art and described in the literature.

[0114] Thus, for example, the monomers of formula (I) and its sub-formulas can be obtained by reacting a perfluoroolefin or a perfluoroalkyl vinyl ether with glycidol or other epoxy alcohols according to methods known to those skilled in the art. Preferred monomers of formula (I) and its sub-formulas and their preparation methods are also described in WO2019 / 063454A1.

[0115] The monomers of formula (II) and (III) and their sub-formulas can be obtained, for example, by reacting the corresponding alkyl alcohols, acids or acid derivatives with epichlorohydrin according to methods known to those skilled in the art and described in the literature. Thus, for example, the monomer of formula (IIb) can be prepared by etherifying a diol with epichlorohydrin or a method similar thereto according to methods known in the literature.

[0116] The required starting materials are themselves commercially available or can be prepared from commercially available products according to methods known to those skilled in the art or in a similar manner.

[0117] According to the MAROP method of the present invention, it is possible to subject an ethylene oxide monomer having a partially fluorinated short-chain group, such as a monomer of formula (I), alone or together with an ethylene oxide monomer having a non-fluorinated group, such as a monomer of formula (II), and / or with an ethylene oxide monomer having a functional group, such as a monomer of formula (III), to controlled polymerization. Thereby, a fluorinated polymer having a good controllable molecular weight and a narrow molecular weight distribution can be synthesized in high yield.

[0118] The MAROP method for polymerizing perfluoroalkyl epoxides described in the above-mentioned literature has to be carried out in a halogen-containing solvent such as hexafluorobenzene due to the low solubility of the monomer, however, the monomer is not suitable for large-scale methods due to its poor ecotoxicological properties.

[0119] In contrast, the short-chain and only partially fluorinated monomers used in the method according to the present invention, in particular those of formula (I), (II) and (III), have better solubility in organic solvents, such that halogen-free solvents can be used.

[0120] The polymers according to the present invention have advantageous properties. Thus, by introducing monomers having relatively short-chain fluorinated groups, in particular those of formula (I), into the polymer, the fluorine content per molecule can be increased and the technical properties of the compound can be improved, for example in the case of use as a surface-active substance having lipophobic and hydrophobic properties or as a surfactant in a copolymer having a hydrophilic comonomer.

[0121] By copolymerizing with non-fluorinated monomers, in particular those of formula (II), the properties of the polymers according to the present invention can be purposefully changed and optimized. Thus, for example, a combination of the lipophobicity and hydrophobicity of the fluorinated groups in the polymer with the hydrophobicity of the alkyl groups can be achieved by introducing a monomer of formula (II) having a long-chain alkyl group. By introducing a monomer of formula (II) having, for example, a diol group, a combination of the lipophobicity and hydrophobicity of the fluorinated groups in the polymer with the hydrophilicity of the diol group can be achieved.

[0122] Alternatively or additionally, by copolymerizing with monomers containing functional groups, in particular those of formula (III), the properties of the polymers according to the present invention, such as their surface adhesion, can be further optimized. Thus, the introduction of functional group anchoring groups, such as acrylate groups, methacrylate groups or trialkoxysilyl groups, can, for example, by forming covalent bonds with the substrate surface, enable the polymer to adhere better to the substrate surface, such as a fabric or glass surface. For binding to a glass surface, the functional group (or the group X in formula (III) 4 ) is preferably a trialkoxysilyl group. For binding to a fabric surface, the functional group (or the group X in formula (III) 4 ) is preferably an acrylate group or a methacrylate group.

[0123] By using the method according to the invention, homopolymers, random copolymers or block copolymers can be prepared.

[0124] Random copolymers can be prepared, for example, by simultaneously using two or more monomers. Block copolymers can be prepared, for example, by sequentially polymerizing two or more monomers or by simultaneously using activated macromonomers such as polyethylene glycol and another monomer.

[0125] Thus, for example, a block copolymer can be synthesized that contains a block of monomer units formed from a fluorinated monomer of formula (I) and a block of monomer units formed from a monomer of formula (II) having, for example, a diol group, which has spatially separated hydrophilic and hydrophobic blocks and thus has a structure similar to that of a low molecular weight surfactant.

[0126] The organic salts acting as initiators are preferably selected from the group consisting of: halides or azides of tetraalkylammonium, tetraarylammonium or alkylarylammonium, halides of tetraalkylphosphonium, tetraarylphosphonium or alkyltriarylphosphonium, meso-azido-bis(triarylphosphine) halides, and alkali metal alkoxides, where

[0127] - the alkyl groups are each independently preferably selected from linear C2-C12-alkyl, branched C3-C12-alkyl or cyclic C5-C12-alkyl, particularly preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-octyl and cyclohexyl, and

[0128] - the aryl groups are each independently preferably selected from phenyl, and

[0129] - the alkoxide groups are each independently preferably selected from C2-C6-alkoxides, particularly preferably ethoxide, n-propoxide, isopropoxide, n-butoxide, isobutoxide, tert-butoxide or tert-pentoxide (tert-pentyloxide).

[0130] Particularly preferred organic salts are selected from the group consisting of: tetra-n-butylammonium bromide ((nBu4N) + Br - ), tetra-n-butylammonium chloride ((nBu4N) + Cl - ), tetra-n-octylammonium bromide ((nOct4N) + Br - ), tetra-n-octylammonium chloride ((nOct4N) + Cl - ), methyltriphenylphosphonium bromide ((MePPh3) + Br - ), methyltriphenylphosphonium chloride ((MePPh3) + Cl- ) μ-Nitrilobis(triphenylphosphine) chloride ((PPN) + Cl - ) tetra-n-butylammonium azide ((nBu4N) + N3 - ) potassium tert-butoxide ((tBuO) - K + ) potassium propoxide (PrO - K + ) and sodium propoxide (PrO - Na + ), very particularly preferably selected from tetra-n-butylammonium bromide ((nBu4N) + Br - ), tetra-n-octylammonium bromide ((nOct4N) + Br - ), potassium propoxide (PrO - K + ) and potassium tert-butoxide ((tBuO - )K + ).

[0131] The Lewis acid acting as a catalyst is preferably selected from the group consisting of: trialkylaluminiums, wherein the alkyl groups are each independently preferably selected from C2-C6-alkyls, particularly preferably selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, and dialkylboranes, trialkylboranes, diarylboranes and triarylboranes, wherein the alkyl groups are each independently preferably selected from C2-C6-alkyls, particularly preferably selected from ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, and wherein two alkyl groups together with the boron atom can also form a cyclic group, in particular a boracyclohexan-1-yl group or a 9-borabicyclo[3.3.1]nonan-1-yl group (9BBN), and the aryl groups are each independently preferably selected from pentafluorophenyl, in particular tris(pentafluorophenyl)borane or bis(pentafluorophenyl)borane.

[0132] Particularly preferred Lewis acids are selected from the group consisting of: triethylaluminium (AlEt3), triisopropylaluminium (Al(iPr)3), triisobutylaluminium (Al(iBu)3) and triethylborane (BEt3), very particularly preferably triisobutylaluminium (Al(iBu)3).

[0133] Preferably, the catalyst is used in excess relative to the initiator, since on the one hand it forms a complex with the initiator, which complex initially activates the halide and subsequently remains at the chain end, and on the other hand it activates the monomer by reducing the electron density in the ring.

[0134] In the process according to the invention, the molar ratio of the Lewis acid (or catalyst) to the organic salt (or initiator) is preferably from 1.05:1 to 10:1, in particular from 1.4:1 to 3:1, very particularly preferably from 1.4:1 to 2:1.

[0135] Another factor influencing the necessary equivalent of the catalyst is the number of oxygen atoms of the monomer, since, as described above, these can complex the aluminum species. Due to this complexing possibility, aprotic organic solvents are preferably used in the process according to the invention, which particularly preferably do not carry oxygen atoms or carry sterically hindered oxygen atoms.

[0136] Preferred solvents for use in the process according to the invention are selected from the group consisting of: tetrahydrofuran, 2-methyltetrahydrofuran, toluene, hexafluorobenzene, cyclohexane, dichloromethane, chlorobenzene, benzene, dioxane, diethylene glycol dimethyl ether and diethyl ether. Organic solvents free of halogens and solvents having few and / or sterically hindered O atoms are preferably used, in particular tetrahydrofuran, 2-methyltetrahydrofuran or toluene, very particularly preferably tetrahydrofuran or 2-methyltetrahydrofuran.

[0137] By increasing the amount of catalyst, the reaction rate can be increased, although this may lead to a broader molecular weight distribution due to side reactions.

[0138] By selecting a suitable initiator and varying the ratio between the catalyst and the initiator, undesired side reactions, such as chain transfer to the catalyst, can also be suppressed or prevented.

[0139] The process according to the invention preferably comprises the following steps:

[0140] - drying the organic salt and subsequently suspending or dissolving it in a dried organic solvent under a protective gas atmosphere, preferably an argon or nitrogen atmosphere, very particularly preferably an argon atmosphere, or under vacuum,

[0141] - adding the dried monomer(s),

[0142] - cooling the reaction mixture to ≤ 0 °C, preferably from 0 to -30 °C,

[0143] - adding the Lewis acid under a protective gas atmosphere, preferably an argon or nitrogen atmosphere, very particularly preferably an argon atmosphere,

[0144] - optionally stirring the reaction mixture for a predetermined time under cooling and a protective gas atmosphere,

[0145] - warming the reaction mixture to room temperature, preferably slowly or by removing the cooling,

[0146] - terminating the polymerization, preferably by adding an alcohol, very particularly preferably methanol or ethanol, an acid, preferably HCl or HBr, or water,

[0147] - Remove the solvent and separate and purify the resulting polymer.

[0148] In another preferred embodiment of the process according to the invention, as the first monomer, a macromonomer is used which is deprotonated by adding an organic salt, preferably in a protective gas atmosphere, followed by adding a second monomer containing an ethylene oxide group and a Lewis acid, where the deprotonated macromonomer is used as a macroinitiator for the second monomer activated by the Lewis acid, the second monomer polymerizing after addition to the deprotonated macromonomer, and where at least one monomer, preferably the second monomer, contains a partially fluorinated organic group.

[0149] The first monomer preferably contains one or more organic groups which may also be fluorinated, preferably one or more non-fluorinated organic groups. The second monomer contains one or more organic groups which may also be fluorinated, preferably one or more partially fluorinated organic groups.

[0150] By the process according to this preferred embodiment, block copolymers can be prepared, for example, which contain a first block formed from the macromonomer and a second block formed from the partially fluorinated monomer.

[0151] The macromonomer is, for example, polyethylene glycol, preferably methoxypolyethylene glycol, in particular methoxypolyethylene glycol of the formula H3C(OCH2CH2) m -OH, where m is an integer from 10 to 200, particularly preferably from 30 to 150. Suitable polyethylene glycols are commercially available, for example mPEG 5000.

[0152] The organic salt for deprotonating the macromonomer is preferably an ammonium salt or a phosphonium salt or an alkali metal alkoxide, in particular selected from the preferred ammonium salts or phosphonium salts and alkali metal alkoxides described above and below, particularly preferably potassium tert-butoxide.

[0153] Preferably, the activation of the macromonomer and / or the polymerization of the second monomer are carried out under the conditions described above and below.

[0154] The processes (such as for work-up), reaction conditions, substances and apparatuses additionally used in the embodiments described above and below of the process according to the invention are known to the person skilled in the art and are described in the literature on anionic polymerization, for example in the abovementioned documents.

[0155] By the process according to the invention, homopolymers, random polymers or block copolymers can be prepared.

[0156] Random copolymers can be prepared, for example, by simultaneously using two or more monomers. Block copolymers can be prepared, for example, by first polymerizing one monomer and adding another monomer to the formed and still activated macromolecule or by simultaneously using pre-deprotonated macromonomers such as polyethylene glycol and another monomer.

[0157] Particularly preferred are the polymers according to the invention, which contain or preferably consist of: one or more monomer units U(I) formed from one or more monomers of formula (I) or its sub-formulas and one or more monomer units U(II) formed from one or more monomers of formula (II) or its sub-formulas.

[0158] Also preferred are the polymers according to the invention, which contain or preferably consist of: one or more monomer units U(I) formed from one or more monomers of formula (I) or its sub-formulas, one or more monomer units U(II) formed from one or more monomers of formula (II) or its sub-formulas, and one or more monomer units U(III) formed from one or more monomers of formula (III) or its sub-formulas.

[0159] Furthermore, preferred are the polymers according to the invention, which consist of: one or more monomer units U(I) formed from one or more monomers of formula (I) or its sub-formulas, in particular formula (Ia), one or more monomer units U(II) formed from one or more monomers of formula (IIa) or its sub-formulas, and one or more monomer units U(III) formed from one or more monomers of formula (IIIa) or (IIIb) or its sub-formulas, in particular formula (IIIa1) or (IIIb1).

[0160] Furthermore, preferred are the polymers according to the invention, which consist of: one or more monomer units U(I) formed from one or more monomers of formula (I) or its sub-formulas, in particular formula (Ia), one or more monomer units U(II) formed from one or more monomers of formula (IIb) or its sub-formulas, and optionally one or more monomer units U(III) formed from one or more monomers of formula (IIIa) or (IIIb) or its sub-formulas, in particular formula (IIIa1) or (IIIb1).

[0161] In another preferred embodiment of the invention, the polymer according to the invention is a block copolymer consisting of block A and block B and / or block C, wherein block A contains or preferably consists of one or more monomer units U(I), block B contains or preferably consists of one or more monomer units U(II), and block C contains or preferably consists of one or more monomer units U(III).

[0162] Such block copolymers according to the invention are represented by way of example by formula (IV):

[0163]

[0164] wherein Ra represents the group Rf-CHF-CF2-Y-CHR as defined in formula (I) 1 -L-, R 2 and R 3 have the meanings given in formulas (II) and (III), and a, b and c represent the total number of the respective monomer units, where a > 1, b ≥ 0, c ≥ 0 and b + c > 0.

[0165] The polymers according to the invention can in principle contain any molar fraction of 1 to 99% of the monomer units U(I), U(II) and / or U(III) defined above, with a total of 100%.

[0166] The particularly preferred molar fractions of the monomer units U(I), U(II) and U(III) in the copolymers (Cp1 - Cp4) according to the invention are shown in Table 1.

[0167] Table 1

[0168]

[0169] The polymers according to the invention preferably have a number-average molecular weight Mn of 500 to 60,000, particularly preferably 1,000 to 40,000, very particularly preferably 1,500 to 25,000 g / mol n . Unless otherwise stated, the molecular weights described above and below are determined by GPC in THF.

[0170] The preferred degrees of polymerization of the monomer units U(I), U(II) and U(III) in the homopolymers (Hp) and copolymers (Cp5 - Cp8) according to the invention are shown in Table 2. Unless otherwise stated, the values of the degrees of polymerization described above and below are determined by 1 1H-NMR.

[0171] Table 2

[0172]

[0173] The variation in the fractions of the different monomer types in the copolymers according to the invention is an important factor in the properties and performance of the copolymers in the formulations containing them or in the coatings prepared therefrom.

[0174] Compared with polymers of the prior art, the polymers according to the invention, in particular those of the preferred embodiments described above and below, can have advantageous properties such as special surface activity, good water repellency and stain resistance.

[0175] Furthermore, compared with polymers of the prior art, the polymers according to the invention can have advantageous and improved environmental properties, since they do not degrade either chemically or biologically into long-chain perfluorinated alkyl substances (PFAS) or perfluorocarboxylic acids (PFCA). Preferably, the compounds according to the invention can be completely converted into mineralizable / renewable compounds by a phase-matched environmental impact.

[0176] Thus, an advantage of the polymers according to the invention is, for example, that due to the presence of specific predefined cleavage positions in the molecule, they can be easily degraded. Thereby, corresponding low molecular weight fragments can be produced, which are common in the atmosphere and can thus decompose in the stratosphere under ultraviolet light.

[0177] The partially fluorinated groups in the polymers according to the invention can be converted, for example, by hydrolysis and oxidation according to Scheme 1 below or similar thereto into volatile and UV-decomposable compounds.

[0178] Scheme 1:

[0179]

[0180] The decomposition products can then be washed out of the atmosphere by rainwater, transferred to the soil and mineralized there.

[0181] The use of the polymers according to the invention and of preparations containing these polymers is likewise the subject of the invention.

[0182] The polymers according to the invention can be used alone or as a mixture, including in combination with other fluorinated and / or non-fluorinated compounds, in particular for the preparation of all types of functional coatings and surface modifications on objects in indoor and outdoor areas. In principle, all surfaces, in particular glass, ceramics, enamel, metals, plastics, elastomers, natural products, fabrics, can be coated, optionally after suitable pretreatment.

[0183] In addition to the polymers according to the invention, the preparations and coatings according to the invention can also contain solvents, additives, auxiliaries and fillers as well as non-fluorinated surfactants. Mention may be made, for example, of silicone particles, plasticizers and optionally surface-modified pigments.

[0184] Preferred fields of application are, for example, the use of the polymers according to the invention in coatings for optical elements or textiles, such as in anti-fingerprint coatings for, for example, displays, optical lenses, spectacle lenses, camera objectives, telescopes, window panes or mirrors, or as a hydrophobizing agent for textile finishing.

[0185] The application of the polymers according to the invention or of preparations containing them on suitable surfaces can be carried out over the entire surface or part of the surface by means of various coating methods known to those skilled in the art, for example by means of CVD, PVD, spraying, inkjet or offset printing methods.

[0186] The subject matter of the invention is also a reagent containing at least one polymer according to the invention, which reagent can also contain solvents, additives, surfactants, auxiliaries and fillers.

[0187] The subject matter of the invention is also a coated article, in particular the abovementioned articles, the coating of which is prepared using at least one compound according to the invention. Preferred are displays, optical lenses, spectacle lenses, camera objectives, telescopes, window panes, mirrors and textiles.

[0188] The polymers according to the invention can preferably be used as surface-active reagents, preferably as surfactants, hydrophobizing agents, interfacial promoters, viscosity depressants, foam stabilizers or emulsifiers. Another subject matter of the invention is therefore the use of the polymers according to the invention and the abovementioned preferred embodiments as surface-active reagents, for example for improving the flow behavior and wetting ability of coating preparations, in particular of the particularly preferred polymers mentioned.

[0189] Further preferred fields of application are, for example, the use of the polymers according to the invention as additives in formulations for surface coatings, such as inks, paints, protective coatings, special coatings, which are used in electronic or semiconductor applications (such as photosensitive paints, top anti-reflection coatings, bottom anti-reflection coatings) or optical applications (such as photographic coatings, coatings of optical elements), in agrochemicals, in polishes and waxes, such as for furniture, floors and automobiles, in particular in floor polishes, in fire extinguishers, in lubricants, in lithographic methods, in particular immersion lithographic methods, such as in developer solutions, rinsing solutions, immersion oils and / or photoresists themselves, in particular for the preparation of printed circuits or in additive formulations of the corresponding formulations with additives.

[0190] Furthermore, the polymers according to the invention which can be used as surfactants are suitable for use in washing and cleaning applications, as well as for use as additives / surfactants in cosmetics such as hair and body care products (such as shampoos, hair rinses and hair conditioners), bubble baths, creams or lotions, which have one or more of the following functions: emulsifier, wetting agent, foaming agent, lubricant, antistatic agent, agent for increasing resistance to skin oils.

[0191] In this case, for applications, the polymers according to the invention are usually introduced into a suitably designed formulation. Based on the entire formulation, the usual use concentration is 0.01 to 30% by weight, preferably 0.01 to 10% by weight, particularly preferably 0.01 to 1.0% by weight of the surfactant according to the invention.

[0192] The corresponding formulations and agents containing the polymers according to the invention are likewise the subject of the present invention.

[0193] Preferably, such agents contain a carrier or solvent suitable for the respective intended use, as well as optionally further active substances and / or optionally auxiliaries. Preferred agents are paint and lacquer formulations, fire extinguishing agents, lubricants, washing and cleaning agents, and deicing agents, or developer solutions, rinsing solutions, immersion oils and photoresists which are used in lithography methods, especially for immersion lithography methods, and especially for the preparation of printed circuits, agrochemicals, floor polishes, cosmetics or hydrophobizing agents for textile finishing or glass treatment. Preferred agents in this case are paint and lacquer formulations and printing inks.

[0194] Furthermore, aqueous paint formulations containing the fluorosurfactants according to the invention either alone or in a mixture with additives are also the subject of the present invention. Paint formulations based on the following synthetic film-forming agents are preferably used: polycondensation resins such as alkyd resins, saturated / unsaturated polyesters, polyamide / imides, silicone resins, phenolic resins, urea resins and melamine resins; addition polymerization resins such as polyurethanes and epoxy resins; polymerization resins such as polyolefins, vinyl compounds and polyacrylates.

[0195] Furthermore, the polymers according to the invention are also suitable for paints based on natural products and modified natural products. Preferred are paints based on oils, polysaccharides such as starch and cellulose, and based on natural resins such as cyclic oligoterpenes, polyterpenes and / or shellac.

[0196] The polymers according to the invention can be used in both physically curable (thermoplastics) and crosslinkable (elastomers and thermosets) aqueous paint systems. Preferably, the fluorosurfactants according to the invention improve the flow and wetting properties of the paint system.

[0197] All uses of the polymers to be used according to the invention, in particular the preferred polymers, mentioned herein are the subject of the invention. The respective applications of the polymers for the above purposes are known to the person skilled in the art, and thus the use of the fluorosurfactants to be used according to the invention does not pose any problems.

[0198] The invention particularly relates to the use of the polymers according to the invention and the formulations containing them according to the preferred embodiments described above and below in functional coatings, for example for improving the water repellency and / or stain resistance and / or oil resistance of formulations of coatings such as epoxy coatings, acrylic coatings or polyurethane coatings.

[0199] The following examples should explain the invention in more detail without limiting the scope of protection.

[0200] Example

[0201] General and Preferred Method Procedures for Polymerization

[0202] To prepare the homopolymers or random copolymers, the organic salts are dissolved in benzene or toluene and transferred to a dried Schlenk flask under a reverse flow of argon.

[0203] The salts are dried under reduced pressure overnight. After adding a suitable solvent such as 2-methyltetrahydrofuran, tetrahydrofuran or toluene and the monomer(s), the solution is cooled. All monomers are dried over calcium hydride before use and stored on molecular sieves, such as on molecular sieves. Trialkylaluminum or trialkylborane is added and the polymerization is carried out while slowly warming to room temperature. As an alternative to trialkylaluminum, triethylborane can also be used, for example, at room temperature and then with warming.

[0204] After adding a termination reagent such as methanol, the solvent is removed under reduced pressure. The polymer is purified by extraction with dichloromethane and deionized water and dried under reduced pressure.

[0205] To prepare block copolymers having polyethylene glycol as a macromonomer, for example, methoxypolyethylene glycol is heated with a base such as potassium tert-butoxide or tetrabutylammonium bromide in a dried Schlenk flask and dried under reduced pressure overnight. The polymerization is carried out analogously to homopolymerization in the presence of a fluorinated comonomer.

[0206] To prepare block copolymers from low molecular weight monomers, they are polymerized by sequential addition in a manner analogous to homopolymerization, i.e., the first block is polymerized from the first monomer and the additional monomer(s) are added to the still-activated macromolecule formed.

[0207] Unless otherwise stated, the molecular weights (Mn ) and the polydispersity (PD) were determined by GPC in THF.

[0208] Example 1

[0209] Homopolymerization of 2-(3,3,4,6,6,7,7,8,8,8-decafluoro-2,5-dioxaoctyl)oxirane (perfluoropropyl vinyl glycidyl ether, PPVEGLY)

[0210]

[0211] In a dried Schlenk flask, 0.6 g of tetrabutylammonium bromide (1 equivalent) was dissolved in 12 mL of benzene and dried under reduced pressure at 50 °C overnight. All subsequent additions were made with a syringe. After adding 15 mL of 2-methyltetrahydrofuran and 5.06 g of PPVEGLY (8 equivalents), the flask was filled with argon and cooled to -10 °C. Polymerization was initiated by adding 3.4 mL of triisobutylaluminum (1.1 mol in toluene, 2 equivalents). It was stirred for 1 d under slow thawing. The reaction was terminated by adding 1 mL of methanol, the solvent was removed under reduced pressure, and the polymer was separated by liquid-liquid extraction of dichloromethane with deionized water, followed by drying under reduced pressure. A colorless viscous liquid product was obtained in 94% yield.

[0212] Mn = 2369 g / mol, PD = 1.10.

[0213] Example 2

[0214] Copolymerization of PPVEGLY and 2-(2,5,8,11-tetraoxadodecyl)oxirane (Me3GE)

[0215]

[0216] Similar to Example 1, tetrabutylammonium bromide (0.1 g, 1 equivalent) was azeotropically dried with benzene, dissolved in 2-methyltetrahydrofuran (4 mL), and incorporated with the comonomers PPVEGLY (0.63 g, 4 equivalents) and Me3GE (1.23 g, 12 equivalents) and triisobutylaluminum (1.1 mol in toluene, 0.85 ml, 2 equivalents). Initiation was carried out at -30 °C under argon. After a reaction time of 1 d, the reaction was terminated with methanol, and a colorless viscous liquid product was obtained in almost quantitative yield by liquid-liquid extraction and drying.

[0217] Mn = 3920 g / mol, PD = 1.10.

[0218] Example 3

[0219] Copolymerization of PPVEGLY and Glycidyl Methacrylate

[0220]

[0221] Similar to Example 1, tetraoctylammonium bromide (0.3 g, 1 equivalent) was azeotropically dried with benzene, dissolved in 2-methyltetrahydrofuran (10 mL), and incorporated with the degassed comonomers PPVEGLY (2.98 g, 16 equivalents) and glycidyl methacrylate (0.31 g, 4 equivalents). The flask was shielded and cooled to 0 °C. After adding triisobutylaluminum (1.1 mol in toluene, 0.85 mL, 1.7 equivalents), it was stirred for 7.5 h and then terminated with ethanol. The product was obtained in almost quantitative yield.

[0222] Mn = 3470 g / mol, PD = 1.16.

[0223] Example 4

[0224] Copolymerization of PPVEGLY and Allyl Glycidyl Ether (AGE)

[0225]

[0226] The method was similar to Example 1, where the equivalent ratio of the monomers PPVEGLY:AGE used was 16:4. The product was obtained in 88% yield.

[0227] Mn = 4230 g / mol, PD = 1.17.

[0228] Example 5

[0229] Copolymerization of PPVEGLY and 1,2-Epoxytetradecane (ETD)

[0230]

[0231] The method was similar to Example 1, where the equivalent ratio of the monomers PPVEGLY:ETD used was 12:24. The product was obtained in 91% yield.

[0232] Mn = 12050 g / mol, PD = 1.23.

[0233] Example 6

[0234] Block Copolymerization of Methoxypolyethylene Glycol (mPEG, m = 123) and PPVEGLY

[0235]

[0236] Dissolve 1.5 g of mPEG 5000 (1 equivalent) and 28 mg of potassium tert-butoxide (0.9 equivalent) in 1 mL of methanol and 12 mL of benzene in a dried Schlenk flask, and stir at 60 °C for 3 h. After drying overnight at 50 °C and under reduced pressure, evacuate for an additional 30 min at 60 °C, in which case the formed tBuOH is removed. Additionally, add tetrahydrofuran (12 mL) and PPVEGLY (0.38 g, 4 equivalents) similar to Example 1, and fill the flask with argon. Initiate polymerization with triisobutylaluminum (1.1 molar in toluene, 0.55 mL, 2.2 equivalents) at -20 °C, and terminate the polymerization with 1 mL of methanol after 5 days. After drying under reduced pressure, a colorless solid polymer is obtained. The product is obtained in almost quantitative yield.

[0237] Mn = 7320 g / mol, PD = 1.15.

[0238] Example 7

[0239] Copolymerization of 2-(3,3,4,6,6,6-hexafluoro-2,5-dioxohexyl)oxirane (perfluoromethyl vinyl glycidyl ether, PMVEGLY) and Me3GE

[0240]

[0241] The method is similar to Example 1, where the used equivalent ratio of monomers PMVEGLY:Me3GE is 4:12. The product is obtained in almost quantitative yield.

[0242] Mn = 3300 g / mol, PD = 1.14 (in DMF containing 1 g / L LiBr).

[0243] Example 8

[0244] Terpolymerization of PPVEGLY, 1,2-epoxyhexadecane (EHD) and AGE

[0245]

[0246] The method is similar to Example 1, where the used equivalent ratio of monomers PPVEGLY:EHD:AGE is 1:2:6. The product is obtained in almost quantitative yield.

[0247] Mn = 7750 g / mol, PD = 1.36.

[0248] Example 9

[0249] Block copolymerization of Me3GE and PMVEGLY

[0250]

[0251] Similar to Example 1, a block copolymer was prepared by sequentially polymerizing the monomers Me3GE and PMVEGLY. The product was obtained in a yield of 78%.

[0252] M n (GPC) = 1810 g / mol, PD(GPC) = 1.05

[0253] Example 10

[0254] Block copolymerization of PMVEGLY and Me3GE

[0255]

[0256] Similar to Example 1, a block copolymer was prepared by sequentially polymerizing the monomers PMVEGLY and Me3GE. The product was obtained in an almost quantitative yield.

[0257] M n (GPC) = 1820 g / mol, PD(GPC) = 1.18

[0258] Examples 11 - 29

[0259] Other copolymers with the following variations were prepared similar to Examples 1 - 10: When using EHD, it was only cooled to -5 °C because the monomers froze and precipitated at lower temperatures due to their melting point of 22 °C. In the case of batches with a high share of EHD, heat was briefly supplied until the initiator / catalyst complex of the aluminum species was formed in order to bring the mixture into solution.

[0260] The copolymers thus obtained are summarized in Table 3.

[0261] Table 3

[0262] Example <![CDATA[PD 1) > Monomer 1 Monomer 2 Monomer 3 <![CDATA[M n 2) (g / mol)]]> <![CDATA[M1:M2:M3 3) > 11 1.27 PPVEGLY ETD - 7690 1:2.3 12 1.37 PPVEGLY ETD - 4820 1:0.55 13 1.28 PPVEGLY ETD - 8460 1:5 14 1.15 PPVEGLY ETD - 14140 1:4.2 15 1.34 PPVEGLY EHD - 9720 1:3.7 16 1.30 PPVEGLY EHD - 11040 1:2 17 1.30 PPVEGLY EHD - 11030 1:3.8 18 1.29 PMVEGLY EHD - 7910 1:3.6 19 1.34 PMVEGLY EHD - 9270 1:1.9 20 1.32 PMVEGLY EHD - 11030 1:3.4 21 1.33 PPVEGLY EHD - 7000 1:3.2 22 1.44 PPVEGLY EHD AGE 13660 2.3:9.5:1 23 1.36 PPVEGLY EHD AGE 11690 2.1:7:1 24 1.41 PMVEGLY EHD AGE 10490 2.6:7.9:1 25 1.49 PMVEGLY EHD AGE 11370 2.5:9.9:1 26 1.44 PPVEGLY EHD AGE 17380 4.2:15.8:1 27 1.54 PPVEGLY EHD AGE 20280 4.4:10.5:1 28 1.48 PPVEGLY EHD AGE 11240 7.3:7.9:1 29 1.49 PMVEGLY ETD - 3650 1:1.3

[0263] 1) Polydispersity according to GPC

[0264] 2) According to GPC

[0265] 3) According to 1 Monomer ratio in the polymer according to 1H-NMR

[0266] Contact Angle Measurement

[0267] Some of the copolymers of Examples 1 to 29 were each applied as a coating to cellulose filter paper, and the contact angle after wetting with water was measured.

[0268] The results are summarized in Table 4.

[0269] Table 4

[0270] Example Contact Angle (°) Maximum Difference Standard Deviation 5 104 7 5 8 108 4 2 13 97 6 4 14 104 4 3 15 115 5 3 17 109 4 3 18 105 4 3 20 112 7 5 21 108 7 5 22 112 5 3 23 106 4 3 24 99 6 4 25 99 5 2 26 114 5 3 27 109 5 3

[0271] As can be seen from Tables 3 and 4, a larger contact angle, and thus poorer wettability or higher hydrophobicity of the filter paper, can be achieved with a higher share of alkyl monomer (Monomer 2).

[0272] An increase in molecular weight also results in a larger contact angle, as shown by using a longer-chain alkyl monomer (Monomer 2) such as epoxyhexadecane (EHD) instead of epoxy tetradecane (ETD), and using a fluorinated monomer with a longer side chain (Monomer 1) such as PPVEGLY instead of PMVEGLY.

[0273] Examples 30 - 54

[0274] Copolymers of Examples 30 to 54 were prepared analogously to Examples 1 - 29. The copolymers thus obtained are summarized in Table 5.

[0275] Table 5

[0276]

[0277]

[0278] 1) Examples 30 - 33 = blends of homopolymer PEG and block copolymer PEG-b-PPVEGLY, PD and M n The values refer to the block copolymer.

[0279] 1) Examples 34 - 54 = random copolymers

[0280] 2) Me2GE = 2-(2,5,8-trioxanonyl)oxirane

[0281] 3) Polydispersity according to GPC

[0282] 4) According to GPC

[0283] 5) According to 1 Monomer ratio in the polymer according to 1H-NMR

[0284] For the copolymers of Examples 30 - 54, the static surface tension (0.1 wt% aqueous solution, according to the Wilhelmy plate method) was measured. The measurement method is described in WO2014 / 012661A1.

[0285] The results are also shown in Table 5. It can be seen therefrom that by selecting the monomers and varying the molecular weight and monomer ratio in the polymer, a low surface tension of as low as 20 mN / m can be achieved.

[0286] For the copolymers of Examples 30 - 54, the dynamic surface tension was measured as a function of the bubble lifetime (bubble pressure method; Examples 30 - 38: 0.05 wt% aqueous solution, Examples 39 - 48: 0.1 wt% aqueous solution). The measurement method is described in WO2014 / 012661A1.

[0287] The results are shown in Figures 1 - 4 .

Claims

1. A process for preparing a polymer, which starts from one or more monomers containing oxirane groups and one or more partially fluorinated organic groups and optionally from one or more further monomers, and uses an organic salt, preferably an ammonium halide or a phosphonium halide or an alkali metal alkoxide or a macromonomer deprotonated by an organic salt as an initiator, and a Lewis acid, preferably a trialkylaluminum or a trialkylborane as a catalyst, and is carried out by monomer-activated anionic ring-opening polymerization of the monomers.

2. The method according to claim 1, wherein The further monomers contain, preferably contain only, oxirane groups and one or more non-fluorinated organic groups.

3. The method according to claim 1 or 2, characterized in that One of the monomers is a macromonomer.

4. The process according to any one or more of claims 1 to 3, which is used for preparing a polymer which contains, preferably contains only, one or more monomer units formed from one or more monomers of formula (I) and optionally one or more monomer units formed from one or more monomers selected from formula (II) and (III), (Rf-CHF-CF2-Y-CHR 1 ) m1 -L-X 1 (I) (R 2 ) m2 -X 2 (II) (R 3 ) m3 -X 3 (III) Among them, Each group and index, independently of one another and in the case of multiple occurrences, are the same or different and have the following meanings: Rf is a perfluorinated alkyl group, preferably a perfluorinated C1-C20-alkyl group, which is straight-chain or branched and optionally contains one or more heteroatoms preferably selected from O, S and N atoms. Y is O or S. R 1 is H or an alkyl group, preferably a C1-C6-alkyl group, L is a single bond or a divalent organic group, preferably an alkylene group, particularly preferably a C1-C20-alkylene group, which is straight-chain or branched and optionally contains one or more heteroatoms preferably selected from O, S and N atoms and optionally one or more functional groups. R 2 is H or an alkyl group, preferably a C1-C30-alkyl group, which is straight-chain, branched, monocyclic or polycyclic and optionally contains one or more heteroatoms preferably selected from O, S and N atoms, and in which one or more CH2 groups may also be replaced by CH=CH, R 3 is an alkyl group, preferably a C1-C30-alkyl group, which is straight-chain, branched, monocyclic or polycyclic and optionally contains one or more heteroatoms preferably selected from O, S and N atoms, where one or more CH2 groups can also be replaced by CH═CH, and where one or more H atoms are replaced by the group X 4 substituted, X 1 , X 2 and X 3 are each independently an epoxy group or a glycidyl group, X 4 is a functional group, preferably an ethylenically unsaturated group, a silyl group, an oxiranyl group, a glycidyl group or a tertiary amino group, m1 is 1, 2 or 3, preferably 1 or 2. m2 and m3 are each independently of one another 1 or 2, preferably 1. The process uses an organic salt, preferably an ammonium halide or a phosphonium halide or an alkali metal alkoxide or a macromonomer deprotonated by an organic salt as an initiator and a Lewis acid, preferably a trialkylaluminum or a trialkylborane as a catalyst, and is carried out by monomer-activated anionic ring-opening polymerization of the monomers of formula (I), (II) and / or (III).

5. The method according to any one or more of claims 1 to 4, characterized in that, Rf is selected from the following groups: CF3-(CF2) 0-3 -, CF3-(CF2) 0-3 -O-、 CF3-(CF2) 0-3 -O-(CF2) 1-3 -、 CF3-(CF2) 0-3 -O-(CF2) 1-3 -O-、 CF3-(CF2) 0-3 -O-(CF2) 1-3 -O-CF2-、 CF3-(CF2) 0-3 -O-(CF2-O) 1-8 - and CF3-(CF2) 0-3 -O-(CF2-O) 1-8 -CF2-。 6. The method according to any one or more of claims 1 to 5, characterized in that R 1 represents an H or C1-C6-alkyl group; and L represents a single bond, or a saturated C1-C20-alkylene group, which is straight-chain or branched and optionally contains one or more heteroatoms selected from O, S and N atoms, and optionally contains one or more functional groups.

7. The method according to any one or more of claims 1 to 6, characterized in that, R 2 represents a C2-C20-alkyl group, which is straight-chain or branched and optionally contains one or more heteroatoms selected from O, S, and N atoms.

8. The method according to any one or more of claims 1 to 7, characterized in that R 3 represents a C1-C20-alkyl group, which is straight-chain or branched and optionally contains one or more heteroatoms selected from O, S and N atoms, and in which one or more CH2 groups may also be replaced by CH═CH, and in which one or more H atoms are replaced by the group X 4 is replaced.

9. The method according to any one or more of claims 1 to 8, characterized in that X 4 represents -SiR 0 3. -NR 00 3. an allyloxy group, an epoxy group, an acrylate group or a methacrylate group, where R 0 is the same or different in each occurrence and represents C2-C6-alkyl, C2-C6-alkoxy, C3-C12-trialkylsilyloxy or C6-C12-aryloxy, where at least one group R 0 is not an alkyl group, and R 00 is the same or different in each occurrence and represents C2-C12-alkyl.

10. The method according to any one or more of claims 1 to 9, characterized in that The polymer further contains one or more monomer units formed from one or more monomers containing an anionically polymerizable group different from an oxirane group, where these further monomers are preferably selected from dimethylcyclosiloxanes, particularly preferably selected from D3 and D4.

11. The method according to any one or more of claims 1 to 10, characterized in that The organic salt is selected from the group consisting of: halides or azides of tetraalkylammonium, tetraarylammonium or alkylarylammonium, halides of tetraalkylphosphonium, tetraarylphosphonium or alkyltriarylphosphonium, meso-azido-bis(triarylphosphine) halides, and alkali metal alkoxides, where - the alkyl groups are each independently of one another preferably selected from straight-chain C2-C12-alkyl, branched C3-C12-alkyl or cyclic C5-C12-alkyl, particularly preferably selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-octyl and cyclohexyl, and - the aryl groups are each independently of one another preferably selected from phenyl, and - The alkoxide groups are each independently preferably selected from C2-C6-alkoxides, particularly preferably ethoxide, n-propoxide, isopropoxide, n-butoxide, isobutoxide, tert-butoxide or tert-pentoxide (tert-pentyloxide).

12. The method according to any one or more of claims 1 to 11, characterized in that, The Lewis acids are selected from the group consisting of: trialkylaluminiums, where the alkyl groups are each independently selected from C2-C6-alkyls, and dialkylboranes, trialkylboranes, diarylboranes and triarylboranes, where the alkyl groups are each independently selected from C2-C6-alkyls, and where two alkyl groups together with the boron atom can also form a monocyclic or polycyclic group, in particular a borinane-1-yl group or a borabicyclo[3.3.1]non-1-yl group, and the aryl groups are each independently selected from pentafluorophenyl.

13. The method according to any one or more of claims 1 to 12, characterized in that The organic salt is selected from the group consisting of: tetra-n-butylammonium bromide ((nBu4N) + Br - ), tetra-n-butylammonium chloride ((nBu4N) + Cl - ), tetra-n-octylammonium bromide ((nOct4N) + Br - ), tetra-n-octylammonium chloride ((nOct4N) + Cl - ), methyltriphenylphosphonium bromide ((MePPh3) + Br - ), methyltriphenylphosphonium chloride ((MePPh3) + Cl - ), μ-nitridobis(triphenylphosphine) chloride ((PPN) + Cl - ), tetra-n-butylammonium azide ((nBu4N) + N3 - ), potassium tert-butoxide ((tBuO) - K + ), potassium propoxide (PrO - K + ), and sodium propoxide (PrO - Na + ), and the Lewis acid is selected from the group consisting of: triethylaluminum (AlEt3), triisopropylaluminum (Al(iPr)3), triisobutylaluminum (Al(iBu)3), and triethylborane (BEt3).

14. The method according to any one or more of claims 1 to 13, characterized in that The method comprises the following steps: - drying the organic salt and subsequently dissolving it in an organic solvent, - adding one or more monomers, - cooling the reaction mixture to ≤0 °C, preferably 0 to -30 °C, - adding the Lewis acid under a protective gas atmosphere, - optionally holding the reaction mixture for a predetermined time under cooling and a protective gas atmosphere, - warming the reaction mixture to room temperature, - terminating the polymerization, preferably by adding an alcohol, particularly preferably methanol or ethanol, an acid, preferably HCl or HBr, or water, - removing the solvent and separating and purifying the resulting polymer.

15. The method according to any one or more of claims 1 to 14, characterized in that, As the first monomer, a macromonomer is used which is deprotonated by adding an organic salt, subsequently a second monomer containing an ethylene oxide group and a Lewis acid are added, where the deprotonated macromonomer is used as a macroinitiator for the second monomer activated by the Lewis acid, and the second monomer polymerizes after addition to the deprotonated macromonomer, where at least one monomer, preferably the second monomer, contains a partially fluorinated organic group.

16. A polymer prepared by the method according to any one or more of claims 1 to 15.

17. A formulation which contains the polymer according to claim 16.

18. Use of the polymer according to claim 16 or the formulation according to claim 17 as a surfactant, in functional coatings or for surface modification, preferably in water-repellent and / or stain-repellent and / or oil-repellent formulations and coatings.

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